Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106006688/ob3001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106006688/ob3001IIIsup2.hkl |
CCDC reference: 609406
Compound (III) was prepared by mixing stoichiometeric quantities of NaS2CNEt2·3H2O (225 mg, 0.10 mmol) and Ag(CF3SO3) (257 mg, 0.10 mmol) in absolute ethanol. The mixture was stirred for 15 min at room temperature. The resulting brown precipitate was filtered and further recrystallized from DMF/THF (1:5 v/v). Dark-red crystals of (III) were obtained after a couple of weeks (yield 116 mg, 45%). 1H NMR (DMSO-d6): δ 1.23 (m, CH3), 3.54 (m, CH2). MS (FAB): m/z 256 (M+ + 1). IR (KBr pepplt, cm−1): ν(C═N), 1479 (s); ν(C—S) 990 (s), 917(m). Analysis calculated for C9H30Ag3N3S6: C 23.35, H 3.94, N 5.47%; found: C 23.25, H 3.91, N 5.43%.
All H atoms were found in difference density maps, but were then placed in calculated positions (C—H = 0.96–0.97%A) and included in the refinement using a riding-model approximation, with Uiso(H) = 1.2Ueq(C). The largest peak in the final difference maps is in the vicinity of the Ag atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[Ag3(C5H10NS2)3] | F(000) = 1512 |
Mr = 768.45 | Dx = 2.136 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.138 (4) Å | Cell parameters from 2887 reflections |
b = 9.5890 (19) Å | θ = 2.3–18.3° |
c = 14.245 (3) Å | µ = 2.97 mm−1 |
β = 105.30 (3)° | T = 153 K |
V = 2389.8 (8) Å3 | Prism, dark red |
Z = 4 | 0.25 × 0.22 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 2853 independent reflections |
Radiation source: fine-focus sealed tube | 2506 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→23 |
Tmin = 0.457, Tmax = 0.586 | k = −12→12 |
7241 measured reflections | l = −11→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0369P)2 + 2.307P] where P = (Fo2 + 2Fc2)/3 |
2853 reflections | (Δ/σ)max = 0.001 |
124 parameters | Δρmax = 1.59 e Å−3 |
0 restraints | Δρmin = −0.97 e Å−3 |
[Ag3(C5H10NS2)3] | V = 2389.8 (8) Å3 |
Mr = 768.45 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.138 (4) Å | µ = 2.97 mm−1 |
b = 9.5890 (19) Å | T = 153 K |
c = 14.245 (3) Å | 0.25 × 0.22 × 0.18 mm |
β = 105.30 (3)° |
Bruker SMART CCD area-detector diffractometer | 2853 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2506 reflections with I > 2σ(I) |
Tmin = 0.457, Tmax = 0.586 | Rint = 0.031 |
7241 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.59 e Å−3 |
2853 reflections | Δρmin = −0.97 e Å−3 |
124 parameters |
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. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 20 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. 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 | ||
Ag1 | 0.519534 (16) | 0.37249 (3) | 0.55071 (2) | 0.02157 (10) | |
Ag2 | 0.5000 | 0.56129 (4) | 0.7500 | 0.01967 (11) | |
