Rb3CoO2, a Novel Oxocobaltate(I) Synthesized via the Azide/Nitrate Route

Mikhail Sofin and Martin Jansen*

Stuttgart, Max-Planck-Institut fuÈr FestkoÈrperforschung

Received March 1st, 2001.

Herrn Professor Hans Georg von Schnering zum 70. Geburtstag gewidmet

Abstract. Rb3CoO2 was prepared via the azide/nitrate route. K3CoO2 and contains Co1+, which is coordinated by two
Stoichiometric mixtures of the precursors (Co3O4, RbN3 and oxygen atoms forming a slightly distorted dumb-bell.
RbNO3) were heated in a special regime up to 500 °C and Rb3CoO2 decomposes at 580 °C to Rb2O, Co and CoO.
annealed at this temperature for 100 h in silver crucibles.
The crystal structure of the obtained red product was solved
and refined by powder methods (Pnma, Z = 4, 12.3489(2), Keywords: Cobalt; Rubidium cobaltate(I); Crystal structure;
7.6648(1), 6.2251(1) A Ê ). Rb3CoO2 is isostructural with Azide/nitrate route

Rb3CoO2, ein neues Oxocobaltat(I) dargestellt uÈber die Azid/Nitrat-Route

InhaltsuÈbersicht. Rb3CoO2 wurde uÈber die Azid/Nitrat- bestimmt und verfeinert (Pnma, Z = 4, 12,3489(2), 7,6648(1),
Route dargestellt. StoÈchiometrische Gemenge der Edukte Ê ). Rb3CoO2 ist isotyp mit K3CoO2 und enthaÈlt
6.2251(1) A
(Co3O4, RbN3 und RbNO3) wurden unter besonderer Tem- Co1+ von zwei Sauerstoffatomen in Form einer leicht defor-
peraturfuÈhrung bis 500 °C aufgeheizt und bei dieser Tem- mierten Hantel koordiniert. Rb3CoO2 zerfaÈllt bei 580 °C in
peratur 100 Stunden in Silbertiegeln getempert. Die Kristall- Rb2O, Co und CoO.
struktur des roten Produkts wurde mit Pulvermethoden

Introduction advantages, but avoids the disadvantages of using alkali

metal oxides. This procedure is based on the fact that
For the synthesis of alkali oxometalates there is a
alkalimetal azides and nitrates (or nitrites) can com-
rather broad choice of how to introduce the alkali me-
proportionate to form nitrogen and the respective alka-
tal components. Among the commonly used sources,
limetal oxides. All starting materials are insensitive to
as there are the alkalimetal monoxides, peroxides, hy-
air, and can be mixed easily, e. g. using a ball mill. By
peroxides, hydroxides, carbonates or nitrates, the mon-
adjusting the azide/nitrate ratio appropriately, the reac-
oxides are most efficient, for a number of reasons.
tion can be run oxidising, reducing or neutral.
First of all, they are the strongest oxide bases avail-
Here, we demonstrate with another example, how
able, thus increasing the thermodynamic driving force
versatile this route is, even by realising an exotic oxi-
for the formation of multinary oxides. In addition,
dation state like cobalt(I) in Rb3CoO2.
among the metal oxides, they exhibit the lowest melt-
All cobaltates(I) known so far (Na3CoO2,
ing points which promotes their reactivity during solid
K3CoO2 [2] and CsK2CoO2 [3]) have been prepared
state reactions. On the other hand, synthetic work em-
and characterised by Hoppe and cowokers.
ploying alkali metal oxides is laborious. In most cases,
their preparation involves producing the metals and
oxidising them to a defined oxygen content. These Experimental
steps, as well as preparing the starting mixtures for Synthesis of Rb3CoO2
the desired reactions, have to be performed at strictly
inert conditions. Starting materials for the preparation of Rb3CoO2 were ru-
bidium nitrate (Johnson Matthey, 99%), rubidium azide and
Recently we presented a novel approach to the
cobalt oxide Co3O4. Rubidium azide was synthesized from
synthesis of alkali oxometalates [1] that preserves the
aqueous HN3 and rubidium carbonate. Cobalt oxide Co3O4
was prepared by heating Co(C2O4) ´ 2 H2O in a flow of oxy-
* Prof. Dr. M. Jansen gen at 350 °C for 10 h. The phase purity of the precursors
Max-Planck-Institut fuÈr FestkoÈrperforschung was controlled by X-ray analysis.
Heisenbergstraûe 1 Starting materials (RbN3, RbNO3 and Co3O4) were mixed
D-70569 Stuttgart in the ratio required according to the equation
Fax: +49-7 11-6 89 15 02
e-mail: [email protected] 25 RbN3 + 2 RbNO3 + 3 Co3O4 = 9 Rb3CoO2 + 38.5 N2,

