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Journal of Fluorine Chemistry 129 (2008) 325–331

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Second sphere interaction in fluoroanion binding: Synthesis,

spectroscopic and X-ray structural study of trans-dichlorobis
(ethylenediamine) cobalt(III) terafluoroborate
Rajni Sharma a, Raj Pal Sharma a,*, B.M. Kariuki b,**
a
Department of Chemistry, Panjab University, Chandigarh 160014, India
b
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
Received 10 October 2007; received in revised form 28 December 2007; accepted 4 January 2008
Available online 25 January 2008

Abstract
Trans-dichlorobis(ethylenediamine) cobalt(III) terafluoroborate was synthesised and detailed packing analysis was undertaken to delineate the
topological complimentarity of [trans-Co(en)2Cl2]+ and BF4 ions by second sphere coordination. The complex was completely characterised by
elemental analyses, solubility product measurement and spectroscopic studies (IR, UV–Vis, multinuclear NMR). In the crystal lattice, discrete ions
[trans-Co(en)2Cl2]+ and BF4 are arranged in A–B–A–B pattern (in both a and c directions of the lattice) forming columns of anions and cations.
Crystal lattice is stabilized by electrostatic forces of attraction and hydrogen bonding interactions, i.e. N–H  F and N–H  Cl involving second
sphere coordination. It appears that the topological features of [trans-Co(en)2Cl2]+ are conducive for generating second sphere interactions. This
strategy may be used as a viable method for the capture of other fluoroanions.
# 2008 Elsevier B.V. All rights reserved.
Keywords: Cobalt(III); Coordination chemistry; Tetrafluoroborate; X-ray crystallography; Spectroscopy and layered solids

1. Introduction lyte materials for double-layer capacitors at low temperature

[4]. Therefore, the development of selective anion receptor
Anionic species play very important roles in chemistry, (binding agent), which may find applications [5] and especially
medicine, catalysis, molecular assembly and in biology, yet in polar solvents such as water is of particular interest [6]. This
their binding characteristics have not received much recogni- may result in the formation of materials that may find
tion. Inorganic fluoroanions are biologically important class of application in anion recovery.
anions. One of them is tetrafluoroborate. The fluoroboric acid, The coordination chemistry of anions may be expected to
HBF4 is used for esterification of cellulose to clean metal yield a great variety of novel structures and properties of both
electrolyte for plating metals (Fe, Cu, Zn, etc.) and as a catalyst chemical and biological significance. In this regard, second
for preparing acetals. The commercially available sodium/ sphere coordination of cationic and anionic groups is an active
potassium salt of fluoroboric acid is used as fluorinating agent area of research in metallosupramolecular chemistry [7].
[1,2] and also has a number of applications in industry (for Cationic organic anion receptors have been extensively
example, flux for soldering and brazing, filtrate in resin bonded investigated [8], but cationic metal complexes have received
grinding wheels and as corrosion-resistant paint for galvaniza- much less attention [9]. We have undertaken an extensive
tion of Fe or Zn surfaces [3]). Moreover, fluoroanion, BF4 and research programme to exploit cationic cobaltammines,
cation, 1-ethyl-3-methylimidazolium were applied to electro- e.g. [trans-Co(en)2Cl2]+, [trans-Co(en)2(NO2)2]+ and [cis-
Co(en)2(N3)2]+, etc. as anion receptors [10] because cationic
cobaltammines are easy to synthesize in high yields from
readily available materials and could be stored for months
* Corresponding author. Tel.: +91 172 2544433; fax: +91 172 2545074.
** Corresponding author. Tel.: +44 121 4147481; fax: +44 121 4144403.
without any noticeable decomposition. The cationic cobaltam-
E-mail addresses: [email protected] (R.P. Sharma), mine [trans-Co(en)2Cl2]+ present in [trans-Co(en)2Cl2]Cl
[email protected] (B.M. Kariuki). fulfills the criterion [7a] of an anion receptor, i.e. unit positive
0022-1139/$ – see front matter # 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2008.01.006
326 R. Sharma et al. / Journal of Fluorine Chemistry 129 (2008) 325–331

