Tetra­imidazolium hexa-μ4-oxido-dodeca-μ2-oxido-dodeca­oxidohexa­arsenate(III)hexa­molybdenum(VI)cuprate(II)

Meiduo Liu; Zhanhua Su; Yongchen Shang

doi:10.1107/S1600536810037414

. 2010 Sep 30;66(Pt 10):m1308. doi: 10.1107/S1600536810037414

Tetraimidazolium hexa-μ₄-oxido-dodeca-μ₂-oxido-dodecaoxidohexaarsenate(III)hexamolybdenum(VI)cuprate(II)

Meiduo Liu ^a,^b, Zhanhua Su ^a,^*, Yongchen Shang ^a

PMCID: PMC2983113 PMID: 21587445

Abstract

The title compound, (C₃H₅N₂)₄[As₆CuMo₆O₃₀], is made up of a centrosymmetric anionic cluster and four imidazolium cations. In the cluster, the central Cu^II atom is six-coordinated and lies on an inversion center. Adjacent clusters are linked via N—H⋯O hydrogen bonds between the imidazole cations and polyoxidoanions into a three-dimensional supramolecular architecture.

Related literature

For general background to polyoxidometalates, see: Müller et al. (1998 ▶). For general background to molybdoarsenates, see: Fidalgo et al. (2002 ▶); Sun et al. (2007 ▶).

Experimental

Crystal data

(C₃H₅N₂)₄[As₆CuMo₆O₃₀]
M _r = 1845.07
Monoclinic,
a = 10.5696 (7) Å
b = 19.2842 (12) Å
c = 10.4678 (7) Å
β = 106.747 (1)°
V = 2043.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 7.22 mm⁻¹
T = 298 K
0.28 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.237, T _max = 0.326
12666 measured reflections
4906 independent reflections
4057 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.073
S = 1.03
4906 reflections
286 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −1.94 e Å⁻³

Data collection: APEX2 (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 datablocks I, global. DOI: 10.1107/S1600536810037414/hy2352sup1.cif

e-66-m1308-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037414/hy2352Isup2.hkl

e-66-m1308-Isup2.hkl^{(240.3KB, 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
N1—H1A⋯O4ⁱ	0.86	1.81	2.664 (5)	173
N2—H2A⋯O3	0.86	1.99	2.748 (5)	146
N2—H2A⋯O9ⁱⁱ	0.86	2.42	3.020 (5)	127
N3—H3A⋯O7ⁱⁱ	0.86	2.09	2.867 (6)	150
N4—H4A⋯O2ⁱⁱⁱ	0.86	2.00	2.834 (6)	165

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

Acknowledgments

This work was supported by the Science and Technology Project of the Education Office of Heilongjiang Province (11531249), the Scientific Research Foundation for Doctors of Harbin Normal University (09XBKQ11) and the Research Project of Harbin Normal University (KM2007–09).

supplementary crystallographic information

Comment

Polyoxometalates have unusual structural chemistry and properties that make them attractive for applications in materials science, electrochemical, catalysis and photochemical (Müller et al., 1998). Molybdenum arsenates are an important part in this field. So far the reports on molybdenum arsenates have been mainly concentrated on several discrete molybdenum arsenate clusters (Fidalgo et al., 2002; Sun et al., 2007). Therefore, further research is necessary to enrich and develop this branch. We try to obtain new materials based on inorganic molybdenum arsenate with novel structures. Here, the synthesis and crystal structure of the title compound is reported.

The structure of the title compound is shown in Fig. 1. The asymmetric unit consists of two protonated imidazole cations and a half cluster anion. The anion is centrosymmetric with the Cu^II atom lying on an inversion center. The cluster is derived from the A-type Anderson anion, in which a central CuO₆ octahedron is coordinated with six MoO₆ octahedra hexagonally arranged by sharing their edges in a plane. Two cyclic As₃O₃ trimers are capped on the opposite faces of the Anderson-type anion plane. The four free protonated imidazole molecules act as charge compensating cations. The adjacent clusters are linked via N—H···O hydrogen bonds between the imidazole cations and polyoxoanions into a three-dimensional supramolecular architecture (Table 1).

Experimental

A mixture of hexaammonium heptamolybdate tetrahydrate (1.11 g, 0.89 mmol), sodium arsenite (0.41 g, 3.03 mmol), cupric chloride (0.20 g, 1.17 mmol), imidazole (0.27 g, 4.01 mmol) and water (20 ml) was placed in a 30 ml Teflon-lined Parr bomb. The bomb was heated to 413 K for 5 d. Blue block shaped crystals were isolated from the cooled solution in a 72% yield based on Mo. Analysis, calculated for C₁₂H₂₀As₆CuMo₆N₈O₃₀: C 7.81, H 1.09, N 6.07%; found: C 7.83, H 1.13, N 6.04%.