The honeycomb network structure of poly[[[μ2-1,3-bis-(1H- benzimidazol-2-yl)benzene-k2 N 3:N 3′] (μ2-terephthalato-μ2 O:O′)zinc(II)] ethanol solvate]

Article abstract of DOI:10.1107/S0108270107027436

The terephthalate dianion and the bis-(imidazol-yl)benzene ligand of the title compound, {[Zn(C8H4O4)(C20H14N4)]·C2H6O} n , each bridges two adjacent zinc centers, resulting in a layer-type coordination polymer; the zinc center shows tetra-hedral coordination. The disordered ethanol solvent mol-ecules occupy the spaces between the layers and are hydrogen bonded to the layers. The two symmetry-independent dianions lie on different inversion sites. International Union of Crystallography 2007.

Full text of DOI:10.1107/S0108270107027436

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
waves (Song et al., 2000), is a ligand that can bind to two metal
centers through its two tertiary nitrogen-donor sites. Spec-
troscopic measurements are available for a small number of
adducts with transition metals, and among the zinc complexes
that have been characterized spectroscopically are the halide
and perchlorate complexes (Chawla & Gill, 1997; Shivaku-
maraiah & Nanje Gowda, 2003), but to date no example of an
adduct has been reported in the literature (CSD, Version 5.28,
November 2006 release; Allen, 2002).
The title 1:1 zinc terephthalate±bis(benzimidazolyl)benzene
adduct, (I), which exists as an ethanol solvate, is a coordina-
tion polymer in which the carboxylate group and benzene
ligand both engage in bridging two tetrahedral zinc centers
(Fig. 1), this bridging mode giving rise to a layer motif. The two
symmetry-independent dianions lie on different inversion
sites. The two benzimidazolyl arms are bent with respect to the
phenylene ring, one (with the N1 atom) being twisted by
31.6 (1)ꢀ and the other (with the N3 atom) being twisted by
15.7 (1)ꢀ. The twist angles parallel the deviation of the metal
atom from the plane of the arms, the atom being displaced by
ISSN 0108-2701
The honeycomb network structure of
poly[[[l2-1,3-bis(1H-benzimidazol-
0
2-yl)benzene-j2N3:N3 ](l2-terephtha-
lato-j2O:O0)zinc(II)] ethanol solvate]
Fa-Yan Meng,a Xu-Qing Liua and Seik Weng Ngb*
aSchool of Chemistry and Materials Engineering, Huangshi Institute of Technology,
Huangshi 435003, People's Republic of China, and bDepartment of Chemistry,
University of Malaya, 50603 Kuala Lumpur, Malaysia
Correspondence e-mail: seikweng@um.edu.my
Received 27 April 2007
Accepted 5 June 2007
Online 23 June 2007
Ê
Ê
0.807 (3) A from the ®rst arm and by 0.507 (3) A from the
second arm.
The terephthalate dianion and the bis(imidazolyl)benzene
ligand of the title compound, {[Zn(C8H4O4)(C20H14N4)]Á-
C2H6O}n, each bridges two adjacent zinc centers, resulting in a
layer-type coordination polymer; the zinc center shows
tetrahedral coordination. The disordered ethanol solvent
molecules occupy the spaces between the layers and are
hydrogen bonded to the layers. The two symmetry-indepen-
dent dianions lie on different inversion sites.
The topology of the layer is a (6,3)-honeycomb (Fig. 2) that
is somewhat buckled as the two bridging components are of
Comment
Zinc terephthalate forms a number of 1:1 adducts with
bidentate N-heterocyclic ligands; crystallographic studies have
focused on rigid heterocycles, such as, for example, 4,40-
bipyridine (Tao et al., 2000) and 1,10-phenanthroline (Sun et
al., 2001). As the terephthalate entity itself is rigid, the adducts
adopt architectures that re¯ect such rigidity, i.e. the 4,40-
bipyridine adduct is a three-dimensional network and the 1,10-
phenanthroline adduct is a linear chain. With a ¯exible ligand
such as 1,3,4-bis(triazol-1-yl)ethane,
a two-dimensional
rhombic network is formed (Li et al., 2004). 1,3,4-Bis(triazol-1-
yl)butane affords a threefold interpenetrating diamondoid
network based on a zinc center (Wang et al., 2006).
Figure 1
The tetrahedral geometry of the Zn atom in the layer structure of (I).
Displacement ellipsoids are drawn at the 70% probability level. The
disordered ethanol solvent molecule is not shown. [Symmetry code: (i)
x, 1 y, 1 z.]
1,3-Bis(benzimidazol-2-yl)benzene, an N-heterocycle that
can be conveniently synthesized by condensing m-phenyl-
enediamine and phthalic acid under the in¯uence of micro-
Figure 2
OLEX (Dolomanov et al., 2003) depiction of the (6,3)-honeycomb
topology, shown projected against the unit cell.
Acta Cryst. (2007). C63, m341±m342
DOI: 10.1107/S0108270107027436
# 2007 International Union of Crystallography m341