charge for electrostatic interaction, eight N–H hydrogen bond three categories (a) solubility >0.1 M (soluble), (b) solubility
donor groups and a relatively stable framework. In the present between 0.01 and 0.1 M (slightly soluble) and (c) solubility
work, we envisaged that the presence of eight N–H hydrogen <0.01 M are (sparingly soluble). The solubility measurements
bond donor groups on each positively charged cation [trans- at room temperature show that the complex salt [trans-
Co(en)2Cl2]+ would facilitate the interaction with properly Co(en)2Cl2]BF4 is slightly soluble in water, as is [trans-
oriented negatively charged fluorine atoms of the fluoroanion Co(en)2(Cl)2]Cl which is readily soluble. The solubility
[BF4], resulting in the formation of a donor-acceptor complex product of [trans-Co(en)2Cl2]BF4 is 1.37  103 which
involving second sphere coordination. indicated that the affinity or binding of cationic cobaltammine
[trans-Co(en)2Cl2]+ is greater for tetrafluoroborate ion than
chloride ion. As reported in the experimental section, when the
appropriate amounts of the reactants were mixed in a minimum
amount of water, the crystals appeared with in few hours,
resulting in the formation of title complex salt. This is because
the ionic product is greater than solubility product, Ksp at the
crystallization point. A comparison of the solubility products of
In the solid state, in all probability, these two ions should various [trans-Co(en)2Cl2]+ salts is given in Table 1. It is
form an intricate network of hydrogen bonds stabilizing the evident from this table that the affinity of [trans-Co(en)2Cl2]+ is
entire lattice. Understanding such a network of interactions of same for ClO3, BrO3 and BF4 ions but more for [CdX4]2,
judicially chosen cations and anions would be rewarding as it X = Br or I and even more for N3.
can provide a means of constructing intricate and novel
molecular entities based on second-sphere coordination. We 2.3. Infrared spectroscopy
report here the potential of the [trans-Co(en)2Cl2]+ cation
present in [trans-Co(en)2Cl2]Cl by isolating and characterizing Infrared spectrum of the newly synthesized complex salt
the solid formed on mixing the appropriate salts. has been recorded in the region 4000–400 cm1 and tentative
assignments have been made on the basis of earlier reports in
2. Results and discussion the literature [11]. The absorption band at 887 cm1 is
assigned to CH2 rocking region and a band at 1592 cm1 is
2.1. Synthesis assigned to NH2 asymmetric deformation [12]. There are four
normal modes of vibration in a tetrahedral BF4 ion. All the
Trans-dichlorobis(ethylenediamine)cobalt(III)chloride can four vibrations are Raman active, whereas only n3, degenerate
react with sodium tetrafluoroborate in number of ways stretching mode (nd) and n4, degenerate deformation mode
depending upon the stoichiometric ratios of reactants. (dd) are IR active [11]. Assignments of the IR bands in
½trans-CoðenÞ2 Cl2 Cl þ NaBF4 1050 cm1 region are complicated as discussed previously
[13]. As reported in the literature there are characteristic
! ½trans-CoðenÞ2 Cl2 BF4 þ NaCl (i)
regions for degenerate stretching mode (1000–1150 cm1)
and degenerate deformation mode (530 cm1) arising from
½trans-CoðenÞ2 Cl2 Cl þ 2NaBF4 þ H2 O
BF4 ion [14]. In the spectrum of the title complex salt
! ½cis=trans-CoðenÞ2 ðH2 OÞClðBF4 Þ2 þ 2NaCl (ii) (Fig. 1) there is strong peak at 1051 cm1 with small
shoulders at 1114 and 1003 cm1 which were assigned to the
½trans-CoðenÞ2 ðH2 OÞClCl2 þ H2 O þ 3NaBF4
degenerate stretching mode, nd for BF4 ion, while the very
! ½trans-CoðenÞ2 ðH2 OÞ2 ðBF4 Þ3 þ 3NaCl (iii) strong band at 522 cm1 corresponded to the degenerate
deformation mode (dd, BF4). These values are also in
½trans  CoðenÞ2 ðH2 OÞ2 Cl3 þ 3NaBF4 agreement with those tetra-butylammonium tetrafluoroborate,
D Bu4N.BF4 [15]. The cation belongs to near D2H symmetry
!½trans  CoðenÞ2 ðBF4 Þ2 BF4 þ 3NaCl þ 2H2 O (iv)
due to which the IR band at 473 cm1 is assigned to
In the present case, reaction of [trans-Co(en)2Cl2]Cl with asymmetric stretching of Co–N while symmetric Co–N
sodium tetrafluoroborate in 1:1 stoichiometric ratio (Eq. (i)) in stretch is IR inactive.
aqueous medium afforded [trans-Co(en)2Cl2]BF4. The che-
mical composition of newly synthesized complex salt was Table 1
initially indicated by elemental analyses. This is freely soluble Solubility products (Ksp) of dichlorobis(ethylenediamine) cobalt(III) salts
in water and DMSO but insoluble in ethanol. It decomposed at Complex salts Solubility (g/l) Ksp
205 8C. [trans-Co(en)2(Cl)2]ClO3 11.0 1  103
[trans-Co(en)2(Cl)2]BrO3 20.0 2  103
2.2. Measurement of solubility product [trans-Co(en)2Cl2]2CdBr4 10.0 1  104
[trans-Co(en)2Cl2]2CdI4 4.0 1  105
[trans-Co(en)2Cl2]N3 10.0 9  106
Solubility of ionic salts in water differs to a great extent and
[trans-Co(en)2Cl2]BF4 12.5 1  103
on the basis of solubility criterion, the salts are classified into
 R. Sharma et al. / Journal of Fluorine Chemistry 129 (2008) 325–331 327

