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

Hongyang Wei; Jinfang Zhang; Chi Zhang

doi:10.1107/S1600536810029235

. 2010 Sep 4;66(Pt 10):m1193–m1194. doi: 10.1107/S1600536810029235

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

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

PMCID: PMC2983176 PMID: 21587356

Abstract

Hexamethylphosphoramide (hmp), tetrathiotungstate, silver sulfide and dysprosium nitrate were self-assembled, forming an anionic [AgWS₄]_nⁿ ⁻ chain in the title compound, {[Dy(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]}_n. The central Dy atom in the cation is coordinated by eight O atoms from two didentate nitrate and four hmp ligands, giving rise to a distorted square antiprismatic structure. Together with the two nitrate ligands, the cation is univalent, which leads to the anionic chain having a [WS₄Ag] repeat unit. The polymeric anionic chain, with W—Ag—W and Ag—W—Ag angles 161.16 (2) and 153.606 (11)°, respectively, presents a distorted linear configuration. The title compound is isotypic with other rare earth complexes.

Related literature

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004 ▶). For their unique properties, see: Zhang et al. (2007a ▶). For the structures of isotypic compounds, see: Cao et al. 2007 ▶) for Yb; Zhang et al. (2007b ▶,c ▶) for Y and Eu; Tang et al. (2008a ▶,b ▶) for Nd and La.

Experimental

Crystal data

[Dy(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]
M _r = 1423.33
Monoclinic,
a = 15.790 (3) Å
b = 29.659 (6) Å
c = 11.376 (2) Å
β = 90.94 (3)°
V = 5326.8 (18) Å³
Z = 4
Mo Kα radiation
μ = 4.24 mm⁻¹
T = 153 K
0.25 × 0.2 × 0.15 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.376, T _max = 0.529
24513 measured reflections
9675 independent reflections
8851 reflections with I > 2.0σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.081
S = 1.08
9675 reflections
532 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536810029235/pv2306sup1.cif

e-66-m1193-sup1.cif^{(34.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029235/pv2306Isup2.hkl

e-66-m1193-Isup2.hkl^{(473.2KB, 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) and unique properties as functional materials, such as third-order nonlinear optical (NLO) materials (Zhang et al., 2007a). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound, {n[Dy(hmp)₄(NO₃)₂][WS₄Ag]_n} (hmp = hexamethylphosphoramide) with a wave-like anionic chain was prepared by following such route using Dy(III)-hmp complex as counterion.

The title complex is isostructural with Yb (Cao et al. 2007), Y (Zhang et al. 2007b), Eu (Zhang et al. 2007c), Nd (Tang et al. 2008a), and La (Tang et al. 2008b) isomorphs. Dy^3- in the cation of the title complex is coordinated by eight O atoms from two nitrate and four hmp ligands. Parts of dimethylamine groups from hmp ligands have large librations reflecting a small degree of thermal disorder. 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. The anionic chain in the title compound (Fig. 2) has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.16 (2) and 153.606 (11) °, respectively, as reported in the other isostructural complexes quoted above.

Experimental

Ag₂S (1 mmol) was added to a solution of [NH₄]₂WS₄ (2 mmol in 30 mL hmp) with thorough stirring for 6 h. The solution underwent an additional stirring for two minute after Dy(NO₃)₃.6H₂O (1 mmol) was added. After filtration the orange-red filtrate was carefully laid on the surface with 30 ml i-PrOH. Orange-red block crystals were obtained after ten days.