Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103003445/jz1546sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103003445/jz1546Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270103003445/jz1546sup3.pdf |
CCDC reference: 208002
Compound (I) was obtained from the reaction of [Zn(S2COEt)2] (0.200 g, 0.651 mmol) with AgClPPh3 (0.528 g, 1.302 mmol) in dichloromethane (20 ml) at room temperature. After 30 min, the solid product [a mixture of Ag(S2COEt) and ZnCl2] was filtered off and the filtrate evaporated to dryness. The addition of isopropyl alcohol to the residue gave (I) as a white solid (yield = 66%). Analysis; calculated for C39H35AgOP2S2: C 62.17, N 4.64, S 8.49; found: C 61.90, N 4.54, S 8.59. Single crystals were obtained by slow diffusion of n-hexane into a dichloromethane solution of (I) at room temperature.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP, SHELXTL (Bruker, 2000); software used to prepare material for publication: XCIF, SHELXTL (Bruker, 2000).
Fig. 1. The structure of (I), showing displacement ellipsoids at the 50% probability level and the atom-numbering scheme. H atoms have been omitted for clarity |
[Ag(C3H5OS2)(C18H15P)2] | Z = 2 |
Mr = 753.60 | F(000) = 772 |
Triclinic, P1 | Dx = 1.454 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3302 (6) Å | Cell parameters from 4690 reflections |
b = 12.8582 (7) Å | θ = 2.3–26.4° |
c = 13.8270 (8) Å | µ = 0.83 mm−1 |
α = 87.432 (1)° | T = 100 K |
β = 74.956 (1)° | Prism, pale yellow |
γ = 76.067 (1)° | 0.25 × 0.18 × 0.16 mm |
V = 1721.17 (17) Å3 |
Bruker SMART APEX CCD diffractometer | 6873 independent reflections |
Radiation source: fine-focus sealed tube | 5720 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 8.26 pixels mm-1 | θmax = 26.4°, θmin = 1.5° |
ω–scan | h = −12→12 |
Absorption correction: multi-scan SADABS (Bruker, 1999) | k = −16→10 |
Tmin = 0.819, Tmax = 0.879 | l = −17→17 |
10445 measured reflections |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0289P)2] where P = (Fo2 + 2Fc2)/3 |
6873 reflections | (Δ/σ)max = 0.001 |
406 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
[Ag(C3H5OS2)(C18H15P)2] | γ = 76.067 (1)° |
Mr = 753.60 | V = 1721.17 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.3302 (6) Å | Mo Kα radiation |
