Tetraaquabis(3,5-dicarboxybenzoato-O)cobalt(II)

Article abstract of DOI:10.1107/S0108270100012312

The hydrothermal reaction of cobalt(II) chloride with trimesate (3,5-dicarboxybenzoate) ions in aqueous solution gives the novel title complex, [Co(C₉H₅O₆)₂ (H₂O)₄]. The Co^II ion

Full text of DOI:10.1107/S0108270100012312

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
1997; Livage et al., 1998, 1999). Trimesic acid (benzene-1,3,-
5-tricarboxylic acid, TMA) has been successfully used by
several authors to design organic supramolecular networks
(Kolotuchin et al., 1999; Sharma & Zaworotko, 1996;
Melendez et al., 1996). Its geometry and hydrogen-bonding
capability (three carboxylic acid groups) make it an interesting
tool for crystal engineering. Condensation of TMA with metal
ISSN 0108-2701
Tetraaquabis(3,5-dicarboxybenzo-
ato-O)cobalt(II)
 Ã
Nathalie Guillou, Carine Livage,* Jerome Marrot and
Â
Â
Gerard Ferey
Â
Institut Lavoisier, UMR CNRS 8637, Universite de Versailles Saint-Quentin-en-
Yvelines, 45 Avenue des Etats-Unis, F-78035 Versailles, France
Correspondence e-mail: livage@chimie.uvsq.fr
Received 6 July 2000
Accepted 7 September 2000
The hydrothermal reaction of cobalt(II) chloride with
trimesate (3,5-dicarboxybenzoate) ions in aqueous solution
gives the novel title complex, [Co(C9H5O6)2(H2O)4]. The CoII
ion lies on an inversion centre and is octahedrally coordinated
to two trimesate anions and four water molecules. Hydrogen
bonds ensure the three-dimensional architecture of the
structure.
Comment
Over the last decade, signi®cant research effort has been
focused on the use of organic molecular building blocks to
generate three-dimensional porous solids via hydrogen
bonding or copolymerization of metal ions (Palmans et al.,
Figure 2
Figure 1
(a) A view of one layer in (I) showing the network of hydrogen bonding
and (b) a projection of the structure of (I) along [010] showing the
stacking of the trimesate layers. Dotted lines correspond to hydrogen
bonds.
A view of complex (I) with the atomic numbering scheme. Displacement
ellipsoids are drawn at the 50% probability level and H atoms are drawn
as spheres of arbitrary radii.
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Acta Cryst. (2000). C56, 1427±1428
# 2000 International Union of Crystallography Printed in Great Britain ± all rights reserved 1427

