catena-Poly[[tetra­kis­(hexa­methyl­phospho­ramide-κO)bis­(nitrato-κ2 O,O′)lutetium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)-di-μ-sulfido]]

Jinfang Zhang

doi:10.1107/S1600536812020983

. 2012 May 16;68(Pt 6):m770–m771. doi: 10.1107/S1600536812020983

catena-Poly[[tetrakis(hexamethylphosphoramide-κO)bis(nitrato-κ² O,O′)lutetium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)-di-μ-sulfido]]

Jinfang Zhang ^a,^*

PMCID: PMC3379104 PMID: 22719325

Abstract

In the title compound, {[Lu(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]}_n, hexamethylphosphoramide (hmp), tetrathiotungstate, silver iodide and lutetium nitrate were self-assembled, forming an anionic {[AgWS₄]⁻}_n chain extending parallel to [001]. The Lu^III atom in the cation is coordinated by eight O atoms from two nitrate groups and four hmp ligands in a distorted square-antiprismatic geometry. Together with the two nitrate groups, the cation is monovalent, which leads to the anionic chain having a [WS₄Ag] repeat unit. The polymeric anionic chain has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.66 (2) and 153.503 (12)°, respectively. The title complex is isotypic with the Y, Yb, Eu, Nd, La, Dy and Sm analogues.

Related literature

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004 ▶); Zhang, Meng et al. (2010 ▶). For the structures of isotypic Y, Yb, Eu, Nd, La, Dy and Sm complexes, see: Zhang, Cao et al. (2007 ▶); Zhang (2010 ▶, 2011a ▶,b ▶); Cao et al. (2007 ▶); Zhang, Qian et al. (2007 ▶); Tang, Zhang & Zhang (2008 ▶); Tang, Zhang, Zhang & Lu (2008 ▶).

Experimental

Crystal data

[Lu(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]
M _r = 1435.80
Monoclinic,
a = 15.714 (3) Å
b = 29.505 (6) Å
c = 11.378 (2) Å
β = 90.54 (3)°
V = 5275.1 (17) Å³
Z = 4
Mo Kα radiation
μ = 4.74 mm⁻¹
T = 293 K
0.21 × 0.15 × 0.12 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T _min = 0.758, T _max = 1.000
26979 measured reflections
9613 independent reflections
8961 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.089
S = 1.09
9613 reflections
532 parameters
H-atom parameters constrained
Δρ_max = 1.35 e Å⁻³
Δρ_min = −1.46 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020983/rz2754sup1.cif

e-68-0m770-sup1.cif^{(34.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020983/rz2754Isup2.hkl

e-68-0m770-Isup2.hkl^{(470.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Natural Science Foundation of Jiangsu High School (10KJB430005) and the Foundation of Jiangsu University (08JDG036).

supplementary crystallographic information

Comment

One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their intriguing structures (Niu et al., 2004 and Zhang, Meng et al. 2010). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound {[Lu(hmp)₄(NO₃)₂][WS₄Ag]}_n (hmp = hexamethylphosphoramide) with a wave-like anionic chain was prepared by following such route using Lu(III)-hmp complex as counterion.

The title complex is isostructural with Y (Zhang, Cao et al., 2007 and Zhang et al., 2011a), Yb (Cao et al., 2007), Eu (Zhang, Qian et al., 2007), Nd (Tang, Zhang & Zhang, 2008), La (Tang, Zhang, Zhang & Lu, 2008), Dy(Zhang et al., 2010) and Sm (Zhang et al., 2011b) isomorphs. Lu³⁺ in the cation is coordinated by eight O atoms from two nitrate and four hmp ligands. In possession of two nitrate ligands, the cation in the title compound is univalent (Fig. 1), which leads to an anionic chain with a univalent repeat unit. As illustrated in Fig. 2, the anionic chain in the title compound has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.66 (2) and 153.503 (12)° respectively.

Experimental

1 mmol AgI was added to a solution of [NH₄]₂WS₄ (1 mmol in 10 ml hmp) with thorough stirring for 30 minutes. The solution underwent additional stirring for two minute after 0.5 mmol Lu(NO₃)₃.6H₂O was added. After filtration the orange filtrate was carefully laid on the surface with 15 ml i-PrOH. Orange block crystals were obtained after about one week.