Author's personal copy

Monatsh Chem
DOI 10.1007/s00706-016-1727-5

ORIGINAL PAPER

A novel schiff base ligand and its Ni(II) complex: synthesis

and characterization
Jafar Attar Gharamaleki1 • Houra Sadat Bolouhari1 • Atousa Goodarzi1 •

Ali Javadi2 • Behrouz Notash3

Received: 6 June 2015 / Accepted: 7 March 2016

Ó Springer-Verlag Wien 2016

Abstract In this paper, synthesis of a novel Schiff base Graphical abstract

ligand based on bis(2-amino-4-pheny1-5-thiazolyl)disul-
fide and its corresponding Ni(II) complex was reported.
This ligand was prepared through the formation of an imine
bond between 2-hydroxy-1-naphthaldehyde and bis(2-
amino-4-phenyl-5-thiazol)disulfide in absolute methanol as
solvent. The characterizations were performed by FT-IR,
1
H NMR, 13C NMR, elemental analysis, and single crystal
X-ray analysis. In the molecular structure, the ligand pos-
sessed anti-conformation around –S–S– bond and
monomeric moieties were linked into the chains through
the C–H_O and p_p interactions. The reaction of the Keywords Schiff base  Thiazoline  Disulfide bond 
synthesized ligand with NiCl2 in methanol afforded the Transition metal complex  UV/Vis spectroscopy 
corresponding Ni(II) complex. The resulting product was Cyclic voltammetry
further investigated by thermal gravimetric and differential
thermal analysis, which confirmed the formation of desired
polymeric complex. The electrochemical behavior and
formation of Ni(II) complex in dimethyl sulfoxide (DMSO) Introduction
solution were investigated by means of cyclic voltammetry
and UV–Vis titration, respectively. Schiff bases (known as azomethines), possessing a carbon–
nitrogen double bond (C=N) functional group, are consid-
ered as important organic compounds. These systems play
a critical role in coordination chemistry due to their ability
to encapsulate metal ions using donor atoms in their
backbones [1, 2]. So far, many biologically important
Schiff bases possessing antibacterial, antifungal, anti-HIV,
herbicidal, antitubercular, and anticancer activities have
been reported in the literature [3–8]. These materials can
& Jafar Attar Gharamaleki
easily coordinate with a wide range of transition metal
[email protected]
ions, yielding stable and intensely colored metal complexes
1
Faculty of Chemistry, Kharazmi University, Tehran, Iran which exhibit interesting physical, chemical, biological,
2
Department of Polymer Engineering, University of Akron, and catalytic properties [9–14]. Most commonly used
Akron, OH 44325, USA Schiff bases have NO or N2O2-donor atoms. However, the
3
Chemistry Department, Shahid Beheshti University, G. C., oxygen atoms can be replaced by other atoms such as
Evin, Tehran 1983963113, Iran sulfur, nitrogen, or selenium atoms. To improve the

123
Open Journal of Inorganic Chemistry, 2016, 6, 76-88
Published Online January 2016 in SciRes. http://www.scirp.org/journal/ojic
http://dx.doi.org/10.4236/ojic.2016.61005

Synthesis, Characterization and Crystal

Structure of a New Schiff Base Ligand from
a Bis(Thiazoline) Template and Hydrolytic
Cleavage of the Imine Bond Induced by a
Co(II) Cation
Jafar Attar Gharamaleki1*, Fahimeh Akbari1, Akram Karbalaei1, Kamran B. Ghiassi2,
Marilyn M. Olmstead2
1
Faculty of Chemistry, Kharazmi University, Tehran, Iran
2
Department of Chemistry, University of California, Davis, CA, USA

Received 23 December 2015; accepted 26 January 2016; published 29 January 2016

Copyright © 2016 by authors and Scientific Research Publishing Inc.

This work is licensed under the Creative Commons Attribution International License (CC BY).
http://creativecommons.org/licenses/by/4.0/

Abstract
The reaction of bis-[2-amino-4-pheny1-5-thiazolyl] disulfide with 5-nitro-salicylaldehyde in ab-
solute ethanol resulted in the formation of a new Schiff base ligand H2L (1). Characterization of the
ligand was performed by FT-IR, 1H NMR, 13C NMR, UV-Vis, elemental analysis and single crystal
X-ray diffraction. The ligand, (1), possesses a disulfide –S–S– bridge of 2.1121 (3) Å length, and the
molecule adopts a cis-conformation around this bond. In the crystal structure of (1), an intramo-
lecular O–H···N hydrogen bond with D… A distance of 2.69 (3) Å was present. The reaction of (1)
with Co(NO3)2·6H2O and CuCl2·2H2O in methanol afforded the corresponding metal complexes.
The obtained solids were further investigated by elemental analysis and UV-Vis titration that con-
firmed the formation of [CoL] and [ClCuHL] complexes. However, recrystallizaion of the Co(II)
complex in dimethylsulfoxide caused the complete hydrolysis of the imine bond and afforded a
Co(II) complex in which two 5-nitro-salicylaldehyde and two DMSO molecules were coordinated to
the central metal in an octahedral fashion. This structure (2) was also confirmed by single crystal
X-ray analysis.

Keywords
Schiff Base, Thiazoline Ligand, Disulfide Bond, Co(II) and Cu(II) Complexes, Hydrolytic Cleavage,
*
Corresponding author.

How to cite this paper: Gharamaleki, J.A., et al. (2016) Synthesis, Characterization and Crystal Structure of a New Schiff
Base Ligand from a Bis(Thiazoline) Template and Hydrolytic Cleavage of the Imine Bond Induced by a Co(II) Cation. Open
Journal of Inorganic Chemistry, 6, 76-88. http://dx.doi.org/10.4236/ojic.2016.61005
J. Chem. Sci. Vol. 127, No. 12, December 2015, pp. 2171–2181. 
c Indian Academy of Sciences.
DOI 10.1007/s12039-015-0979-7

Synthesis, characterization and crystal structure of four new asymmetric

triazene ligands: An example of linear HgII complex with Hg...π
secondary bonding interactions

MOHAMMAD REZA MELARDIa , FATEMEH BABER SHAMSI MOGOIIa ,

AYOOB BABAII SAJIRANIa , JAFAR ATTAR GHARAMALEKIb , BEHROUZ NOTASHc and
MOHAMMAD KAZEM ROFOUEIb,∗
a
Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran
b
Faculty of Chemistry, Kharazmi University, Tehran, Iran
c
Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
e-mail: [email protected]

MS received 29 May 2015; revised 31 August 2015; accepted 7 September 2015

Abstract. In this work, the asymmetric ligands [1-(phenyl)-3-(2-nitro-4-methylphenyl)]triazene (1), [1-(4-

methylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (2), [1-(4-ethylphenyl)-3-(2-nitro-4-methylphenyl)]tria-
zene (3) and [1-(4-ethoxyphenyl)-3-(2-nitro-4-methylphenyl)]triazene (4), were synthesized. The reaction of
the ligand (3) with HgCl2 in methanol resulted in the formation of the [HgL2 ] complex, (5). All compounds
were characterized by means of CHN analysis, FT-IR, 1 H NMR, 13 C NMR spectroscopy. In addition, the crys-
tal structures of the ligands (2) to (4) were investigated by single crystal X-ray analysis. In the solid state,
all ligands exhibited trans conformation about the –N=N– double bond. The HgII complex (5) crystallized in
monoclinic system with C2/c space group. The triazene ligand was found to be deprotonated prior to coordina-
tion and acts as monodentate ligand. The HgII which lies on inversion center (site symmetry ı̄), is surrounded
by two N atoms from L ligands forming a linear geometry. The other two Hg–N bonds are relatively longer
and can only be regarded as weak secondary bonds. Also, Hg-η3 -arene π-interactions are present in this com-
pound. Hydrogen bonds, π · · · π and C–H· · · π stacking interactions help in the stabilization of the resulted
frameworks. These C–H· · · π edge-to-face interactions are present with H· · · π distance of 3.00 Å.
Keywords. Mercury(II) complex; Hg· · · π interaction; asymmetric triazene; crystal structure.

1. Introduction asymmetric-substituted triazenide complexes of HgII

which have a remarkable ability to self-assemble in dif-
Aryl triazenes have been studied over several years ferent manners through metal-η-arene π-interactions
for their interesting structural and anticancer reac- have been reported.11 In recent years, our group
tivity properties.1–5 The study of transition-metal has been involved in the complexation of transition
complexes containing 1,3-diaryltriazene ligands has metal ions with several triazene compounds, starting
greatly increased in the past few years due to the from different bis(diaryl) symmetric and asymmetric-
potential reactivity of these ligands.6,7 As ligands, substituted triazenides. In this regard, the synthesis
the (–NH–N=N–) moieties can show different types of 1,3-bis(2-methoxyphenyl)]triaz-1-ene19 [1,3-bis(2-
of coordination in metal complexes. The coordina- ethoxyphenyl)]triaz-1-ene20 [1,3-bis(2-cyanophenyl)]
tion modes can be monodentate, (N1, N3)-chelating triaz-1-ene21 1-(3,5-dichlorophenyl)-3-(2-methoxyphe-
towards one metal atom or (N1, N3)-bridging over two nyl)triaz-1-ene22 and 3-(2-ethoxyphenyl)-1-(3-nitrophe-
metal atoms over a wide variety of transition metal nyl)triaz-1-ene23 molecules have been reported to act
complexes.8–10 In these compounds secondary bonds or as ligands. Additionally, we have published the HgII
interactions such as hydrogen bonds and metal π-aryl complexes with [1,3-bis(2-methoxyphenyl)]triazene by
interactions can play important roles in the struc- using HgCl2 24 HgBr2 25 Hg(CH3 COO)2 and Hg(SCN)2
tural stability.11–18 Several bis(diaryl) symmetric and salts as starting materials.26 Just recently, a HgII com-
plex with [1,3-bis(2-ethoxyphenyl)]triazene as ligand
has been reported, in which HgCl2 has been used as
∗ For correspondence starting salt.27 From recent structural studies, it was

2171
 Journal of Coordination Chemistry, 2014
Vol. 67, No. 12, 2171–2183, http://dx.doi.org/10.1080/00958972.2014.931573

Mercury(II) complexes containing new ortho-functionalized

asymmetric triazene ligands: synthesis, crystal structures, and
solution studies
V. GHOULIPOUR†*, F. HOSSEINZADEH†, S. FARAZI†, J. ATTAR GHARAMALEKI†,
B. NOTASH‡ and M.K. ROFOUEI†
†Faculty of Chemistry, Kharazmi University, Tehran, Iran
Downloaded by [Jafar Attar] at 08:45 03 October 2014

‡Department of Chemistry, Shahid Beheshti University, Tehran, Iran

(Received 17 October 2013; accepted 23 April 2014)

Synthesis of two new asymmetric ligands: 1-(2-ethoxyphenyl)-3-(2-methoxycarbonylphenyl)triazene

