catena-Poly[2-methyl­pyridinium [tungstate-di-μ-selenido-silver-di-μ-selenido] 2-methyl­pyridine monosolvate]

Lu-Jun Zhou; Hua-Tian Shi; Chao Xu; Qun Chen; Qian-Feng Zhang

doi:10.1107/S1600536813028213

. 2013 Oct 19;69(Pt 11):m608. doi: 10.1107/S1600536813028213

catena-Poly[2-methylpyridinium [tungstate-di-μ-selenido-silver-di-μ-selenido] 2-methylpyridine monosolvate]

Lu-Jun Zhou ^a, Hua-Tian Shi ^b, Chao Xu ^b, Qun Chen ^a, Qian-Feng Zhang ^b,^a,^*

PMCID: PMC3884262 PMID: 24454038

Abstract

The title compound, {(C₆H₈N)[AgWSe₄]·C₆H₇N}_n, consists of anionic [WAgSe₄]_n chains, 2-methylpyridinium cations and neutral 2-methylpyridine molecules. The Se atoms bridge the Ag and W atoms, forming a polymeric chain extending along the b-axis direction. Both the Ag and W atoms are located on a twofold rotation axis and each metal atom is coordinated by four Se atoms in distorted tetrahedral geometry. In the crystal, the 2-methylpyridinium cation and 2-methylpyridine molecule are linked via N—H⋯N hydrogen bonding. Weak C—H⋯Se interactions link the organic components and polymeric anions into a three-dimensional architecture.

Related literature

For applications of compounds with [M,M′Se₄] anions (M,M′ = transition metals), see: Zhang et al. (2002 ▶, 2006 ▶). For related structures, see: Huang et al. (1997 ▶); Lang et al. (1993 ▶); Müller et al. (1983 ▶); Yu et al. (1998 ▶); Dai et al. (2007 ▶); Zhang et al. (2000 ▶). graphic file with name e-69-0m608-scheme1.jpg

Experimental

Crystal data

(C₆H₈N)[AgWSe₄]·C₆H₇N
M _r = 794.82
Monoclinic,
a = 7.859 (2) Å
b = 5.9448 (15) Å
c = 19.830 (5) Å
β = 100.962 (3)°
V = 909.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 15.39 mm⁻¹
T = 296 K
0.15 × 0.12 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.206, T _max = 0.655
5398 measured reflections
2051 independent reflections
1565 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.078
S = 0.97
2051 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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/S1600536813028213/xu5746sup1.cif

e-69-0m608-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028213/xu5746Isup2.hkl

e-69-0m608-Isup2.hkl^{(100.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

W1—Se1	2.3347 (9)
W1—Se2	2.3379 (9)
Ag1—Se1ⁱ	2.6224 (11)
Ag1—Se2	2.6210 (10)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N1ⁱⁱ	0.86	1.93	2.786 (12)	172
C1—H1⋯Se1	0.93	2.96	3.732 (8)	141
C4—H4⋯Se1ⁱⁱⁱ	0.93	2.90	3.832 (8)	176

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

Acknowledgments

This work was supported by the Natural Science Foundation of China (20871002) and the Program for New Century Excellent Talents in Universities of China (NCET-08–0618). QFZ is grateful to the State Key Laboratory of Coordination Chemistry at Nanjing University for assistance with the data collection.