S1 | 0.57677 (5) | 0.31786 (9) | 0.40397 (6) | 0.01522 (18) | |
S2 | 0.57616 (5) | 0.32543 (9) | 0.72706 (6) | 0.01755 (18) | |
S3 | 0.37699 (5) | 0.41359 (9) | 0.48830 (6) | 0.01747 (19) | |
N1 | 0.70878 (16) | 0.4503 (3) | 0.4185 (2) | 0.0137 (6) | |
N2 | 0.5000 | 0.0960 (4) | 0.7500 | 0.0150 (8) | |
C1 | 0.64259 (19) | 0.4536 (3) | 0.4414 (2) | 0.0149 (7) | |
C2 | 0.5000 | 0.2339 (5) | 0.7500 | 0.0157 (9) | |
C11 | 0.76313 (19) | 0.5670 (4) | 0.4412 (2) | 0.0169 (7) | |
H11A | 0.7351 | 0.6536 | 0.4396 | 0.020* | |
H11B | 0.7911 | 0.5724 | 0.3920 | 0.020* | |
C12 | 0.81906 (19) | 0.5506 (4) | 0.5403 (3) | 0.0207 (8) | |
H12A | 0.8542 | 0.6274 | 0.5520 | 0.031* | |
H12B | 0.8468 | 0.4649 | 0.5422 | 0.031* | |
H12C | 0.7917 | 0.5490 | 0.5895 | 0.031* | |
C13 | 0.7341 (2) | 0.3304 (4) | 0.3700 (3) | 0.0192 (7) | |
H13A | 0.7102 | 0.2462 | 0.3856 | 0.023* | |
H13B | 0.7890 | 0.3198 | 0.3948 | 0.023* | |
C14 | 0.7144 (2) | 0.3475 (5) | 0.2611 (3) | 0.0289 (9) | |
H14A | 0.7320 | 0.2675 | 0.2326 | 0.043* | |
H14B | 0.7387 | 0.4298 | 0.2452 | 0.043* | |
H14C | 0.6601 | 0.3560 | 0.2360 | 0.043* | |
C21 | 0.56207 (19) | 0.0118 (4) | 0.7296 (2) | 0.0169 (7) | |
H21A | 0.5671 | −0.0748 | 0.7659 | 0.020* | |
H21B | 0.6100 | 0.0622 | 0.7507 | 0.020* | |
C22 | 0.5461 (2) | −0.0203 (4) | 0.6220 (3) | 0.0213 (8) | |
H22A | 0.5882 | −0.0713 | 0.6101 | 0.032* | |
H22B | 0.5394 | 0.0653 | 0.5858 | 0.032* | |
H22C | 0.5004 | −0.0752 | 0.6019 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.02415 (17) | 0.02126 (16) | 0.02314 (17) | 0.00380 (11) | 0.01298 (12) | 0.00766 (11) |
Ag2 | 0.0214 (2) | 0.01563 (19) | 0.0194 (2) | 0.000 | 0.00092 (14) | 0.000 |
S1 | 0.0172 (4) | 0.0133 (4) | 0.0156 (4) | −0.0013 (3) | 0.0050 (3) | −0.0007 (3) |
S2 | 0.0187 (4) | 0.0163 (4) | 0.0196 (4) | −0.0015 (3) | 0.0085 (3) | 0.0004 (3) |
S3 | 0.0189 (4) | 0.0175 (4) | 0.0177 (4) | −0.0013 (3) | 0.0077 (3) | −0.0057 (3) |
N1 | 0.0170 (14) | 0.0124 (14) | 0.0132 (14) | −0.0005 (11) | 0.0066 (11) | −0.0003 (11) |
N2 | 0.018 (2) | 0.019 (2) | 0.0096 (19) | 0.000 | 0.0063 (15) | 0.000 |
C1 | 0.0158 (16) | 0.0144 (16) | 0.0131 (15) | 0.0008 (13) | 0.0016 (12) | 0.0023 (13) |
C2 | 0.017 (2) | 0.018 (2) | 0.012 (2) | 0.000 | 0.0025 (17) | 0.000 |
C11 | 0.0177 (17) | 0.0162 (17) | 0.0182 (17) | −0.0040 (13) | 0.0070 (13) | 0.0029 (14) |
C12 | 0.0177 (18) | 0.0196 (18) | 0.0250 (19) | −0.0028 (14) | 0.0058 (14) | 0.0006 (15) |
C13 | 0.0200 (18) | 0.0192 (18) | 0.0205 (18) | 0.0045 (14) | 0.0092 (14) | −0.0017 (15) |
C14 | 0.033 (2) | 0.038 (2) | 0.0184 (19) | 0.0036 (17) | 0.0111 (16) | −0.0082 (17) |
C21 | 0.0185 (17) | 0.0153 (16) | 0.0190 (18) | 0.0013 (13) | 0.0084 (13) | 0.0009 (14) |
C22 | 0.0245 (18) | 0.0232 (19) | 0.0197 (18) | −0.0036 (15) | 0.0118 (14) | −0.0058 (15) |