(HL) (1) and 1-(2-methoxyphenyl)-3-(2-methoxycarbonylphenyl)triazene (HL′) (2) are reported.
The prepared triazenes are functionalized by ethoxy and methoxy groups in the ortho positions,
respectively. The related monomeric complexes, [HgL2] (3) and [HgL′2] (4), were prepared by the
reacting of the corresponding ligands with Hg(NO3)2 salt in methanol as solvent. All compounds
were characterized by CHN analysis, FT-IR, 1H NMR, and 13C NMR spectroscopy. According to
the crystal structures of 1 and 2, the N–N bond distances indicate the presence of alternating single
and double bonds, and hence the –N=N–NH– moiety. On coordination, each triazene was
deprotonated and as a result, a resonance structure is formed between nitrogens which let them to be
a tridentate ligand. In the crystal structure of 3, [HgL2], the central Hg(II) is surrounded by two N
atoms from interlocked L forming linear geometry, in which the other four Hg–N and Hg–O bonds
are longer and can only be regarded as weak secondary bonds. An interesting feature of 3 is also the

*Corresponding author. Email: [email protected]

© 2014 Taylor & Francis

 research papers

Structures of CoII and ZnII complexes of the

proton-transfer compound derived from pyrazine-
ISSN 2053-2296 2,3-dicarboxylic acid and piperazine

Mohammad Ghadermazi,a* Jafar Attar Gharamaleki,b Marilyn M. Olmsteadc and

Mehdi Almasia
Received 25 March 2015
a
Accepted 3 June 2015 Department of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran, bFaculty of Chemistry, Kharazmi
University, Tehran, Iran, and cDepartment of Chemistry, University of California, Davis, CA 95616, USA.
*Correspondence e-mail: [email protected]
Edited by A. G. Oliver, University of Notre
Dame, USA
The reaction of the proton-transfer compound piperazine-1,4-diium pyrazine-
Keywords: pyrazine-2,3-dicarboxylic acid; 2,3-dicarboxylate 4.5-hydrate, C4H12N22+C6H2N2O424.5H2O or (pipzH2)-
piperazinediium; proton transfer; one-dimen-
(pyzdc)4.5H2O (pyzdcH2 is pyrazine-2,3-dicarboxylic acid and pipz is piper-
sional CoII coordination polymer; ZnII dimer;
hydrogen bonding; commensurate superlattice;
azine), (I), with Zn(NO3)26H2O and CoCl26H2O results in the formation of
order–disorder transition; crystal structure. bis(piperazine-1,4-diium) bis(-pyrazine-2,3-dicarboxylato)-3N1,O2:O3;3O3:-
N1,O2-bis[aqua(pyrazine-2,3-dicarboxylato-2N1,O2)zinc(II)] decahydrate, (C4-
CCDC references: 898180; 898181; 898179 H12N2)2[Zn2(C6H2N2O4)4(H2O)2]10H2O or (pipzH2)2[Zn(pyzdc)2(H2O)]2-
10H2O, (II), and catena-poly[piperazine-1,4-diium [cobalt(II)-bis(-pyrazine-
Supporting information: this article has 2,3-dicarboxylato)-3N1,O2:O3;3O3:N1,O2] hexahydrate], {(C4H12N2)[Co(C6H2-
supporting information at journals.iucr.org/c
N2O4)2]6H2O}n or {(pipzH2)[Co(pyzdc)2]6H2O}n, (III), respectively. In (I),
pyzdcH2 is doubly deprotonated on reaction with piperazine as a base.
Compound (II) crystallizes as a dimer, whereas compound (III) exists as a one-
dimensional coordination polymer. In (II), two pyzdc2 groups chelate to each
of the two ZnII atoms through a ring N atom and an O atom of the 2-carboxylate
group. In one ligand, the adjacent 3-carboxylate group bridges to a neighbouring
metal atom. A water molecule ligates in the sixth coordination site. The structure
of (II) can be described as a commensurate superlattice due to an ordering in the
hydrogen-bonded network. In (III), no water is coordinated to the metal atom
and the coordination sphere is comprised of two N,O-chelates plus two bridging
O atoms. A large number of hydrogen bonds are observed in all three
compounds. These interactions, as well as – and C O   stacking
interactions, play important structural roles.

1. Introduction
Pyrazine-2,3-dicarboxylic acid (pyzdcH2) is interesting be-
cause the dianion (pyzdc2) has two adjacent carboxylate
groups that can coordinate to a metal atom through a total of
four potential O-atom donors and the pyrazine ring can
coordinate through one or two N-atom donors (Takusagawa &
Shimada, 1973; Nepveu et al., 1993). Multiple hydrogen-
bonding opportunities lead to the possibility of extended
multidimensional structures. Crystal structures of transition
metal complexes include those of manganese (Wang & Wang,
2009), copper (Mirzaei et al., 2012), zinc (Gunay et al., 2013),
iron (Xu et al., 2008), silver (Alisir et al., 2013) and cadmium
(Gunay et al., 2011), as well as mixed-metal species (Sun et al.,
2012). In addition, those of f-block and group 1 and 2 cations
have been characterized crystallographically (Zou et al., 1999;
Konar et al., 2004; Tombul et al., 2007; Ptasiewicz-Bak &
Leciejewicz, 1997). At least 16 ZnII coordination polymers
# 2015 International Union of Crystallography with the pydzc2 ligand are known, for example, [Zn(pydzc)-

Acta Cryst. (2015). C71, 539–544 http://dx.doi.org/10.1107/S2053229615010761 539

electronic reprint
 Author's personal copy
J Inorg Organomet Polym (2015) 25:892–905
DOI 10.1007/s10904-015-0185-6

Synthesis, Crystal Structure, Solution Study and In Silico ADME

Profiling of Various Asymmetric Functionalized Triazenes
Jafar Attar Gharamaleki • Atousa Goodarzi •
Houra Sadat Bolouhari • Shabnam Hooshmand •

Mohammad Kazem Rofouei • Behrouz Notash

Received: 23 November 2014 / Accepted: 5 February 2015 / Published online: 18 February 2015
Ó Springer Science+Business Media New York 2015

Abstract Syntheses of some ligands based on asymmetric complexes (7) and (8), respectively. Finally, the chemical
triazenes consisting 1-(2-methoxycarbonylphenyl)-3-(2- structures of the investigated ligands were correlated to their
methylphenyl)triazene (1), 1-(2-methoxycarbonylphenyl)-3- pharmacokinetic behaviour using five pre-calculated models
(3-methylphenyl)triazene (2), 1-(2-methoxycarbonylphenyl)- implemented in VolSurf program.
3-(4-methylphenyl)triazene (3), 1-(2-methoxycarbonylph- Graphical Abstract Polyhedron around HgII atom coor-
enyl)-3-(3,5-dichlorophenyl)triazene (4), 1-(4-chlorophenyl)- dinated by two triazenide ligands in an octahedron fashion.
3-(4-methylphenyl)-triazene (5) and their related HgII
complexes were reported. The characterizations were per-
formed by FT-IR, 1H NMR and 13C NMR spectroscopies. In
(3) and (4), both triazenes possess trans-conformation
around the (–N=N–) bond and monomeric moieties are
linked to pairs and wave-like chains through C–H


O and C–
H


N hydrogen bonds which are further assembled by
stacking through secondary p


p interactions [3.829(1) and
3.736(1) Å]. The reaction of (1) and Hg(NO3)2 in methanol
produces the corresponding HgII complex (6) where each
triazenide binds to the HgII atom through two nitrogen atoms
of triazenide and one oxygen atom of pendant methoxycar-
bonyl group forming distorted MN4O2 octahedral around the
HgII atom. The stoichiometry and formation of complex (6)
and (8) in methanol solution were investigated by UV–Vis
titration. Moreover, Reaction of substituted 1,3-diaryltri-
azenes (2) and (5) with HgII salts afford a family of orange

Keywords Asymmetric triazenes
Hg complexes

J. Attar Gharamaleki (&)
A. Goodarzi
Crystal structure
Solution studies
Pharmacokinetic
H. S. Bolouhari
M. K. Rofouei
Faculty of Chemistry, Kharazmi University, Tehran, Iran
e-mail: [email protected]

S. Hooshmand 1 Introduction
Chemistry Department, Faculty of Science, Golestan University,
Gorgan, Iran Experimentally, 1,3-diaryl triazenes, ArN = NNHAr, are
easily prepared from the coupling reaction of a diazonium
B. Notash
Department of Chemistry, Shahid Beheshti University, G. C., salt with a primary aromatic amine [1]. Up to now, many
Evin, 1983963113 Tehran, Iran derivatives of the triazene have been synthesized, the most

123
DOI: 10.1002/chem.201103852

Isolation of Four Isomers of C96 and Crystallographic Characterization of

Nanotubular D3d(3)-C96 and the Somewhat Flat-Sided Sphere C2ACHTUNGRE(181)-C96

Hua Yang,[a] Hongxiao Jin,[a] Yuliang Che,[a] Bo Hong,[a] Ziyang Liu,*[a]

Jafar Attar Gharamaleki,[c] Marilyn M. Olmstead,*[b] and Alan L. Balch*[b]

Fullerenes are now known to come in a variety of sizes the isolated pentagon rule (IPR), which alleviates strain in
and shapes, with the latter ranging from highly symmetrical the cage by requiring that each of the twelve pentagons of a
(e. g. the iconic Ih-C60) to minimally symmetric, (e. g. C1(30)- fullerene to be surrounded by five hexagons.[1] Theoretical
C90).[1, 2] The structures and potential properties of very large calculations of Zhao, Slanina, and Goto indicated that the
fullerene cages have produced some fanciful conjectures. D2ACHTUNGRE(183) isomer was the most stable at temperatures up to
For example, computation efforts have focused upon pre- 1400 K, but at higher temperatures the C2ACHTUNGRE(181), C1ACHTUNGRE(144), C1-
dicting structural details for the series of Ih fullerenes with ACHTUNGRE(145), C1ACHTUNGRE(175), and C1ACHTUNGRE(143) isomers gained stability.[16, 17] Ex-
60, 240, 540, 960, 1500, 2160, 2940, 3840, 4860, 6000, 7260, perimentally, Kikuchi, Achiba and co-workers briefly re-
and 8640 carbon atoms in the cage.[3–5] Other studies have ported that they had isolated ten isomers of C96 and identi-
suggested that large, empty-cage fullerenes may be unusual, fied their symmetries through 13C NMR spectroscopy as C1
low-density materials (bucky balloons).[6, 7] Experimental ob- (4 isomers), C2 (3 isomers), Cs (l isomer), D2 (1 isomer), and
servations of large fullerene-like structures include electron D3d (l isomer).[18] Kemnitz and Troyanov reacted C2F5I with
microscopic studies of carbon onions, which appear to con- a mixture of higher fullerenes and were able to obtain crys-
sist of concentric shells of fullerene-like cages,[8, 9] and mass tals of the adduct C96ACHTUNGRE(C2F5)12, which were shown by single-
spectrometric studies on electric arc generated soot, which crystal X-ray diffraction to utilize the C1ACHTUNGRE(145)-C96 cage.[19]
reveal the presence of carbon clusters with even numbers of Vaporization of a graphite rod filled with Sm2O3 and
atoms up to at least C600.[10] Additionally, a range of soluble graphite powder in an electric arc produced the carbon soot
carbon clusters have been extracted from this sort of carbon used for isolating the C96 isomers.[20, 21] This soot was extract-
soot.[11, 12] However, isolation of these higher fullerenes in ed with o-dichlorobenzene. The soluble extract was subject-
isomerically pure form is difficult because of the small quan- ed to a multi-stage, high-pressure liquid chromatographic
tities that form and the possibility of producing a variety of (HPLC) isolation process using three different chromato-
isomers. To date, three isomers of C90 (D5h(1)-C90, C1(30)- graphic columns (Buckyprep-M, Buckyprep and 5PBB) with
C90, and C1(32)-C90) are the largest empty-cage fullerenes to either chlorobenzene or toluene as eluent. Four individual
be structurally characterized in pristine form.[2, 13] Larger isomers of C96 were obtained. Figure 1 shows the HPLC
fullerene cages have been structurally characterized for the traces for the purified isomers and Table 1 shows their re-
endohedral fullerenes La2@D5ACHTUNGRE(450)-C100 and Sm2@D3dACHTUNGRE(822)- tention times on three different columns. C96(I) was the
C104.[14, 15]
Here we report the isolation of four isomers of C96 and
the structural characterization of two of these by single-crys-
tal X-ray diffraction. For C96 there are 187 isomers that obey

