Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035180/xu2287sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035180/xu2287Isup2.hkl |
CCDC reference: 661674
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.
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).
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).
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).
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.
[Ag(C15H14NS2)] | Dx = 1.782 Mg m−3 |
Mr = 380.26 | Melting point = 491–492 K |
Trigonal, P31 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 31 | Cell parameters from 2450 reflections |
a = 15.6505 (19) Å | θ = 2.4–25.0° |
c = 5.0120 (14) Å | µ = 1.70 mm−1 |
V = 1063.2 (3) Å3 | T = 293 K |
Z = 3 | Block, yellow |
F(000) = 570 | 0.15 × 0.10 × 0.10 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 2500 independent reflections |
Radiation source: fine-focus sealed tube | 1519 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.094 |
φ and ω scans | θmax = 25.2°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −18→18 |
Tmin = 0.785, Tmax = 0.848 | k = −18→18 |
7409 measured reflections | l = −6→6 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2500 reflections | Δρmax = 0.46 e Å−3 |
172 parameters | Δρmin = −0.41 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1227 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (5) |
[Ag(C15H14NS2)] | Z = 3 |
Mr = 380.26 | Mo Kα radiation |
Trigonal, P31 | µ = 1.70 mm−1 |
a = 15.6505 (19) Å | T = 293 K |
c = 5.0120 (14) Å | 0.15 × 0.10 × 0.10 mm |
V = 1063.2 (3) Å3 |
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 = 0.848 | Rint = 0.094 |
7409 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.080 | Δρmax = 0.46 e Å−3 |
S = 1.00 | Δρmin = −0.41 e Å−3 |
2500 reflections | Absolute structure: Flack (1983), with 1227 Friedel pairs |
172 parameters | Absolute structure parameter: 0.07 (5) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0066 (5) | 0.2099 (6) | 0.5559 (15) | 0.0355 (19) | |
C2 | 1.0318 (6) | 0.3398 (6) | 0.8847 (15) | 0.043 (2) | |
H2A | 0.9870 | 0.3301 | 1.0303 | 0.051* | |
H2B | 1.0825 | 0.3273 | 0.9528 | 0.051* | |
C3 | 1.0786 (5) | 0.4436 (6) | 0.7943 (16) | 0.039 (2) | |
C4 | 1.0607 (7) | 0.5107 (7) | 0.9319 (19) | 0.053 (2) | |
H4 | 1.0165 | 0.4894 | 1.0739 | 0.064* | |
C5 | 1.1086 (8) | 0.6088 (7) | 0.857 (2) | 0.067 (3) | |
H5 | 1.0963 | 0.6529 | 0.9504 | 0.081* | |
C6 | 1.1742 (7) | 0.6428 (7) | 0.646 (2) | 0.069 (3) | |
H6 | 1.2070 | 0.7092 | 0.6005 | 0.083* | |
C7 | 1.1905 (7) | 0.5768 (8) | 0.506 (2) | 0.064 (3) | |
H7 | 1.2335 | 0.5980 | 0.3613 | 0.077* | |
C8 | 1.1424 (7) | 0.4788 (6) | 0.5810 (17) | 0.051 (2) | |
H8 | 1.1537 | 0.4347 | 0.4835 | 0.062* | |
C9 | 0.8849 (6) | 0.2674 (6) | 0.5893 (16) | 0.041 (2) | |
H9A | 0.8627 | 0.2342 | 0.4187 | 0.049* | |
H9B | 0.8997 | 0.3350 | 0.5667 | 0.049* | |
C10 | 0.8041 (6) | 0.2174 (6) | 0.7892 (17) | 0.040 (2) | |