b = 12.8582 (7) Å | µ = 0.83 mm−1 |
c = 13.8270 (8) Å | T = 100 K |
α = 87.432 (1)° | 0.25 × 0.18 × 0.16 mm |
β = 74.956 (1)° |
Bruker SMART APEX CCD diffractometer | 6873 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 1999) | 5720 reflections with I > 2σ(I) |
Tmin = 0.819, Tmax = 0.879 | Rint = 0.019 |
10445 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.79 e Å−3 |
6873 reflections | Δρmin = −0.49 e Å−3 |
406 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. 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 | 0.078862 (18) | 0.338615 (16) | 0.258549 (14) | 0.01725 (6) | |
S1 | 0.03573 (6) | 0.19811 (6) | 0.41849 (5) | 0.02165 (16) | |
S2 | −0.16351 (6) | 0.30637 (6) | 0.30286 (5) | 0.02031 (15) | |
P1 | 0.10533 (6) | 0.51915 (5) | 0.27054 (5) | 0.01546 (15) | |
P2 | 0.24930 (6) | 0.20063 (5) | 0.14396 (5) | 0.01576 (15) | |
O1 | −0.21572 (16) | 0.16904 (14) | 0.43733 (13) | 0.0212 (4) | |
C1 | −0.1170 (2) | 0.2192 (2) | 0.39022 (18) | 0.0178 (6) | |
C2 | −0.1904 (3) | 0.0939 (2) | 0.5157 (2) | 0.0273 (7) | |
H2A | −0.1591 | 0.1273 | 0.5658 | 0.033* | |
H2B | −0.1185 | 0.0293 | 0.4869 | 0.033* | |
C3 | −0.3247 (3) | 0.0645 (3) | 0.5636 (2) | 0.0341 (8) | |
H3A | −0.3120 | 0.0132 | 0.6170 | 0.051* | |
H3B | −0.3548 | 0.0320 | 0.5131 | 0.051* | |
H3C | −0.3947 | 0.1291 | 0.5921 | 0.051* | |
C4 | 0.2519 (2) | 0.5257 (2) | 0.31782 (17) | 0.0146 (5) | |
C5 | 0.2519 (3) | 0.6031 (2) | 0.38452 (19) | 0.0199 (6) | |
H5 | 0.1702 | 0.6570 | 0.4103 | 0.024* | |
C6 | 0.3714 (3) | 0.6020 (2) | 0.41364 (19) | 0.0239 (6) | |
H6 | 0.3712 | 0.6547 | 0.4597 | 0.029* | |
C7 | 0.4905 (3) | 0.5240 (2) | 0.37542 (19) | 0.0218 (6) | |
H7 | 0.5725 | 0.5242 | 0.3944 | 0.026* | |
C8 | 0.4908 (3) | 0.4458 (2) | 0.30978 (19) | 0.0216 (6) | |
H8 | 0.5726 | 0.3921 | 0.2839 | 0.026* | |
C9 | 0.3717 (2) | 0.4464 (2) | 0.28219 (18) | 0.0195 (6) | |
H9 | 0.3714 | 0.3918 | 0.2382 | 0.023* | |
C10 | 0.1461 (2) | 0.5772 (2) | 0.14646 (18) | 0.0158 (5) | |
C11 | 0.0471 (3) | 0.5942 (2) | 0.09196 (19) | 0.0209 (6) | |
H11 | −0.0410 | 0.5807 | 0.1217 | 0.025* | |
C12 | 0.0761 (3) | 0.6307 (2) | −0.0056 (2) | 0.0241 (6) | |
H12 | 0.0076 | 0.6426 | −0.0420 | 0.029* | |
