Tetra­kis[tris­(2,2′-bi-1H-benzimidazole)nickel(II)] bis­(phosphate) sulfate

Chun-Sheng Ling; Lin Yan

doi:10.1107/S1600536808032571

. 2008 Oct 15;64(Pt 11):m1399. doi: 10.1107/S1600536808032571

Tetrakis[tris(2,2′-bi-1H-benzimidazole)nickel(II)] bis(phosphate) sulfate

Chun-Sheng Ling ^a, Lin Yan ^a,^*

PMCID: PMC2959627 PMID: 21580849

Abstract

The title compound, [Ni(C₁₄H₁₀N₄)₃]₄(PO₄)₂(SO₄), consists of [Ni(C₁₄H₁₀N₄)₃]²⁺ complex cations (.3. symmetry) and disordered anions ( Inline graphic symmetry) with occupancy factors of two-thirds for PO₄ ³⁻ and one-third for SO₄ ²⁻. The Ni²⁺ centre is chelated by three bidentate 2,2′-bi-1H-benzimidazole molecules in a distorted octahedral coordination. N—H⋯O hydrogen bonds consolidate the building units into a framework structure.

Related literature

For the potential applications of metal–organic coordination compounds in gas absorption and separation, catalysis, non-linear optics, luminescence and magnetism, see: Kitagawa & Matsuda (2007 ▶); Maspoch et al. (2007 ▶).

Experimental

Crystal data

[Ni(C₁₄H₁₀N₄)₃]₄(PO₄)₂(SO₄)
M _r = 3331.96
Cubic,
a = 24.964 (7) Å
V = 15558 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 296 (2) K
0.32 × 0.27 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.834, T _max = 0.876
20222 measured reflections
2551 independent reflections
1782 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.098
S = 1.01
2551 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ▶), 1182 Friedel pairs
Flack parameter: −0.02 (2)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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 datablocks global, I. DOI: 10.1107/S1600536808032571/at2642sup1.cif

e-64-m1399-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808032571/at2642Isup2.hkl

e-64-m1399-Isup2.hkl^{(126.3KB, 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
N4—H4B⋯O1ⁱ	0.86	1.96	2.766 (4)	156
N2—H2B⋯O1ⁱⁱ	0.86	1.82	2.675 (4)	170

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

Acknowledgments

This work was supported by the Basic Research Foundation for Natural Science of Henan University.

supplementary crystallographic information

Comment

More attentions have been paid to metal-organic coordination compounds (MOCCs) because of their potential applications in gas absorption and separation, catalysis, nonlinear optics, luminescence and magnetism (Kitagawa & Matsuda 2007, Maspoch et al. 2007). In the field of coordination chemistry, the N,N-bidentate ligands, such as 2,2'-bipyridine, 1,10-phenanthroline and their derivatives act as versatile ligands owing to the stable coordination configuration in the bidentate N-donors chelating manner. Herein, we report the title compound (I).

The title compound (I) consists of four [Ni(C₁₄H₁₀N₄)₃]²⁺ complex cations, one [SO₄]^2- and two [PO₄]^3- anions. In the mlecular structure, the Ni²⁺ centre is coordinated by six N atoms from three bidentate 1H,1'H-2,2'-bi-1H-benzimidazole molecules (Fig.1). The 1H,1'H-2,2'-bi-1H-benzimidazole ligand was prepared in situ and coordinated to the Ni²⁺ cations in hydrothermal reaction. Additionally, the [SO₄]^2- and [PO₄]^3- anions statistically distribute in one position with 1/3 probability for S and 2/3 probability for P atoms. The environment of the Ni²⁺ caion is in a distorted octahedral geometry with the Ni—N distances ranging from 2.088 (3) to 2.122 (3) Å (Table 1).

In addition, the [Ni(C₁₄H₁₀N₄)₃]²⁺ complex cations, [SO₄]^2- and [PO₄]^3- anions in the complexes are linked together via many N—H···O hydrogen bonds resulting in a three-dimensional structural frameworks (Fig.2 and Table 2).

Experimental

All reagents were commercially available and of analytical grade. The mixture of NiSO₄.6H₂O, H₃PO₄, oxalic acid, and 1,2-diaminobenzene in the mole ratio of 1: 1.5: 6: 6 was dissolved in 25 ml H₂O, which was heated in a Teflon-lined steel autoclave inside a programmable electric furnace at 393 K for five days. After cooling the autoclave to room temperature, green block crystals of (I) were obtained.