Ag1—S2 | 2.4915 (11) | C1—S3i | 1.714 (4) |
Ag1—S3 | 2.5333 (11) | C2—S2iii | 1.739 (3) |
Ag1—S1 | 2.6205 (11) | C11—C12 | 1.513 (5) |
Ag1—Ag1i | 2.8336 (7) | C11—H11A | 0.9700 |
Ag1—S3i | 2.9308 (10) | C11—H11B | 0.9700 |
Ag2—S1ii | 2.5457 (11) | C12—H12A | 0.9600 |
Ag2—S1i | 2.5457 (11) | C12—H12B | 0.9600 |
Ag2—S2iii | 2.7145 (10) | C12—H12C | 0.9600 |
Ag2—S2 | 2.7145 (10) | C13—C14 | 1.507 (5) |
S1—C1 | 1.751 (3) | C13—H13A | 0.9700 |
S1—Ag2i | 2.5457 (11) | C13—H13B | 0.9700 |
S2—C2 | 1.739 (3) | C14—H14A | 0.9600 |
S3—C1i | 1.714 (4) | C14—H14B | 0.9600 |
S3—Ag1i | 2.9308 (10) | C14—H14C | 0.9600 |
N1—C1 | 1.325 (4) | C21—C22 | 1.514 (5) |
N1—C11 | 1.470 (4) | C21—H21A | 0.9700 |
N1—C13 | 1.476 (4) | C21—H21B | 0.9700 |
N2—C2 | 1.322 (6) | C22—H22A | 0.9600 |
N2—C21iii | 1.476 (4) | C22—H22B | 0.9600 |
N2—C21 | 1.476 (4) | C22—H22C | 0.9600 |
S2—Ag1—S3 | 119.54 (4) | N1—C11—C12 | 111.8 (3) |
S2—Ag1—S1 | 128.56 (3) | N1—C11—H11A | 109.3 |
S3—Ag1—S1 | 109.49 (4) | C12—C11—H11A | 109.3 |
S2—Ag1—Ag1i | 130.65 (3) | N1—C11—H11B | 109.3 |
S3—Ag1—Ag1i | 65.92 (3) | C12—C11—H11B | 109.3 |
S1—Ag1—Ag1i | 82.20 (2) | H11A—C11—H11B | 107.9 |
S2—Ag1—S3i | 101.75 (3) | C11—C12—H12A | 109.5 |
S3—Ag1—S3i | 118.03 (2) | C11—C12—H12B | 109.5 |
S1—Ag1—S3i | 65.19 (3) | H12A—C12—H12B | 109.5 |
Ag1i—Ag1—S3i | 52.11 (2) | C11—C12—H12C | 109.5 |
S1ii—Ag2—S1i | 125.84 (4) | H12A—C12—H12C | 109.5 |
S1ii—Ag2—S2iii | 117.10 (3) | H12B—C12—H12C | 109.5 |
S1i—Ag2—S2iii | 107.63 (3) | N1—C13—C14 | 112.3 (3) |
S1ii—Ag2—S2 | 107.63 (3) | N1—C13—H13A | 109.1 |
S1i—Ag2—S2 | 117.10 (3) | C14—C13—H13A | 109.1 |
S2iii—Ag2—S2 | 67.15 (4) | N1—C13—H13B | 109.1 |
C1—S1—Ag2i | 95.63 (11) | C14—C13—H13B | 109.1 |
C1—S1—Ag1 | 89.44 (12) | H13A—C13—H13B | 107.9 |
Ag2i—S1—Ag1 | 110.76 (3) | C13—C14—H14A | 109.5 |
C2—S2—Ag1 | 98.30 (5) | C13—C14—H14B | 109.5 |
C2—S2—Ag2 | 86.75 (15) | H14A—C14—H14B | 109.5 |
Ag1—S2—Ag2 | 83.28 (3) | C13—C14—H14C | 109.5 |
C1i—S3—Ag1 | 105.08 (12) | H14A—C14—H14C | 109.5 |
C1i—S3—Ag1i | 80.35 (12) | H14B—C14—H14C | 109.5 |
Ag1—S3—Ag1i | 61.97 (2) | N2—C21—C22 | 111.0 (3) |
C1—N1—C11 | 121.8 (3) | N2—C21—H21A | 109.4 |
C1—N1—C13 | 123.2 (3) | C22—C21—H21A | 109.4 |
C11—N1—C13 | 115.0 (3) | N2—C21—H21B | 109.4 |
C2—N2—C21iii | 123.19 (19) | C22—C21—H21B | 109.4 |
C2—N2—C21 | 123.2 (2) | H21A—C21—H21B | 108.0 |
C21iii—N2—C21 | 113.6 (4) | C21—C22—H22A | 109.5 |
N1—C1—S3i | 120.1 (3) | C21—C22—H22B | 109.5 |
N1—C1—S1 | 119.8 (3) | H22A—C22—H22B | 109.5 |
S3i—C1—S1 | 120.0 (2) | C21—C22—H22C | 109.5 |
N2—C2—S2 | 120.32 (14) | H22A—C22—H22C | 109.5 |
N2—C2—S2iii | 120.32 (14) | H22B—C22—H22C | 109.5 |
S2—C2—S2iii | 119.4 (3) | ||
S2—Ag1—S1—C1 | −72.66 (11) | S2—Ag1—S3—Ag1i | 124.54 (3) |
S3—Ag1—S1—C1 | 125.33 (11) | S1—Ag1—S3—Ag1i | −71.58 (3) |
Ag1i—Ag1—S1—C1 | 64.37 (11) | S3i—Ag1—S3—Ag1i | 0.0 |
