catena-poly[[(1,10-phenanthroline-κ2N,N′)copper(I I)]-μ-(dihydrogenbenzene-1,2,4,5-tetracarboxylato)-κ2 O1:O4]

Article abstract of DOI:10.1107/S0108270103021097

In the title compound, [Cu(C₁₀H₄O₈)(C₁₂H₈N₂ )]_n, the Cu^II cation has a four-coordination environment completed by two N atoms from one 1,10-phenanthroline (phen) ligand and two O atoms belonging to two dihydrogen benzene-1,2,4,5-tetracarboxylate anions (H₂TCB^2-). There is a twofold axis passing through the Cu^II cation and the centre of the phen ligand. The [Cu(phen)]²⁺ moieties are bridged by H₂TCB^2- anions to form an infinite one-dimensional coordination polymer with a zigzag chain structure along the c axis. A double-chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π-π stacking interactions between the phen ligands, with an average distance of 3.64 A, resulting in a two-dimensional network structure.

Full text of DOI:10.1107/S0108270103021097

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
(H2TCB)]n, (I). It is entirely possible to prepare [Cu2-
(TCB)(phen)2] and [Cu(phen)(H2TCB)] separately. The
compositions of the complexes can be controlled by using
different molar ratios of the reactants and different H-atom
receptors, such as phen alone, phen and NaOH, etc.
ISSN 0108-2701
catena-Poly[[(1,10-phenanthroline-
j2N,N0)copper(II)]-l-(dihydrogen
benzene-1,2,4,5-tetracarboxylato)-
j2O1:O4]
Mao-Lin Hu,* Hong-Ping Xiao, Shun Wang and Xin-Hua Li
Department of Chemistry and Material Science, Wenzhou Normal College,
Wenzhou 325027, People's Republic of China
Correspondence e-mail: hml64@sohu.com
Received 15 September 2003
Accepted 24 September 2003
Online 11 October 2003
In the title compound, [Cu(C10H4O8)(C12H8N2)]n, the CuII
cation has a four-coordination environment completed by two
N atoms from one 1,10-phenanthroline (phen) ligand and two
O atoms belonging to two dihydrogen benzene-1,2,4,5-tetra-
carboxylate anions (H2TCB2 ). There is a twofold axis passing
through the CuII cation and the centre of the phen ligand. The
[Cu(phen)]2+ moieties are bridged by H2TCB2 anions to
form an in®nite one-dimensional coordination polymer with a
zigzag chain structure along the c axis. A double-chain
structure is formed by hydrogen bonds between adjacent
zigzag chains. Furthermore, there are ꢀ±ꢀ stacking inter-
actions between the phen ligands, with an average distance of
In (I), the CuII cation is coordinated by two N atoms from
one phen ligand and two O atoms from two H2TCB2 anions
(Fig. 1 and Table 1). There is a twofold axis passing through
the CuII cation and the centre of the phen ligand. An in®nite
one-dimensional coordination polymer with a zigzag chain
structure is formed by the CuII cations, the ꢁ2-bridging
H2TCB2 anions and the terminal phen ligands.
Ê
3.64 A, resulting in a two-dimensional network structure.
Comment
In recent years, intense research activity has been directed
toward the assembly of coordination polymers, due to their
potential application in gas adsorption, catalysis and opto-
electronic devices (Fujita et al., 1994; Sato et al., 1996). The key
step in the design of coordination polymers is to select suitable
multidentate bridging ligands and spacers. Accordingly,
benzene-1,2,4,5-tetracarboxylic acid (H4TCB) has a very
versatile coordination behaviour, since it can form bridges
between metallic centres, generating varied and sometimes
surprising molecular architectures. Therefore, numerous
complexes with the H4TCB ligand have been extensively
studied (Cheng et al., 2001; Chu et al., 2001; Wang et al., 2000),
although the construction of complexes from H4TCB, 1,10-
phenanthroline (phen) and CuII building blocks is still limited
(Shi et al., 2001; Zou et al., 1998). To the best of our knowledge,
only a one-dimensional double-chain polymer, [Cu2(TCB)-
(phen)2]nÁnH2O, has been reported to date (Shi et al., 2001).
We report here the hydrothermal synthesis and structure of
the title one-dimensional zigzag chain polymer, [Cu(phen)-
Figure 1
The coordination environment of the CuII cation in (I), with the atom-
numbering scheme and displacement ellipsoids drawn at the 50%
probability level. H atoms are shown as small spheres of arbitrary radii.
[Symmetry code: (i) 2 x; y; 12 z.]
m454 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103021097
Acta Cryst. (2003). C59, m454±m455