Fig. 1. FT-IR spectrum of [trans-Co(en)2Cl2]BF4.

2.4. UV–vis spectroscopy up field from H3BO3 as an internal standard. The spectrum
(Fig. 2a) shows the characteristic single peak at 2.3 due to
The electronic spectrum of the newly synthesized complex BF4, which is in agreement with the 11B NMR reported for
salt has been recorded in H2O. The solution state UV–Vis ionic BF4, i.e. 2.2 ppm [20].
19
absorption spectrum of the title complex show strong F NMR spectrum of the title complex salt was recorded in
absorptions at 616, 344 and 247 nm. These absorptions D2O. The chemical shift values are expressed as d value (ppm)
correspond to d–d transitions typical for octahedral low spin up field from CFCl3 as an internal standard. The spectrum
cobalt(III) complexes [16]. These transitions are from 1A1g (Fig. 2b) shows the characteristic single peak at 150.0 ppm
ground state of cobalt(III) to singlet state 1T1g (low energy) and due to BF4 ion. This is in agreement with the chemical shift
from 1A1g ground state to 1T2g (higher energy). In the value reported for ionic BF4, i.e. 151.1 ppm [20]. These
complexes of the type CoA4B2 (cis or trans) the 1T1g state split, signals are observed at 155.13 and 155.24 ppm in
the splitting in trans isomer being more [17], thus justifying the (phen)(Bu4N.BF4) and Pb(phen)(Bu4N.BF4)3(NO3)2, respec-
three absorption peaks in the title complex salt. tively [14]. This clearly confirmed the presence of fluoroanion,
in the complex salt.
2.5. NMR spectroscopy
2.6. X-ray crystallography
NMR spectra of the complex salt were recorded in D2O and
DMSO-d6. The chemical shift values are expressed as d value X-ray crystal structure of [trans-Co(en)2Cl2]BF4 has been
(ppm) downfield from tetramethylsilane as an internal standard. unambiguously determined by single crystal X-ray crystal-
When 1H NMR is recorded in DMSO (Fig. 2c), the singlet at lography and the ORTEP diagram is shown in Fig. 3. All other
5.25 ppm is observed due to NH2 protons and singlet at relevant information about the data collection is presented in
2.81 ppm is observed due to CH2 protons. The peak area Table 2.The asymmetric unit of the newly formed complex
observed is 8:8 for both types of protons as indicated by the salt consists of trans-dichlorobis(ethylenediamine)cobalt(III)
chemical formula of the complex salt and no coupling was cations split over two sites of symmetry and a disordered
observed. But when 1H NMR is recorded in D2O, the singlet at tetrafluoroborate ion (major occupancy 56%). The disorder in
5.26 ppm is observed due to NH2 protons and singlet at BF4 is more a rule than an exception as can be seen in many
2.93 ppm is observed due to CH2 protons [18]. The peak area BF4 compounds [21,22]. A view of the crystal structure is
observed is again 1:1 for both type of protons and coupling was shown in Fig. 4. The unit cell of the complex has layers of [trans-
also observed between protons of –CH2-group and –NH2-group Co(en)2Cl2]+ spanning to both b and c directions (view of the
of the ligand ethylenediammine, which may be due to the packing down the a axis is shown in Fig. 4) and tetrahedral BF4
exchange of some of the hydrogens by deuterium. The value of is located in between these layers. Probably, this layered nature
the coupling constant calculated is J = 3 Hz. The 13C NMR of [trans-Co(en)2Cl2]+ provides sufficient volume for alternate
spectrum showed the characteristic signal [19] at 45 ppm for orientation of small tetrahedral BF4 ions in the lattice (without
carbon atoms of ethylenediamine group. much expenditure of lattice energy) paving way for their
11
B NMR spectrum the complex salt was also recorded in disorder. Nevertheless, these ions are held to their position by
D2O. The chemical shift values are expressed as d value (ppm) unison of weak N–H  F interactions Table 3 as depicted in
328 R. Sharma et al. / Journal of Fluorine Chemistry 129 (2008) 325–331

