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

Hongyang Wei; Jinfang Zhang; Chi Zhang

doi:10.1107/S1600536810044260

. 2010 Nov 27;66(Pt 12):m1657–m1658. doi: 10.1107/S1600536810044260

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

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

PMCID: PMC3011570 PMID: 21589322

Abstract

Hexamethylphosphoramide (hmp), tetrathiotungstate, silver sulfide and cerium nitrate were self-assembled to form a one-dimensional anionic [Ag₄W₄S₁₆]_n ⁴ⁿ⁻ chain in the title compound, {[Ce(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]}_n. The asymmetric unit contains four crystallographically independent [Ce(hmp)₄(NO₃)₂]⁺ cations, which leads to a one-dimensional polymeric anionic chain having a tetravalent [W₄S₁₆Ag₄] repeat unit. Each central Ce atom is coordinated by eight O atoms from two chelating nitrate and four hmp ligands, which gives rise to a distorted square-antiprismatic structure. The polymeric chain with average W—Ag—W and Ag—W—Ag bond angles of 163.75 and 151.84°, respectively, presents a distorted linear configuration. The title complex with a non-centrosymmetric structure, is analogous to the Yb, Y, Eu, Nd, La and Dy isomorphs, which exhibit centrosymmetric structures.

Related literature

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004 ▶). For their unique properties, see: Zhang, Song et al. (2007 ▶). For analogous centrosymmetric complexes, see: Cao et al. (2007 ▶); Zhang, Cao et al. (2007 ▶); Zhang, Qian et al. (2007 ▶); Tang, Zhang & Zhang (2008 ▶); Tang, Zhang, Zhang & Lu (2008 ▶); Wei et al. (2010 ▶).

Experimental

Crystal data

[Ce(NO₃)₂(C₆H₁₈N₃OP)₄][AgWS₄]
M _r = 1400.92
Monoclinic,
a = 15.639 (3) Å
b = 30.002 (6) Å
c = 22.532 (4) Å
β = 90.53 (3)°
V = 10572 (3) Å³
Z = 8
Mo Kα radiation
μ = 3.72 mm⁻¹
T = 153 K
0.30 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.390, T _max = 0.475
49779 measured reflections
34142 independent reflections
32497 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.068
S = 1.06
34142 reflections
2221 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.96 e Å⁻³
Absolute structure: Flack (1983 ▶), 14534 Friedel pairs
Flack parameter: 0.286 (4)

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 datablocks I, global. DOI: 10.1107/S1600536810044260/zq2066sup1.cif

e-66-m1657-sup1.cif^{(105.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044260/zq2066Isup2.hkl

e-66-m1657-Isup2.hkl^{(1.6MB, hkl)}

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 50472048) and the Program for New Century Excellent Talents in University (grant No. 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, 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 {4n[Ce(hmp)₄(NO₃)₂][Ag₄W₄S₁₆]_n} (hmp = hexamethylphosphoramide) with a wave-like anionic chain was prepared by following such route using Ce(III)-hmp complex as counterion.

Each Ce^3- in the cation is coordinated by eight O atoms from two nitrate and four hmp ligands (Fig. 1). Parts of dimethylamine groups from hmp ligands have large librations reflecting a small degree of thermal disorder. The cation in the title compound contains four univalent [Ce(hmp)₄(NO₃)₂]⁺, which leads to a 1-D anionic chain having a tetravalent repeat unit. As illustrated in Fig. 2, the anionic chain in the title compound has a distorted linear configuration with average W—Ag—W and Ag—W—Ag angles of 163.75 and 151.84 °, respectively. The title complex is analogous to Yb (Cao et al. 2007), Y (Zhang, Cao et al. 2007), Eu (Zhang, Qian et al. 2007), Nd (Tang, Zhang & Zhang, 2008), La (Tang, Zhang, Zhang & Lu, 2008) and Dy (Wei et al. 2010) isomorphs.

Experimental

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