Poly[bis[μ-1,3-bis­(imidazol-1-ylmeth­yl)benzene-κ2 N 3:N 3′]bis­(nitrato-κO)cadmium]

Xi-Ying Hu; Guang-Rui Yang; Wen-Wen Shan

doi:10.1107/S1600536811021027

. 2011 Jun 11;67(Pt 7):m899. doi: 10.1107/S1600536811021027

Poly[bis[μ-1,3-bis(imidazol-1-ylmethyl)benzene-κ² N ³:N ^3′]bis(nitrato-κO)cadmium]

Xi-Ying Hu ^a,^*, Guang-Rui Yang ^a, Wen-Wen Shan ^a

PMCID: PMC3151839 PMID: 21836888

Abstract

A novel metal–organic framework based on 1,3-bis(imidazol-1-ylmethyl)benzene (1,3-bimb), [Cd(NO₃)₂(C₁₄H₁₄N₄)₂]_n, has been synthesized hydrothermally. The structure exhibits a two-dimensional metal–organic (4,4)-net composed of Cd^II atoms and bimb ligands, and such layers are further joined through interlayer C—H⋯O hydrogen bonds to generate a three-dimensional supramolecular structure.

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. (2006 ▶); Zhang et al. (2009 ▶). For synthesis and related structures with the bimb ligand, see: Hoskins et al. (1997 ▶). For C—H⋯O hydrogen bonds, see: Desiraju (1996 ▶); Broder et al. (2002 ▶).

Experimental

Crystal data

[Cd(NO₃)₂(C₁₄H₁₄N₄)₂]
M _r = 713.00
Monoclinic,
a = 8.4542 (8) Å
b = 19.3910 (18) Å
c = 9.2222 (8) Å
β = 102.415 (10)°
V = 1476.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.850, T _max = 0.863
5606 measured reflections
2578 independent reflections
2253 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.123
S = 1.06
2578 reflections
199 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.95 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811021027/hp2007sup1.cif

e-67-0m899-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021027/hp2007Isup2.hkl

e-67-0m899-Isup2.hkl^{(126.6KB, 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
C3—H3⋯O2ⁱ	0.93	2.71	3.525 (8)	147
C4—H4B⋯O1ⁱ	0.97	2.67	3.525 (6)	148
C4—H4B⋯O2ⁱ	0.97	2.83	3.633 (9)	141
C10—H10⋯O2ⁱ	0.93	2.63	3.506 (9)	158
C11—H11A⋯O1ⁱⁱ	0.97	2.70	3.518 (7)	142
C12—H12⋯O1ⁱⁱ	0.93	2.37	3.210 (6)	151

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

Acknowledgments

This work was supported financially by the Natural Science Foundation of Henan Province (grant No. 2010A140009) and the International Technology Cooperation Project of the Science and Technology Department of Henan Province of China (grant No. 104300510044).

supplementary crystallographic information

Comment

Extensive research has been focused on the supramolecular coordination assemblies not only for their variety of architectures but also for the potential applications as functional materials (Maspoch et al., 2007; Ockwig et al., 2005). Many imidazole-containing ligands have been successfully employed in the generation of many interesting systems in possession of multidimensional networks and properties (Zang et al., 2006; Zhang et al., 2009). To further explore various factors that influence the formation of result structures in the assembly reactions, we undertake synthetic and structural studies on one novel Cd^II coordination polymers based on the highly flexible bidentate ligand 1,3-bis(imidazol-1-ylmethyl)-benzene (1,3-bimb): [Cd(bimb)₂(NO₃)₂]_n (1).

X-ray crystallographic analysis revealed that 1 crystallizes in monoclinic space group P2₁/c. As depicted in Fig. 1, the asymmetric unit consists of a half Cd^II atom, one bimb ligand and one nitrate ion. Each Cd ion is in a slightly elongated octahedral coordination environment and coordinated by four N atoms from different bimb ligands and two O atoms from two nitrate ions. Four N atoms comprise the equatorial plane, while two O atoms occupy the axial positions. Each bimb ligand acts as a µ₂-bridge in trans-conformation with the dihedral angle of the two imidazole rings being ca 68.40 (16)°. Adjacent metal atoms are bridged by bimb ligands from two directions which are almost mutually perpendicular to form a (4,4)-net with the Cd···Cd distances of ca 14.2654 (10) Å (Fig. 2). The coordinated nitrate ions hang from the layer. Neighboring layers are arranged parallel with the uncoordinated O atoms closed to some H atoms from adjacent layer, and a number of interlayer C—H···O hydrogen bonds can be detected which contribute to the formation of the three-dimensional supromolecular structure, as shown in Fig. 3. The hydrogen-bonding geometry is listed in Table 1.

Experimental

1,3-bis(imidazol-1-ylmethyl)-benzene (bimb) was prepared according to the literature (Hoskins et al., 1997), all other starting materials were of analytical grade and obtained from commercial sources without further purification. Compound 1 was synthesized hydrothermally in a Teflon-lined stainless steel container by heating a mixture of 1,3-bis(imidazol-1-ylmethyl)-benzene (bimb) (0.0119 g, 0.05 mmol), Cd(NO₃)₂.4H₂O (0.0154 g, 0.05 mmol) and KOH (0.0056 g, 0.1 mmol) in 7 ml of distilled water at 120°C for 3 d, and then cooled to room temperature. Colorless rectangular crystals of 1 were obtained in 79% yield based on Cd.