C13 | 0.2042 (3) | 0.6498 (2) | −0.05001 (19) | 0.0240 (6) | |
H13 | 0.2240 | 0.6748 | −0.1167 | 0.029* | |
C14 | 0.3034 (3) | 0.6322 (2) | 0.00349 (19) | 0.0224 (6) | |
H14 | 0.3918 | 0.6448 | −0.0269 | 0.027* | |
C15 | 0.2750 (2) | 0.5966 (2) | 0.10063 (18) | 0.0181 (6) | |
H15 | 0.3439 | 0.5852 | 0.1366 | 0.022* | |
C16 | −0.0424 (2) | 0.6188 (2) | 0.34006 (18) | 0.0157 (5) | |
C17 | −0.1461 (2) | 0.5843 (2) | 0.40994 (18) | 0.0208 (6) | |
H17 | −0.1375 | 0.5099 | 0.4220 | 0.025* | |
C18 | −0.2625 (3) | 0.6585 (2) | 0.4621 (2) | 0.0258 (6) | |
H18 | −0.3326 | 0.6348 | 0.5107 | 0.031* | |
C19 | −0.2764 (3) | 0.7658 (2) | 0.4437 (2) | 0.0259 (7) | |
H19 | −0.3570 | 0.8160 | 0.4784 | 0.031* | |
C20 | −0.1730 (3) | 0.8017 (2) | 0.37432 (19) | 0.0239 (6) | |
H20 | −0.1823 | 0.8760 | 0.3618 | 0.029* | |
C21 | −0.0571 (3) | 0.7279 (2) | 0.32404 (19) | 0.0206 (6) | |
H21 | 0.0143 | 0.7521 | 0.2774 | 0.025* | |
C22 | 0.2954 (2) | 0.2296 (2) | 0.01008 (18) | 0.0166 (6) | |
C23 | 0.3112 (3) | 0.1549 (2) | −0.06383 (19) | 0.0217 (6) | |
H23 | 0.2988 | 0.0852 | −0.0457 | 0.026* | |
C24 | 0.3451 (3) | 0.1814 (2) | −0.1643 (2) | 0.0260 (6) | |
H24 | 0.3550 | 0.1299 | −0.2145 | 0.031* | |
C25 | 0.3645 (3) | 0.2819 (2) | −0.1914 (2) | 0.0264 (7) | |
H25 | 0.3876 | 0.2998 | −0.2602 | 0.032* | |
C26 | 0.3501 (3) | 0.3565 (2) | −0.1183 (2) | 0.0252 (6) | |
H26 | 0.3653 | 0.4255 | −0.1369 | 0.030* | |
C27 | 0.3137 (3) | 0.3313 (2) | −0.0179 (2) | 0.0221 (6) | |
H27 | 0.3013 | 0.3838 | 0.0320 | 0.026* | |
C28 | 0.4152 (2) | 0.1666 (2) | 0.17535 (18) | 0.0161 (5) | |
C29 | 0.4172 (3) | 0.1675 (2) | 0.27561 (19) | 0.0224 (6) | |
H29 | 0.3328 | 0.1847 | 0.3261 | 0.027* | |
C30 | 0.5408 (3) | 0.1436 (2) | 0.3024 (2) | 0.0244 (6) | |
H30 | 0.5405 | 0.1438 | 0.3712 | 0.029* | |
C31 | 0.6646 (2) | 0.1194 (2) | 0.23020 (19) | 0.0209 (6) | |
H31 | 0.7493 | 0.1029 | 0.2489 | 0.025* | |
C32 | 0.6641 (2) | 0.1195 (2) | 0.13038 (19) | 0.0201 (6) | |
H32 | 0.7490 | 0.1035 | 0.0803 | 0.024* | |
C33 | 0.5405 (2) | 0.1427 (2) | 0.10282 (19) | 0.0194 (6) | |
H33 | 0.5414 | 0.1423 | 0.0340 | 0.023* | |
C34 | 0.2035 (2) | 0.0723 (2) | 0.14536 (18) | 0.0163 (5) | |
C35 | 0.2907 (3) | −0.0244 (2) | 0.15798 (18) | 0.0193 (6) | |
H35 | 0.3768 | −0.0252 | 0.1709 | 0.023* | |
