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Acta Cryst. (2007). E63, m2273    [ doi:10.1107/S1600536807035180 ]

Poly[([mu]3-N,N-dibenzyldithiocarbamato-[kappa]4S,S':S:S')silver(I)]

X. Yin, M.-B. Xie, W.-G. Zhang and J. Fan

Abstract top

The title AgI coordination polymer, [Ag(C15H14NS2)]n, was synthesized by a solvothermal reaction of AgNO3 with sodium N,N-dibenzyldithiocarbamate in a methanol solution. The compound displays a helical structure and each AgI ion is four-coordinated by four S atoms from two dithiocarbamate ligands and can be described as a distorted tetrahedral configuration. While the AgI ions are bridged by both S atoms of the dithocarbamate group to form the polymeric structure, the Ag...Ag distance of 3.0633 (11) Å suggests weaker metal bonding between AgI ions.

Comment top

Synthesis and crystal structure of the Ag(I) complexes with dialkyldithiocarbamates have been widely studied owing to variable coordination configurations since the first description by Akerström (1959). Monomeric, dimeric, hexameric and polymeric structure etc in the Ag(I) complexes have been reported in the past decade years, which was indicated that differently substituted alkyl groups and reaction conditions may play crucial roles in the formation of a variety of complexes with unprecedented structures (Zhang et al., 2002; Liu et al., 2006; Song et al., 2006). We have maintained an interest in silver(I)-dithiocarbamate complexes and report herein the structure of the title compound, [(AgC15H14NS2)3]n.

In the solid state, the title complex has a one-dimensional chain-like polymeric structure and the each repeated Ag(I) units consists of three silver(I) cations and three ligand anions (Fig. 1). Each Ag(I) cation is coordinated with four sulfur atoms from three N,N-dibenzyldithiocarbamate (DBTC) ligands and shown as an distorted tetrahedral coordination environment. There are two types of sulfur atoms: S1 and the symmetry equivalents are acting as bridges between each two silver atoms with Ag—S distances of 2.446 (1) and 2.478 (2) Å (Table 1). On the other hand, the distances between the Ag(I) atoms and the S2 atoms (2.860 and 3.010 Å) are appreciably different, and both are much longer than the Ag—S(dithiocarbamate) distances [2.5–2.6 Å] (Song et al., 2006; Yin et al., 2007), but smaller Ag1—C1—S1 angles of 94.92° suggests the weaker Ag1—S2 bonding in the compound, as pointed out by Li et al. (2005). This grees with the related compounds reported previously [Anacker-Eickhoff et al., 1982; Song et al., 2006]. Thus the DBTC displays both roles of chelating ligand and asym-bridging ligand.

The Ag—Ag distances between adjacent AgI ions are 3.0633 (11) Å, which are longer than 2.886 Å found in metallic Ag (Greenwood et al., 1989) but shorter than the sum of the van der Waals radii of Ag atoms. This may suggest the existence of the weaker metal bonding between AgI ions (Tang et al., 2004). So multi-dentate bridging coordination modes of the chelating ligands and the agentophilic Ag—Ag interactions linked in the [(AgC15H14NS2)3] units leads to formation of the one-dimensional chain-like coordination polymer (Fig. 2).

Related literature top

For general background, see Akerström (1959); Zhang et al. (2002); Liu et al. (2006); Song et al. (2006). For related structures, see: Yin et al. (2007); Anacker-Eickhoff et al. (1982); Li et al. (2005); Greenwood & Earnshaw (1989). For synthesis, see: Fan et al. (2004).

For related literature, see: Tang et al. (2004).

