Poly[diaqua­[μ-1,4-bis­(1H-imidazol-1-yl)benzene-κ2 N 3:N 3′](μ-fumarato-κ2 O 1:O 4)nickel(II)]

Chang-Xin Bian; Xiao-Qiang Yao; Yu-Min Song

doi:10.1107/S1600536812038895

. 2012 Sep 22;68(Pt 10):m1286–m1287. doi: 10.1107/S1600536812038895

Poly[diaqua[μ-1,4-bis(1H-imidazol-1-yl)benzene-κ² N ³:N ^3′](μ-fumarato-κ² O ¹:O ⁴)nickel(II)]

Chang-Xin Bian ^a, Xiao-Qiang Yao ^a, Yu-Min Song ^a,^*

PMCID: PMC3470161 PMID: 23125605

Abstract

In the title compound, [Ni(C₄H₂O₄)(C₁₂H₁₀N₄)(H₂O)₂]_n, the Ni^II ion has a distorted octahedral coordination geometry. The asymmetric unit is composed of an Ni²⁺ ion, located on a twofold rotation axis, one half of a 1,4-bis(1H-imidazol-1-yl)benzene (BIMB) ligand and one half of a fumarte (fum²⁻) dianion, both ligands being located about inversion centers, and a coordinating water molecule. The Ni^II ions are linked by two BIMB ligands and two fum²⁻ dianions, forming a four-connected layered structure parallel to (010) with a 4⁴-sql topology. Within each layer, there are rhombic grids with dimensions of ca 13.5 × 9.0 Å and approximate angles of 109 and 70°. The crystal packing features a two-dimensional → two-dimensional parallel/parallel interpenetration in which one undulating layer is catenated to another equivalent one, forming a new bilayer. Moreover, the entangled two-dimensional layers are connected by O—H⋯O and C—H⋯O hydrogen bonds, generating a three-dimensional structure.

Related literature

For multi-dimensional coordination polymers and their applications, see: Batten & Robson (1998 ▶); Carlucci et al. (2003a ▶,b ▶); Moulton & Zaworotko (2001 ▶); Sun et al. (2006 ▶); Wu et al. (2011 ▶); Bu et al. (2004 ▶). For their potential applications in electron transfer and drug delivery, see: Harriman & Sauvage (1996 ▶); Raymo & Sauvage (1999 ▶). For the structures of some related compounds, see: Chen et al. (2010 ▶); Li et al. (2012 ▶); Bu et al. (2004 ▶).

Experimental

Crystal data

[Ni(C₄H₂O₄)(C₁₂H₁₀N₄)(H₂O)₂]
M _r = 419.04
Orthorhombic,
a = 11.2806 (4) Å
b = 16.3703 (7) Å
c = 9.0253 (3) Å
V = 1666.67 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.21 mm⁻¹
T = 296 K
0.23 × 0.22 × 0.20 mm

Data collection

Bruke APEXII CCD area-dector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.768, T _max = 0.794
8512 measured reflections
2108 independent reflections
1827 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.093
S = 1.08
2108 reflections
123 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038895/su2481sup1.cif

e-68-m1286-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038895/su2481Isup2.hkl

e-68-m1286-Isup2.hkl^{(103.8KB, 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
O3—H3Y⋯O2ⁱ	0.85	1.96	2.7033 (18)	146
O3—H3X⋯O2ⁱⁱ	0.85	2.03	2.8361 (18)	159
C3—H3⋯O2ⁱⁱ	0.93	2.49	3.360 (2)	155

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

Acknowledgments

This work was supported financially by the Key Laboratory of Eco-Environment-Related Polymer Materials (Northwest Normal University) and the Ministry of Education of Gansu (No. 1101–05).