C36 | 0.2538 (3) | −0.1205 (2) | 0.15195 (19) | 0.0226 (6) | |
H36 | 0.3144 | −0.1865 | 0.1609 | 0.027* | |
C37 | 0.1284 (3) | −0.1197 (2) | 0.13286 (18) | 0.0216 (6) | |
H37 | 0.1041 | −0.1852 | 0.1261 | 0.026* | |
C38 | 0.0391 (3) | −0.0233 (2) | 0.1237 (2) | 0.0235 (6) | |
H38 | −0.0480 | −0.0227 | 0.1124 | 0.028* | |
C39 | 0.0745 (2) | 0.0724 (2) | 0.13063 (19) | 0.0213 (6) | |
H39 | 0.0114 | 0.1383 | 0.1254 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.01452 (10) | 0.01736 (11) | 0.01931 (11) | −0.00492 (8) | −0.00235 (8) | 0.00053 (8) |
S1 | 0.0155 (3) | 0.0302 (4) | 0.0212 (4) | −0.0070 (3) | −0.0077 (3) | 0.0065 (3) |
S2 | 0.0148 (3) | 0.0243 (4) | 0.0233 (4) | −0.0060 (3) | −0.0073 (3) | 0.0072 (3) |
P1 | 0.0133 (3) | 0.0165 (4) | 0.0162 (3) | −0.0041 (3) | −0.0028 (3) | 0.0012 (3) |
P2 | 0.0143 (3) | 0.0163 (4) | 0.0165 (3) | −0.0042 (3) | −0.0031 (3) | 0.0009 (3) |
O1 | 0.0178 (9) | 0.0246 (11) | 0.0231 (10) | −0.0104 (8) | −0.0049 (8) | 0.0076 (8) |
C1 | 0.0159 (12) | 0.0187 (14) | 0.0174 (13) | −0.0042 (11) | −0.0013 (11) | −0.0036 (11) |
C2 | 0.0265 (14) | 0.0290 (17) | 0.0284 (16) | −0.0100 (13) | −0.0096 (13) | 0.0134 (14) |
C3 | 0.0285 (15) | 0.0366 (19) | 0.0364 (18) | −0.0118 (14) | −0.0056 (14) | 0.0163 (15) |
C4 | 0.0137 (11) | 0.0166 (14) | 0.0146 (13) | −0.0063 (11) | −0.0037 (10) | 0.0061 (11) |
C5 | 0.0191 (13) | 0.0194 (15) | 0.0196 (14) | −0.0027 (11) | −0.0040 (11) | 0.0021 (12) |
C6 | 0.0287 (14) | 0.0263 (16) | 0.0214 (14) | −0.0129 (13) | −0.0086 (12) | 0.0004 (12) |
C7 | 0.0184 (13) | 0.0294 (16) | 0.0223 (14) | −0.0114 (12) | −0.0095 (12) | 0.0083 (13) |
C8 | 0.0161 (12) | 0.0256 (16) | 0.0212 (14) | −0.0030 (12) | −0.0036 (11) | 0.0035 (12) |
C9 | 0.0194 (13) | 0.0207 (15) | 0.0182 (14) | −0.0041 (11) | −0.0048 (11) | −0.0003 (12) |
C10 | 0.0164 (12) | 0.0121 (13) | 0.0177 (13) | −0.0027 (10) | −0.0028 (11) | −0.0007 (11) |
C11 | 0.0162 (12) | 0.0233 (15) | 0.0228 (14) | −0.0047 (11) | −0.0043 (11) | −0.0010 (12) |
C12 | 0.0277 (14) | 0.0253 (16) | 0.0225 (15) | −0.0040 (13) | −0.0143 (12) | 0.0002 (12) |
C13 | 0.0327 (15) | 0.0210 (15) | 0.0159 (14) | −0.0049 (13) | −0.0036 (12) | 0.0010 (12) |
C14 | 0.0215 (13) | 0.0214 (15) | 0.0230 (15) | −0.0085 (12) | −0.0004 (12) | 0.0008 (12) |
