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

Hongyang Wei; Jinfang Zhang; Chi Zhang

doi:10.1107/S1600536812049987

. 2012 Dec 12;69(Pt 1):m43–m44. doi: 10.1107/S1600536812049987

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

Hongyang Wei ^a, Jinfang Zhang ^b, Chi Zhang ^a,^*

PMCID: PMC3588238 PMID: 23476340

Abstract

In the title compound, {[Er(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]}_n, the polymeric anionic chain {[AgWS₄]⁻}_n extends along [001]. The Er^III atom in the cation is coordinated by eight O atoms from two bidentate nitrate anions and four hexamethylphosphoramide ligands in a distorted square-antiprismatic geometry. Together with the two nitrate ligands, 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 161.37 (2) and 153.548 (12)°, respectively. The title complex is isotypic with the Y, Yb, Eu, Nd, La, Dy, Sm, Lu and Tb analogues.

Related literature

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004 ▶); Zhang et al. (2010 ▶). For their unique properties, see: Zhang, Song et al. (2007 ▶). For isotypic compounds, see: Zhang, Cao et al. (2007 ▶); Cao et al. (2007 ▶); Zhang, Qian et al. (2007 ▶); Tang, Zhang & Zhang (2008 ▶); Tang, Zhang, Zhang & Lu (2008 ▶); Zhang (2010 ▶); Zhang (2011a ▶,b ▶); Zhang (2012a ▶,b ▶).

Experimental

Crystal data

[Er(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]
M _r = 1428.09
Monoclinic,
a = 15.763 (3) Å
b = 29.579 (6) Å
c = 11.368 (2) Å
β = 90.83 (3)°
V = 5299.8 (17) Å³
Z = 4
Mo Kα radiation
μ = 4.43 mm⁻¹
T = 150 K
0.2 × 0.17 × 0.15 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T _min = 0.428, T _max = 0.514
26753 measured reflections
9597 independent reflections
8722 reflections with I > 2σ(I)
R _int = 0.044
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.092
S = 1.08
9597 reflections
532 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −1.04 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

Click here for additional data file.^{(34.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812049987/rz5031sup1.cif

e-69-00m43-sup1.cif^{(34.3KB, cif)}

Click here for additional data file.^{(469.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049987/rz5031Isup2.hkl

e-69-00m43-Isup2.hkl^{(469.4KB, hkl)}

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 50472048) and the Program for New Century Excellent Talents in Universities (NCET-05–0499).

supplementary crystallographic information

Comment

One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their configurational isomerism (Niu et al., 2004; Zhang, Meng et al., 2010) and unique properties as functional materials, such as third-order nonlinear optical (NLO) materials (Zhang, Song et al., 2007). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound, {[Er(hmp)₄(NO₃)₂][WS₄Ag]}_n (hmp = hexamethylphosphoramide) with a wave-like anionic chain, was prepared by following such route using Er(III)-hmp complex as counterion.

The title complex is isostructural with Y (Zhang, Cao et al., 2007; Zhang, 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, 2010), Sm (Zhang, 2011b), Lu (Zhang, 2012a) and Tb (Zhang, 2012b) isomorphs. Er^III 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 161.37 (2) and 153.548 (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 an additional stir for two minute after 0.5 mmol Er(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.