supplementary crystallographic information

1. Comment

Tetraselenometalates [MSe₄]^2- (M =Mo, W) have been extensively used in the synthesis of heterselenometallic clusters with third-order nonlinear properties (Zhang et al., 2002). Of special which argentoselenometallic clusters are of good photostability and relatively stable optical limiting effects (Zhang et al., 2006). It has been found that the assembling of [MS₄]^2- (M =Mo, W) and Ag⁺ is flexible through non-bonding interactions with complementary small molecules (or cations) and the solvent, which can assemble into polymeric heterothiometallic clusters with different configurations, such as single linear, zigzag and helical and double chains (Huang et al., 1997; Lang et al., 1993; Müller et al., 1983; Yu et al., 1998). However, it has been noted that the difficulty in the synthesis of argentoselenometallic clusters is probably due to the low solubility of Ag⁺ species that are involved in the self-assembly with the [MSe₄]^2- (M =Mo, W) anion. It is thus understood that only two examples of structurally characterized argentoselenometallic clusters including one-dimensional linear {[Et₄N][(µ-WSe₄)Ag]}_n (Dai et al., 2007) and helical {[La(Me₂SO)₈][(µ₃-WSe₄)₃Ag₃]}_n (Zhang et al., 2000) have been appeared up to date. The one-dimensional chain structure of the title heteroselenometallic polymer {[(2-MepyH)(2-Mepy)][(µ-WSe₄)Ag]}_n is herein described as an addition of this family.

The title heteroselenometallic complex crystallizes in the monoclinic with P2/c space group. An analogous heterothiometallic complex, {[\>a-MepyH][MoS₄Ag]}_n, has been reported, which crystallizes in a monoclinic Pc space group (Lang et al., 1993). The structure determination shows that the title heteroselenometallic complex consists of [(2-MepyH)(2-Mepy)]₊ (py = pyridine) cations with the N—H···N hydrogen bonds and polymeric linear chain of [(µ-WSe₄)Ag]^- anions, as shown in Fig. 1. The anion chain is composed of extended rhombic networks of co-planar [Ag(µ-Se₂)W] units and the neighbouring rhombi in the chain are alternately almost perpendicular to each other. Both metal atoms display tetrahedron coordination in a selenium-rich environment, comparatively, the coordination geometry of the silver atoms (Se—Ag—Se: 97.67 (5)—115.91 (3)°) is more distorted than the tungsten atoms (Se—W—Se: 106.25 (3)—115.47 (5)°). The chain has a straight linear configuration with an Ag—W—Ag angle of 180°. The average W—µ-Se and Ag—µ-Se bond lengths are 2.3363 (9) and 2.6217 (10) Å, respectively. The average W···Ag distance of 2.9725 (11) Å in the title heteroselenometallic complex is comparable to those in {[Et₄N][(µ-WSe₄)Ag]}_n (av. 3.0169 (2) Å) (Dai et al., 2007), {[La(Me₂SO)₈][(µ₃-WSe₄)₃Ag₃]}_n (av. 3.0038 (12) Å) (Zhang, et al., 2000), and [(µ-WSe₄)(AgPPh₃){Ag(PPh₃)₂}] (av. 2.996 (1) Å) (Zhang et al., 2002). The hydrogen-bonding interactions exist between the nitrogen atom of pyridinium caion and the nitrogen atom of the pyridine molecule, forming a molecular [(2-MepyH)(2-Mepy)]⁺ cation with the N—H···N distance and angle of 2.786 (12) Å and 171.9 (3)°, respectively. Relatively weak interactions exist between organic cations and polymeric anions via the C—H···Se hydrogen-bonds with the C—H···Se distance and angle of 3.731 (2) Å and 141.9 (3)°, respectively, as shown in Fig. 1.

2. Experimental

A solution of AgNO₃ (42.5 mg, 0.25 mmol) in MeCN (5 ml) was added dropwise to a solution of [Et₄N]₂[WSe₄] (190 mg, 0.25 mmol) in DMF (5 ml). The mixture was stirred for 30 min at room temperature, resulting in a large amount of black precipitate. Upon addition of 2 ml 2-picoline solution, the black precipitate was re-dissolved. The resultant solution was stirred for additional 30 min at room temperature and filtered to afford a dark red filtrate. Dark-red prism crystals of the title complex were obtained after allowing the filtrate to stand at room temperature for three days. Anal. Calc. for C₁₂H₁₅N₂Se₄WAg: C, 18.13; H, 1.90; N, 3.53%. Found: C, 18.05; H, 1.87; N, 3.49%.