Experimental top

The title compound was prepared by the reaction of AgNO3 (0.170 g, 1.0 mmol), sodium N, N-dibenzyldithiocardbanmate (NaDBTC) (0.296 g, 2.0 mmol) (Fan et al., 2004) and anhydrous methanol (7 ml) in an 15 ml Teflon liner sealed in a Parr autoclave. The autoclave was placed in a programmable furnace and heated to 353 K for 2 days. Yellow crystals were obtained after cooling to room temperature at 5 K.h−1 (yield 50%). The compound is hardly soluble in general organic solvent.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene) and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, YEAR?); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing diagram of the title compound viewed down the b axis (H atoms have been omitted for clarity).
Poly[(µ3-N,N-dibenzyldithiocarbamato-κ4S,S':S:S')silver(I)] top
Crystal data top
[Ag(C15H14NS2)]Z = 3
Mr = 380.26F000 = 570
Trigonal, P31Dx = 1.782 Mg m−3
Hall symbol: P 31Melting point = 491–492 K
a = 15.6505 (19) ÅMo Kα radiation
λ = 0.71073 Å
b = 15.6505 (19) ÅCell parameters from 2450 reflections
c = 5.0120 (14) Åθ = 2.4–25.0º
α = 90ºµ = 1.70 mm−1
β = 90ºT = 293 (2) K
γ = 120ºBlock, yellow
V = 1063.2 (3) Å30.15 × 0.10 × 0.10 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2500 independent reflections
Radiation source: fine-focus sealed tube1519 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.094
T = 293(2) Kθmax = 25.2º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		h = −18→18
Tmin = 0.785, Tmax = 0.848k = −18→18
7409 measured reflectionsl = −6→6
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045  w = 1/[σ2(Fo2)]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080(Δ/σ)max < 0.001
S = 1.00Δρmax = 0.46 e Å−3
2500 reflectionsΔρmin = −0.41 e Å−3
172 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), with 1227 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.07 (5)
Secondary atom site location: difference Fourier map
Crystal data top
[Ag(C15H14NS2)]γ = 120º
Mr = 380.26V = 1063.2 (3) Å3
Trigonal, P31Z = 3
a = 15.6505 (19) ÅMo Kα
b = 15.6505 (19) ŵ = 1.70 mm−1
c = 5.0120 (14) ÅT = 293 (2) K
α = 90º0.15 × 0.10 × 0.10 mm
β = 90º
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2500 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		1519 reflections with I > 2σ(I)
Tmin = 0.785, Tmax = 0.848Rint = 0.094
7409 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.080Δρmax = 0.46 e Å−3
S = 1.00Δρmin = −0.41 e Å−3
2500 reflectionsAbsolute structure: Flack (1983), with 1227 Friedel pairs
172 parametersFlack parameter: 0.07 (5)
1 restraint
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*/Ueq
C11.0066 (5)0.2099 (6)0.5559 (15)0.0355 (19)
C21.0318 (6)0.3398 (6)0.8847 (15)0.043 (2)
H2A0.98700.33011.03030.051*
H2B1.08250.32730.95280.051*
C31.0786 (5)0.4436 (6)0.7943 (16)0.039 (2)
C41.0607 (7)0.5107 (7)0.9319 (19)0.053 (2)
H41.01650.48941.07390.064*
C51.1086 (8)0.6088 (7)0.857 (2)0.067 (3)
H51.09630.65290.95040.081*
C61.1742 (7)0.6428 (7)0.646 (2)0.069 (3)
H61.20700.70920.60050.083*
C71.1905 (7)0.5768 (8)0.506 (2)0.064 (3)
H71.23350.59800.36130.077*
C81.1424 (7)0.4788 (6)0.5810 (17)0.051 (2)
H81.15370.43470.48350.062*
C90.8849 (6)0.2674 (6)0.5893 (16)0.041 (2)
H9A0.86270.23420.41870.049*
H9B0.89970.33500.56670.049*
C100.8041 (6)0.2174 (6)0.7892 (17)0.040 (2)
C110.7728 (6)0.2713 (7)0.9324 (17)0.050 (2)
H110.80280.33890.90360.059*
C120.6973 (6)0.2274 (7)1.1197 (18)0.054 (3)
H120.67660.26491.21470.065*
C130.6544 (7)0.1282 (8)1.161 (2)0.060 (3)
H130.60400.09761.28530.072*
C140.6844 (6)0.0740 (7)1.0219 (19)0.052 (3)
H140.65390.00631.05150.063*
C150.7590 (7)0.1168 (6)0.8386 (18)0.052 (2)