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
ions was ®rst developed by Yaghi et al. (1996, 1997, 1998) to
generate coordination polymers (Chui et al., 1999; Chui, Los et
al., 1999; Daiguebonne et al., 1999; Li et al., 1999). Herein, we
describe the synthesis and crystal structure of a new
cobalt(II)±TMA complex, (I), and demonstrate that this
species can be used as a synthon to generate supramolecular
networks.
ꢁ
Ê
Co1ÐO1
Co1ÐO7
2.1117 (9)
2.0720 (9)
Co1ÐO8
2.1107 (10)
88.86 (4)
O1ÐCo1ÐO7
O1ÐCo1ÐO8
90.52 (4)
88.24 (4)
O7ÐCo1ÐO8
The centrosymmetric structure of (I) is shown in Fig. 1 with
the atom-labelling scheme. Two monodentate carboxylate
groups and four water molecules octahedrally coordinate the
Co atom. Each trimesate ligand presents one bonding and two
pendant protonated carboxylate groups, leading to a single
negative charge on the ligand. The TMA anion and two of
the coordinated water molecules lie in planes, the Co atom
being located between these planes. A network of strong
hydrogen bonds (Table 2), between TMA ions, and between
TMA ions and water molecules, provides the basis of this
two-dimensional network (Fig. 2a). The Co atom ensures the
three-dimensionality of the architecture by linking adjacent
layers (Fig. 2b).
Table 2
Hydrogen-bonding geometry (A, ).
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O4ÐH4AÁ Á ÁO2i
O6ÐH6AÁ Á ÁO3ii
O7ÐH7AÁ Á ÁO5ii
O7ÐH7BÁ Á ÁO1iii
O8ÐH8AÁ Á ÁO2iv
0.82
0.82
0.80 (2)
0.86 (2)
0.87 (2)
1.80
1.81
1.95 (3)
1.89 (2)
1.86 (3)
2.589 (2)
2.631 (2)
2.740 (2)
2.748 (2)
2.726 (2)
161
175
168 (2)
175 (2)
177 (2)
Symmetry codes: (i)
x; 2 y; z.
x; 1 y; z; (ii)
2
x; 12 ‡ y; 12 z; (iii) 1 ‡ x; y; z; (iv)
H atoms from the water molecules were found via difference
Fourier maps and isotropically re®ned. H atoms from the trimesate
Ê
molecules were treated as riding (OÐH = 0.82 and CÐH = 0.93 A).
These results illustrate the clear tendency of trimesate
complexes to pack into planes in order to maximize hydrogen
bonding. The solid-state arrangement is therefore dominated
by the formation of trimesate layers, as previously described
for lanthanide complexes by Daiguebonne et al. (1999).
All H-atom positions (trimesate and water) could be deduced from
difference Fourier maps. However, H atoms from the trimesate were
placed in calculated positions in order to have perfect sp2 geometry.
Data collection: XSCANS (Siemens, 1996); cell re®nement:
XSCANS; data reduction: SHELXTL (Siemens, 1994); program(s)
used to solve structure: SHELXS97 (Sheldrick, 1997); program(s)
used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular
graphics: SHELXTL; software used to prepare material for publi-
cation: SHELXTL.
Experimental
Complex (I) was hydrothermally synthesized from a mixture of
cobalt(II) chloride hexahydrate, trimesic acid, potassium hydroxide
and water in the molar ratio 1:1:1:60. The starting mixture was heated
for 12 h at 453 K under autogenous pressure (®nal pH = 2). The
resulting solid phase, consisting of pink needles of (I), was ®ltered off
and dried at room temperature.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GS1105). Services for accessing these data are
described at the back of the journal.
References
Crystal data
Chui, S. S.-Y., Los, S. M.-F., Charmant, J. P. H., Orpen, A. G. & Williams, I. D.
(1999). Science, 238, 1148±1150.
Chui, S. S.-Y., Siu, A. & Williams, I. D. (1999). Acta Cryst. C55, 194±196.
3
[Co(C9H5O6)2(H2O)4]
Mr = 549.26
Monoclinic, P21/c
Dx = 1.818 Mg m
Mo Kꢁ radiation
Cell parameters from 5763
re¯ections
Â
Daiguebonne, C., Guillou, O., Gerault, Y., Lecerf, A. & Boubekeur, K. (1999).
Inorg. Chim. Acta, 284, 139±145.
Ê
a = 5.1160 (1) A
b = 13.0080 (2) A
ꢂ = 2.07±29.77ꢁ
ꢃ = 0.946 mm
T = 296 (2) K
Ê
Kolotuchin, S. V., Thiessen, P. A., Fellon, E. E., Wilson, S. R., Loweth, C. J. &
Zimmerman, S. C. (1999). Chem. Eur. J. 5, 2537±2547.
Li, H., Eddaoudi, M., O'Keeffe, M. & Yaghi, O. M. (1999). Nature, 402, 276±
279.
1
Ê
c = 15.1890 (1) A
ꢀ = 96.853 (1)ꢁ
V = 1003.59 (3) A
Z = 2
3
Ê
Needle, pink
0.76 Â 0.14 Â 0.08 mm
Â
Livage, C., Egger, C. & Ferey, G. (1999). Chem. Mater. 11, 1546±1550.
Livage, C., Egger, C., Nogues, M. & Ferey, G. (1998). J. Mater. Chem. 8, 2743±
Â
Data collection
2747.
Siemens SMART 1K diffractometer
! scans
Absorption correction: semi-
empirical (SADABS; Sheldrick,
1996)
2590 independent re¯ections
2281 re¯ections with I > 2ꢄ(I)
Rint = 0.022
Melendez, R. E., Sharma, C. V. K., Zaworotko, M. J., Bauer, C. & Rogers, R. D.
(1996). Angew. Chem. Int. Ed. Engl. 35, 2213±2215.
Palmans, A. R. A., Vekemans, J. A. J. M., Kooijman, H., Spek, A. L. & Meijer,
E. W. (1997). J. Chem. Soc. Chem. Commun. pp. 2247±2248.
Sharma, C. V. K. & Zaworotko, R. J. (1996). J. Chem. Soc. Chem. Commun. pp.
2655±2656.
ꢂ
max = 29.77ꢁ
h = 6 ! 7
Tmin = 0.533, Tmax = 0.928
6860 measured re¯ections
k = 17 ! 14
l = 20 ! 19
È
Sheldrick G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Gott-
È
Re®nement
ingen, Germany.
Siemens (1994). SHELXTL. Release 5.10. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
Siemens (1996). XSCANS. Version 2.2. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.025
wR(F2) = 0.073
S = 1.090
2590 re¯ections
179 parameters
w = 1/[ꢄ2(Fo2) + (0.042P)2
+ 0.0785P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.36 e A
Yaghi, O. M., Davis, C. E., Li, G. & Li, H. (1997). J. Am. Chem. Soc. 119, 2861±
2868.
3
Ê
0.40 e A
Áꢅmin
=
H atoms treated by a mixture of
independent and constrained
re®nement
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.031 (2)
Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. L. (1998). Acc. Chem.
Res. 31, 474±484.
Yaghi, O. M., Li, H. & Groy, T. L. (1996). J. Am. Chem. Soc. 118, 9096±9101.
ꢀ
1428 Nathalie Guillou et al. [Co(C9H5O6)2(H2O)4]
Acta Cryst. (2000). C56, 1427±1428