Catena-poly[[[(benzene-1,3,5-tricarboxylic acid)(1,10-phenanthroline) cadmium(II)] -μ- oxalato] 1H-benzotriazole solvate monohydrate]

Article abstract of DOI:10.1107/S0108270107064578

In the title compound, [Cd(C₂O4)(C₁₂H ₈N₂)(C₉H₆O₆)] ·C₆H₅N₃·H₂O, the Cd^II atom has a distorted penta-gonal-bipyramidal geometry, defined by two N atoms and five O atoms from bidentate 1,10-phenanthroline ligands, oxalate ligands and benzene-1,3,5-tricarboxylic acid ligands. The oxalate ligands in the asymmetric unit possess inversion symmetry. The triazole molecule is not coordinated to the Cd atom. The structure of the title compound features a one-dimensional chain running along the crystallographic a axis, and a three-dimensional supra-molecular network is formed via aromatic π-π inter-actions and hydrogen-bonding inter-actions.

Full text of DOI:10.1107/S0108270107064578

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
catena-[(ꢁ2-benzene-1,3-dicarboxylato-5-carboxylic acid)-
aqua(1,10-phenanthroline)cobalt(II)] (Plater et al., 2001) and
bis[diaquabis(1,10-phenathroline)manganese(II)] hexaaqua-
copper(II) bis(1,3,5-benzenetricarboxylate) docosahydrate
clathrate (Qiu et al., 2005). We report here the structure of the
title compound, (I), which contains four different organic
ligands.
ISSN 0108-2701
catena-Poly[[[(benzene-1,3,5-tricar-
boxylic acid)(1,10-phenanthroline)-
cadmium(II)]-l-oxalato] 1H-benzo-
triazole solvate monohydrate]
Chao Qin,* Xin-Long Wang and En-Bo Wang
Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal
University, Changchun 130024, People's Republic of China
Correspondence e-mail: qinc703@nenu.edu.cn
Received 21 October 2007
Accepted 29 November 2007
Online 12 January 2008
In the title compound, [Cd(C2O4)(C12H8N2)(C9H6O6)]Á-
C6H5N3ÁH2O, the CdII atom has a distorted pentagonal±
bipyramidal geometry, de®ned by two N atoms and ®ve O
atoms from bidentate 1,10-phenanthroline ligands, oxalate
ligands and benzene-1,3,5-tricarboxylic acid ligands. The
oxalate ligands in the asymmetric unit possess inversion
symmetry. The triazole molecule is not coordinated to the Cd
atom. The structure of the title compound features a one-
dimensional chain running along the crystallographic a axis,
and a three-dimensional supramolecular network is formed
via aromatic ꢀ±ꢀ interactions and hydrogen-bonding inter-
actions.
As shown in Fig. 1, the asymmetric unit contains one Cd
atom, one H3BTC ligand, one 1,10-phenanthroline ligand, two
half oxalate ligands, one uncoordinated benzotriazole mol-
ecule and one solvent water molecule. The CdII ion is coor-
dinated by ®ve O atoms of one H3BTC ligand and two oxalate
ligands, and two N atoms from the 1,10-phenanthroline ligand,
showing a distorted pentagonal±bipyramidal geometry. The
two half oxalate ligands in the asymmetric unit possess
inversion symmetry. The CdÐO bond distances range from
Ê
2.287 (3) to 2.525 (4) A, and the CdÐN bond distances are
Ê
2.334 (4) and 2.351 (4) A (Fig. 1). Adjacent Cd atoms are
linked by oxalate ligands, forming one-dimensional chains
running along the crystallographic a axis (Fig. 2). The dihedral
Comment
Rational design and synthesis of metal±organic polymers is
of current interest in the ®eld of supramolecular chemistry
and crystal engineering. Benzene-1,3,5-tricarboxylic acid
(H3BTC), as a popular organic ligand, has been investigated in
the construction of metal±organic frameworks. As a multi-
carboxylate ligand, H3BTC exhibits versatile binding modes in
the construction of polymeric complexes. It can act as
H2BTC (Ying & Mao, 2004), HBTC2 (Shi et al., 2004) and
BTC3 (Almeida Paz & Kilnowski, 2004) anions and serve as a
ꢁ2 (Cheng et al., 2004), ꢁ3 (Zheng et al., 2004), ꢁ4 (Shi et al.,
2003), ꢁ5 (Wang et al., 2003) and ꢁ6 (Serre et al., 2004) linker.
So far, some structures of metal±organic polymers containing
H3BTC and 1,10-phenanthroline have been reported, exam-
ples being catena-[bis(ꢁ3-benzenecarboxylic acid-3,5-dicarb-
oxylato)bis(1,10-phenanthroline)dicadmium(II) (ꢁ2-benzene-
carboxylic acid-3,5-dicarboxylato)bis(1,10-phenanthroline)-
cadmium(II)] (Shi et al., 2004), catena-[(ꢁ3-1,3,5-benzene-
tricarboxylato)(1,10-phenanthroline)indium] (Gomez-Lor et
al., 2005), catena-[(ꢁ2-1,3-dicarboxybenzene-5-carboxylato)-
diaqua(1,10-phenanthroline)manganese(II) 1,3-dicarboxy-
benzene-5-carboxylate monohydrate] (Majumder et al., 2005),
Figure 1
The molecular structure of the title compound, shown with 50%
probability displacement ellipsoids. [Symmetry codes: (i) x + 1, y,
z + 1; (ii) x, y, z + 1.]
Acta Cryst. (2008). C64, m73±m75
DOI: 10.1107/S0108270107064578
# 2008 International Union of Crystallography m73