Fig. 2. Multinuclear NMR spectra of [trans-Co(en)2Cl2]BF4. (a) 11B NMR spectrum for [trans-Co(en)2Cl2]BF4 (solvent: D2O), (b) 19F NMR spectrum for [trans-
Co(en)2Cl2]BF4 (solvent: D2O), and (c) 1H NMR spectrum for [trans-Co(en)2Cl2]BF4 (solvent: DMSO-d6).

Fig. 5. Thus, alternate layers of cations and anions are arranged in Table 2
repeated –A–B–A–B– pattern along the c direction of the lattice. Crystal data and structure refinement parameters of [trans-Co(en)2Cl2]BF4
What is noteworthy here is that, this packing is reminiscent of the Empirical formula C4H16BCl2CoF4N4
packing of [trans-Co(en)2Cl2]ClO3, which also forms the layered
Formula weight 336.85 g/mol
–A–B–A–B– packing with the aid of weak interactions [23] as
Wavelength 1.54178 Å
Crystal system Triclinic
Space group P1̄
Unit cell dimensions a = 6.4127(7) Å a = 78.067(8)8
b = 8.3210(10) Å b = 78.673(8)8
c = 12.2407(13) Å g = 75.170(8)8
Volume 610.61(12) Å3
Z 2
Calculated density 1.832 g/cm3
Absorption coefficient 15.386 mm1
F(0 0 0) 340
Crystal size 0.18 mm  0.18 mm  0.18 mm
Theta range for data collection 3.73–70.298
Limiting indices 7  h  7, 10  k  9,
14  l  14
Reflections collected 3840
Independent reflections 2025 [R(int) = 0.0560]
Completeness to u = 70.298 86.6%
Max. and min. transmission 0.1682 and 0.6810
Refinement method Full-matrix least-squares on F2
Data/restraints/parameters 2025/138/177
Goodness-of-fit on F2 1.041
Final R indices [I > 2s(I)] R1 = 0.0621, wR2 = 0.1625
R indices (all data) R1 = 0.0669, wR2 = 0.1676
Fig. 3. An ORTEP (50% probability) view of [trans-Co(en)2Cl2]BF4 showing
Largest diff. peak and hole 0.973 and 0.671 e Å3
just the major component for BF4.
 R. Sharma et al. / Journal of Fluorine Chemistry 129 (2008) 325–331 329

Table 3
Hydrogen bonding parameters (Å, 8) of [trans-Co(en)2Cl2]BF4
D–H  A D–H D  A H  A nD–H  A
N1–H1C  Cl2 0.900 3.392 2.585 149.55
N1–H1D  F2i 0.900 3.276 2.558 137.20
N1–H1D  Cl1i 0.900 3.447 2.701 141.04
N2–H2C  F1ii 0.900 3.052 2.262 146.35
N2–H2D  F2Aiii 0.900 2.911 2.043 161.61
N2–H2D  F2iii 0.900 2.973 2.130 155.68
N3–H3C  Cl2iv 0.900 3.476 2.679 148.13
N3–H3D  Cl1v 0.900 3.436 2.704 139.23
N4–H4C  F4Avi 0.900 3.022 2.197 151.97
N4–H4C  F3vi 0.900 3.222 2.568 130.15
N4–H4D  F1 0.900 3.112 2.242 162.43
Fig. 4. A view of the crystal structure down the a-axis showing intermolecular Symmetry transformations used to generate equivalent atoms: (i) x + 1, y, z; (ii)
N–H  F contacts as dashed lines. Also can be seen the alternate cation–anion x, y + 1, z + 2; (iii) x  1, y + 1, z + 2; (iv) x + 1, y + 1, z + 1;
layers forming A–B–A–B– pattern throughout the lattice. (v) x, y + 1, z + 1; (vi) x  1, y + 2, z + 1.

