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Acta Cryst. (2013). E69, m608    [ doi:10.1107/S1600536813028213 ]

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

L.-J. Zhou, H.-T. Shi, C. Xu, Q. Chen and Q.-F. Zhang

CCDC reference: 938862

Abstract top

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.

Comment top

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.

Related literature top

For applications of tetraselenometal compounds, 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).

Experimental top

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%.

Refinement top

H atoms were placed in geometrically idealized positions and refined in a riding model with N—H = 0.86, C—H = 0.93–0.97 Å, Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C,N) for the others. N-bound H atom has 0.5 site occupancy in the crystal.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A perspective view of molecular structure of heteroselenometallic polymeric complex {[(2-MepyH)(2-Mepy)][(µ-WSe4)Ag]}n. The ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown in the dash lines.
catena-Poly[2-methylpyridinium [tungstate-di-µ-selenido-silver-di-µ-selenido] 2-methylpyridine monosolvate] top
Crystal data top
(C6H8N)[AgWSe4]·C6H7NF(000) = 716
Mr = 794.82Dx = 2.902 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 1243 reflections
a = 7.859 (2) Åθ = 2.6–24.5°
b = 5.9448 (15) ŵ = 15.39 mm1
c = 19.830 (5) ÅT = 296 K
β = 100.962 (3)°Prism, dark red
V = 909.5 (4) Å30.15 × 0.12 × 0.03 mm
Z = 2
Data collection top
Bruker APEXII CCD area-detector
2051 independent reflections
Radiation source: fine-focus sealed tube1565 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
phi and ω scansθmax = 27.4°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 106
Tmin = 0.206, Tmax = 0.655k = 77
5398 measured reflectionsl = 2425
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0357P)2]
where P = (Fo2 + 2Fc2)/3
2051 reflections(Δ/σ)max = 0.001
93 parametersΔρmax = 0.86 e Å3
0 restraintsΔρmin = 1.06 e Å3
Crystal data top
(C6H8N)[AgWSe4]·C6H7NV = 909.5 (4) Å3
Mr = 794.82Z = 2
Monoclinic, P2/cMo Kα radiation
a = 7.859 (2) ŵ = 15.39 mm1
b = 5.9448 (15) ÅT = 296 K
c = 19.830 (5) Å0.15 × 0.12 × 0.03 mm
β = 100.962 (3)°
Data collection top
Bruker APEXII CCD area-detector
2051 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1565 reflections with I > 2σ(I)
Tmin = 0.206, Tmax = 0.655Rint = 0.041
5398 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.078H-atom parameters constrained
S = 0.97Δρmax = 0.86 e Å3
2051 reflectionsΔρmin = 1.06 e Å3
93 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
W10.50000.30930 (6)0.75000.03027 (13)
Ag10.50000.80929 (13)0.75000.0524 (2)
Se10.24423 (10)0.09964 (13)0.72794 (4)0.0417 (2)
Se20.50518 (11)0.51956 (12)0.65078 (4)0.0434 (2)
N10.0998 (7)0.3192 (10)0.4854 (3)0.0389 (14)
C10.1778 (10)0.1984 (14)0.5389 (4)0.0478 (19)
C20.2676 (11)0.0041 (13)0.5329 (5)0.053 (2)
C30.2838 (12)0.0653 (16)0.4690 (5)0.062 (2)