Z. Anorg. Allg. Chem. 2001, 627, 2115±2117 Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 0044±2313/01/6272115±2117 $ 17.50+.50/0 2115
 M. Sofin, M. Jansen

milled in a planet ball mill, pressed in pellets under 105 N,

dried under vacuum (10±2 mbar) at 150 °C for 12 h and
placed under argon in a tightly closed steel vessel (for its
design c. f. [1]) provided with a silver inlay. In a flow of
dry argon the following temperature profile was applied:
25 ® 260 °C (100 K/h); 260 ® 380 °C (5 K/h), 380 ® 500 °C
(50 K/h) and subsequent annealing for 100 h at 500 °C.
The obtained red powder being extremely sensitive to air
was sealed in glass ampoules under argon atmosphere and
all following manipulations with this substance were per-
formed in inert atmospheres of purified argon or nitrogen.
X-ray study. The X-ray investigation was performed on a
STOE Stadi P diffractometer with Co±Ka radiation (k =
1.78896 AÊ) at room temperature using a position sensitive de- Fig. 1 Experimental and calculated XRD pattern for
tector and a curved germanium monochromator. The powder Rb3CoO2. Crosses mark the experimental, full line the calcu-
di€raction data were collected in the range of 10 to 90 degrees lated profile. Bragg-positions and the difference between ex-
in 2 h. perimental and refined data are given in the lower part.

DTA/TG study. Thermal analyses were carried out using a

DAT/TG device (STA 409, Netzsch, Selb) coupled with a
quadrupole mass spectrometer (QMG 421, Balzers, Wetzlar).
The probe (m = 102.7 mg) was heated at a rate of 5 K/min in
a corundum crucible under dry argon.

Structure determination. The obtained powder diffraction

data were processed with STOE WinXPOW programs [4].
As a starting model for the Rietveld profile refinement
(Fullprof [5]) we used the structural data for the isostructur-
al K3CoO2 [2].

Results and Discussion

Rb3CoO2 can be easily prepared by the azide/nitrate
route as a micro-crystalline powder. The brilliant red
products are extremely sensitive to air and moisture,
and turn black immediately when exposed to humid
air.
The DTA/TG analysis has shown that no chemical
reactions or phase transitions occur during heating of
the substance up to ~ 550 °C. At this temperature
Rb3CoO2 begins to decompose into Rb2O, Co and
CoO.
Experimental and calculated XRD patterns are
given in Fig. 1. The refined structural parameters and Fig. 2 Crystal structure of Rb3CoO2.
the atom coordinates of Rb3CoO2 are given in
Tables 1 and 2, correspondingly. The structure of
Rb3CoO2 is given in Fig. 2. ordination, and Rb2 in a strongly bent two fold coor-
Relevant bond lengths and angels of Rb3CoO2 and dination.
K3CoO2 are compiled in Table 3. The structural fea- Now, four oxocobaltates(I) are known (Na3CoO2,
tures related to the cobaltate(I) anion are in close K3CoO2, CsK2CoO2, and Rb3CoO2). As we have
agreement for the two different representatives. Also, checked, all of them can be prepared by the azide/ni-
the amazingly low coordination number (2) for one of trate route and it seems viable to extend the still small
the crystallographically independent alkali metals is group of oxocobaltates(I) using this method.
confirmed (c. f. Table 4). Furthermore, the variations However the azide/nitrate route can not only be ap-
in the alkali metal ± oxygen bond length follow the plied to the synthesis of ternary alkali metal oxides
same pattern in both compounds. containing elements in low oxidation states (such
Rb1 and oxygen are forming a partial structure con- Co1+, Fe1+, Ni1+, Ti3+ etc.) but also of those with rare
sisting of linearly, through trans-edges, connected high oxidation states like Co4+ (Na4CoO4), or Ni3+
RbO4-tetrahedra. The resulting chains, running along (NaNiO2). In general, this method appears rather pro-
[010], are linked by cobalt(I), in a virtually linear co- mising for its versatility and ease to use.

