catena-Poly[[[aqua­(4,4′-dimethyl-2,2′-bipyridine-κ2 N,N′)zinc]-μ-3-chloro­benzene-1,2-dicaboxylato-κ2 O 2:O 3] [[(4,4′-dimethyl-2,2′-bipyridine-κ2 N,N′)zinc]-μ-3-chloro­benzene-1,2-dicaboxylato-κ2 O 2:O 3]]

Yu Zhu; Hai-Yang Li; Ming-Li Ma

doi:10.1107/S1600536812014006

. 2012 Apr 13;68(Pt 5):m574–m575. doi: 10.1107/S1600536812014006

catena-Poly[[[aqua(4,4′-dimethyl-2,2′-bipyridine-κ² N,N′)zinc]-μ-3-chlorobenzene-1,2-dicaboxylato-κ² O ²:O ³] [[(4,4′-dimethyl-2,2′-bipyridine-κ² N,N′)zinc]-μ-3-chlorobenzene-1,2-dicaboxylato-κ² O ²:O ³]]

Yu Zhu ^a,^*, Hai-Yang Li ^a, Ming-Li Ma ^a

PMCID: PMC3344323 PMID: 22590089

Abstract

In the title compound, {[Zn(C₈H₃ClO₄)(C₁₂H₁₂N₂)(H₂O)]·[Zn(C₈H₃ClO₄)(C₁₂H₁₂N₂)]}_n, one Zn²⁺ ion is five-coordinated by two O atoms from two different 3-chlorobenzene-1,2-dicarboxylate ligands, one O atom from a water molecule and two N atoms from a 4,4′-dimethyl-2,2′-bipyridine ligand, while the second Zn²⁺ ion is four-coordinated by two O atoms from two different 3-chlorobenzene-1,2-dicarboxylate ligands, and two N atoms from a 4,4′-bimethyl-2,2′-bipyridine ligand. The crystal structure exhibits a three-dimensional supramolecular structure composed of alternate Zn(C₈H₃O₄Cl)(C₁₂H₁₂N₂) and Zn(C₈H₃O₄Cl)(C₁₂H₁₂N₂)(H₂O) chains, which are linked together by face-to-face π–π interactions [shortest centroid–centroid distances of 3.661 (4) and 3.6901 (3) Å], O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For background to the network topologies and applications of coordination polymers, see: Maspoch et al. (2007 ▶); Ockwig et al. (2005 ▶); Zang et al. (2011 ▶). For related O—H⋯O hydrogen bonds, see: Desiraju et al. (2004 ▶). For related π–π interactions, see: Zang et al. (2010 ▶). For related C—H⋯O hydrogen bonds, see: Desiraju et al. (1996 ▶). For related C—H⋯π interactions, see: Nishio et al. (1998 ▶).

Experimental

Crystal data

[Zn(C₈H₃ClO₄)(C₁₂H₁₂N₂)(H₂O)]·[Zn(C₈H₃ClO₄)(C₁₂H₁₂N₂)]
M _r = 914.38
Orthorhombic,
a = 34.050 (4) Å
b = 14.1831 (10) Å
c = 7.8764 (6) Å
V = 3803.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 291 K
0.20 × 0.18 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T _min = 0.971, T _max = 1.000
10533 measured reflections
6396 independent reflections
5076 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.104
S = 1.07
6396 reflections
518 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ▶), 2200 Friedel pairs
Flack parameter: 0.093 (14)

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014006/zq2156sup1.cif

e-68-0m574-sup1.cif^{(33.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014006/zq2156Isup2.hkl

e-68-0m574-Isup2.hkl^{(313.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4ⁱ	0.85	2.10	2.768 (6)	135
O1W—H1WB⋯O4ⁱⁱ	0.85	1.79	2.644 (6)	179
O1W—H1WB⋯O3ⁱⁱ	0.85	2.43	2.930 (5)	118
C17—H17⋯O4ⁱ	0.93	2.36	3.202 (8)	150
C20—H20⋯O6ⁱⁱⁱ	0.93	2.28	3.171 (8)	160
C23—H23⋯O6ⁱⁱⁱ	0.93	2.40	3.306 (8)	164
C32—H32⋯O2ⁱ	0.93	2.57	3.459 (8)	161
C35—H35⋯O2ⁱ	0.93	2.45	3.353 (8)	165

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

supplementary crystallographic information

Comment

In recent years, metallosupramolecular compounds have received much attention due to their variety of architectures and the potential applications as functional materials (Maspoch et al., 2007; Ockwig et al., 2005). Early reports have shown that carboxylate compounds and nitrogen heterocyclic ligands have been successfully employed in the generation of many novel structures (Zang et al., 2011). To further explore various factors that influence the properties and construction of coordination compounds, we undertake synthetic and structural studies on a novel Zn^II complex based on 3-chlorophthalic acid (H2cp) and 4,4'-dimethyl-2,2'-bipyridine (dmbpy).

The X-ray diffraction study revealed that the title compound crystallizes in the orthorhombic space group Pna2₁. The Zn1 atom is five-coordinated by two O atoms from two different 3-chlorobenzene-1,2-dicarboxylato ligands, one O atom from a water molecule and two N atoms from a 4,4'-dimethyl-2,2'-bipyridine ligand, while the Zn2 atom is four-coordinated by two O atoms from two different 3-chlorobenzene-1,2-dicarboxylato ligands, and two N atoms from a 4,4'-bimethyl-2,2'-bipyridine ligand (Fig. 1). Each cp^2- ligand acts as a µ₂-bridge linking two Zn atoms with both carboxylate groups in monodentate fashion resulting into two chains along the c axis. These two chains are further connected together by face-to-face π–π interactions (Zang et al., 2010) involving pyridine rings of different chains. The shortest Cg···Cg distances of 3.661 (4) and 3.6901 (3) are observed between Cg2 and Cg4, and Cg1 and Cg3, respectively (Cg1 is the centroid of the N1/C17–C21 ring, Cg2 of N2/C22–C26, Cg3 of N3/C34–C38, and Cg4 of N4/C29–C33). Adjacent zippered structures are linked together to form tetra-chain units by intermolecular O1w—H1wa···O4ⁱⁱⁱ hydrogen bonds (Desiraju et al., 2004) and C17—H17···O4ⁱⁱⁱ interactions (symmetry code: iii = -x + 1, -y + 1, z + 1/2). Each unit is further connected to other units through C20—H20···O6^iv, C23—H23···O6^iv (symmetry code: iv = -x + 1, -y + 1, z - 1/2), C32—H32···O2ⁱⁱⁱ, C35—H35···O2ⁱⁱⁱ (Desiraju et al., 1996) and C—H···π interactions (the shortest one being C37—H37···Cg5^v = 2.79 Å; Cg5 centroid of C11–C16; symmetry code: v = -x + 3/2, y - 1/2, z - 1/2) (Nishio et al., 1998) to form a three-dimensional supramolecular structure (Fig. 3).

Experimental

The title compound was synthesized hydrothermally in a Teflon-lined stainless steel container by heating a mixture of 3-chlorophthalic acid (H₂cp) (0.0100 g, 0.05 mmol), 4,4'-bimethyl-2,2'-bipyridine (dmbpy) (0.0092 g, 0.05 mmol), Zn(NO₃)₂.6H₂O (0.0149 g, 0.05 mmol) and NaOH (0.0040 g, 0.1 mmol) in 7 ml of distilled water at 120°C for 3 days, and then cooled to room temperature. Colourless block crystals were obtained in 71% yield (based on zinc).