C40.2043 (11)0.0586 (15)0.4116 (4)0.053 (2)
C50.1125 (10)0.2507 (14)0.4203 (4)0.0447 (19)
C60.0282 (12)0.3915 (15)0.3622 (4)0.059 (2)
Atomic displacement parameters (Å2) top
W10.0371 (2)0.0225 (2)0.0303 (2)0.0000.00409 (16)0.000
Ag10.0704 (6)0.0280 (4)0.0565 (5)0.0000.0061 (5)0.000
Se10.0412 (4)0.0389 (4)0.0425 (4)0.0057 (3)0.0020 (3)0.0049 (3)
Se20.0587 (5)0.0342 (4)0.0377 (4)0.0027 (4)0.0101 (4)0.0051 (3)
N10.035 (3)0.046 (4)0.035 (3)0.005 (3)0.004 (3)0.005 (3)
C10.049 (5)0.060 (5)0.034 (4)0.001 (4)0.005 (4)0.005 (4)
C20.056 (5)0.039 (5)0.064 (5)0.005 (4)0.010 (5)0.010 (4)
C30.053 (5)0.053 (6)0.089 (7)0.004 (5)0.032 (5)0.007 (5)
C40.052 (5)0.059 (6)0.051 (5)0.009 (5)0.016 (4)0.015 (4)
C50.040 (4)0.054 (5)0.040 (4)0.008 (4)0.007 (3)0.004 (4)
C60.062 (6)0.078 (6)0.033 (4)0.006 (5)0.001 (4)0.008 (4)
Geometric parameters (Å, º) top
W1—Se12.3347 (9)N1—H1N0.8600
W1—Se1i2.3347 (9)C1—C21.371 (10)
W1—Se2i2.3379 (9)C1—H10.9300
W1—Se22.3379 (9)C2—C31.361 (12)
W1—Ag12.9723 (11)C2—H20.9300
W1—Ag1ii2.9725 (11)C3—C41.400 (12)
Ag1—Se1iii2.6224 (11)C3—H30.9300
Ag1—Se1iv2.6224 (11)C4—C51.380 (11)
Ag1—Se22.6210 (10)C4—H40.9300
Ag1—Se2i2.6210 (10)C5—C61.475 (11)
Ag1—W1iv2.9725 (11)C6—H6A0.9600
N1—C11.330 (9)C6—H6B0.9600
N1—C51.376 (9)C6—H6C0.9600
Se1—W1—Se1i115.47 (5)Se1iv—Ag1—W1iv48.84 (2)
Se1—W1—Se2i106.92 (3)W1—Ag1—W1iv180.0
Se1i—W1—Se2i106.25 (3)W1—Se1—Ag1ii73.43 (3)
Se1—W1—Se2106.25 (3)W1—Se2—Ag173.40 (3)
Se1i—W1—Se2106.92 (3)C1—N1—C5119.0 (6)
Se2i—W1—Se2115.36 (4)C1—N1—H1N120.5
Se1—W1—Ag1122.27 (2)C5—N1—H1N120.5
Se1i—W1—Ag1122.27 (2)N1—C1—C2123.5 (7)
Se2i—W1—Ag157.68 (2)N1—C1—H1118.2
Se2—W1—Ag157.68 (2)C2—C1—H1118.2
Se1—W1—Ag1ii57.73 (2)C3—C2—C1118.5 (8)
Se1i—W1—Ag1ii57.73 (2)C3—C2—H2120.7
Se2i—W1—Ag1ii122.32 (2)C1—C2—H2120.7
Se2—W1—Ag1ii122.32 (2)C2—C3—C4119.4 (8)
Ag1—W1—Ag1ii180.000 (1)C2—C3—H3120.3
Se2—Ag1—Se2i97.84 (4)C4—C3—H3120.3
Se2—Ag1—Se1iii115.91 (3)C5—C4—C3119.8 (7)
Se2i—Ag1—Se1iii115.35 (3)C5—C4—H4120.1
Se2—Ag1—Se1iv115.35 (3)C3—C4—H4120.1
Se2i—Ag1—Se1iv115.91 (3)N1—C5—C4119.7 (7)
Se1iii—Ag1—Se1iv97.67 (5)N1—C5—C6117.6 (7)
Se2—Ag1—W148.92 (2)C4—C5—C6122.7 (7)
Se2i—Ag1—W148.92 (2)C5—C6—H6A109.5
Se1iii—Ag1—W1131.16 (2)C5—C6—H6B109.5
Se1iv—Ag1—W1131.16 (2)H6A—C6—H6B109.5
Se2—Ag1—W1iv131.08 (2)C5—C6—H6C109.5
Se2i—Ag1—W1iv131.08 (2)H6A—C6—H6C109.5
Se1iii—Ag1—W1iv48.84 (2)H6B—C6—H6C109.5
Symmetry codes: (i) x+1, y, z+3/2; (ii) x, y1, z; (iii) x+1, y+1, z+3/2; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
N1—H1N···N1v0.861.932.786 (12)172
C1—H1···Se10.932.963.732 (8)141
C4—H4···Se1vi0.932.903.832 (8)176
Symmetry codes: (v) x, y+1, z+1; (vi) x, y, z1/2.
Selected bond lengths (Å) top
W1—Se12.3347 (9)Ag1—Se1i2.6224 (11)
W1—Se22.3379 (9)Ag1—Se22.6210 (10)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
N1—H1N···N1ii0.861.932.786 (12)172
C1—H1···Se10.932.963.732 (8)141
C4—H4···Se1iii0.932.903.832 (8)176
Symmetry codes: (ii) x, y+1, z+1; (iii) x, y, z1/2.
Acknowledgements top

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.