Tetra­aqua­tetra­kis­(4,4′-bipyridine dioxide-κO)terbium(III) octa­cyanido­molybdate(V)

Su-Yan Qian; Ai-Hua Yuan

doi:10.1107/S1600536811020022

. 2011 Jun 4;67(Pt 7):m845. doi: 10.1107/S1600536811020022

Tetraaquatetrakis(4,4′-bipyridine dioxide-κO)terbium(III) octacyanidomolybdate(V)

Su-Yan Qian ^a, Ai-Hua Yuan ^a,^*

PMCID: PMC3152000 PMID: 21836848

Abstract

In the title compound, [Tb(C₁₀H₈N₂O₂)₄(H₂O)₄][Mo(CN)₈], both metal atoms are eight-coordinated. The Tb^III atom displays a dodecahedral geometry, while the Mo^V ion exhibits a distorted square-antiprismatic geometry. The Tb atoms are located on a special position of site symmetry Inline graphic , whereas the Mo atoms are located on a twofold rotation axis. The cations are linked by O—H⋯O hydrogen bonds.

Related literature

For general background to octacyanidometallate-based complexes involving lanthanide ions, see: Chelebaeva et al. (2009 ▶); Ma et al. (2009 ▶); Qian et al. (2010 ▶); Wang et al. (2006 ▶); Zhou et al. (2010 ▶). For the preparation of the title compound, see: Bok et al. (1975 ▶). For related structures, see: Kozieł et al. (2010 ▶); Przychodzeń et al. (2007 ▶).

Experimental

Crystal data

[Tb(C₁₀H₈N₂O₂)₄(H₂O)₄][Mo(CN)₈]
M _r = 1287.72
Tetragonal,
a = 17.9226 (7) Å
c = 7.8877 (6) Å
V = 2533.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 291 K
0.22 × 0.21 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.693, T _max = 0.843
21243 measured reflections
2921 independent reflections
2730 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.043
S = 1.08
2921 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020022/bt5505sup1.cif

e-67-0m845-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020022/bt5505Isup2.hkl

e-67-0m845-Isup2.hkl^{(143.5KB, 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—H3WA⋯O2ⁱ	0.83	1.85	2.6702 (15)	169
O3—H3WB⋯O2ⁱⁱ	0.84	1.92	2.7417 (16)	164

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

Acknowledgments

The work was supported by the Project of the Priority Academic Program Development of Jiangsu Higher Education Institutions.

supplementary crystallographic information

Comment

In the past few years, octacyanometallate-based complexes have attracted considerable attention in the field of cyanide-bridged hetero-metallic system. Many assemblies based on [M^V(CN)₈]^3- (M = Mo or W) and lanthanide ions can take a variety of structures (Chelebaeva et al., 2009; Kozieł et al., 2010; Ma et al., 2009; Przychodzeń et al., 2007; Qian et al., 2010; Wang et al., 2006; Zhou et al., 2010). Recently, we have used [Mo(CN)₈]^3- as a building block to react with Tb³⁺ and 4,4'-bipyridine dioxide (4,4'-dpdo) obtaining a new ionic complex, [Tb(4,4'-bpdo)₄(H₂O)₄][Mo(CN)₈.

In the structure, the eight-coordinated Tb^III center displays a decahedron geometry, while each [Mo^V(CN)₈] moiety exhibits a distorted square antiprismic geometry. The average values of Mo—C and C—N bond distances are 2.171 and 1.155 Å, respectively, while the Mo—C—N units are nearly linear. The anions are linked by O-H..O hydrogen bonds.

Experimental

Single crystals of the title compound were prepared at room temperature in the dark by slow diffusion of a H₂O solution (3 ml) containing Tb(NO₃)₃.6H₂O (0.05 mmol) and 4,4'-dpdo (0.05 mmol) into a CH₃CN solution (15 ml) of [HN(n-C₄H₉)₃]₃[Mo(CN)₈].4H₂O (0.05 mmol) (Bok et al., 1975). After two weeks, yellow block crystals were obtained.