supplementary crystallographic information

Comment

Entanglement, one of the ubiquitous phenomena in nature, has received considerable attention due to their intrinsic aesthetic architectures (Bu et al., 2004; Carlucci et al., 2003a; Wu et al., 2011) and potential applications (Sun et al., 2006; Moulton & Zaworotko, 2001). Many structurally interesting entangled structures, such as polyrotaxane, polycatenation, polythreading, have been discussed in detail by (Batten et al., 1998; Carlucci et al., 2003b). Polycatenation as a type of interesting networks of entangled systems has attracted much attention for their potential application in energy of electron transfer and drug delivery (Harriman & Sauvage, 1996; Raymo & Sauvage, 1999). Herein, we report on the crystal structure of a Ni^II coordination polymer built from linear BIMB and fum^2- ligands, which features a two-dimensional → two-dimensional parallel/parallel polycatenation network.

The asymmetric unit of the title compound contains half a Ni^II ion located on a two-fold rotation axis, half a fum^2- dianion and half a BIMB ligand both located about inversion centers, and a coordinated water molecule. Each Ni^II ion is coordinated by two water molecules, two different carboxylate O atoms from two different fum^2- dianions and by two N atoms from two different BIMB ligands, and has a distorted octahedral geometry (Fig. 1).

It is interesting to note that the maleic acid (hydrolysis product of maleic anhydride) is converted into fumaric acid on the self-assembly of the title compound. This is probably because trans-fumaric has a higher thermal stability than cis-maleic acid.

In the crystal, each Ni^II ion is connected by two BIMB ligands and two fum^2- ligands to form an infinite two-dimensional puckered sheet with rhombic grids (Fig. 2). Within each layer, the rhombic grids have dimensions of ca. 13.5 Å × 9.0 Å with angles of of ca. 109.60 and 70.40° (defined by Ni···Ni distances and Ni···Ni···Ni angles). The large size of the grids in two adjacent layers allow a two-dimensional → two-dimensional parallel/parallel polycatenation to occur (Fig. 3). From a topological perspective, each Ni^II ion can be regarded as a four-connected node, thus this two-dimensional network can be assigned to the 4⁴-sql topology.

Moreover, the entangled two-dimensional layers are further connected by O–H···O hydrogen bonds to generate a three-dimensional structure (Fig. 4).

The structure of a similar Ni^II coordination polymer assembled by BIMB ligand and adipic acid has been described by (Chen et al., 2010). However, compared with the title compound, the adipic acid is a longer spacer length and more flexible, and crystallizes in the lower symmetry triclinic space group P1 rather than orthorhombic space group Pbcn for the title compound with the short fumarate spacer.

Another relevant example reported by (Bu et al., 2004) is a Zn^II coordination polymer (Li et al. 2012). Like the title complex, it is also built from BIMB and fum^2- ligands. However, the difference in the metal center results in an interesting 5-fold interpenetrated three-dimensional framework based on a diamondoid topology.

In summary, we have synthesized a Ni^II coordination polymer by the hydrothermal reaction of Ni(NO₃)₂ with H₂fum and BIMB ligands, which features a two-dimensional → two-dimensional parallel/parallel polycatenation network. On comparing with two relevant complexes based on the BIMB ligand, we found that the coordination geometry of the central metal ions and the flexibility of the auxiliary carboxylate ligands indeed have a significant effect on the architecture of the target complexes.

Experimental

A mixture of 1,4-Bis(1-imidazolyl)benzene (BIMB) (0.032 g, 0.15 mmol), maleic anydride (0.015 g, 0.15 mmol) and Ni(NO₃)₂ (0.045 g, 0.25 mmol) in N,N'-dimethylformamide (DMF) (4 ml) and H₂O (2 ml) was placed in a Teflon-lined stainless steel vessel and heated at 363 K for 3 days. On cooling to room temperature green block-like single crystals suitable for X-ray diffraction were obtained [70% yield (based on BIMB ligand)]. Anal. Calcd for C₁₆H₁₆N₄O₆Ni: C, 45.86; H, 3.85; N, 13.37%. Found: C, 45.93; H, 3.87; N, 13.41%. Spectroscopic data for the title compound are given in the archived CIF.