H150.77940.07850.74710.062*
N10.9764 (4)0.2672 (4)0.6704 (13)0.0360 (16)
S10.93514 (15)0.12847 (14)0.3071 (5)0.0439 (5)
S21.11785 (16)0.21987 (18)0.6397 (5)0.0543 (7)
Ag11.07051 (5)0.10767 (5)0.12225 (17)0.0688 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.023 (4)0.036 (5)0.045 (5)0.012 (4)0.005 (4)0.006 (4)
C20.050 (6)0.040 (5)0.032 (5)0.018 (5)0.000 (4)−0.012 (4)
C30.036 (5)0.038 (5)0.038 (5)0.016 (4)−0.006 (4)0.006 (4)
C40.051 (5)0.039 (6)0.060 (6)0.016 (5)0.002 (5)0.004 (5)
C50.081 (8)0.054 (7)0.073 (8)0.038 (6)−0.014 (7)−0.012 (6)
C60.056 (7)0.047 (7)0.085 (9)0.010 (6)−0.007 (6)0.022 (6)
C70.050 (6)0.067 (7)0.056 (7)0.015 (6)0.001 (5)0.016 (6)
C80.063 (6)0.034 (5)0.047 (6)0.016 (5)−0.005 (5)0.008 (5)
C90.046 (5)0.035 (5)0.048 (6)0.024 (4)0.004 (5)0.008 (4)
C100.038 (5)0.053 (6)0.040 (5)0.032 (5)−0.003 (4)0.010 (5)
C110.044 (5)0.057 (6)0.057 (6)0.033 (5)0.009 (5)0.009 (5)
C120.057 (6)0.067 (7)0.061 (7)0.048 (6)0.018 (5)0.006 (5)
C130.056 (6)0.071 (7)0.058 (7)0.037 (6)0.020 (5)0.017 (6)
C140.041 (6)0.040 (5)0.071 (7)0.016 (5)0.001 (5)0.008 (5)
C150.063 (6)0.050 (6)0.048 (6)0.033 (5)0.008 (5)0.006 (5)
N10.034 (4)0.033 (4)0.045 (4)0.019 (3)0.003 (4)0.004 (3)
S10.0467 (14)0.0406 (13)0.0462 (13)0.0232 (12)0.0014 (11)0.0026 (12)
S20.0424 (14)0.0696 (18)0.0624 (17)0.0367 (14)0.0043 (12)0.0062 (14)
Ag10.0639 (5)0.0686 (6)0.0880 (5)0.0438 (5)0.0161 (5)−0.0017 (5)
Geometric parameters (Å, °) top
C1—N11.336 (9)C9—H9B0.9700
C1—S21.720 (8)C10—C111.370 (11)
C1—S11.734 (8)C10—C151.387 (10)
C2—C31.480 (10)C11—C121.392 (11)
C2—N11.487 (9)C11—H110.9300
C2—H2A0.9700C12—C131.365 (11)
C2—H2B0.9700C12—H120.9300
C3—C81.376 (10)C13—C141.350 (12)
C3—C41.398 (12)C13—H130.9300
C4—C51.381 (13)C14—C151.369 (11)
C4—H40.9300C14—H140.9300
C5—C61.380 (13)C15—H150.9300
C5—H50.9300S1—Ag1i2.446 (2)
C6—C71.375 (13)S1—Ag12.478 (2)
C6—H60.9300S2—Ag13.010 (2)
C7—C81.381 (12)S2—Ag1ii2.860 (2)
C7—H70.9300Ag1—S1iii2.446 (2)
C8—H80.9300Ag1—S2iv2.860 (2)
C9—N11.489 (9)Ag1—Ag1iii3.0633 (11)
C9—C101.493 (10)Ag1—Ag1i3.0633 (11)
C9—H9A0.9700
N1—C1—S2121.1 (6)C11—C10—C9119.9 (8)
N1—C1—S1119.2 (6)C15—C10—C9122.1 (8)
S2—C1—S1119.6 (5)C10—C11—C12121.8 (8)
C3—C2—N1113.4 (6)C10—C11—H11119.1
C3—C2—H2A108.9C12—C11—H11119.1
N1—C2—H2A108.9C13—C12—C11118.4 (8)
C3—C2—H2B108.9C13—C12—H12120.8
N1—C2—H2B108.9C11—C12—H12120.8
H2A—C2—H2B107.7C14—C13—C12120.7 (9)
C8—C3—C4117.5 (8)C14—C13—H13119.7
C8—C3—C2122.6 (8)C12—C13—H13119.7
C4—C3—C2119.9 (8)C13—C14—C15121.1 (9)
C5—C4—C3120.0 (9)C13—C14—H14119.4
C5—C4—H4120.0C15—C14—H14119.4
C3—C4—H4120.0C14—C15—C10120.1 (8)
C6—C5—C4121.5 (10)C14—C15—H15120.0
C6—C5—H5119.3C10—C15—H15120.0
C4—C5—H5119.3C1—N1—C2123.8 (6)
C7—C6—C5119.0 (9)C1—N1—C9123.2 (6)
C7—C6—H6120.5C2—N1—C9113.0 (6)
C5—C6—H6120.5C1—S1—Ag1i107.1 (3)
C6—C7—C8119.5 (9)C1—S1—Ag194.9 (3)
C6—C7—H7120.3Ag1i—S1—Ag176.92 (6)
C8—C7—H7120.3C1—S2—Ag1ii102.2 (2)
C3—C8—C7122.6 (9)S1iii—Ag1—S1171.87 (8)
C3—C8—H8118.7S1iii—Ag1—S2iv85.02 (8)
C7—C8—H8118.7S1—Ag1—S2iv102.21 (7)
N1—C9—C10112.3 (6)S1iii—Ag1—Ag1iii52.01 (6)
N1—C9—H9A109.1S1—Ag1—Ag1iii123.76 (6)
C10—C9—H9A109.1S2iv—Ag1—Ag1iii88.38 (5)
N1—C9—H9B109.1S1iii—Ag1—Ag1i120.83 (6)
C10—C9—H9B109.1S1—Ag1—Ag1i51.07 (5)
H9A—C9—H9B107.9S2iv—Ag1—Ag1i140.89 (5)
C11—C10—C15118.0 (8)Ag1iii—Ag1—Ag1i86.91 (2)
Symmetry codes: (i) −y+1, x−y−1, z+1/3; (ii) x, y, z+1; (iii) −x+y+2, −x+1, z−1/3; (iv) x, y, z−1.
Table 1
Selected geometric parameters (Å) top
C1—N11.336 (9)S1—Ag12.478 (2)
C1—S21.720 (8)S2—Ag13.010 (2)
C1—S11.734 (8)S2—Ag1ii2.860 (2)
S1—Ag1i2.446 (2)Ag1—Ag1i3.0633 (11)
Symmetry codes: (i) −y+1, x−y−1, z+1/3; (ii) x, y, z+1.
Acknowledgements top