C11 | 0.7728 (6) | 0.2713 (7) | 0.9324 (17) | 0.050 (2) | |
H11 | 0.8028 | 0.3389 | 0.9036 | 0.059* | |
C12 | 0.6973 (6) | 0.2274 (7) | 1.1197 (18) | 0.054 (3) | |
H12 | 0.6766 | 0.2649 | 1.2147 | 0.065* | |
C13 | 0.6544 (7) | 0.1282 (8) | 1.161 (2) | 0.060 (3) | |
H13 | 0.6040 | 0.0976 | 1.2853 | 0.072* | |
C14 | 0.6844 (6) | 0.0740 (7) | 1.0219 (19) | 0.052 (3) | |
H14 | 0.6539 | 0.0063 | 1.0515 | 0.063* | |
C15 | 0.7590 (7) | 0.1168 (6) | 0.8386 (18) | 0.052 (2) | |
H15 | 0.7794 | 0.0785 | 0.7471 | 0.062* | |
N1 | 0.9764 (4) | 0.2672 (4) | 0.6704 (13) | 0.0360 (16) | |
S1 | 0.93514 (15) | 0.12847 (14) | 0.3071 (5) | 0.0439 (5) | |
S2 | 1.11785 (16) | 0.21987 (18) | 0.6397 (5) | 0.0543 (7) | |
Ag1 | 1.07051 (5) | 0.10767 (5) | 0.12225 (17) | 0.0688 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.023 (4) | 0.036 (5) | 0.045 (5) | 0.012 (4) | 0.005 (4) | 0.006 (4) |
C2 | 0.050 (6) | 0.040 (5) | 0.032 (5) | 0.018 (5) | 0.000 (4) | −0.012 (4) |
C3 | 0.036 (5) | 0.038 (5) | 0.038 (5) | 0.016 (4) | −0.006 (4) | 0.006 (4) |
C4 | 0.051 (5) | 0.039 (6) | 0.060 (6) | 0.016 (5) | 0.002 (5) | 0.004 (5) |
C5 | 0.081 (8) | 0.054 (7) | 0.073 (8) | 0.038 (6) | −0.014 (7) | −0.012 (6) |
C6 | 0.056 (7) | 0.047 (7) | 0.085 (9) | 0.010 (6) | −0.007 (6) | 0.022 (6) |
C7 | 0.050 (6) | 0.067 (7) | 0.056 (7) | 0.015 (6) | 0.001 (5) | 0.016 (6) |
C8 | 0.063 (6) | 0.034 (5) | 0.047 (6) | 0.016 (5) | −0.005 (5) | 0.008 (5) |
C9 | 0.046 (5) | 0.035 (5) | 0.048 (6) | 0.024 (4) | 0.004 (5) | 0.008 (4) |
C10 | 0.038 (5) | 0.053 (6) | 0.040 (5) | 0.032 (5) | −0.003 (4) | 0.010 (5) |
C11 | 0.044 (5) | 0.057 (6) | 0.057 (6) | 0.033 (5) | 0.009 (5) | 0.009 (5) |
C12 | 0.057 (6) | 0.067 (7) | 0.061 (7) | 0.048 (6) | 0.018 (5) | 0.006 (5) |
C13 | 0.056 (6) | 0.071 (7) | 0.058 (7) | 0.037 (6) | 0.020 (5) | 0.017 (6) |
C14 | 0.041 (6) | 0.040 (5) | 0.071 (7) | 0.016 (5) | 0.001 (5) | 0.008 (5) |
C15 | 0.063 (6) | 0.050 (6) | 0.048 (6) | 0.033 (5) | 0.008 (5) | 0.006 (5) |
N1 | 0.034 (4) | 0.033 (4) | 0.045 (4) | 0.019 (3) | 0.003 (4) | 0.004 (3) |
S1 | 0.0467 (14) | 0.0406 (13) | 0.0462 (13) | 0.0232 (12) | 0.0014 (11) | 0.0026 (12) |
S2 | 0.0424 (14) | 0.0696 (18) | 0.0624 (17) | 0.0367 (14) | 0.0043 (12) | 0.0062 (14) |
Ag1 | 0.0639 (5) | 0.0686 (6) | 0.0880 (5) | 0.0438 (5) | 0.0161 (5) | −0.0017 (5) |
C1—N1 | 1.336 (9) | C9—H9B | 0.9700 |
C1—S2 | 1.720 (8) | C10—C11 | 1.370 (11) |
C1—S1 | 1.734 (8) | C10—C15 | 1.387 (10) |
C2—C3 | 1.480 (10) | C11—C12 | 1.392 (11) |
C2—N1 | 1.487 (9) | C11—H11 | 0.9300 |
C2—H2A | 0.9700 | C12—C13 | 1.365 (11) |
C2—H2B | 0.9700 | C12—H12 | 0.9300 |
C3—C8 | 1.376 (10) | C13—C14 | 1.350 (12) |
C3—C4 | 1.398 (12) | C13—H13 | 0.9300 |
C4—C5 | 1.381 (13) | C14—C15 | 1.369 (11) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.380 (13) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | S1—Ag1i | 2.446 (2) |
C6—C7 | 1.375 (13) | S1—Ag1 | 2.478 (2) |