S3i—Ag1—S1—C1 | 12.66 (11) | C11—N1—C1—S3i | −7.8 (4) |
S2—Ag1—S1—Ag2i | −168.48 (3) | C13—N1—C1—S3i | 171.4 (2) |
S3—Ag1—S1—Ag2i | 29.52 (4) | C11—N1—C1—S1 | 174.9 (2) |
Ag1i—Ag1—S1—Ag2i | −31.45 (3) | C13—N1—C1—S1 | −5.9 (4) |
S3i—Ag1—S1—Ag2i | −83.16 (4) | Ag2i—S1—C1—N1 | −95.0 (3) |
S3—Ag1—S2—C2 | 33.91 (15) | Ag1—S1—C1—N1 | 154.2 (3) |
S1—Ag1—S2—C2 | −126.53 (15) | Ag2i—S1—C1—S3i | 87.69 (19) |
Ag1i—Ag1—S2—C2 | 116.36 (15) | Ag1—S1—C1—S3i | −23.12 (19) |
S3i—Ag1—S2—C2 | 165.95 (14) | C21iii—N2—C2—S2 | 178.98 (16) |
S3—Ag1—S2—Ag2 | −51.79 (4) | C21—N2—C2—S2 | −1.02 (16) |
S1—Ag1—S2—Ag2 | 147.77 (3) | C21iii—N2—C2—S2iii | −1.02 (16) |
Ag1i—Ag1—S2—Ag2 | 30.65 (4) | C21—N2—C2—S2iii | 178.98 (16) |
S3i—Ag1—S2—Ag2 | 80.24 (3) | Ag1—S2—C2—N2 | 97.28 (4) |
S1ii—Ag2—S2—C2 | 112.63 (4) | Ag2—S2—C2—N2 | 180.0 |
S1i—Ag2—S2—C2 | −98.84 (4) | Ag1—S2—C2—S2iii | −82.72 (4) |
S2iii—Ag2—S2—C2 | 0.0 | Ag2—S2—C2—S2iii | 0.000 (1) |
S1ii—Ag2—S2—Ag1 | −148.61 (3) | C1—N1—C11—C12 | 90.4 (4) |
S1i—Ag2—S2—Ag1 | −0.08 (4) | C13—N1—C11—C12 | −88.9 (4) |
S2iii—Ag2—S2—Ag1 | 98.76 (4) | C1—N1—C13—C14 | 94.4 (4) |
S2—Ag1—S3—C1i | 54.42 (13) | C11—N1—C13—C14 | −86.4 (4) |
S1—Ag1—S3—C1i | −141.70 (12) | C2—N2—C21—C22 | −90.5 (3) |
Ag1i—Ag1—S3—C1i | −70.11 (12) | C21iii—N2—C21—C22 | 89.5 (3) |
S3i—Ag1—S3—C1i | −70.11 (12) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1, z+1/2; (iii) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag3(C5H10NS2)3] |
Mr | 768.45 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 153 |
a, b, c (Å) | 18.138 (4), 9.5890 (19), 14.245 (3) |
β (°) | 105.30 (3) |
V (Å3) | 2389.8 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.97 |
Crystal size (mm) | 0.25 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.457, 0.586 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7241, 2853, 2506 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.079, 1.09 |
No. of reflections | 2853 |
No. of parameters | 124 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.59, −0.97 |
Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SAINT-Plus, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Ag1—S2 | 2.4915 (11) | Ag1—S3i | 2.9308 (10) |
Ag1—S3 | 2.5333 (11) | Ag2—S1i | 2.5457 (11) |
Ag1—S1 | 2.6205 (11) | Ag2—S2 | 2.7145 (10) |
Ag1—Ag1i | 2.8336 (7) | ||
S2—Ag1—S3 | 119.54 (4) | S1—Ag1—S3i | 65.19 (3) |
S2—Ag1—S1 | 128.56 (3) | S1ii—Ag2—S1i | 125.84 (4) |
S3—Ag1—S1 | 109.49 (4) | S1ii—Ag2—S2 | 107.63 (3) |
S2—Ag1—S3i | 101.75 (3) | S1i—Ag2—S2 | 117.10 (3) |
S3—Ag1—S3i | 118.03 (2) | S2iii—Ag2—S2 | 67.15 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1, z+1/2; (iii) −x+1, y, −z+3/2. |