[a] H. Yang, H. Jin, Y. Che, B. Hong, Prof. Dr. Z. Liu

College of Materials Science and Engineering
China Jiliang University, Hangzhou 310018 (P. R. China)
Fax: (+ 86) 571-86876296
E-mail: [email protected]
[b] Prof. Dr. M. M. Olmstead, Prof. Dr. A. L. Balch
Department of Chemistry, University of California
Davis, CA 95616 (USA)
E-mail: [email protected]
[email protected]
[c] Dr. J. A. Gharamaleki
Faculty of Chemistry
Tarbiat Moallem University, Tehran (Iran) Figure 1. Chromatograms of the isolated C96(I, II, III, IV) isomers on a
Supporting information for this article is available on the WWW Buckyprep column with toluene as the eluent. The HPLC conditions are:
under http://dx.doi.org/10.1002/chem.201103852. flow rate of 4.5 mL min 1 and detection wavelength of 450 nm.

2792  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2012, 18, 2792 – 2796
metal-organic compounds
Acta Crystallographica Section E Data collection
Structure Reports Bruker SMART 1000 CCD 32229 measured reflections
Online diffractometer 4116 independent reflections
Absorption correction: multi-scan 2884 reflections with I > 2(I)
ISSN 1600-5368
(SADABS; Bruker, 1998) Rint = 0.068
Tmin = 0.884, Tmax = 0.970

Bis(guanidinium) tris(pyridine-2,6- Refinement

dicarboxylato-j3O2,N,O6)zirconate(II) R[F 2 > 2(F 2)] = 0.056
wR(F 2) = 0.146
223 parameters
H-atom parameters constrained
tetrahydrate S = 1.07
max = 0.87 e Å3
4116 reflections
min = 0.47 e Å3

Masoumeh Tabatabaee,a* Mahnaz Adineh,a Zohreh

Derikvandb and Jafar Attar Gharamalekic Table 1
a
Hydrogen-bond geometry (Å,  ).
Department of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran,
b
Department of Chemistry, Faculty of Science, Khorramabad Branch, Islamic Azad, D—H  A D—H H  A D  A D—H  A
University, Khorramabad, Iran, and cFaculty of Chemistry, Tarbiat Moallem
N3—H3NA  O1 0.77 2.23 3.003 (4) 175
University, 49 Mofateh Avenue, Tehran, Iran
N3—H3NB  O2W i 0.86 2.15 2.930 (4) 150
Correspondence e-mail: [email protected] N4—H4NA  O2W i 0.83 2.04 2.818 (4) 156
N4—H4NB  O1W ii 0.78 2.06 2.834 (4) 175
Received 4 March 2012; accepted 15 March 2012 N5—H5NA  O2 0.88 1.95 2.828 (4) 171
N5—H5NB  O3iii 0.79 2.45 3.143 (4) 148
Key indicators: single-crystal X-ray study; T = 120 K; mean (C–C) = 0.005 Å; N5—H5NB  O4iii 0.79 2.52 3.171 (4) 141
R factor = 0.056; wR factor = 0.146; data-to-parameter ratio = 18.5. O1W—H1WA  O3iv 0.84 2.33 3.041 (3) 143
O1W—H1WA  O5iv 0.84 2.38 3.076 (3) 140
O1W—H1WB  O6 0.89 1.87 2.761 (3) 175
O2W—H2WA  O5iv 0.86 2.07 2.909 (3) 165
In the title complex, (CH6N3)2[Zr(C7H3NO4)3]4H2O, the ZrIV O2W—H2WA  O6iv 0.86 2.57 3.085 (3) 119
O2W—H2WB  O4v 0.94 1.84 2.745 (3) 160
ion lies on a twofold rotation axes and is coordinated by six O
and three N atoms of three tridentate pyridine-2,6-dicarboxyl- Symmetry codes: (i) x þ 1; y; z þ 12; (ii) x þ 12; y þ 12; z þ 12; (iii) x  12; y  12; z þ 12;
(iv) x þ 1; y þ 1; z; (v) x; y  1; z.
ate ligands, forming a slightly distorted tricapped trigonal–
prismatic geometry. In the crystal, O—H  O and N—H  O Data collection: SMART (Bruker, 1998); cell refinement: SAINT
hydrogen bonds link the components into a three-dimensional (Bruker, 1998); data reduction: SAINT; program(s) used to solve
network. structure: SHELXTL (Sheldrick, 2008); program(s) used to refine
structure: SHELXTL; molecular graphics: SHELXTL, DIAMOND
(Brandenburg, 1999) and Mercury (Macrae et al., 2006); software
Related literature used to prepare material for publication: SHELXTL.
For related structures, see: Aghabozorg et al. (2005); Tabata-
baee (2010); Tabatabaee et al. (2009, 2011a,b,c, 2012); Derik- The authors wish to express their deepest appreciation to
vand et al. (2010); Attar Gharamaleki et al. (2009). the late Professor Dr. H Aghabozorg who has inspired,
advised and assisted during this study.

Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: LH5430).

References
Aghabozorg, H., Moghimi, A., Manteghi, F. & Ranjbar, M. (2005). Z. Anorg.
Allg. Chem. 631, 909–913.
Attar Gharamaleki, J., Aghabozorg, H., Derikvand, Z. & Yousefi, M. (2009).
Acta Cryst. E65, m824–m825.
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (1998). SAINT, SMART and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Derikvand, Z., Talei, G. R., Aghabozorg, H., Olmstead, M. M., Azadbakht, A.,
Experimental Nemati, A. & Attar Gharamaleki, J. (2010). Chin. J. Chem. 28, 2167–2173.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor,
Crystal data R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
(CH6N3)2[Zr(C7H3NO4)3]4H2O V = 3094.6 (3) Å3 Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Mr = 778.77 Z=4 Tabatabaee, M. (2010). Acta Cryst. E66, m647–m648.
Orthorhombic, Pbcn Mo K radiation Tabatabaee, M., Abbasi, F., Kukovec, B. M. & Nasirizadeh, N. (2011b). J.
a = 17.2444 (9) Å  = 0.45 mm1 Coord. Chem. 64, 1718–1728.
b = 10.8583 (5) Å T = 120 K Tabatabaee, M., Aghabozorg, H., Attar Gharamaleki, J. & Sharif, M. A.
c = 16.5268 (8) Å 0.17  0.15  0.07 mm (2009). Acta Cryst. E65, m473–m474.

m462 Tabatabaee et al. doi:10.1107/S1600536812011439 Acta Cryst. (2012). E68, m462–m463

ARTICLE

DOI: 10.1002/zaac.201100557

Synthesis, Structure, and Solution Study of a Mercury(II) Complex with the

Ligand [1-(2-Methoxyphenyl)-3-(4-chlorophenyl)]triazene
Mohammad Kazem Rofouei,[a] Zahra Ghalami,[a] Jafar Attar Gharamaleki,*[a]
Vanik Ghoulipour,[a] Giuseppe Bruno,[b] and Hadi Amiri Rudbari[b]

Keywords: Mercury; Triazene; X-ray diffraction; Solution study; C–H···π interaction

Abstract. The title ligand, [1-(2-methoxyphenyl)-3-(4-chlorophen- C–H···π interactions form a layer structure along the crystallographic
yl)]triazene, HL (1), was prepared. In a reaction with Hg(NO3)2 it ab plane [110]. In compound 2, the HgII atom is hexacoordinated by
forms the complex [Hg(C26H22Cl2N6O2)], [HgL2] (2). Both com- two tridentate [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazenide li-
pounds were characterized by means of X-ray crystallography, CHN gands through a N2O2 set. In addition, in the structure of 2, monomeric
analysis, FT-IR, 1H NMR, and 13C NMR spectroscopy. In the structure complexes are connected to each other by C–H···π stacking interac-
of compound 1, two independent fragments are present in the unit cell. tions, resulting in a 2D architecture. These C–H···π edge-to-face inter-
They exhibit trans arrangement about the –N=N– double bond. The actions are present with H···π distances of 3.156 and 3.027 Å. The
dihedral angles between two benzene rings in both fragments are 4.36 results of studies of the stoichiometry and formation of complex 2 in
and 18.79 Å, respectively. Non-classic C–H···N hydrogen bonding and methanol solution were found to support its solid state stoichiometry.

1 Introduction tio,[18] nature of the ligands,[19] solvents,[20] and/or counter-

anions,[21] or even the reaction temperature and pH value.[22,23]
Triazene compounds having a diazoamino group We have previously reported the synthesis of 1,3-bis(2-
(–N=NNH–) commonly adopt a trans configuration in the methoxyphenyl)]triazene,[24] [1,3-bis(2-ethoxyphenyl)]triaz-
ground state.[1] Transition-metal complexes containing 1,3-di- ene,[25] and [1,3-bis(2-cyanophenyl)]triazene[26] molecules that
aryltriazenide ligands have been extensively studied because can act as ligands. Additionally, we have published the HgII
of the versatility of their coordination, which yield a variety complexes with [1,3-bis(2-methoxyphenyl)]triazene by using
of coordination compounds with large structural diversity.[2,3] HgCl2,[27] HgBr2,[28] Hg(CH3COO)2, and Hg(SCN)2 salts as
Triazenes and anionic triazenide ligands show different types starting materials.[29] Moreover, AgI and CdII complexes with
of coordination in metal complexes like monodentately, this ligand are known.[30,31] Just recently, a HgII complex with
(N1,N3)-chelating towards one metal atom or (N1,N3)-bridg- [1,3-bis(2-ethoxyphenyl)]triazene as ligand has been reported,
ing over two metal atoms,[4] showing a remarkable ability to in which HgCl2 has been used as starting salt.[32] From recent
support the stereochemical requisites of a wide variety of metal structural studies, it was argued that counter-anions play an
transition complexes.[5,6] In these compounds secondary bonds important role in determining the solid state lattices of these
or interactions such as hydrogen bonds and metal π-aryl inter- compounds. Moreover, we are performing the synthesis and
actions can play important roles in the structural stability.[7–11] spectroscopic study of some new asymmetric ligands and their
In this regard, organic ligands play an important role in ad- complexes with transition metal ions in our laboratory. In con-
justing the architectures of the resulting metal complexes, so tinuation with our previous work, we herein report the synthe-
proper selection of ligands is the key issue in the construction sis, characterization, and molecular structure of a new asym-
of supramolecular networks.[12–14] However, the crystal engi- metric triazene [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]tria-
neering with desired topologies and specific properties still re- zene, HL (1), and its HgII complex [Hg(C26H22Cl2N6O2)],
mains a difficult challenge since a variety of factors influence [HgL2], (2) in methanol as solvent.
the self-assembly processes such as coordination arrangement
and oxidation state of the metal ions,[15–17] metal-to-ligand ra-
2 Experimental Section
* Dr. J. Attar Gharamaleki
Fax: +98-2188820993 2.1 Materials and Physical Techniques
E-Mail: [email protected]
[a] Faculty of Chemistry All chemicals were of analytical grade and were used as commercially
Tarbiat Moallem University obtained without further purification. IR spectra were recorded with a
Tehran, Iran Perkin-Elmer RXI spectrometer using KBr disks. Elemental analysis
[b] Dipartimento di Chimica Inorganica
Universita di Messina was carried out with a Perkin-Elmer 2400(II) CHNS/O analyzer. Melt-
Messina, Italy ing points were measured with a Barnstead Electrothermal 9200 appa-