metal-organic compounds
angles between the oxalate and 1,10-phenanthroline ligands
are 72.790 (14) and 82.139 (12)ꢀ. The chains of (I) are linked
by OÐHÁ Á ÁO hydrogen bonds involving the hydroxy groups
of H3BTC ligands and the carboxylate groups of oxalate
ligands (O2ÐH1Á Á ÁO8v and O6ÐH3Á Á ÁO9ii; all symmetry
codes as in Table 1), resulting in two-dimensional layers
(Fig. 3). Although the benzotriazole ligands are not coordi-
nated to the Cd atom, they take part in the construction of the
three-dimensional hydrogen-bond network. These sheets are
further linked into a three-dimensional supramolecular
network via O ÐHÁ Á ÁN, NÐHÁ Á ÁO and OÐHÁ Á ÁO hydrogen
bonds (O4ÐH2Á Á ÁN3, N5ÐH5AÁ Á ÁO1Wiv, O1WÐH4Á Á ÁO1iii
and O1WÐH5Á Á ÁO10; Fig. 3), and details are given in Table 1.
Meanwhile, the three-dimensional network is stabilized by
strong ꢀ±ꢀ stacking interactions between the 1,10-phenan-
throline ligands and H3BTC ligands. As shown in Fig. 3, the
face-to-face distance between adjacent 1,10-phenanthroline
Experimental
The title compound was prepared by hydrothermal methods. A
mixture of Cd(NO3)2Á6H2O (0.17 g, 0.5 mmol), H3BTC (0.13 g,
0.6 mmol), 1,10-phenanthroline (0.1 g, 0.6 mmol), oxalic acid (0.027 g,
0.3 mmol), benzotriazole (0.06 g, 0.5 mmol) and water (10 ml) was
stirred for 20 min in air. The mixture was then transferred to a 23 ml
Te¯on reactor and kept at 433 K for 72 h under autogenous pressure.
Crystals suitable for X-ray analysis were obtained after the mixture
was cooled to room temperature.
Crystal data
[Cd(C2O4)(C9H6O6)(C12H8N2)]Á-
C6H5N3ÁH2O
ꢃ = 73.28 (3)ꢀ
ꢄ = 84.63 (3)ꢀ
V = 1381.3 (5) A
Z = 2
Mo Kꢂ radiation
ꢁ = 0.87 mm
T = 298 (2) K
3
Ê
Mr = 727.91
Triclinic, P1
Ê
a = 9.4531 (19) A
1
Ê
b = 10.869 (2) A
Ê
c = 14.100 (3) A
ꢂ = 87.86 (3)ꢀ
0.26 Â 0.25 Â 0.16 mm
Ê
Data collection
ligands is 3.324 (3) A, and that between the H3BTC ligands
Ê
and the benzotriazole system is 3.414 (3) A. These strong ꢀ±ꢀ
Rigaku R-AXIS RAPID IP
diffractometer
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.806, Tmax = 0.874
13575 measured re¯ections
6247 independent re¯ections
4186 re¯ections with I > 2ꢅ(I)
Rint = 0.073
stacking and hydrogen-bonding interactions play important
roles in forming the resulting three-dimensional supra-
molecular network.
Re®nement
R[F2 > 2ꢅ(F2)] = 0.056
wR(F2) = 0.119
S = 1.03
6247 re¯ections
