Bis{4,4′-[oxalylbis(aza­nedi­yl)]dipyridinium} octa­molybdate

Jianbo Qin; Jingren Dong; Jinghua Li; Yun Gong

doi:10.1107/S1600536810020714

. 2010 Jun 5;66(Pt 7):m743. doi: 10.1107/S1600536810020714

Bis{4,4′-[oxalylbis(azanediyl)]dipyridinium} octamolybdate

Jianbo Qin ^a, Jingren Dong ^a, Jinghua Li ^b, Yun Gong ^a,^*

PMCID: PMC3006793 PMID: 21587682

Abstract

In the crystal structure of the title compound, (C₁₂H₁₂N₄O₂)₂[Mo₈O₂₆], the amino and pyridinium groups of the N ¹,N ²-di(pyridinium-4-yl)oxalamide cations are hydrogen bonded to the O atoms of the centrosymmetric isopolyoxometalate β-[Mo₈O₂₆]⁴⁻ anions, forming a three-dimensional supramolecular architecture.

Related literature

For polyoxometalates (POMs), see: Cronin et al. (2002 ▶); Fukaya & Yamase (2003 ▶); Katsoulis (1988 ▶); Pope & Müller (1991 ▶). For the applications of POMs in biology and materials sciences, see: Cui et al. (2003 ▶); Luan et al. (2002 ▶); Wang et al. (2003 ▶). For the structure of N ¹,N ²-di(pyridin-4-yl)oxalamide, see: Tzeng et al. (2007 ▶). For details of the geometrical parameters in the same isopolyoxometalate anion, see: Gong et al. (2007 ▶).

Experimental

Crystal data

(C₁₂H₁₂N₄O₂)₂[Mo₈O₂₆]
M _r = 1672.03
Monoclinic,
a = 10.633 (2) Å
b = 11.552 (2) Å
c = 17.240 (4) Å
β = 101.553 (3)°
V = 2074.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.45 mm⁻¹
T = 293 K
0.23 × 0.22 × 0.05 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.829, T _max = 1.000
14669 measured reflections
4534 independent reflections
4215 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.098
S = 1.40
4534 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 1.40 e Å⁻³
Δρ_min = −2.27 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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 global, I. DOI: 10.1107/S1600536810020714/su2182sup1.cif

e-66-0m743-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020714/su2182Isup2.hkl

e-66-0m743-Isup2.hkl^{(222.1KB, 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
N2—H2A⋯O7ⁱ	0.86	2.61	3.368 (4)	148
N1—H1⋯O8ⁱⁱ	0.86	1.89	2.699 (4)	158
N3—H3⋯O5ⁱⁱⁱ	0.86	1.94	2.779 (4)	165
N4—H4A⋯O1	0.86	2.25	2.669 (4)	110
N4—H4A⋯O4^iv	0.86	2.26	3.059 (4)	154

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

Acknowledgments

This work was supported by the Chongqing University Postgraduate Science Fund (No. 200911A1B0010317) and the Fundamental Research Funds for the Central Universities (No. CDJZR10 22 00 09)

supplementary crystallographic information

Comment

Polyoxometalates (POMs) are early transition metal oxygen anion clusters. They are an outstanding class of anionic compounds due to their wealthy topology, superior physical and chemical properties (Pope & Muller, 1991; Katsoulis, 1988). The nanoscopic sizes (Cronin, et al., 2002; Fukaya & Yamase, 2003,) and thier diversified shapes of discrete POMs have attracted great interest. The design, synthesis and structural characterization of inorganic-organic hybrid compounds base on POMs, for which many properties and applications can be predicted, have established a new field of research in the chemistry of biology and materials sciences (Luan, et al., 2002; Cui, et al., 2003; Wang, et al., 2003). Different N-heterocycle ligands can lead to different inorganic-organic hybrid compounds based on POMs. N¹,N²-di(pyridin-4-yl)oxalamide (L), is a bis-pyridine ligand, which has been reported only rarely in the construction of hybrid compounds based on POMs. In the present work, the title complex was synthesized hydrothermally by reacting L with the isopolyoxometalate, Mo₈O₂₆.

The molecular structure of the title complex is illustrated in Fig. 1. In the asymmetric unit there is a doublely protonated L molecule, and half an isopolyoxometalate unit. The bond distances and angles in the cation are similar to those observed previously for N¹,N²-di(pyridin-4-yl)oxalamide (Tzeng, et al., 2007). For the anion, [Mo₈O₂₆]^4-, the geometrical parameters are similar to those reported by (Gong, et al., 2007).

In the crystal the protonated pyrdidinium groups and the amino group form N-H···O hydrogen bonds with the oxygen atoms of the centrosymmetric [Mo₈O₂₆]^4- anions, leading to the formation of a three dimensional supramolecular network (Table 1 and Fig. 2).

Experimental

A mixture of L (0.05 mmol, 0.012 g), Na₂MoO₄(0.05 mmol, 0.012 g) and water(10 ml) was adjusted to pH = 3.0 by HCl. The synthesis was carried out hydrothermally using a Teflon-lined autoclave. The reaction mixture was heated at 393 K for 3 days, followed by slow cooling to rt. The resulting colorless prismatic crystals were filtered off and washed with water (yield: ca. 90% based on Mo). Elemental analyse - found: C, 17.45; H, 1.58; N, 6.56; Mo, 46.11; calcd: C, 17.22; H, 1.44; N, 6.70; Mo, 45.93.