798 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2012, 638, (5), 798–803
 organic compounds
Acta Crystallographica Section E Experimental
Structure Reports
Crystal data
Online
C9H11NO2 V = 1782.25 (14) Å3
ISSN 1600-5368 Mr = 165.19 Z=8
Orthorhombic, Pbca Mo K radiation
a = 7.9079 (4) Å  = 0.09 mm1
N-(2-Ethoxyphenyl)formamide b = 14.1253 (6) Å
c = 15.9555 (7) Å
T = 296 K
0.45  0.23  0.18 mm

Mohammad Kazem Rofouei,a Jafar Attar Gharamaleki,a* Data collection

Fereshteh Younesian,b Giuseppe Brunoc and Hadi Amiri Bruker APEXII CCD 8725 measured reflections
Rudbaric diffractometer 1961 independent reflections
Absorption correction: multi-scan 1248 reflections with I > 2(I)
a (SADABS; Bruker, 2007) Rint = 0.024
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, bDepartment of
Tmin = 0.671, Tmax = 0.746
Chemistry, Islamic Azad University, Tehran Central Branch, Tehran, Iran, and
c
Dipartimento di Chimica Inorganica, Universita di Messina, Messina, Italy
Refinement
Correspondence e-mail: [email protected]
R[F 2 > 2(F 2)] = 0.043 110 parameters
Received 4 January 2012; accepted 17 January 2012 wR(F 2) = 0.120 H-atom parameters constrained
S = 1.03
max = 0.12 e Å3
Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.003 Å;
1961 reflections
min = 0.14 e Å3
R factor = 0.043; wR factor = 0.120; data-to-parameter ratio = 17.8.

Table 1
The title compound, C9H11NO2, was obtained as an unex- Hydrogen-bond geometry (Å,  ).
pected product in an attempt to synthesize a triazene ligand. Cg is the centroid of the C3–C9 ring.
The title molecule is almost planar, with the formamide and D—H  A D—H H  A D  A D—H  A
ethoxy groups oriented at 2.7 (3) and 12.9 (2) , respectively,
with respect to the mean plane of the benzene ring. In the N1—H1  O2 i
0.86 2.24 2.9741 (18) 144
C2—H2A  Cgii 0.97 2.78 3.5853 (19) 141
crystal, molecules are linked by intermolecular N—H  O
Symmetry codes: (i) x þ 12; y þ 12; z; (ii) x þ 12; y; z þ 12.
hydrogen bonds, forming a chain along the a axis. Weak C—
H   interactions with an H   distance of 2.78 Å reinforce
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
the crystal packing, resulting in a three-dimensional network. (Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
Related literature structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW in
SHELXTL (Sheldrick, 2008); software used to prepare material for
For preparation of several trizene compounds in our labora- publication: SHELXTL.
tory, see: Melardi et al. (2011). For similar crystal structures,
see: Landman et al. (2011); Chitanda et al. (2008); Hu et al.
(2010). Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: PV2505).

References
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA
Chitanda, J. M., Quail, J. W. & Foley, S. R. (2008). Acta Cryst. E64, o1728.
Hu, H.-L., Wu, C.-J., Cheng, P.-C. & Chen, J.-D. (2010). Acta Cryst. E66, o180.
Landman, M., van der Westhuizen, B., Bezuidenhout, D. I. & Liles, D. C.
(2011). Acta Cryst. E67, o120.
Melardi, M. R., Ghannadan, A., Peyman, M., Bruno, G. & Amiri Rudbari, H.
(2011). Acta Cryst. E67, o3485.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Acta Cryst. (2012). E68, o505 doi:10.1107/S160053681200205X Rofouei et al. o505

electronic reprint
 Polyhedron 44 (2012) 138–142

Contents lists available at SciVerse ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Synthesis, characterization and crystal structures of HgII complexes with

asymmetric ortho-functionalized 1,3-bis(aryl)triazenide ligands
Mohammad Kazem Rofouei a,⇑, Jafar Attar Gharamaleki a, Mohammad Reza Melardi b,
Seyed Mahdi Hosseini a, Fatemeh Hosseinzadeh a, Mitra Peyman b, Atefeh Ghannadan b, Behrouz Notash c,
Giuseppe Bruno d, Hadi Amiri Rudbari d
a
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
b
Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran
c
Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
d
Dipartimento di Chimica Inorganica, Universita di Messina, Messina, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The synthesis of two [Hg(L1)2] and [Hg(L2)2] complexes using asymmetric triazenes as ligands are
Received 28 March 2012 reported. The triazene ligands are substituted with cyano and chloride groups in the ortho positions of
Accepted 19 June 2012 the aryl rings (where HL1 and HL2 are 1-(2-ethoxyphenyl)-3-(2-cyanophenyl)triazene and 1-(2-ethoxy-
Available online 28 June 2012
phenyl)-3-(2-chlorophenyl) triazene, respectively). These complexes were prepared by the reaction of
corresponding triazenes with Hg(NO3)2 and were characterized by FT-IR, NMR, elemental and single crys-
Keywords: tal X-ray analyses. Both triazene ligands were found to deprotonate on coordination and act as tridentate
Mercury(II)
chelating ligands forming distorted N4O2 octahedral geometry around HgII atoms. Hydrogen bonds, p


p
Triazene
X-ray crystal structure
and C–H


p stacking interactions help to the stabilization of the resulted frameworks.
p


p Stacking Ó 2012 Elsevier Ltd. All rights reserved.
C–H


p interaction

1. Introduction hydrogen bonding. We have previously reported the synthesis of

[1,3-bis(2-methoxyphenyl)]triazene [16], [1,3-bis(2-ethoxy-
Hydrogen-bonding and other types of non-covalent interactions phenyl)]triazene [17] and [1,3-bis(2-cyanophenyl)]triazene [18]
like p


p and C–H


p stacking interactions play an important role molecules that can act as ligands. Also, we have published the
in the building of supramolecular systems [1,2]. Aryl triazenes Hg(II) complexes with [1,3-bis(2-methoxyphenyl)]triazene by
have been studied over several years for their interesting struc- using HgCl2 [19], HgBr2 [20], Hg(CH3COO)2 and Hg(SCN)2 [21] salts
tural, anticancer, and reactivity properties [3–10]. Triazene com- as starting materials. More recently, a Hg(II) complex with [1,3-
pounds characterized by having a diazoamino group (–N@NNH–) bis(2-ethoxyphenyl)]triazene as ligand is reported in which
commonly adopt a trans configuration in the solid state. As ligands, Hg(NO3)2 is used as starting salt [22]. To investigate the effect of
the N@NNH moieties can show different types of coordination in the substituted derivatives on coordination behavior of the tria-
metal complexes. They can be monodentate, (N1,N3)-chelating to- zene ligands, we have introduced ortho-, meta- and para-bis(phe-
wards one metal atom or (N1,N3)-bridging over two metal atoms nyltriazene)benzenes (and substituted derivatives), with two
[11], toward wide variety of metal transition complexes [12,13]. triazene groups in one molecule as ligands. In this work we studied
In these compounds secondary bonds, or interactions, such as the complexation of 1-(2-ethoxyphenyl)-3-(2-chlorophenyl)tria-
hydrogen bonds and metal
p-aryl interactions, can play an impor- zene and 1-(2-ethoxyphenyl)-3-(2-cyanophenyl)triazene) with ni-
tant role in their structural stability [14,15]. In recent years, we trate salt of HgII ion in aqueous solution, in order to investigate the
have been involved in the complexation of transition metal ions stoichiometry of the resulting mercury(II) complexes.
with several triazene compounds as ligands. Starting from different
bis(diaryl) symmetric and asymmetric-substituted triazenide as li- 2. Experimental
gand. Recently, we have shown that several complexes of HgII have
a remarkable ability to self-assemble in different manners through 2.1. Materials and physical techniques
metal–g2–g2-arene p-interactions and non-classical C–H


O
All chemicals were of analytical grade and were used as
⇑ Corresponding author. Tel.: +98 2188848949; fax: +98 2188820993. commercially obtained without further purification. IR spectra in
E-mail address: [email protected] (M.K. Rofouei). the frequency range of 4000–400 cm 1 were recorded using

0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.06.045
ARTICLE

DOI: 10.1002/zaac.201100350

Structural and Solution Studies of two Mercury(II) Complexes with [1,3-

Bis(2-ethoxy)benzene]triazene
Mohammad Kazem Rofouei,*[a] Jafar Attar Gharamaleki,[a] Ehsan Fereyduni,[b]
Aboulfazl Aghaei,[a] Giuseppe Bruno,[c] and Hadi Amiri Rudbari[c]
Keywords: Mercury; Triazene; X-ray diffraction; Solution studies; C–H···π interaction

Abstract. The reaction of [1,3-bis(2-ethoxy)benzene]triazene, [HL], HgII atom is chelated by one L ligand and one SCN ligand, whereas
with Hg(SCN)2 and Hg(CH3COO)2, resulted in the formation of the in compound 2, the HgII atom is surrounded by two L ligands. In
complexes [HgL(SCN)] (1) and [HgL2]·CH3OH (2). They were char- addition, 1D chains formed by metal–π interactions are connected to
acterized by means of X-ray crystallography, CHN analysis, FT-IR, 1H each other by C–H···π stacking interactions in the structure of 1, which
NMR, and 13C NMR spectroscopy. The structure of compound 1 con- results in a 2D architecture. An interesting feature of compound 2 is
sists of two independent complexes in which the HgII atoms are the presence of C–H···π edge-to-face interactions.
stacked along the crystallographic a axis to form infinite chains. Each

Introduction two HgII complexes [HgL(SCN)] (1) and [HgL2]·CH3OH (2)

{HL = [1,3-bis(2-ethoxy)benzene]triazene} with
The study of transition-metal complexes containing 1,3-di- Hg(CH3COO)2 and Hg(SCN)2 in methanol. Scheme 1 presents
aryltriazenide ligands has greatly increased in the past few the starting materials and the reaction procedures.
years because of the versatility of their coordination forms,
which yielded various coordination compounds with a large
structural diversity. The coordination modes can be mono-
dentate, (N1, N3)-chelating towards one metal atom or (N1,
N3)-bridging over two metal atoms,[1] showing remarkable
ability to support the stereochemical requisites of a wide vari-
ety of transition metal complexes.[2,3] In these compounds sec-
ondary bonds or interactions such as hydrogen bonds and
metal π-aryl interactions can play an important role to stabilize
their structures.[4,5] We have previously reported the synthesis
of the ligands 1,3-bis(2-methoxyphenyl)]triazene,[6] [1,3-bis(2-
ethoxyphenyl)]triazene,[7] and [1,3-bis(2-cyanophenyl)]triaz-
ene[8]. Additionally, we have published HgII complexes with
[1,3-bis(2-methoxyphenyl)]triazene by using HgCl2[9] and
HgBr2[10] as starting materials. In addition, AgI and CdII com-
plexes with this ligand are known.[11,12] More recently, a HgII
complex with [1,3-bis(2-ethoxyphenyl)]triazene as ligand has
been reported, in which HgCl2 was used as starting salt.[13]
In continuation of our previous work, we herein report the Scheme 1.
syntheses, characterizations and molecular structures of the