metal-organic compounds
Table 2
Hydrogen-bond geometry (A, ).
different sizes. The atoms comprising the layer framework
constitute only about 79% of the volume, as calculated by
PLATON (Spek, 2003). The layers are consolidated by NÐ
HÁ Á ÁO hydrogen bonds (Table 2), but the space between
layers is large enough to accommodate ethanol molecules.
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH2nÁ Á ÁO4ii
N4ÐH4nÁ Á ÁO2
O5ÐH5oÁ Á ÁO1
0.84 (2)
0.86 (2)
0.86 (4)
1.94 (2)
2.11 (2)
2.14 (4)
2.777 (2)
2.895 (3)
2.999 (4)
176 (3)
152 (3)
176 (7)
Experimental
Symmetry code: (ii) x; y ‡ 1; z.
The N-heterocycle was prepared according to a reported procedure
(Chawla & Gill, 1997). Zinc nitrate hexahydrate (0.074 g, 0.25 mmol),
benzene-1,4-dicarboxylic acid (0.021 g, 0.125 mmol), 1,3-bis(benz-
imidazol-2-ylmethyl)benzene (0.039 g, 0.125 mmol), ethanol (2 ml)
and water (15 ml) were placed in a 23 ml Te¯on-lined stainless steel
Parr bomb. (Neither sodium nor potassium hydroxide was added.)
The bomb was heated at 433 K for 5 d and cooled to room
temperature at a rate of 5 K h 1. Colorless block-shaped crystals
were obtained in 20% yield.
Carbon-bound H atoms were positioned geometrically (CÐH =
Ê
0.93 and 0.97 A), and were included in the re®nement in the riding-
model approximation, with Uiso(H) values set at 1.2±1.5Ueq(C). The
water and amino H atoms were located in a difference Fourier map,
and were re®ned with a distance restraint of OÐH = NÐH =
Ê
0.85 (1) A.
Data collection: SMART (Bruker, 2004); cell re®nement: SAINT
(Bruker, 2004); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
X-SEED (Barbour, 2001); software used to prepare material for
publication: publCIF (Westrip, 2007).
Crystal data
[Zn(C8H4O4)(C20H14N4)]ÁC2H6O
ꢂ = 87.931 (1)ꢀ
3
Ê
Mr = 585.90
Triclinic, P1
a = 9.0660 (8) A
V = 1331.1 (2) A
Z = 2
Ê
Ê
Mo Kꢀ radiation
1
b = 9.3077 (9) A
ꢃ = 0.97 mm
T = 291 (2) K
Ê
c = 15.921 (2) A
The authors thank the Key Laboratory of Non-Ferrous
Metal Materials and New Processing Technology, Ministry of
Education, China, Huangshi Institute of Technology and the
University of Malaya for supporting this work.
ꢀ = 86.731 (1)ꢀ
ꢁ = 83.140 (1)ꢀ
0.28 Â 0.21 Â 0.18 mm
Data collection
Bruker APEX area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.712, Tmax = 0.845
10765 measured re¯ections
5834 independent re¯ections
4918 re¯ections with I > 2ꢄ(I)
Rint = 0.020
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BG3037). Services for accessing these data are
described at the back of the journal.
Re®nement
R[F2 > 2ꢄ(F2)] = 0.035
wR(F2) = 0.098
S = 1.03
5834 re¯ections
389 parameters
31 restraints
H atoms treated by a mixture of
independent and constrained
re®nement
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Ê
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ꢀ
Ê
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The ethanol solvent molecule is disordered in the C atoms and was
re®ned with two ethyl components in a 0.72:0.28 ratio. The OÐC
Ê
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Ê
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ꢁ
m342 Meng et al. [Zn(C8H4O4)(C20H14N4)]ÁC2H6O
Acta Cryst. (2007). C63, m341±m342