C15 | 0.0173 (12) | 0.0177 (14) | 0.0193 (14) | −0.0034 (11) | −0.0054 (11) | 0.0006 (11) |
C16 | 0.0139 (12) | 0.0203 (14) | 0.0134 (13) | −0.0044 (11) | −0.0042 (10) | 0.0004 (11) |
C17 | 0.0217 (13) | 0.0227 (15) | 0.0175 (14) | −0.0075 (12) | −0.0018 (11) | −0.0011 (12) |
C18 | 0.0196 (13) | 0.0380 (18) | 0.0194 (14) | −0.0110 (13) | 0.0000 (12) | −0.0012 (13) |
C19 | 0.0174 (13) | 0.0347 (18) | 0.0225 (15) | 0.0022 (13) | −0.0060 (12) | −0.0077 (13) |
C20 | 0.0284 (14) | 0.0200 (15) | 0.0209 (14) | 0.0009 (12) | −0.0084 (12) | 0.0002 (12) |
C21 | 0.0198 (13) | 0.0233 (15) | 0.0176 (14) | −0.0060 (12) | −0.0023 (11) | 0.0015 (12) |
C22 | 0.0117 (11) | 0.0201 (14) | 0.0175 (13) | −0.0026 (11) | −0.0044 (10) | 0.0023 (11) |
C23 | 0.0237 (13) | 0.0204 (15) | 0.0226 (14) | −0.0072 (12) | −0.0069 (12) | 0.0018 (12) |
C24 | 0.0317 (15) | 0.0278 (17) | 0.0177 (14) | −0.0057 (13) | −0.0059 (12) | −0.0028 (13) |
C25 | 0.0266 (14) | 0.0324 (18) | 0.0190 (14) | −0.0055 (13) | −0.0058 (12) | 0.0060 (13) |
C26 | 0.0272 (14) | 0.0210 (15) | 0.0258 (15) | −0.0076 (13) | −0.0035 (13) | 0.0073 (13) |
C27 | 0.0224 (13) | 0.0212 (15) | 0.0219 (14) | −0.0057 (12) | −0.0038 (12) | −0.0007 (12) |
C28 | 0.0171 (12) | 0.0134 (13) | 0.0186 (13) | −0.0052 (11) | −0.0048 (11) | 0.0022 (11) |
C29 | 0.0173 (12) | 0.0274 (16) | 0.0195 (14) | −0.0044 (12) | −0.0009 (11) | 0.0026 (12) |
C30 | 0.0240 (14) | 0.0305 (17) | 0.0204 (14) | −0.0083 (13) | −0.0071 (12) | 0.0012 (13) |
C31 | 0.0162 (12) | 0.0213 (15) | 0.0262 (15) | −0.0049 (11) | −0.0070 (12) | 0.0003 (12) |
C32 | 0.0149 (12) | 0.0208 (15) | 0.0234 (14) | −0.0063 (11) | −0.0012 (11) | 0.0001 (12) |
C33 | 0.0198 (13) | 0.0211 (15) | 0.0177 (14) | −0.0065 (12) | −0.0041 (11) | 0.0000 (12) |
C34 | 0.0162 (12) | 0.0189 (14) | 0.0127 (13) | −0.0068 (11) | 0.0007 (10) | −0.0002 (11) |
C35 | 0.0196 (13) | 0.0212 (15) | 0.0181 (14) | −0.0072 (12) | −0.0047 (11) | 0.0022 (12) |
C36 | 0.0268 (14) | 0.0161 (14) | 0.0220 (15) | −0.0038 (12) | −0.0032 (12) | 0.0039 (12) |
C37 | 0.0274 (14) | 0.0202 (15) | 0.0176 (14) | −0.0129 (12) | 0.0004 (12) | 0.0003 (12) |
C38 | 0.0163 (13) | 0.0276 (16) | 0.0264 (15) | −0.0087 (12) | −0.0022 (12) | 0.0012 (13) |