* Prof. Dr. M. K. Rofouei Experimental Section

Fax: +98-2188820993.
E-Mail: [email protected] Materials and Physical Techniques: All chemicals were of analytical
[a] Faculty of Chemistry
Tarbiat Moallem University grade and were used as commercially obtained without further purifi-
Tehran, Iran cation. IR spectra in the frequency range of 4000–400 cm–1 were re-
[b] Department of Chemistry corded with a Perkin–Elmer RXI spectrometer using KBr disks. Ele-
Tabriz Branch, Islamic Azad University mental analysis was carried out with a Perkin–Elmer 2400(II) CHNS/
Tabriz, Iran O analyzer. Melting points were measured with a Barnstead Electro-
[c] Dipartimento di Chimica Inorganica
Universita di Messina thermal 9200 apparatus. UV-Vis spectra were recorded with a Perkin–
Messina, Italy Elmer Lambda 25 spectrophotometer, using two matched 10 mm

220 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2012, 638, (1), 220–223
 Polyhedron 58 (2013) 129–133

Contents lists available at SciVerse ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

A single crystal X-ray diffraction study of a fully ordered cocrystal of pristine

Sc3N@D3h(5)–C78
Brandon Q. Mercado a, Manuel N. Chaur b,c, Luis Echegoyen d,⇑, Jafar Attar Gharamaleki a,e,
Marilyn M. Olmstead a,⇑, Alan L. Balch a,⇑
a
Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616, USA
b
Department of Chemistry, Clemson University, Clemson, SC, USA
c
Departamento de Química, Facultad de Ciencias, Universidad del Valle, AA 25360 Cali, Colombia
d
Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968, USA
e
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Black crystals of Sc3N@D3h(5)–C78
NiII(OEP)
2(benzene) contain a fully ordered endohedral fullerene cage
Available online 23 August 2012 and fully ordered contents. Thus, the X-ray crystallographic study allows detailed examination of its
structural properties. The planar Sc3N group lies perpendicular to the threefold axis of the fullerene cage
To the memory of our friend, Michelle
Millar, the first undergraduate to join ALB’s with the scandium ions bound to the three 6:6 ring junctions that lie in the horizontal mirror plane of the
research group. molecule. The Sc–N distances are 2.0111(10), 2.0106(10), and 1.9998(10) Å and the shortest Sc–C dis-
tances fall in the range 2.2371(13)–2.2591(13) Å. Those six carbon atoms nearest the scandium ions
Keywords: are the most pyramidalized carbon atoms in the molecule with an average hp = 13.9° compared to
Endohedral fullerenes hp = 11.6° for C60 and to average hp = 11.3° for the 12 carbon atoms along the C3 axis at the poles of the
X-ray crystallography molecule. The C–C bond distances at the 6:6 and 5:6 ring junctions do not show the distinct variations
Cocrystal that are found in C60. The shortest average C–C bond length, 1.391(2) Å, and the longest average bond
length, 1.466(1) Å, occur at 6:6 ring junctions.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction incorporate a variety of trivalent metals including Sc, Y, Gd, Tb, Tm,
and Lu, and a range of different cage sizes [8,9]. The process by
Fullerenes and endohedral fullerenes are nearly spherical mole- which Sc3N@Ih–C80 was made also produced its isomer Sc3N@D5h–
cules with a clearly differentiated inner and outer surfaces. They C80 [10], as well as Sc3N@D3h(5)–C78 [11], and Sc3N@D3(6140)–C68
have potential uses as electron acceptors in solar cells [1] and as [12], each of which has been characterized crystallographically.
contrast agents for magnetic resonance imaging [2]. For fullerenes The initial characterization of Sc3N@D3h(5)–C78 also utilized the
and endohedral fullerenes, their high symmetry and smooth outer cocrystallization process [8]. However, crystals of Sc3N@D3h(5)–
surface, which is made up of similarly sized pentagons and hexa- C78
CoII(OEP)
1.5(C6H6)
0.3(CHCl3) were disordered. There are five
gons, produces crystals that are prone to disorder [3–5]. Cocrystal- possible IPR isomers for the C78 cage [13]. Although it was possible
lization of fullerenes with a metalloporphyrin such as NiII(OEP) or to determine that D3h(5)–C78 cage was present from the crystallo-
CoII(OEP) has been shown to produce crystals with sufficient order graphic data, three orientations of the cage and three orientations
to allow structure determination by single crystal X-ray diffraction of the Sc3N unit were present. Of necessity, the first refinement
[6]. Sc3N@Ih–C80 was the first endohedral fullerene to be character- used a rigid model for the fullerene cage. Subsequently, the crystal-
ized by X-ray diffraction [7]. The process employed the cocrystal lographic data were re-refined and improved using a computed
Sc3N@Ih–C80
CoII(OEP)
1.5CHCl3
0.5C6H6. Sc3N@Ih–C80 is also the model that resulted from density functional calculations [14].
third most-abundant fullerene; only C60 and C70 are more abun- While these studies provided clear evidence about the basic struc-
dant. The isolation and characterization of Sc3N@Ih–C80 led to the ture of Sc3N@D3h(5)–C78, the crystallographic disorder precluded
discovery of many new molecules of the type M3N@C2n that could detailed analysis of the bond parameters within this molecule.
The structure of an adduct of Sc3N@D3h(5)–C78 formed by the Prato
reaction has been crystallographically characterized [15]. Since
⇑ Corresponding authors. Tel.: +1 530 752 0941; fax: +1 530 752 8995.
functionalization can distort the shape of fullerene cages and alter
E-mail addresses: [email protected] (L. Echegoyen), mmolmstead@ucdavi-
the placement of metal ions within endohedral fullerenes [16,17],
s.edu (M.M. Olmstead), [email protected] (A.L. Balch).
it is important to have structural studies of intact, pristine
fullerenes.

0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.08.035
organic compounds
Acta Crystallographica Section E Experimental
Structure Reports
Crystal data
Online
C13H11Cl2N3O V = 2706.0 (9) Å3
ISSN 1600-5368 Mr = 296.15 Z=8
Monoclinic, C2=c Mo K radiation
a = 15.422 (3) Å  = 0.47 mm1
1-(3,5-Dichlorophenyl)-3-(2-methoxy- b = 23.068 (5) Å
c = 7.6141 (15) Å
T = 298 K
0.5  0.3  0.15 mm
phenyl)triaz-1-ene  = 92.60 (3)

Data collection
Mohammad Reza Melardi,a Maryam Aghamohamadi,a
Stoe IPDS 2T diffractometer 2178 reflections with I > 2(I)
Jafar Attar Gharamaleki,b* Mohammad Kazem Rofoueib 15133 measured reflections Rint = 0.162
and Behrouz Notashc 3659 independent reflections

a
Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, Refinement
b
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, and cDepartment of R[F 2 > 2(F 2)] = 0.066 H atoms treated by a mixture of
Chemistry, Shahid Beheshti University, G.C., Evin, Tehran 1983963113, Iran wR(F 2) = 0.137 independent and constrained
Correspondence e-mail: [email protected] S = 1.07 refinement
3659 reflections
max = 0.24 e Å3
Received 2 February 2012; accepted 6 February 2012 177 parameters
min = 0.28 e Å3
1 restraint
Key indicators: single-crystal X-ray study; T = 298 K; mean (C–C) = 0.004 Å;
R factor = 0.066; wR factor = 0.137; data-to-parameter ratio = 20.7.
Table 1
Hydrogen-bond geometry (Å,  ).
The title molecule, C13H11Cl2N3O, is almost planar and adopts
Cg1 is the centroid of the C2–C7 ring.
a trans conformation with respect to the –N N– bond; the
dihedral angle between the rings is 3.47 (2) . The N—N bond D—H  A D—H H  A D  A D—H  A
lengths indicate the presence of single- and double-bond N1—H1  Cl1 i
0.85 (2) 2.69 (2) 3.529 (2) 170 (3)
characters and hence the –N N—NH– moiety. In the crystal, C1—H1C  Cg1ii 0.96 2.76 3.553 (4) 140
inversion dimers linked by pairs of N—H  Cl hydrogen Symmetry codes: (i) x; y þ 1; z þ 1; (ii) x; y; z þ 32.
bonds occur, and C—H   and – stacking interactions are
also observed. Data collection: X-AREA (Stoe & Cie, 2005); cell refinement:
X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005); program(s)
used to solve structure: SHELXS97 (Sheldrick, 2008); program(s)
Related literature used to refine structure: SHELXL97 (Sheldrick, 2008); molecular
For background literature and the synthesis of related graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to
compounds, see: Rofouei et al. (2009). For the synthesis and prepare material for publication: WinGX (Farrugia, 1999).
molecular structure of a similar monochloro-substituted tria-
zene, see: Rofouei et al. (2012).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: PV2511).

References
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Rofouei, M. K., Attar Gharamaleki, J., Ghalami, Z., Bruno, G. & Amiri
Rudbari, H. (2012). Z. Anorg. Allg. Chem. Accepted.
Rofouei, M. K., Hematyar, M., Ghoulipour, V. & Attar Gharamaleki, J. (2009).
Inorg. Chim. Acta, 362, 3777–3784.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Stoe & Cie (2005). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.

o724 Melardi et al. doi:10.1107/S1600536812005132 Acta Cryst. (2012). E68, o724

ChemComm Dynamic Article Links

Cite this: Chem. Commun., 2012, 48, 9882–9884

www.rsc.org/chemcomm COMMUNICATION
Molecular nesting in co-crystals of tetrabenzoquadrannulene and
C60: application of the sphere in a cone modelwz
Benjamin T. King,*a Marilyn M. Olmstead,b Kim K. Baldridge,c Bharat Kumar,a
Alan L. Balchb and Jafar Attar Gharamalekid
Received 22nd June 2012, Accepted 4th August 2012
DOI: 10.1039/c2cc34472f

We report the X-ray crystal structure of TMS4-TBQ with C60

and analyse their interaction using a sphere in a cone model.