This work was supported by the Natural Science Foundation of Guangdong Province, China (grant No. 990463) and the National Natural Science Foundation of China (grant No. 29561002).

references
References top

Akerström, S. (1959). Ark. Kemi, 14, 413–420.

Anacker-Eickhoff, H., Hesse, R., Jennische, P. & Wahlberg, A. (1982). Acta Chem. Scand. B, 36, 251–259.

Bruker (1998). SHELXTL. Version 6.12. Bruker AXS Inc, Madison, Wisconsin, USA. [Note SMART cannot be used with an APEXII machine, so it has been removed]

Bruker (1999). SAINT. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (YEAR?). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. [Please complete details for missing reference]

Fan, J., Yin, X., Zhang, W. G., Zhang, Q. J., Lai, C. S., Tiekink, E. R. T., Fan, Y. & Huang, M. Y. (2004). Acta Chim. Sinica, 62, 1626–1634.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Greenwood, N. N. & Earnshaw, A. (1989). Chemistry of the Elements. Oxford: Pergamon Press.

Li, H., Yin, K.-L. & Xu, D.-J. (2005). Acta Cryst. C61, m19–m21.

Liu, N., Fan, J., Zhang, W.-G., Yin, X. & Xie, M.-B. (2006). Acta Cryst. E62, m2588–m2590.

Sheldrick, G. M. (2002). SADABS. Version 2.03. University of Göttingen, Germany.

Song, Y.-W., Yu, Z. & Zhang, Q.-F. (2006). Acta Cryst. C62, m214–m216.

Tang, K.-L., Xie, X.-J., Zhao, L., Zhang, Y.-H. & Jin, X.-L. (2004). Eur. J. Inorg. Chem. pp. 78–85.

Yin, X., Xie, M.-B., Zhang, W.-G., Fan, J. & Zeller, M. (2007). Acta Cryst. E63, m2063–m2064.

Zhang, W.-G., Zhong, Y., Tan, M.-Y., Liu, W.-S. & Su, C.-Y. (2002). Chin. J. Chem. . 20, 420–423.