C39 | 0.0179 (13) | 0.0196 (15) | 0.0254 (15) | −0.0040 (12) | −0.0040 (12) | 0.0000 (12) |
Ag1—P1 | 2.4196 (7) | C16—C17 | 1.390 (3) |
Ag1—P2 | 2.4612 (7) | C17—C18 | 1.391 (4) |
Ag1—S2 | 2.5489 (6) | C17—H17 | 0.9500 |
Ag1—S1 | 2.8055 (7) | C18—C19 | 1.372 (4) |
S1—C1 | 1.680 (2) | C18—H18 | 0.9500 |
S2—C1 | 1.693 (3) | C19—C20 | 1.392 (4) |
P1—C16 | 1.817 (3) | C19—H19 | 0.9500 |
P1—C4 | 1.818 (2) | C20—C21 | 1.378 (3) |
P1—C10 | 1.827 (2) | C20—H20 | 0.9500 |
P2—C34 | 1.820 (3) | C21—H21 | 0.9500 |
P2—C28 | 1.823 (2) | C22—C23 | 1.385 (4) |
P2—C22 | 1.833 (2) | C22—C27 | 1.390 (4) |
O1—C1 | 1.347 (3) | C23—C24 | 1.390 (3) |
O1—C2 | 1.452 (3) | C23—H23 | 0.9500 |
C2—C3 | 1.502 (3) | C24—C25 | 1.375 (4) |
C2—H2A | 0.9900 | C24—H24 | 0.9500 |
C2—H2B | 0.9900 | C25—C26 | 1.381 (4) |
C3—H3A | 0.9800 | C25—H25 | 0.9500 |
C3—H3B | 0.9800 | C26—C27 | 1.386 (3) |
C3—H3C | 0.9800 | C26—H26 | 0.9500 |
C4—C5 | 1.387 (3) | C27—H27 | 0.9500 |
C4—C9 | 1.391 (3) | C28—C33 | 1.392 (3) |
C5—C6 | 1.391 (3) | C28—C29 | 1.393 (3) |
C5—H5 | 0.9500 | C29—C30 | 1.381 (3) |
C6—C7 | 1.383 (4) | C29—H29 | 0.9500 |
C6—H6 | 0.9500 | C30—C31 | 1.379 (3) |
C7—C8 | 1.383 (4) | C30—H30 | 0.9500 |
C7—H7 | 0.9500 | C31—C32 | 1.382 (3) |
C8—C9 | 1.378 (3) | C31—H31 | 0.9500 |
C8—H8 | 0.9500 | C32—C33 | 1.387 (3) |
C9—H9 | 0.9500 | C32—H32 | 0.9500 |
C10—C11 | 1.392 (3) | C33—H33 | 0.9500 |
C10—C15 | 1.396 (3) | C34—C35 | 1.382 (3) |
C11—C12 | 1.390 (3) | C34—C39 | 1.399 (3) |
C11—H11 | 0.9500 | C35—C36 | 1.389 (4) |
C12—C13 | 1.382 (4) | C35—H35 | 0.9500 |
C12—H12 | 0.9500 | C36—C37 | 1.385 (3) |
C13—C14 | 1.384 (3) | C36—H36 | 0.9500 |
C13—H13 | 0.9500 | C37—C38 | 1.379 (4) |
C14—C15 | 1.380 (3) | C37—H37 | 0.9500 |
C14—H14 | 0.9500 | C38—C39 | 1.379 (4) |
C15—H15 | 0.9500 | C38—H38 | 0.9500 |
C16—C21 | 1.387 (4) | C39—H39 | 0.9500 |
P1—Ag1—P2 | 123.04 (2) | C21—C16—C17 | 118.9 (2) |
P1—Ag1—S2 | 118.85 (2) | C21—C16—P1 | 122.41 (19) |
P2—Ag1—S2 | 113.08 (2) | C17—C16—P1 | 118.7 (2) |
P1—Ag1—S1 | 125.71 (2) | C16—C17—C18 | 120.1 (3) |
P2—Ag1—S1 | 94.25 (2) | C16—C17—H17 | 120.0 |
S2—Ag1—S1 | 67.345 (19) | C18—C17—H17 | 120.0 |
C1—S1—Ag1 | 80.29 (9) | C19—C18—C17 | 120.1 (2) |
C1—S2—Ag1 | 88.26 (9) | C19—C18—H18 | 119.9 |
C16—P1—C4 | 107.20 (11) | C17—C18—H18 | 119.9 |