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Dithiocarbamates (R2NCS2−) are a versatile class of monoanionic 1,1'-dithio ligand and, as they are easily prepared, a wide range of chemistry has been developed around them (Coucouvanis, 1979). The chemistry of transition metal–dithiocarbamate complexes is still of much current interest becasue of their applications in inorganic analysis, such as separation of different metal ions by high-performance liquid chromatography (Liśka et al., 1979) and capillary gas chromatography (Riekkola, 1982), and as rubber vulcanization accelerators, fungicides and pesticides (Hogarth, 2005). A large number of transition metal–dithiocarbamate complexes have been synthesized to date and have been reported to exhibit very abundant reactivities and a variety structures (Hogarth, 2005).
Simple silver(I)–dithiocarbamate complexes, [Ag(S2CNR2)]n, have been known since the 1950 s (Akerström, 1959), yet in the intervening years little further work had been carried out. The low solubility of these complexes probably hindered research in this field. Early crystallographic studies revealed the hexameric nature of Ag—S2CNR2 (R = Et and Pr) complexes in the solid state (Hesse, 1963), although in solution they are believed to be in equilibrium with monomeric species. Recently, the silver–N,N-diethyldithiocarbamate complex has been the subject of two further crystallographic studies. The known monoclinic α-modification, (I), characterized by X-ray powder diffraction data, is hexameric and consists of a distorted octahedron of Ag atoms (Hesse & Nilson, 1969). The dithiocarbamate anions cap six of the faces in a η1,η2-fashion; the remaining two faces with long silver–silver interactions remain uncapped. The β-modification, (II), characterized by single-crystal X-ray diffraction, exhibits a polymeric chain structure in which each Ag atom is coordinated in a distorted fashion by three dithiocarbamate ligands (Anacker-Eickhoff et al., 1982), one acting as a chelate and the others as µ2-bridges. Although the reaction of the hexameric α-modification, [Ag(S2CNEt2)]6, with (SCN)2 resulted in the formation of the postulated products [Ag6(S2CNEt2)5(SCN)] and [Ag6(S2CNEt2)6(SCN)4] (Calabro et al., 1981), poor solubility in common organic solvents made the characterization of the complexes possible only on the basis of spectroscopic data; accordingly, no X-ray crystallographic study was reported. Huang et al. (1992) prepared a polynuclear silver(I)–diethyldithiocarbamate cluster, [Ag11S(S2CNEt2)9], with a centered µ5-S atom. One of the authors also isolated and crystallographically characterized an Se analog, [Ag11(µ5-Se)(µ3-S2CNEt2)6(µ4-S2CNEt2)3], which contains six triply and three quadruply bridging dithiocarbamate ligands (Zhang et al., 1998). We have maintained an interest in silver(I)–dithiocarbamate complexes and we report here the structure of the title compound, (III), which is the γ-modification of [Ag(S2CNEt2)]n.