metal-organic compounds
Ê
The CuÐO bond lengths are 1.9363 (19) A, which is within
the normal range for CuÐOcarboxylate distances (1.927±
Ê
2.010 A; Zou et al., 1998), while the CuÐN distance of
Re®nement
Re®nement on F2
w = 1/[ꢅ2(Fo2) + (0.0491P)2]
R[F2 > 2ꢅ(F2)] = 0.041
wR(F2) = 0.100
S = 0.96
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max < 0.001
Ê
2.006 (2) A is longer than that in [Cu2(TCB)(phen)2]nÁnH2O
3
Ê
Áꢆmax = 0.49 e A
II
[1.984 (4) A]. The bond angles around the Cu cation are
3
Ê
Ê
0.39 e A
2129 re¯ections
155 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
Áꢆmin
=
Extinction correction: SHELXL97
in SHELXTL (Bruker, 2000)
Extinction coef®cient: 0.67 (3)
characteristic of a distorted square-planar geometry.
1
An O3ÐH1Á Á ÁO2(32 x, 21 + y,
z) hydrogen bond
(Table 2) is formed between neighbouring one-dimensional
zigzag chains. This leads to a one-dimensional double-chain
2
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Cu1ÐO1
1.9363 (19)
Cu1ÐN1
2.006 (2)
O1iÐCu1ÐO1
O1ÐCu1ÐN1i
88.55 (12)
95.93 (9)
O1ÐCu1ÐN1
N1iÐCu1ÐN1
168.32 (9)
81.78 (13)
Symmetry code: (i) 2 x; y; 12 z.
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
O3ÐH1Á Á ÁO2ii
Symmetry code: (ii)
DÐH
HÁ Á ÁA
1.74 (3)
DÁ Á ÁA
DÐHÁ Á ÁA
Figure 2
The double-chain structure in (I).
0.85 (3)
2.577 (3)
165 (4)
x; 12 ‡ y; 12 z.
3
2
structure and the two chains interweave with each other
(Fig. 2). Furthermore, there are ꢀ±ꢀ stacking interactions
between the aromatic rings of the phen ligands and the
H2TCB2 anions of two neighbouring chains, with an average
Ê
The OÐH distances were re®ned subject to OÐH = 0.85 (1) A.
The other H atoms were positioned geometrically and allowed to ride
Ê
on their parent atoms at CÐH distances of 0.93 A and with Uiso(H) =
1.2Ueq(C).
Ê
distance of 3.64 A, which is different from the interactions
between phen ligands observed in [Cu2(TCB)(phen)2]nÁnH2O
Data collection: SMART (Bruker, 2000); cell re®nement: SMART;
data reduction: SAINT (Bruker, 2000); program(s) used to solve
structure: SHELXTL (Bruker, 2000); program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL.
and which results in a two-dimensional network structure.
Experimental
The title compound was synthesized by a hydrothermal method from
a mixture of benzene-1,2,4,5-tetracarboxylic acid (1 mmol, 0.25 g),
CuSO4Á5H2O (1 mmol, 0.25 g), 1,10-phenanthroline (3 mmol, 0.54 g)
and water (20 ml) in a 30 ml Te¯on-lined stainless steel reactor. The
solution was heated at 433 K for 3 d. After slow cooling of the
reaction system to room temperature, blue prism-shaped crystals of
(I) were collected and washed with distilled water.
We acknowledge ®nancial support from the Zhejiang
Provincial Natural Science Foundation of China (grant No.
202137).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OB1146). Services for accessing these data are
described at the back of the journal.
Crystal data
3
[Cu(C10H4O8)(C12H8N2)]
Mr = 495.88
Dx = 1.797 Mg m
Mo Kꢃ radiation
Cell parameters from 596
re¯ections
References
Monoclinic, C2=c
Bruker (2000). SMART (Version 5.618), SAINT (Version 6.02a), SADABS
(Version 2.03) and SHELXTL (Version 5.03). Bruker AXS Inc., Madison,
Wisconsin, USA.
Cheng, Y. Q., Lin, W. Z., Hu, M. L., Yuan, J. X., Wang, S. & Wang, J. G. (2001).
Chin. J. Chem. 19, 321±324.
Ê
Ê
a = 10.718 (5) A
b = 14.292 (7) A
ꢄ = 2.6±21.4ꢀ
ꢁ = 1.25 mm
T = 298 (2) K
1
Ê
c = 12.192 (6) A
ꢂ = 101.119 (7)ꢀ
V = 1832.5 (16) A
Z = 4
3
Ê
Prism, blue
0.37 Â 0.18 Â 0.12 mm
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1151±1152.
Data collection
Bruker SMART APEX CCD area-
detector diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
Tmin = 0.763, Tmax = 0.860
5730 measured re¯ections
2129 independent re¯ections
1567 re¯ections with I > 2ꢅ(I)
Rint = 0.036
Sato, O., Iyoda, T., Fujishima, A. & Hashimoto, K. (1996). Science, 271, 49±51.
Shi, Q., Cao, R., Sun, D. F., Hong, M. C. & Liang, Y. C. (2001). Polyhedron, 20,
3287±3293.
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ꢄ
max = 27.9ꢀ
h = 14 ! 11
k = 16 ! 18
l = 16 ! 15
Zou, J. Z., Liu, Q., Xu, Z., You, X. Z. & Huang, X. Y. (1998). Polyhedron, 17,
1863±1869.
ꢁ
Acta Cryst. (2003). C59, m454±m455
Hu, Xiao, Wang and Li [Cu(C10H4O8)(C12H8N2)] m455