The supramolecular recognition of C60 brings out the child in

us – what chemist would not want to catch a molecular ball
with a molecular glove? This game of molecular catch is also
instructive by helping us develop guidelines for molecular
recognition. It can even be useful. Cyclodextrins can distinguish
C60 from C70, providing a convenient method for their separation,1
and this game of catch might someday provide methods to control
the nanoscale organization of C60 or its congeners in bulk hetero-
junction photovoltaic cells and other electronic devices.
C60 is, however, a slippery ball, offering only weak van der
Waals (vdW) interactions for grip. A good glove, or receptor, Fig. 1 The chemical structure of 1 and the crystal structure of the
must be correctly fitted to maximize these weak vdW interactions. ordered C60–1 nested pair with ellipsoids drawn at 50% probability.
Thus, nearly all C60 hosts provide a concave palm in which the Hydrogen atoms and solvent of crystallization are omitted.
C60 ball nestles. These hosts include calix[n]arenes,2,3 cyclic
paraphenyleneacetylenes,4 cyclotriveratrylenes,5 p-extended C60 was only recently reported.17 [10]Cycloparaphenylene
tetrathiafulvalenes,6 porphyrins,7–9 and cyclothiophenes.10,11 forms a 1 : 1 complex with C60 in solution.19
Balch, Catalano, Lee, and Olmstead prepared one of the first Kumar et al. recently reported the synthesis of a non-
receptors, a fullerene bearing two phenyl benzyl ether arms classical fullerene fragment, tetrakis(trimethylsilyl)tetrabenzo
that, in the solid-state, embraced the fullerene moiety of quadrannulene (1, Fig. 1).20 This molecule is the first example
another molecule.12 Corannulene-based receptors are especially of a [4]circulene and is the smaller sibling of corannulene, a
interesting because corannulene’s concave surface matches [5]circulene. The walls of bowl 1 are steeper than those of
nicely with the convex surface of C60.13 Fullerene–corannulene corannulene, and this is reflected in its depth. The bowl depth
interactions have been studied in the gas phase,14 observed in of 1, measured from the perimeter C atoms of the central
solution with corannulene-based, Venus flycatcher receptors,15 [4]circulene unit to the centroid of the four-membered ring, is
on surfaces,16 and in the solid-state.15,17 Highly substituted 1.44 Å. The bowl depth of corannulene, measured in a similar
corannulenes bind C60 weakly in solution.18 Parent corannulene way, is 0.87 Å. The four cata-fused rings in 1 provide a large
does not associate with C60 in solution and its co-crystal with surface to maximize vdW contact.
We were gratified to find that 1 co-crystallizes with C60.
a
Department of Chemistry, University of Nevada, Reno, NV 89503, Slow evaporation of a solution of C60 and 1 in benzene/toluene
USA. E-mail: [email protected]; Fax: +1 775-784-6804 gave tiny (0.031 mm  0.005 mm  0.001 mm) red crystals of
b
Department of Chemistry, University of California, One Shields
2(1)2C601.25(toluene)0.75(benzene). X-ray diffraction data
Avenue, Davis, CA 95616, USA. E-mail: [email protected],
[email protected]; Fax: +1 530 752 2820; Tel: +1 530 752 0941 were collected using synchrotron radiation.y Disorder, data quality,
c
Organic Chemistry Institute, University of Zürich, CH-8057 Zürich, and ambiguity in space group assignment made the solution
Switzerland. E-mail: [email protected]; Fax: +41 44 635 6888; especially challenging. A good solution was nonetheless obtained.
Tel: +41 44 635 4281
d
Faculty of Chemistry Tarbiat Moallem University, Tehran, Iran. The X-ray structure (Fig. 1) shows that C60 nests into the
E-mail: [email protected] concave face of 1 with many C60-arene and C60-TMS close
w This article is part of the ChemComm ‘Aromaticity’ web themed contacts. The asymmetric unit contains two nested pairs
issue. (red–blue and yellow–green, Fig. 2). Molecules of 1 are fully
z Electronic supplementary information (ESI) available: Details of
DFT calculations. CCDC 888325. For ESI and crystallographic data ordered in both pairs, while the C60 molecules are ordered in
in CIF or other electronic format see DOI: 10.1039/c2cc34472f the red–blue pair, as shown in Fig. 2, but disordered in the

9882 Chem. Commun., 2012, 48, 9882–9884 This journal is c The Royal Society of Chemistry 2012
organic compounds
Acta Crystallographica Section E Monoclinic, C2=c Z=8
Structure Reports a = 15.398 (2) Å Mo K radiation
b = 12.132 (2) Å  = 0.29 mm1
Online c = 14.276 (2) Å T = 293 K
ISSN 1600-5368  = 107.65 (1) 0.30  0.17  0.11 mm
V = 2541.3 (7) Å3

Data collection
4-[(4-Chlorophenyl)diazenyl]-3-methoxy-
Bruker APEXII CCD 42735 measured reflections
aniline diffractometer 2778 independent reflections
Absorption correction: multi-scan 2481 reflections with I > 2(I)
(SADABS; Bruker, 2005) Rint = 0.019
Mohammad Kazem Rofouei,a* Zahra Ghalami,a Jafar Tmin = 0.698, Tmax = 0.746
Attar Gharamaleki,a Giuseppe Brunob and Hadi Amiri
Rudbarib Refinement
R[F 2 > 2(F 2)] = 0.039 H atoms treated by a mixture of
a
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, and bDipartimento wR(F 2) = 0.118 independent and constrained
di Chimica Inorganica, Universita di Messina, Messina, Italy S = 1.04 refinement
Correspondence e-mail: [email protected] 2778 reflections
max = 0.37 e Å3
172 parameters
min = 0.39 e Å3
Received 13 May 2011; accepted 23 June 2011

Key indicators: single-crystal X-ray study; T = 293 K; mean (C–C) = 0.002 Å; Table 1
R factor = 0.039; wR factor = 0.118; data-to-parameter ratio = 16.2. Hydrogen-bond geometry (Å,  ).
D—H  A D—H H  A D  A D—H  A
The title compound, C13H12ClN3O, exhibits a trans geometry N1—H1A  Oi 0.85 (2) 2.47 (2) 3.222 (2) 147 (2)
about the N N double bond in the solid state. The dihedral C12—H12  N3ii 0.93 2.62 3.379 (2) 140
angle between the rings is 22.20 (8) . Intermolecular N— Symmetry codes: (i) x; y þ 1; z þ 12; (ii) x þ 1; y; z þ 32.
H  O hydrogen bonds between the amine and methoxy
groups lead to the formation of a chain-like polymer along the Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-
c axis with a C(6) graph set. There is also weak non-classical Plus (Bruker, 2005); data reduction: SAINT-Plus; program(s) used to
C—H  N hydrogen bonds involving an aromatic C—H group solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
and a diazenyl N atom, which connect the chains into a two- refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
SHELXTL (Sheldrick, 2008); software used to prepare material for
dimensional framework.
publication: SHELXTL.

Related literature
For applications of diazonium compounds, see: Patai (1978); Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: BH2358).
Hunger et al. (2005). For the synthesis and crystal structures of
Hg(II) and Cd(II) complexes with [1,3-bis(2-methoxyphen-
yl)]triazene, see: Rofouei, Hematyar et al. (2009); Rofouei, References
Melardi et al. (2009). Bruker (2005). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA
Hunger, K., Mischke, P., Rieper, W., Raue, R., Kunde, K. & Engel, A. (2005).
Azo Dyes, in Ullmann Encyclopedia of Industrial Chemistry. Weinheim:
Wiley-VCH.
Patai, S. (1978). Chemistry of the Diazonium and Diazo Groups, Part 1. New
York: Wiley-Blackwell.
Rofouei, M. K., Hematyar, M., Ghoulipour, V. & Gharamaleki, J. A. (2009).
Inorg. Chim. Acta, 362, 3777–3784.
Rofouei, M. K., Melardi, M. R., Khalili Ghaydari, H. R. & Barkhi, M. (2009).
Acta Cryst. E65, m351.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Experimental
Crystal data
C13H12ClN3O Mr = 261.71

o1852 Rofouei et al. doi:10.1107/S160053681102472X Acta Cryst. (2011). E67, o1852

 Author's personal copy

Spectrochimica Acta Part A 78 (2011) 88–95

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Synthesis, X-ray crystallography characterization, vibrational spectroscopic,

molecular electrostatic potential maps, thermodynamic properties studies of
N,N -di(p-thiazole)formamidine
M.K. Rofouei a,∗ , E. Fereyduni a , N. Sohrabi a , M. Shamsipur b , J. Attar Gharamaleki a , N. Sundaraganesan c
a
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
b
Department of Chemistry, Razi University, Kermanshah, Iran
c
Department of Physics (Engg.), Annamalai University, Annamalai Nagar 608002, India

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we will report a combined experimental and theoretical study on molecular and vibrational
Received 14 April 2010 structure of N,N -di(p-thiazole)formamidine (DpTF). DpTF has been synthesized and characterized by
Received in revised form 9 August 2010 elemental analysis, FT-IR, FT-Raman, 1 H NMR, 13 C NMR spectroscopy and X-ray single crystal diffraction.
Accepted 26 August 2010
The FT-IR and FT-Raman spectra of DpTF were recorded in the solid phase. The optimized geometry
was calculated by HF and B3LYP methods using 6-31G(d) basis set. The FT-IR and FT-Raman spectra of
Keywords:
DpTF was calculated at the HF/B3LYP/6-31G(d) level and were interpreted in terms of potential energy
N,N -di(p-thiazole)formamidine
distribution (PED) analysis. The scaled theoretical wavenumber showed very good agreement with the
FT-IR
FT-Raman
experimental values. A detailed interpretation of the infrared and Raman spectra of DpTF was reported.
Vibrational analysis On the basis of vibrational analyses, the thermodynamic properties of the title compound at different
Crystal structure temperatures have been calculated, revealing the correlations between Cp,m ◦ , Sm ◦ , Hm ◦ and temperatures.
DFT Furthermore, molecular electrostatic potential maps (MESP) and total dipole moment properties of the
compound have been calculated.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction during recent years. They have applications in various fields. For
example, they can serve as multidentate ligands to form bridges
1,3-Thiazoles and their derivatives have been considered as between metal atoms [15,16] and auxiliaries in asymmetric syn-
the important class of S and N-containing heterocycles [1–3]. thesis [17]. Recently, synthesis and spectroscopic study of some
There is an increasing interest in the study of 1,3-thiazoles N-containing ligands such as triazenes and their complexes with
and their derivatives due to their biological activity and coor- transition metal ions have been studied [18,19]. Moreover, we
dination chemistry. The thiazole moiety is the constituent of are performing the synthesis and spectroscopic study of some
many biomolecules, including thiamine (vitamin B1 ) and some new formamidines and their complexes with transition metal ions
thiazole containing compounds are valuable medicines include in our laboratory. It is expected that compounds with both thi-
antibacterial [4], antimicrobial [5], antitumor [6], anti-HIV [7], anti- azole and formamidine groups will increase the complexation
tubercular [8], anti-inflammatory and analgesic [9] agents and ability of these compounds with transition metal ions. Therefore,
some have agrochemical applications such as herbicide [10] and we were interested in synthesis of these types of compounds.
insecticide [11]. Thiazoles are also important in heterocyclic and With the best of our knowledge, no HF/DFT frequency calcula-
organometallic chemistry. They can form bi- and multinuclear tions and synthesis of N,N -di(p-thiazole)formamidine (DpTF) is
complexes with transition metal ions [12,13]. Some transition performed. In this work, DpTF was synthesized and the struc-
metal complexes with thiazoles are important due to their dif- tural properties were calculated by DFT and Hartree–Fock (HF)
ferent shapes and different coordination numbers and some of calculations. The FT-IR and FT-Raman spectra were calculated
them have antitumor activity [14]. It is also revealed that for- and compared with experimental results. Ab initio and DFT cal-
mamidines, a class of amidines, have been investigated extensively culations have been performed to support our wave number
assignments. Furthermore, we interpreted the calculated spec-
tra in terms of potential energy distributions (PEDs) and made
∗ Corresponding author. Tel.: +98 2188848949; fax: +98 2188820993. the assignment of the experimental bands due to PED analysis
E-mail address: [email protected] (M.K. Rofouei). results.