C6—H6 | 0.9300 | S2—Ag1 | 3.010 (2) |
C7—C8 | 1.381 (12) | S2—Ag1ii | 2.860 (2) |
C7—H7 | 0.9300 | Ag1—S1iii | 2.446 (2) |
C8—H8 | 0.9300 | Ag1—S2iv | 2.860 (2) |
C9—N1 | 1.489 (9) | Ag1—Ag1iii | 3.0633 (11) |
C9—C10 | 1.493 (10) | Ag1—Ag1i | 3.0633 (11) |
C9—H9A | 0.9700 | ||
N1—C1—S2 | 121.1 (6) | C11—C10—C9 | 119.9 (8) |
N1—C1—S1 | 119.2 (6) | C15—C10—C9 | 122.1 (8) |
S2—C1—S1 | 119.6 (5) | C10—C11—C12 | 121.8 (8) |
C3—C2—N1 | 113.4 (6) | C10—C11—H11 | 119.1 |
C3—C2—H2A | 108.9 | C12—C11—H11 | 119.1 |
N1—C2—H2A | 108.9 | C13—C12—C11 | 118.4 (8) |
C3—C2—H2B | 108.9 | C13—C12—H12 | 120.8 |
N1—C2—H2B | 108.9 | C11—C12—H12 | 120.8 |
H2A—C2—H2B | 107.7 | C14—C13—C12 | 120.7 (9) |
C8—C3—C4 | 117.5 (8) | C14—C13—H13 | 119.7 |
C8—C3—C2 | 122.6 (8) | C12—C13—H13 | 119.7 |
C4—C3—C2 | 119.9 (8) | C13—C14—C15 | 121.1 (9) |
C5—C4—C3 | 120.0 (9) | C13—C14—H14 | 119.4 |
C5—C4—H4 | 120.0 | C15—C14—H14 | 119.4 |
C3—C4—H4 | 120.0 | C14—C15—C10 | 120.1 (8) |
C6—C5—C4 | 121.5 (10) | C14—C15—H15 | 120.0 |
C6—C5—H5 | 119.3 | C10—C15—H15 | 120.0 |
C4—C5—H5 | 119.3 | C1—N1—C2 | 123.8 (6) |
C7—C6—C5 | 119.0 (9) | C1—N1—C9 | 123.2 (6) |
C7—C6—H6 | 120.5 | C2—N1—C9 | 113.0 (6) |
C5—C6—H6 | 120.5 | C1—S1—Ag1i | 107.1 (3) |
C6—C7—C8 | 119.5 (9) | C1—S1—Ag1 | 94.9 (3) |
C6—C7—H7 | 120.3 | Ag1i—S1—Ag1 | 76.92 (6) |
C8—C7—H7 | 120.3 | C1—S2—Ag1ii | 102.2 (2) |
C3—C8—C7 | 122.6 (9) | S1iii—Ag1—S1 | 171.87 (8) |
C3—C8—H8 | 118.7 | S1iii—Ag1—S2iv | 85.02 (8) |
C7—C8—H8 | 118.7 | S1—Ag1—S2iv | 102.21 (7) |
N1—C9—C10 | 112.3 (6) | S1iii—Ag1—Ag1iii | 52.01 (6) |
N1—C9—H9A | 109.1 | S1—Ag1—Ag1iii | 123.76 (6) |
C10—C9—H9A | 109.1 | S2iv—Ag1—Ag1iii | 88.38 (5) |
N1—C9—H9B | 109.1 | S1iii—Ag1—Ag1i | 120.83 (6) |
C10—C9—H9B | 109.1 | S1—Ag1—Ag1i | 51.07 (5) |
H9A—C9—H9B | 107.9 | S2iv—Ag1—Ag1i | 140.89 (5) |
C11—C10—C15 | 118.0 (8) | Ag1iii—Ag1—Ag1i | 86.91 (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. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C15H14NS2)] |
Mr | 380.26 |
Crystal system, space group | Trigonal, P31 |
Temperature (K) | 293 |
a, c (Å) | 15.6505 (19), 5.0120 (14) |
V (Å3) | 1063.2 (3) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.785, 0.848 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7409, 2500, 1519 |
Rint | 0.094 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.080, 1.00 |
No. of reflections | 2500 |
No. of parameters | 172 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.41 |
Absolute structure | Flack (1983), with 1227 Friedel pairs |
Absolute structure parameter | 0.07 (5) |
Computer programs: APEX2 (Bruker, YEAR?), SAINT (Bruker, 1999), SAINT, SHELXTL (Bruker, 1998), SHELXTL.
C1—N1 | 1.336 (9) | S1—Ag1 | 2.478 (2) |
C1—S2 | 1.720 (8) | S2—Ag1 | 3.010 (2) |
C1—S1 | 1.734 (8) | S2—Ag1ii | 2.860 (2) |
S1—Ag1i | 2.446 (2) | Ag1—Ag1i | 3.0633 (11) |
Symmetry codes: (i) −y+1, x−y−1, z+1/3; (ii) x, y, z+1. |
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).