shown in Fig. 6. The small size, unit negative charge and shape Table 4
complementarity of these anions (ClO3, BF4, both tetrahedral) Selected bond distances (Å) and angles (8) of [trans-Co(en)2Cl2]BF4
may play the similar role, thus getting sandwiched between the N(1)–Co(1) 1.956 (4) N(4)–Co(2) 1.954 (5)
layers of [trans-Co(en)2Cl2]+ ions in their respective crystal N(2)–Co(1) 1.940 (4) Cl(1)–Co(1) 2.2466 (12)
structures. N(3)–Co(2) 1.951 (4) Cl(2)–Co(2) 2.2473 (12)
N(2)#1–Co(1)–N(2) 180.0 N(3)–Co(2)–N(3)#2 180.0
The N–H  F bond length is in the range 2.33–2.57 Å in
N(2)#1–Co(1)–N(1) 93.7 (2) N(3)–Co(2)–N(4) 85.9 (2)
[cis-Co(tren)(NO2)2]BF4 [24] and 2.07–2.56 Å in [Co(NH3)6] N(2)–Co(1)–N(1) 86.3 (2) N(3)#2–Co(2)–N(4) 94.1 (2)
Cl2BF4 [25] which is comparable with the N–H  F bond N(1)–Co(1)–N(1)#1 180.0 N(4)–Co(2)–N(4)#2 180.0 (3)
length in the title complex salt (2.04–2.56 Å). Cation N(2)–Co(1)–Cl(1)#1 90.56 (15) N(3)–Co(2)–Cl(2) 90.07 (13)
coordination is in the form of slightly distorted octahedral N(1)–Co(1)–Cl(1)#1 89.53 (13) N(3)#2–Co(2)–Cl(2) 89.93 (13)
N(2)–Co(1)–Cl(1) 89.44 (15) N(4)–Co(2)–Cl(2) 90.03 (16)
(Table 4), with Co–N bonds in the range 1.940(4)–1.956(4) Å,
N(1)–Co(1)–Cl(1) 90.47 (13) N(4)#2–Co(2)–Cl(2) 89.97 (16)
Co–Cl bond distances of 2.2473(12) and 2.2466(12) Å and N– Cl(1)#1–Co(1)–Cl(1) 180.0 Cl(2)–Co(2)–Cl(2)#2 180.0
Co–N angles in the range 85.9(2)–94.1(2)8.
Symmetry transformations used to generate equivalent atoms: #1 x, y + 1,
z + 2 #2 x, y + 1, z + 1.
2.7. Conclusions

The potential of cationic cobaltammine [trans-Co(en)2Cl2]+ for X-ray structure determination were obtained within half an
has been explored by isolating and characterizing the solid hour. The crystals were collected by drawing off the mother
obtained by mixing the aqueous solutions of [trans- liquor and air-dried (yield, 80%). The elemental analysis is
Co(en)2Cl2]Cl and NaBF4. Single crystal X-ray structure consistent with the composition [trans-Co(en)2Cl2]BF4. Found:
determination revealed the presence of discrete ions and the C, 14.4; H, 4.6; N, 16.8; Co, 17.5 for the complex salt, the
crystal lattice is stabilized by and hydrogen bonding interactions calculated values C, 14.3; H, 4.7; N, 16.7; Co, 17.6. Solubility:
involving N–H  F and N–H  Cl besides electrostatic forces of 1.25 g/100 ml at 25 8C, Ksp = 1.3  103.
attraction. The present study shows that cationic cobaltammine
[trans-Co(en)2Cl2]+ is a promising anion receptor for the [BF4]
anion in aqueous medium in contrast to other synthetic receptors
which are effective in non-aqueous solvents.

3. Experimental

Analytical grade reagents were used without any further

purification. [trans-Co(en2)Cl2]Cl has been prepared according
to literature method [26].

3.1. Synthesis of [trans-Co(en)2Cl2]BF4

One gram (0.003 mol) of [trans-Co(en)2Cl2]Cl was dis-

solved in 25 ml water and filtered. 0.38 g (0.003 mol) of sodium
tetrafluoroborate dissolved in minimum amount of water was
added to this solution. Green coloured single crystals suitable Fig. 5. A section of the cation layer showing N–H  Cl interactions.
330 R. Sharma et al. / Journal of Fluorine Chemistry 129 (2008) 325–331

Fig. 6. (a) Multiple sandwich’ packing of [Co(en)2Cl2]ClO3 viewed down b-axis showing the formation of molecular tapes through N–H  Cl hydrogen bonding.
Four such tapes are shown. Slice B has tapes formed through Co2 anions whereas slice A has the same with Co1. Note the occupation of chlorate anions in between the
layers. (b) The bifurcated N–H  O hydrogen bonding pattern of the chlorate anion in the crystal lattice. The oxygen atoms are saturated in terms of their proton
accepting capability.