Compound (III) has a polymeric structure (Fig. 1). There is a twofold axis through atoms Ag2, C2 and N2. The trigonally and tetrahedrally coordinated Ag atoms are bridged by µ3– and µ4-S2CNEt2 ligands to form a ribbon structure along the c axis (Fig. 2). Similar to (I) (Hesse & Nilson, 1969) and (II) (Anacker-Eickhoff et al., 1982), the formula of (III) is also defined as [Ag(S2CNEt2)]n on the basis of X-ray analysis, together with microanalyses and spectroscopy. We conclude that it is reasonable to name complex (III), which has a new structural mode, as the γ-modification of [Ag(S2CNEt2)]n. The S2CNEt2 ligands coordinate the Agr atoms in η1,η2– and η2,η2-fashions, depending on the bridging S atoms.
The distances between the trigonal Ag (Ag1) and S atoms are 2.4915 (11)–2.6205 (11) Å (Table 1), and the S—Ag1—S bond angles are 109.49 (4)–128.56 (3)°, indicating a highly distorted coordination geometry around atom Ag1. The tetrahedral Ag atom (Ag2) is bound by two µ3-S atoms from two η1,η2-S2CNEt2 ligands and chelated by two µ3-S atoms from one η2,η2-S2CNEt2 ligand. The coordination geometry of atom Ag2 is severely distorted, as observed in other silver–dithiocarbamate complexes with tetrahedral Ag atoms, such as [Ag(S2CNC4H9)(PPh3)2] (Othman et al., 1996) and [Ag(S2CNEt2)(PFc2Ph)] (Fc is ferrocenyl; Gimeno et al., 1998). The distortion arises from the restricted bite angle of S2—Ag2—S2C [67.15 (4)°; symmetry codes A–C are as in Fig. 1]. There is also a large deviation of the S1A—Ag2—S1B angle [125.84 (4)°] from the ideal tetrahedral value. Each tetrahedral Ag atom has a pair of long and short Ag—S bonds [Ag2—S2 = 2.7145 (10) Å and Ag2—S1A = 2.5457 (11) Å]; interatomic Ag···S distances longer than 2.80 Å are considered to be non-bonding. The Ag···Ag distance between two adjacent trigonal Ag atoms [2.8336 (7) Å] is shorter than twice the van der Waals radius (1.7 Å) of Ag atoms, indicating a weak Ag···Ag interaction, which is obviously compatible with the Ag···Ag distance in metallic silver [2.889 (6) Å]. The reported Ag···Ag distances where bonding is considered to occur are in the range 2.729–3.065 Å (Kanatzidis & Huang, 1989; Huang et al., 1992; Yam et al., 1996; Zhang et al., 1998). The separation of adjacent trigonal and tetrahedral Ag atoms is 3.463 (6) Å, indicating that these atoms are non-bonded. The C—S bond lengths [1.714 (4)–1.751 (3) Å] are comparable to those in related silver–dithiocarbamate complexes. The C1—N1 and C2—N2 bond lengths are 1.325 (4) and 1.322 (6) Å, respectively, suggesting considerable partial double-bond character because the N-atom lone pair is involved in delocalized π-bonding over the NCS2 group (Eisenberg, 1970).