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

Jinfang Zhang

doi:10.1107/S1600536811035574

. 2011 Sep 14;67(Pt 10):m1365. doi: 10.1107/S1600536811035574

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

Jinfang Zhang ^a,^*

PMCID: PMC3201561 PMID: 22064929

Abstract

The Sm atom in the cation of the title salt, {[Sm(NO₃)₂(C₆H₁₈N₃OP)₄][AgS₄W]}_n, is coordinated by eight O atoms derived from two chelating nitrate anions, and four hexamethylphosphoramide ligand, defining a distorted square-antiprismatic geometry. The anions self-assemble into polymeric chains via W—S—Ag bridges having a [AgS₄W] repeat unit; the W—Ag—W and Ag—W—Ag angles are 161.657 (17) and 153.978 (9)°, respectively. The title complex is isostructural with the Y, Yb, Eu, Nd, La and Dy isomorphs.

Related literature

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

Experimental

Crystal data

[Sm(NO₃)₂(C₆H₁₈N₃OP)₄][AgS₄W]
M _r = 1411.19
Monoclinic,
a = 15.817 (3) Å
b = 29.768 (6) Å
c = 11.372 (2) Å
β = 91.03 (3)°
V = 5353.5 (18) Å³
Z = 4
Mo Kα radiation
μ = 3.92 mm⁻¹
T = 293 K
0.2 × 0.16 × 0.1 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.476, T _max = 0.676
24655 measured reflections
9738 independent reflections
9057 reflections with I > 2σ(I)
R _int = 0.022
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.078
S = 1.03
9738 reflections
532 parameters
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); 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/S1600536811035574/rz2631sup1.cif

e-67-m1365-sup1.cif^{(34KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035574/rz2631Isup2.hkl

e-67-m1365-Isup2.hkl^{(476.3KB, hkl)}

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

Acknowledgments

This work was supported by the Natural Science Foundation of Jiangsu High School (grant No. 10KJB430005) and the Foundation of Jiangsu University (grant No. 08JDG036).

supplementary crystallographic information

Comment

One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their configurational isomerism (Niu et al., 2004) and unique properties as functional materials, such as third-order nonlinear optical (NLO) materials (Zhang, Song & Wang, 2007). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound {[Sm(hmp)₄(NO₃)₂][WS₄Ag]}_n (hmp = hexamethylphosphoramide) with a wave-like anionic chain was prepared by following such route using Sm(III)-hmp complex as counterion.

The title complex is isostructural with Y (Zhang, Cao et al., 2007; Zhang, 2011), Yb (Cao et al., 2007), Eu (Zhang, Qian et al., 2007), Nd (Tang, Zhang & Zhang, 2008), La (Tang, Zhang, Zhang & Lu, 2008) and Dy (Zhang, 2010) isomorphs. The Sm atom 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 161.657 (17) and 153.978 (9) °, 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 an additional stirring for two minute, then 0.5 mmol Sm(NO₃)₃.6H₂O was added. After filtration the orange filtrate was carefully laid on the surface with 12 ml i-PrOH. Orange block crystals were obtained after about one week.