3.2. Instrumentation [7] (a) C.R. Bondy, P.A. Gale, S.J. Loeb, J. Am. Chem. Soc. 126 (2004)
5030–5031;
(b) R.P. Sharma, R. Bala, R. Sharma, P. Venugopalan, Cryst. Eng.
Cobalt was determined by standard method [27] and C, H, N Commun. 8 (2006) 215–221;
were estimated micro-analytically by automatic PerkinElmer (c) A.M. Madalan, N. Avarvari, M. Andruh, New J. Chem. 30 (2006) 521–
2400 CHN elemental analyser. IR spectrum was recorded as 523;
KBr pellets on a PerkinElmer Spectrum RXFT-IR system. 1H, (d) S. Nieto, J. Perez, L. Riera, V. Riera, D. Miguel, New J. Chem. 30
13
C NMR, 11B and 19F spectra were recorded in D2O (2006) 838–841.
[8] (a) M.A. Hossaini, S. Lucarini, D. Powell, K. Bowman-James, Inorg.
respectively on JEOL AL 300MHz FT NMR spectrophot- Chem. 43 (2004) 7275–7277;
ometer. UV–vis spectrum was recorded in water using Hitachi (b) Special Issue 35 years of synthetic anion receptor chemistry, Coord.
330 spectrometer. Chem. Rev. 240 (2003).
(c) A.C. Warden, M. Warren, M.T.W. Hearn, L. Spiccia, New J. Chem. 28
(2004) 130–1308;
3.3. Crystal structure determination (d) C.A. Ilioudis, D.A. Tocher, J.W. Steed, J. Am. Chem. Soc. 126 (2004)
12395–12402;
X-ray data recorded at room temperature on a Bruker Smart (e) B.P. Hay, T.K. Firman, B.A. Moyer, J. Am. Chem. Soc. 127 (2005)
6000 diffractometer equipped with a CCD detector and a 1810–1819.
copper tube source. A single crystal was mounted on a glass [9] S. Nieto, J. Perez, V. Riera, D. Miguel, C. Alvarez, Chem. Commun.
(2005) 546–548.
fibre using epoxy resin and structure solution as well as [10] (a) R.P. Sharma, R. Sharma, R. Bala, L. Pretto, V. ferretti, J. Mol. Struct.
refinement were performed using SHELXL [28]. Hydrogen 800 (2006) 93–99;
atoms were located in the difference Fourier map and refined (b) R.P. Sharma, R. Sharma, R. Bala, P. Venugopalan, J. Mol. Struct. 787
using a riding model. (2006) 69–75;
Crystallographic data for the structural analysis of the title (c) R.P. Sharma, R. Sharma, R. Bala, U. Rychlewska, B. Warzajtis, J. Mol.
Struct. 738 (2005) 291–298;
compound has been deposited at the Cambridge Crystal- (d) R.P. Sharma, R. Sharma, R. Bala, B.K. Vermani, P. Venugopalan, J.
lographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, Coord. Chem. 58 (2005) 309–316;
UK, and are available free of charge from the Director on (e) R.P. Sharma, R. Sharma, R. Bala, M. Quiros, J.M. Salas, J. Coord.
request quoting the deposition number CCDC 609220 (Fax: Chem. 58 (2005) 1099–1104;
(f) R.P. Sharma, R. Sharma, R. Bala, P. Venugopalan, J. Coord. Chem. 58
+44 1223 336033, email: [email protected]).
(2005) 899–908;
(g) R.P. Sharma, R. Sharma, R. Bala, A. Bond, Acta Cryst. E61 (2005)
Acknowledgement m997–m1000;
(h) R.P. Sharma, R. Sharma, R. Bala, M. Quiros, J.M. Salas, J. Chem.
The authors gratefully acknowledge the financial support of Cryst. 35 (2005) 769–775;
UGC vide grant no. F.12-38/2003 (SR). (i) R.P. Sharma, R. Sharma, R. Bala, M. Quiros, J.M. Salas, J. Coord.
Chem. 56 (2003) 1581–1586;
(j) R.P. Sharma, R. Sharma, R. Bala, A. Bond, Acta Cryst. C61 (2005)
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