Poly[[μ2-1,3-bis­(imidazol-1-ylmeth­yl)benzene][μ2-2,2′-dihy­droxy-1,1′-methyl­enebis(naphthalene-3-carboxyl­ato)]zinc]

Yanqiang Peng; Xilian Wei; Dacheng Li; Suna Wang

doi:10.1107/S1600536811054584

. 2012 Jan 7;68(Pt 2):m125–m126. doi: 10.1107/S1600536811054584

Poly[[μ₂-1,3-bis(imidazol-1-ylmethyl)benzene][μ₂-2,2′-dihydroxy-1,1′-methylenebis(naphthalene-3-carboxylato)]zinc]

Yanqiang Peng ^a, Xilian Wei ^a, Dacheng Li ^a, Suna Wang ^a,^*

PMCID: PMC3274865 PMID: 22346812

Abstract

In the title compound, [Zn(C₂₃H₁₄O₆)(C₁₄H₁₄N₄)]_n, the Zn^II ion is four-coordinated in a distorted tetrahedral geometry. The 1,3-bis(imidazol-1-ylmethyl)benzene and 2,2′-dihydroxy-1,1′-methylenebis(naphthalene-3-carboxylate) ligands connect the Zn^II ions alternately in different directions, forming a layered structure parallel to the ac plane. Topological analysis reveals that the whole structure is a (4,4) network. The layers are further assembled into a three-dimensional supramolecular structure via C—H⋯O and C—H⋯π interactions.

Related literature

For background to metal-organic frameworks, see: Luo et al. (2009 ▶); Wei et al. (2010 ▶). For related structures, see: Wang et al. (2011 ▶); Fan et al. (2005 ▶); Zhou et al. (2008 ▶); Li et al. (2010 ▶); Feng et al. (2009 ▶); Xu et al. (2009 ▶); Batten & Robson (1998 ▶).

Experimental

Crystal data

[Zn(C₂₃H₁₄O₆)(C₁₄H₁₄N₄)]
M _r = 690.00
Monoclinic,
a = 10.8382 (9) Å
b = 17.3428 (16) Å
c = 17.7939 (17) Å
β = 100.781 (1)°
V = 3285.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 298 K
0.23 × 0.17 × 0.15 mm

Data collection

Bruker SMART-1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.837, T _max = 0.889
16511 measured reflections
5800 independent reflections
2460 reflections with I > 2σ(I)
R _int = 0.111

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.127
S = 1.00
5800 reflections
433 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811054584/vm2140sup1.cif

e-68-0m125-sup1.cif^{(37.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811054584/vm2140Isup2.hkl

e-68-0m125-Isup2.hkl^{(284KB, hkl)}

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

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

Cg1, Cg2 and Cg3 are the centroids of the C8–C13, C18–C23 and C4–C9 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.81	2.555 (5)	150
O6—H6⋯O5	0.82	1.76	2.502 (5)	150
C30—H30B⋯O6ⁱ	0.97	2.54	3.350 (7)	141
C26—H26⋯Cg1ⁱⁱ	0.93	2.79	3.676 (8)	161
C29—H29⋯Cg2ⁱⁱⁱ	0.93	2.76	3.502 (7)	137
C30—H30A⋯Cg3ⁱⁱ	0.97	2.71	3.628 (6)	158

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

Acknowledgments

This work was supported by the National Natural Science Foundation of PR China (grant No. 20801025) and the Shandong Tai-Shan Scholar Research Fund.

supplementary crystallographic information

Comment

In the past several years, the design and construction of metal-organic frameworks (MOFs) have received more attention due to their intriguing architectures and potential applications in ion-exchange, heterogeneous catalysis and gas storage (Luo et al., 2009; Wei et al., 2010). Much interest was focused on the coordination chemistry of semirigid polycarboxylate ligands and flexible exo-bidentate N-heterocycle ligands (Wang et al., 2011; Fan et al., 2005; Zhou et al., 2008; Li et al., 2010; Feng et al., 2009; Xu et al., 2009). Herein, we selected pamoic acid (H₂PA, 4,4^'-methylenebis(3-hydroxy-2-naphthalenecarboxylic acid)) as building unit. Coexistence of naphthalene rings and the central sp³ carbon atom makes this symmetrical aromatic dicarboxylate ligand possess both rigid and flexible character. Solvothermal reactions of this ligand with m-bix (1,3-bis(imidazol-1-ylmethyl)benzene) and Zn^II salt led to the title compound, [Zn(PA)(m-bix)]_n.

The title compound crystallizes in the space group P2₁/c and exhibits a two-dimensional layered structure. The asymmetric unit is composed of one crystallographically independent Zn^II ion, one PA^2- anion ligand as well as one m-bix ligand. The Zn^II ion is four-coordinated by two carboxylate oxygen atoms from two different PA^2- ligands and two nitrogen atoms from two m-bix ligands. The Zn-O and Zn-N bond lengths lie in the normal range of 1.957 (4)-2.009 (5)Å, while the O···Zn···N and O···Zn···O angles are in the range of 98.40 (16)-128.6 (2)°, indicating a much distorted tetrahedral coordination geometry around the metal center. As shown in Fig.1, m-bix ligand in this case adopts a bis(monodentate) bridging coordination mode, linking Zn^II ions to form one-dimensional chains along the a axis with a dihedral angle between the two terminal imidazole rings of 49.5 (7)°. These chains are connected further by the deprotonated PA^2- ligand in trans conformation bis(monodentate) bridging coordination mode with the dihedral angle between two naphthyl rings of 97.1 (9)°. As a result, a two-dimensional corrugated layer structure is generated along the ac plane (Fig. 2). The metal···metal distances separated by m-bix and PA^2- ligands are 15.27 (5) and 10.83 (8)Å, respectively. From a topological viewpoint, the whole structure is a (4, 4) network (Batten et al., 1998) considering the Zn^II ions as four-connected nodes (Fig. 4). The carboxyl groups and adjacent hydroxyl groups are linked by intramolecular O-H···O hydrogen bonds. Adjacent layers are further stacked through C-H···O and C-H···π weak interactions, resulting in the present three-dimensional supramolecular structure (Fig. 3 and Table 1).

Experimental

A mixture of Zn(NO₃)₂.6H₂O(0.1mmol), H₂PA(0.1mmol), m-bix(0.1mmol), DMF(6ml) and H₂O(4ml) was placed in a teflon reactor and heated at 80°C for 48h. After cooling to room temperature, colorless crystals suitable for X-ray diffraction were obtained with 42% yield based on Zn(NO₃)₂.6H₂O.