1386-1425/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2010.08.077
Struct Chem (2011) 22:1365–1377
DOI 10.1007/s11224-011-9829-5

ORIGINAL RESEARCH

Syntheses, crystal, molecular structures, and solution studies

of Cu(II), Co(II), and Zn(II) coordination compounds containing
pyridine-2,6-dicarboxylic acid and 1,4-pyrazine-2,3-dicarboxylic
acid: comparative computational studies of Cu(II) and Zn(II)
complexes
M. Mirzaei • H. Eshtiagh-Hosseini • N. Alfi • H. Aghabozorg •
J. Attar Gharamaleki • S. A. Beyramabadi • H. R. Khavasi •
A. R. Salimi • A. Shokrollahi • R. Aghaei • E. Karami

Received: 9 February 2011 / Accepted: 23 June 2011 / Published online: 12 July 2011
Ó Springer Science+Business Media, LLC 2011

Abstract Three new coordination compounds of hydrogen bonding (such as O–HO and N–HO) and/or
Cu(II), Co(II), and Zn(II) based on different dicarboxylic slipped or offset p–p stacking interactions, 3D supramo-
acids formulated as (AcrH)[Cu(pydc)(pydcH)]5H2O (1) lecular networks are constructed in these complexes. In the
(2a-4mpyH)2[M(pyzdc)2(H2O)2]6H2O; M = Co(II) (2) crystalline network, O–HO hydrogen bonding create
and Zn(II) (3) have been synthesized and structurally (H2O)n water clusters, so the hydrogen bond interactions
characterized by elemental analyses, IR spectroscopy, and play an important role in sustaining of the supramolecular
single crystal X-ray diffraction (where pydcH2 = pyridine- solid-state architectures in compounds 1–3. The species in
2,6-dicarboxylic acid; Acr = acridine; 2a-4mpy = 2- the solution media were studied by potentiometric method.
amino-4-methyl pyridine; pyzdcH2 = 1,4-pyrazin-2, The protonation constants of 2a-4mpy, 2-apy = 2-amino-
3-dicarboxylic acid). In all cases, the metal centers have pyridine, pydc and pyzdc in aqueous solution, pydc and
distorted octahedral coordination geometries. Through Acr in a 50% dioxane–50% water (v/v) solvent, as well as
the equilibrium constants for three proton-transfer systems,
pyzdc-2a-4mpy, pydc-2-apy, and pydc-Acr were calculated
Electronic supplementary material The online version of this using potentiometrical method. The stoichiometry and
article (doi:10.1007/s11224-011-9829-5) contains supplementary
material, which is available to authorized users.
stability of complexation during the first proton-transfer
system with Cu2?, Co2?, and Zn2? ions and also the sec-
M. Mirzaei (&)  H. Eshtiagh-Hosseini (&)  N. Alfi  ond proton-transfer system with Fe3? and Cr3? ions in
A. R. Salimi aqueous solution were investigated by potentiometric pH
Department of Chemistry, Ferdowsi University of Mashhad,
titration method, from point of comparison view of their
917751436 Mashhad, Iran
e-mail: [email protected] behaviors in the solution state. The stoichiometry and
stability of complexation of third system with Cu2? and
H. Eshtiagh-Hosseini
e-mail: [email protected] Zn2?, metal ions in 50% dioxane–50% water (v/v) solvent
were also investigated by the cited method. The stoichi-
H. Aghabozorg  J. A. Gharamaleki ometry of the most complex species in solution were
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
compared with corresponding crystalline metal ion com-
S. A. Beyramabadi plexes. Furthermore, DFT calculations have been carried
Department of Chemistry, Faculty of Science, Islamic Azad out on the Cu(II) and Zn(II) complexes in the presence of
University, Mashhad Branch, Mashhad, Iran pydcH2 and pyzdcH2 in order to better understanding of
their molecular orbital structures of HOMO and LUMO.
H. R. Khavasi
Departement of Chemistry, Shahid Beheshti University,
G. C., Evin, 1983963113 Tehran, Iran Keywords Pyridine-2,6-dicarboxylic acid  1,4-Pyrazine-
2,3-dicarboxylic acid  Acridine  Coordination compound 
A. Shokrollahi  R. Aghaei  E. Karami
Crystal structures  Solution studies  DFT
Department of Chemistry, Yasouj University, Yasouj, Iran

123
organic compounds
Acta Crystallographica Section E
Data collection
Structure Reports
Online Bruker SMART X2S benchtop 8299 measured reflections
diffractometer 2408 independent reflections
ISSN 1600-5368 Absorption correction: multi-scan 1775 reflections with I > 2(I)
(SADABS; Bruker, 2009) Rint = 0.075
Tmin = 0.383, Tmax = 0.755
4-[(4-Bromophenyl)diazenyl]-2-ethoxy- Refinement
aniline R[F 2 > 2(F 2)] = 0.065 H atoms treated by a mixture of
wR(F 2) = 0.198 independent and constrained
S = 1.00 refinement
Mohammad Reza Melardi,a* Jafar Attar Gharamaleki,b 2408 reflections
max = 0.98 e Å3
Soheyla Rezabeyka and Mohammad Kazem Rofoueib 178 parameters
min = 1.11 e Å3
2 restraints
a
Department of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, and
b
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
Correspondence e-mail: [email protected]
Table 1
Hydrogen-bond geometry (Å,  ).
Received 28 October 2011; accepted 16 November 2011
D—H  A D—H H  A D  A D—H  A
Key indicators: single-crystal X-ray study; T = 200 K; mean (C–C) = 0.008 Å;
R factor = 0.065; wR factor = 0.198; data-to-parameter ratio = 13.5. N3—H3A  N2i 0.88 (1) 2.38 (2) 3.228 (6) 163 (5)
N3—H3B  O1 0.88 (1) 2.28 (5) 2.628 (5) 103 (4)
Symmetry code: (i) x  12; y þ 12; z  12.
The title compound, C14H14BrN3O, exhibits a trans geometry
about the –N N– double bond. The dihedral angle between Data collection: SMART X2S (Bruker, 2009); cell refinement:
the benzene rings is 24.01 (5) . An intramolecular N—H  O SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to
hydrogen bond occurs. In the crystal, intermolecular N— solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
H  N hydrogen bonds between the amine groups lead to the
SHELXTL (Sheldrick, 2008); software used to prepare material for
formation of a C(8) polymeric chain along [101].
publication: SHELXTL.

Related literature JAG thanks the American Crystallographic Association for

For the synthesis and crystal structures of similar diazenyl a scholarship to the ACA summer school, and Bruce C. Noll of
compounds, see: de Wit et al. (2008); Yazici et al. (2006). For Bruker AXS Inc., and Peter Müller of the Massachusetts
crystal structure of a chloro analogue of the title compound, Institute of Technology for their assistance in this work.
see: Rofouei et al. (2011). For graph-set motifs, see: Bernstein
et al. (1995). Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: PV2476).

References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Bruker (2009). SMART X2S, SAINT and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA
Experimental Rofouei, M. K., Ghalami, Z., Attar Gharamaleki, J., Bruno, G. & Amiri
Rudbari, H. (2011). Acta Cryst. E67, o1852.
Crystal data Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
C14H14BrN3O V = 1380.6 (4) Å3 Wit, J. de, Alberda van Ekenstein, G. O. R., ten Brinke, G. & Meetsma, A.
Mr = 320.19 Z=4 (2008). Acta Cryst. E64, o1048.
Monoclinic, P21 =n Mo K radiation Yazıcı, S., Albayrak, C., Ağar, E., Şenel, I. & Büyükgüngör, O. (2006). Acta
a = 13.219 (2) Å  = 2.97 mm1 Cryst. E62, o521–o522.
b = 8.8289 (17) Å T = 200 K
c = 13.506 (2) Å 0.40  0.20  0.10 mm
 = 118.855 (6)

o3396 Melardi et al. doi:10.1107/S160053681104877X Acta Cryst. (2011). E67, o3396

electronic reprint
 metal-organic compounds
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

Poly[[piperazine-1,4-dium [diaqua-
tetrakis(l-sulfanediyldiacetato)-
dicerate(III)]] trihydrate]
Mohammad Ghadermazi,a* Marilyn M. Olmstead,b
Shahideh Rostamia and Jafar Attar Gharamalekic
a
Department of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Experimental
Iran, bDepartment of Chemistry, One Shields Ave., University of California, Davis, Crystal data
CA, USA, and cFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
Correspondence e-mail: [email protected]
(C4H12N2)[Ce2(C4H4O4S)4-  = 104.646 (3)
(H2O)2]3H2O  = 101.192 (3)
Mr = 1051.00 V = 839.76 (16) Å3
Received 17 December 2010; accepted 21 January 2011
Triclinic, P1 Z=1
a = 6.4361 (7) Å Mo K radiation
Key indicators: single-crystal X-ray study; T = 90 K; mean (C–C) = 0.003 Å; H-atom b = 11.1135 (12) Å  = 3.01 mm1
completeness 85%; disorder in solvent or counterion; R factor = 0.021; wR factor = c = 12.5627 (14) Å T = 90 K
0.056; data-to-parameter ratio = 19.6.  = 96.693 (4) 0.25  0.22  0.05 mm

Data collection
The title compound, (C4H12N2)[Ce2(C4H4O4S)4(H2O)2]- Bruker SMART APEXII 11816 measured reflections
3H2O, features a polymeric anion with a centrosymmetric diffractometer 4482 independent reflections
Absorption correction: multi-scan 4433 reflections with I > 2(I)
Ce2O2 core and a Ce  Ce distance of 4.3625 (4) Å. The (SADABS; Sheldrick, 1996) Rint = 0.021
anions form ribbons {[Ce2(C4H4O4S)4(H2O)2]2}n extending Tmin = 0.520, Tmax = 0.864
along [100]. The doubly protonated piperazinium cations
reside on centers of inversion and link the polymeric ribbons Refinement
via N—H  O hydrogen bonding. Each CeIII cation is ten- R[F 2 > 2(F 2)] = 0.021 H atoms treated by a mixture of
coordinated by an O2S donor set from two tridentate wR(F 2) = 0.056 independent and constrained
S = 1.11 refinement
sulfanediyldiacetate (tda) ligands, one water molecule and 4482 reflections
max = 1.79 e Å3
three other tda O donors from adjacent {Ce(tda)2(H2O)} units 229 parameters
min = 1.81 e Å3
3 restraints
in a distorted bicapped cubic environment. Additional O—
H  O hydrogen bonding involving the coordinated and
solvent water molecules is also present. H atoms of the crystal
Table 1
water molecules could not be located and were not included in Selected bond lengths (Å).
the refinement.
Ce1—S1 3.2903 (6) Ce1—O7 2.5117 (15)
Ce1—S2 3.1445 (6) Ce1—O8i 2.5024 (15)
Ce1—O1 2.5359 (15) Ce1—O3ii 2.6137 (16)
Related literature Ce1—O4 2.5069 (14) Ce1—O4ii 2.6542 (15)
Ce1—O5 2.4278 (14) Ce1—O9 2.6644 (15)
For the structure determination of a bis-sulfanediyldi-
Symmetry codes: (i) x  1; y; z; (ii) x þ 1; y þ 1; z.
acetatonickelate(II), see: Delaunay et al. (1976). For a dinuc-
lear sulfanediyldiacetato complex, see: Baggio et al. (1999).
For an example with a solely bidentate coordination mode of
the sulfanediyldiacetato ligand, see: Marek et al. (2003). For
Table 2
bond-valence-sum calculations, see: Zhang et al. (2004). Hydrogen-bond geometry (Å,  ).
D—H  A D—H H  A D  A D—H  A
i
O9—H9C  O7 0.82 (2) 2.00 (2) 2.793 (2) 163 (3)
O9—H9D  O1ii 0.83 (2) 1.92 (2) 2.729 (2) 167 (3)
N1—H1A  O6iii 0.92 1.84 2.732 (2) 162
N1—H1B  O9iv 0.92 2.10 2.988 (2) 161
Symmetry codes: (i) x  1; y; z; (ii) x þ 1; y þ 1; z; (iii) x; y þ 1; z; (iv)
x; y þ 1; z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT

