Tetra­aquabis(6-carboxy-1H-benzimid­azole-5-carboxyl­ato-κN 3)nickel(II) dimethyl­formamide disolvate dihydrate

Hao Wang; Wen-Dong Song; Shi-Jie Li; Pei-Wen Qin; Shi-Wei Hu

doi:10.1107/S1600536809038069

. 2009 Sep 30;65(Pt 10):m1258. doi: 10.1107/S1600536809038069

Tetraaquabis(6-carboxy-1H-benzimidazole-5-carboxylato-κN ³)nickel(II) dimethylformamide disolvate dihydrate

Hao Wang ^a, Wen-Dong Song ^b,^*, Shi-Jie Li ^a, Pei-Wen Qin ^c, Shi-Wei Hu ^a

PMCID: PMC2970488 PMID: 21577771

Abstract

The title compound, [Ni(C₉H₄₅N₂O₄)₂(H₂O)₄]·2C₃H₇NO·2H₂O, has the Ni^II center coordinated by four water molecules and two N atoms from two 1H-benzimidazole-5,6-dicarboxylate ligands in an octahedral geometry. The molecule interacts with the solvent water and dimethylformamide molecules through N—H⋯O and O—H⋯O hydrogen bonds to form a three-dimensional supramolecular network. The metal atom lies on a center of inversion.

Related literature

For the crystal structures of 1H-benzimidazole-5,6-dicarboxylate complexes, see: Gao et al. (2008 ▶); Lo et al. (2007 ▶); Song et al. (2009 ▶).

Experimental

Crystal data

[Ni(C₉H₅N₂O₄)₂(H₂O)₄]·2C₃H₇NO·2H₂O
M _r = 723.30
Triclinic,
a = 8.5327 (17) Å
b = 9.1387 (18) Å
c = 11.624 (2) Å
α = 100.80 (3)°
β = 103.03 (3)°
γ = 114.04 (3)°
V = 765.7 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.27 × 0.18 × 0.17 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T _min = 0.830, T _max = 0.888
6116 measured reflections
2737 independent reflections
2613 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.137
S = 1.20
2737 reflections
217 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL9.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038069/ng2646sup1.cif

e-65-m1258-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038069/ng2646Isup2.hkl

e-65-m1258-Isup2.hkl^{(134.4KB, 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—H2W⋯O1ⁱ	0.84	1.86	2.693 (3)	173
O1W—H1W⋯O3ⁱⁱ	0.84	2.00	2.801 (3)	160
O4—H4A⋯O5ⁱⁱⁱ	0.82	1.78	2.585 (3)	167
O2W—H4W⋯O2^iv	0.84	1.79	2.624 (3)	176
O2W—H3W⋯O1W^v	0.84	1.92	2.741 (2)	166
O3W—H5W⋯O1W^v	0.84	2.06	2.810 (3)	148
O3W—H6W⋯O1^vi	0.84	1.81	2.634 (3)	169
N2—H2⋯O5^vii	0.86	1.98	2.779 (3)	155

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

The authors acknowledge Guang Dong Ocean University for supporting this work.

supplementary crystallographic information

Comment

From the structuralpoint of view, 1H-benzimidazole-5,6-dicarboxylic acid possesses two nitrogen atoms of imidazole ring and four oxygen atoms of carboxylate groups, and might be used as versatile linker in constructing coordination polymers with abundant hydrogen bonds. And several coordination polymers fomed by this ligand have been reported recently:Pentaaqua(1H-benzimidazole-5,6-dicarboxylato-kN³)copper(II) pentahydrate(Gao et al.,2008), Bis(1H-benzimidazole-5,6-dicarboxylato)bis[tetraaquadicobalt(II)] pentahydrate(Lo et al.,2007), Pentaaqua(1H-benzimidazole-5,6-dicarboxylato-kN³) cobalt(II)pentahydrate(Song et al.,2009).In the present paper, we synthesized a novel coordination complex [Ni(C₉H₄N₂O₄)₂(H₂O)₄].2H₂O.2C₃H₇NO.

As shown in Figure 1, the Ni^II atom exhibits an octahedral coordination sphere, defined by two N atoms from two different 1H-benzimidazole-5,6-dicarboxylate ligands, and four water molecules. The equatorial plane is defined by O2w, O3w, O2wⁱ and O3wⁱ atoms, while N1 and N1ⁱ occupy the axial position (symmetry codes: i = 1 - x, 1 - y, 1 - z). Inter/intramolecular O—H···O and N—H···O hydrogen bonds between the carboxylate O atoms of 1H-benzimidazole-5,6-dicarboxylate and the coordinated water molecule lead to the structure more stable(Fig 2).The hydrogen bonds are in the normal range(Table 1).

Experimental

A C₃H₇NO solution (20 mL)containing Ni(NO₃)₂(0.1 mmol)and 1H-benzimidazole-5,6-dicarboxylic acid(0.2 mmol) was stirred for a few minutes in air,and left to stand at room temperature for about four weeks, then the green crystals were obtained.