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

Jinfang Zhang

doi:10.1107/S1600536811030996

. 2011 Aug 6;67(Pt 9):m1206–m1207. doi: 10.1107/S1600536811030996

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

Jinfang Zhang ^a,^*

PMCID: PMC3200717 PMID: 22065643

Abstract

In the cation of the title compound, {[Y(NO₃)₂(C₆H₁₈N₃OP)₄][AgMoS₄]}_n, the Y atom is coordinated by eight O atoms from two chelating nitrate groups and four hexamethylphosphoramide (hmp) ligands, which gives rise to a distorted square-antiprismatic environment. Together with the two nitrate ligands, the overall charge for the complex cation is +1, which leads to the anionic chain having a monovalent repeat unit. The polymeric anionic chain, with Mo—Ag—Mo and Ag—Mo—Ag angles of 161.916 (13) and 153.915 (13)°, respectively, presents a distorted linear configuration. The cations and the anions are linked via weak C—H⋯S hydrogen-bonding interactions while the cations exhibit intermolecular C—H⋯O interactions. The structure is isotypic with the corresponding W, Yb, Eu, Nd, La and Dy complexes.

Related literature

For one-dimensional Mo(W)/S/Ag anionic polymers, see: Niu et al. (2004 ▶) and for their properties, see: Zhang, Song et al. (2007 ▶). For isotypic W, Yb, Eu, Nd, La and Dy complexes, 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 ▶), respectively.

Experimental

Crystal data

[Y(NO₃)₂(C₆H₁₈N₃OP)₄][AgMoS₄]
M _r = 1261.84
Monoclinic,
a = 15.777 (3) Å
b = 29.650 (6) Å
c = 11.339 (2) Å
β = 90.90 (3)°
V = 5303.6 (17) Å³
Z = 4
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 153 K
0.35 × 0.20 × 0.15 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.622, T _max = 0.739
25568 measured reflections
10435 independent reflections
8978 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.091
S = 1.02
10435 reflections
556 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.79 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 datablock(s) I, global. DOI: 10.1107/S1600536811030996/pv2435sup1.cif

e-67-m1206-sup1.cif^{(34.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030996/pv2435Isup2.hkl

e-67-m1206-Isup2.hkl^{(501.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯S2ⁱ	0.96	2.79	3.710 (6)	160
C16—H16A⋯O10ⁱⁱ	0.96	2.49	3.292 (6)	141
C18—H18A⋯O10ⁱⁱⁱ	0.96	2.54	3.470 (9)	162

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

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 configurational isomerism (Niu et al., 2004) 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). In hexamethylphosphoramide (hmp), tetrathiomolybdate, silver iodide and dysprosium nitrate were self-assembled to form a one-dimensional anionic [AgMoS₄]^- chain in the compound, {[bi(nitrato-κ²O,O')tetrakis(hexamethylphosphoramide-κO) yttrium(III)]catena-[tetra-µ₂-sulfidosilver(I)molybdenum(VI)\ ]} with a formula of {[Y(hmp)₄(NO₃)₂][MoS₄Ag]}_n.

In the title complex, Y^3- in the cation is coordinated by eight O atoms from two nitrate and four hmp ligands. In the presence of two nitrate ligands, the cation in the title compound is univalent (Fig. 1). The anionic chain in the title compound (Fig. 2) has a distorted linear configuration with Mo—Ag—Mo and Ag—Mo—Ag angles 161.916 (13) and 153.915 (13) °, respectively. The cations and the anions are linked via weak hydrogen bondeing interactions of the type C—H···S while the cations exhibit C—H···O type intermolecular interactions (Table 1). The title complex is isostructural with W (Zhang, Cao et al., 2007), 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.

Experimental

AgI (2 mmol) was added to a solution of [NH₄]₂MoS₄ (2 mmol, in 28 mL hmp) with thorough stirring for 1.5 h. The solution was stirred for two minute after Y(NO₃)₃.6H₂O (1 mmol) was added. After filtration the black-red filtrate was carefully laid on the surface with 30 ml i-PrOH. Black-red block crystals were obtained after about two weeks.