(Bruker, 2009); data reduction: SAINT; program(s) used to solve

Acta Cryst. (2011). E67, m291–m292 doi:10.1107/S1600536811002923 Ghadermazi et al. m291

organic compounds
Acta Crystallographica Section C Comment
Crystal Structure
4-Oxo-4H-pyran-2,6-dicarboxylic acid, also called chelidonic
Communications
acid, is a weak acid extracted from the perennial herb celan-
ISSN 0108-2701
dine (Chelidonium majus) as a white crystalline substance
(m.p. 538 K). The structures of several metal complexes
Statistically disordered short hydrogen containing the 4-oxo-4H-pyran-2,6-dicarboxylate dianion,
(cdo)2, illustrate the versatile ability of this ligand to coor-
bonds in (pipzH2)(cdoH)2 and a dinate in a monodentate, bidentate or bridging fashion.
comparison with (pipzH2)(cdo)H2O Crystal structures include complexes of Ag+, Be2+, Ca2+, Mn2+,
Cu2+, Cd2+, Sn2+, Zn2+ and Tb3+ (Manojlovic-Muir et al., 1999;
(pipz is piperazine and cdoH2 is Ng et al., 2000; Olovsson et al., 2001; Fainerman-Melnikova et
chelidonic acid) al., 2006; Yasodha, Govindarajan, Low & Glidewell, 2007;
Chen, 2009; Zhang et al., 2009; Zhou et al. 2009). A salt of
[Ni(H2O)6](cdo) (Yasodha, Govindarajan, Manivannan &
Mohammad Ghadermazi,a* Marilyn M. Olmstead,b Jafar
Büyükgüngör, 2007) has also been reported.
Attar Gharamalekic and Shahideh Rostamia
As a continuation of our research on the synthesis of
a
Department of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, proton-transfer compounds by the use of different dicarb-
Iran, bDepartment of Chemistry, University of California, One Shields Avenue, Davis, oxylic acids and numerous amines [for a similar proton-
CA 95616-5292, USA, and cFaculty of Chemistry, Tarbiat Moallem University, transfer compound of pyridine-2,6-dicarboxylic acid with
Tehran, Iran piperazine, see Aghabozorg, Ghadermazi et al. (2006), and for
Correspondence e-mail: [email protected]
a proton-transfer compound of piperazine with oxalate, see
Received 24 February 2011 Aghabozorg, Ghadermazi & Sheshmani (2006)], we report
Accepted 3 March 2011 here the synthesis and structure determination of two proton-
Online 11 March 2011 transfer compounds, (I) and (II), obtained from 4-oxo-4H-
pyran-2,6-dicarboxylic acid (cdoH2) and piperazine (pipz).
Two related proton-transfer compounds, namely piperazine-
1,4-diium 4-oxo-4H-pyran-2,6-dicarboxylate monohydrate,
C4H12N22+C7H2O62H2O or (pipzH2)(cdo)H2O, (I), and
piperazine-1,4-diium bis(6-carboxy-4-oxo-4H-pyran-2-carbox-
ylate), C4H12N22+2C7H3O6 or (pipzH2)(cdoH)2, (II), were
obtained by the reaction of 4-oxo-4H-pyran-2,6-dicarboxylic
acid (chelidonic acid, cdoH2) and piperazine (pipz). In (I),
both carboxyl H atoms of chelidonic acid have been
transferred to piperazine to form the piperazine-1,4-diium
ion. The structure is a monohydrate. All potential N—H
donors are involved in N—H  O hydrogen bonds. The water
molecule spans two anions via the 4-oxo group of the pyranose
ring and a carboxylate O atom. The hydrogen-bonding motif is
essentially two-dimensional. The structure is a pseudomero-
hedral twin. In the asymmetric unit of (II), the anion consists
of monodeprotonated chelidonic acid, while the piperazine-
1,4-diium cation is located on an inversion centre. The single
carboxyl H atom is disordered in two respects. Firstly, the
disordered H atom is shared equally by both carboxylic acid
groups. Secondly, the H atom is statistically disordered
between two positions on either side of a centre of symmetry In (pipzH2)(cdo)H2O, (I) (Fig. 1), both H atoms of cdoH2
and is engaged in a very short hydrogen-bonding inter- are transferred to pipz, and the negative charge of (cdo)2 is
action; the relevant O  O distances are 2.4549 (11) and balanced by the doubly protonated piperazine-1,4-diium ion.
2.4395 (11) Å, and the O—H  O angles are 177 (6) and All possible N—H donors are engaged in hydrogen bonds to
177 (5) , respectively. Further hydrogen bonding of the type O atoms (see Table 1). The water molecule spans two different
N—H  O places the (pipzH2)2+ cations in pockets formed by anions via the 4-oxo group of the pyranose ring (O4) and a
the chains of (cdoH) anions. In contrast with (I), the carboxylate O atom (O2). Atom O2 is also hydrogen bonded
(pipzH2)2+ cations form hydrogen-bonding arrays that are to an N—H donor. These hydrogen-bonding interactions form
perpendicular to the anions, yielding a three-dimensional a motif that is two-dimensional and lies parallel to the (101)
hydrogen-bonding motif. The structures of both (I) and (II) plane (Fig. 2).
also feature – stacking interactions between aromatic In (pipzH2)(cdoH)2, (II) (Fig. 3), the H atom of the (cdoH)
rings. anion is disordered with respect to exchange between the two

o134 # 2011 International Union of Crystallography doi:10.1107/S0108270111008110 Acta Cryst. (2011). C67, o134–o138
electronic reprint
 Inorganica Chimica Acta 362 (2009) 3777–3784

Contents lists available at ScienceDirect

Inorganica Chimica Acta

journal homepage: www.elsevier.com/locate/ica

Syntheses, structures, thermal behavior and solution studies of two types

of Hg(II) complexes with [1,3-di(2-methoxy)benzene]triazene
Mohammad K. Rofouei *, Marjan Hematyar, Vanik Ghoulipour, Jafar Attar Gharamaleki
Faculty of Chemistry, Tarbiat Moallem University, 49 Mofateh Ave., Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The reaction of [1,3-di(2-methoxy)benzene]triazene, [HL], with Hg(CH3COO)2 and Hg(SCN)2 in methanol
Received 12 November 2008 as solvent, resulted in the formation of [HgL2] (1) and [HgL(SCN)] (2), respectively. These compounds
Accepted 24 April 2009 were characterized by means of X-ray diffraction, FT-IR spectroscopy, CHN and TGA–DTA analysis. In
Available online 7 May 2009
the lattice of the compound 1, the mono-nuclear complexes were connected to dimer structure by inter-
molecular non-classical C–H


O hydrogen bonds. Also, weak Hg-g2-arene p-interactions link the dimers
Keywords: into 1D supramolecular chains. The compound 2 is a 2D coordination polymer induced by C–H


p stack-
Mercury(II)
ing interactions between 1D chains produced by weak Hg-g3-g3-arene p-interactions. The results of
Triazene
Crystal structure
studies of the stoichiometry and formation of complexes of 1 and 2 in methanol solution were found
Solution studies to be in support of their solid state stoichiometry.
C–H


p stacking interactions Ó 2009 Elsevier B.V. All rights reserved.
Hg-g-arene p-interactions

1. Introduction by Popovic et al. [21,22]. On the other hand, triazenes and anionic
triazenide ligands could show different types of coordination in me-
In recent years, the self-assembled metal–organic complexes tal complexes like monodentate, (N1,N3)-chelating towards one
have attracted intense attention because of their fascinating metal atom or (N1,N3)-bridging over two metal atoms [23].
molecular structures and crystal-packing motif [1–3], along with We have previously reported the synthesis of Ag(I) complex with
their potential application in the area of functional materials [1,3-di(2-methoxy)benzene]triazene, [HL], as ligand [24,25]. Also,
[4,5]. Aside from the fundamental and strong metal–ligand coordi- we have published the Hg(II) complexes with this ligand by using
nation covalent bond, other relatively weak intermolecular inter- HgCl2 and HgBr2 as starting materials [26,27]. From recent struc-
actions such as hydrogen-bonding and p–p stacking interactions tural studies, it has been argued that counter-anions play an impor-
are also useful tools in assembling such supramolecular complexes tant role in determining the solid state lattices of such compounds.
[6–8]. In this regard, the organic ligands play an important role in Continuing with our previous works, here we report the syntheses,
adjusting the architectures of their metal complexes, so proper characterization and molecular structure of two new Hg(II) coordi-
selection of ligands is the key issue in construction of supramolec- nation polymers obtained from the mentioned ligand with
ular networks [9–11]. However, the crystal engineering with de- Hg(CH3COO)2 and Hg(SCN)2 in methanol as solvent. Scheme 1 pre-
sired topologies and specific properties still remains a difficult sents the procedure of the applied reactions and starting materials.
challenge since there are a variety of factors influencing the self-
assembly process such as the coordination geometry and the oxi- 2. Experimental
dation state of the metal ions [12–14], metal-to-ligand ratio [15],
nature of the ligands [16], solvents [17] and/or counter-anions 2.1. Materials and physical techniques
[18], even the reaction temperature and pH value [19,20].
Hg(II) is a diamagnetic ion and maintains d10 electron configura- All chemicals were of analytical grade and were used as com-
tion which minimizes intrinsic coordination geometry preferences mercially obtained without further purification. IR spectra were re-
while favoring coordination by softer ligands. Thus, mercury(II) is corded using Perkin–Elmer RXI spectrometer using KBr disks.
capable of forming various binding coordination modes when do- Elemental analysis was carried out using a Perkin–Elmer 2400(II)
nor atoms provided by suitable ligands [21]. The tendency of mer- CHNS/O analyzer. Melting points were measured on a Barnstead
cury to achieve effective coordination by spatial arrangement of Electrothermal 9200 apparatus. UV–Vis spectra were recorded
donor atoms of different types of counterions has been reported with a Perkin–Elmer Lambda 25 spectrophotometer, using two
matched 10-mm quartz cells. TGA–DTA were carried out with a
* Corresponding author. Tel.: +98 21 88848949; fax: +98 21 88820993. Rheometric Scientific 1500 at a heating rate of 10 °C/min in air.
E-mail address: [email protected] (M.K. Rofouei). Crystallographic measurements were made at 296(2) K using a

0020-1693/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.04.041