2116 Z. Anorg. Allg. Chem. 2001, 627, 2115±2117

Rb3CoO2, a Novel Oxocobaltate(I) Synthesized via the Azide/Nitrate Route

Table 1 The structural data for Rb3CoO2 Table 4 Interatomic distances (in AÊ ), coordination numbers
(CN), effective coordination numbers (EcoN) and mean fic-
Empirical formula Rb3CoO2 tive ionic radii (MEFIR) [6] for Rb3CoO2
Formula weight, g/mol 347.34
Crystal system Orthorhombic
Atom O1 O2 CN EcoN MEFIR
Space group Pnma (No 62)
Ê
Lattice constants, A a = 12.3489(2) Rb1 2.808 2.892 4 3.9 1.476
b = 7.6648(1) 2.929 2.958
c = 6.2251(1) Rb2 2.800 2.825 2 2.0 1.412
Z 4 Co 1.756 1.754 2 2.0 0.355
Ê3
Cell volume, A 589.22(13)
Calculated density, g/cm3 3.915
Number of refined parameters 28
Profile pseudo-Voigt
Rp, % 6.14 References
Rwp, % 7.79
RBragg, % 8.79 [1] D. Trinschek, M. Jansen, Angew. Chem. 1999, 111, 234;
v2 3.05 Angew. Chem. Int. Ed. Engl. 1999, 38, 133.
DW 0.5984
[2] W. Burow, J. Birx, F. Bernhardt, R. Hoppe, Z. Anorg.
Allg. Chem. 1993, 619, 923.
[3] F. Bernhardt, R. Hoppe, R. K. Kremer Z. Anorg. Allg.
Table 2 Atom coordinates and isotropic temperature para- Chem. 1994, 620, 187.
Ê 2) for Rb3CoO2
meters (in A [4] STOE & Cie GmbH Darmstadt, STOE WinXPOW, Ver-
Ion Position x y z Uiso
sion 1.04.
[5] J. Rodriguez-Carvajal, Loboratoire Leon Brillouin, Full-
Rb1 8d 0.3618(1) 0.9982(4) 0.1813(2) 0.0250(8) Prof, ver. 3.5.
Rb2 4c 0.6015(3) 0.25 0.2809(5) 0.029(1)
Co1 4c 0.6195(3) 0.75 0.3095(4) 0.012(2) [6] R. Hoppe, Z. Kristallogr. 1979, 150, 23.
O1 4c 0.7133(8) 0.75 0.522(2) 0.030(2)
O2 4c 0.538(1) 0.75 0.079(1) 0.032(2)

Table 3 Some structural data (distances in AÊ and angles

in °) for Rb3CoO2 and K3CoO2 [2] in comparison

Formula Rb3CoO2 K3CoO2

Molar weight 347.33 175.79

Cell volume 589.22(13) 523.26(17)
Calculated density 3.92 2.64
Co±O(1) 1.757(6) 1.759(4)
Co±O(2) 1.753(6) 1.751(4)
ÐO(1)±Co±O(2) 173.8(1) 176.4(2)
MI(2)±O(1) 2.800(5) 2.663(4)
MI(2)±O(2) 2.825(5) 2.689(4)
ÐO(1)±MI(2)-O(2) 92.3(1) 89.77(1)
MI(1)±O(1)1 2.808(5) 2.704(3)
MI(1)±O(1)2 2.929(5) 2.789(3)
MI(1)±O(2)1 2.892(4) 2.716(3)
MI(1)±O(2)2 2.958(4) 2.764(3)

Z. Anorg. Allg. Chem. 2001, 627, 2115±2117 2117