415 parameters
1 restraint
H-atom parameters constrained
3
Ê
Áꢆmax = 0.77 e A
3
Ê
1.12 e A
Áꢆmin
=
Table 1
Hydrogen-bond geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1WÐH4Á Á ÁO1iii
N5ÐH5AÁ Á ÁO1Wiv
O6ÐH3Á Á ÁO9ii
O2ÐH1Á Á ÁO8v
O4ÐH2Á Á ÁN3
0.85
0.86
0.85
0.85
0.85
0.85
1.99
1.93
1.83
1.79
1.94
2.12
2.824 (5)
2.775 (6)
2.659 (5)
2.636 (5)
2.711 (6)
2.942 (5)
165
166
163
172
150
164
O1WÐH5Á Á ÁO10
Symmetry codes: (ii) x; y; z ‡ 1; (iii) x; y; z ‡ 1; (iv) x ‡ 1; y ‡ 1; z 1; (v)
x; y; z 1.
Figure 2
A view of the one-dimensional zigzag chain running along the a axis.
All H atoms were initially located in a difference Fourier map. H
atoms of hydroxy groups and water molecules were then constrained
Ê
to an ideal geometry, with OÐH distances of 0.85 A and Uiso(H)
values of 1.5Ueq(O). All other H atoms were placed in geometrically
idealized positions and constrained to ride on their parent atoms, with
Ê
Ê
CÐH distances of 0.93 A, an NÐH distance of 0.86 A and Uiso(H)
values of 1.2Ueq(C,N).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell re®ne-
ment: PROCESS-AUTO; data reduction: PROCESS-AUTO;
program(s) used to solve structure: SHELXS97 (Sheldrick, 1997);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3
(Farrugia, 1997) and DIAMOND (Brandenburg, 2005); software used
to prepare material for publication: SHELXTL (Bruker, 2001).
Figure 3
Perspective views of the two- (left) and three-dimensional (right)
supramolecular networks along the b axis.
This work was supported ®nancially by the Science Foun-
dation for Young Teachers of Northeast Normal University
ꢁ
m74 Qin et al. [Cd(C2O4)(C9H6O6)(C12H8N2)]ÁC6H5N3ÁH2O
Acta Cryst. (2008). C64, m73±m75

metal-organic compounds
Gomez-Lor, B., Gutierrez-Puebla, E., Iglesias, M., Monge, M. A., Ruiz-Valero,
C. & Snejko, N. (2005). Chem. Mater. 17, 2568±2573.
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Excellent Youth of Jilin, China (grant No. 20070103).
Plater, M. J., Foreman, M. R. St J., Howie, R. A., Skakle, J. M. S., Coronado, E.,
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Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SF3065). Services for accessing these data are
described at the back of the journal.
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Acta Cryst. (2008). C64, m73±m75
Qin et al.
[Cd(C2O4)(C9H6O6)(C12H8N2)]ÁC6H5N3ÁH2O m75