C16—P1—C10 | 103.25 (11) | C18—C19—C20 | 120.4 (3) |
C4—P1—C10 | 102.67 (11) | C18—C19—H19 | 119.8 |
C16—P1—Ag1 | 117.95 (8) | C20—C19—H19 | 119.8 |
C4—P1—Ag1 | 113.43 (8) | C21—C20—C19 | 119.1 (3) |
C10—P1—Ag1 | 110.80 (8) | C21—C20—H20 | 120.5 |
C34—P2—C28 | 103.73 (11) | C19—C20—H20 | 120.5 |
C34—P2—C22 | 102.82 (12) | C20—C21—C16 | 121.4 (2) |
C28—P2—C22 | 103.39 (11) | C20—C21—H21 | 119.3 |
C34—P2—Ag1 | 114.89 (8) | C16—C21—H21 | 119.3 |
C28—P2—Ag1 | 111.97 (8) | C23—C22—C27 | 118.9 (2) |
C22—P2—Ag1 | 118.37 (8) | C23—C22—P2 | 122.8 (2) |
C1—O1—C2 | 119.32 (19) | C27—C22—P2 | 118.3 (2) |
O1—C1—S1 | 122.45 (18) | C22—C23—C24 | 120.4 (3) |
O1—C1—S2 | 113.66 (17) | C22—C23—H23 | 119.8 |
S1—C1—S2 | 123.87 (15) | C24—C23—H23 | 119.8 |
O1—C2—C3 | 106.7 (2) | C25—C24—C23 | 120.3 (3) |
O1—C2—H2A | 110.4 | C25—C24—H24 | 119.9 |
C3—C2—H2A | 110.4 | C23—C24—H24 | 119.9 |
O1—C2—H2B | 110.4 | C24—C25—C26 | 119.7 (2) |
C3—C2—H2B | 110.4 | C24—C25—H25 | 120.2 |
H2A—C2—H2B | 108.6 | C26—C25—H25 | 120.2 |
C2—C3—H3A | 109.5 | C25—C26—C27 | 120.3 (3) |
C2—C3—H3B | 109.5 | C25—C26—H26 | 119.8 |
H3A—C3—H3B | 109.5 | C27—C26—H26 | 119.8 |
C2—C3—H3C | 109.5 | C26—C27—C22 | 120.3 (3) |
H3A—C3—H3C | 109.5 | C26—C27—H27 | 119.8 |
H3B—C3—H3C | 109.5 | C22—C27—H27 | 119.8 |
C5—C4—C9 | 119.2 (2) | C33—C28—C29 | 118.4 (2) |
C5—C4—P1 | 124.95 (19) | C33—C28—P2 | 122.61 (19) |
C9—C4—P1 | 115.87 (19) | C29—C28—P2 | 118.93 (19) |
C4—C5—C6 | 120.0 (2) | C30—C29—C28 | 120.7 (2) |
C4—C5—H5 | 120.0 | C30—C29—H29 | 119.6 |
C6—C5—H5 | 120.0 | C28—C29—H29 | 119.6 |
C7—C6—C5 | 119.9 (3) | C31—C30—C29 | 120.5 (2) |
C7—C6—H6 | 120.0 | C31—C30—H30 | 119.7 |
C5—C6—H6 | 120.0 | C29—C30—H30 | 119.7 |
C8—C7—C6 | 120.4 (2) | C30—C31—C32 | 119.4 (2) |
C8—C7—H7 | 119.8 | C30—C31—H31 | 120.3 |
C6—C7—H7 | 119.8 | C32—C31—H31 | 120.3 |
C9—C8—C7 | 119.5 (2) | C31—C32—C33 | 120.5 (2) |
C9—C8—H8 | 120.2 | C31—C32—H32 | 119.8 |
C7—C8—H8 | 120.2 | C33—C32—H32 | 119.8 |
C8—C9—C4 | 121.0 (2) | C32—C33—C28 | 120.5 (2) |
C8—C9—H9 | 119.5 | C32—C33—H33 | 119.8 |
C4—C9—H9 | 119.5 | C28—C33—H33 | 119.8 |
C11—C10—C15 | 118.5 (2) | C35—C34—C39 | 118.8 (2) |
C11—C10—P1 | 118.03 (18) | C35—C34—P2 | 123.35 (19) |
C15—C10—P1 | 123.19 (18) | C39—C34—P2 | 117.80 (19) |
C12—C11—C10 | 120.6 (2) | C34—C35—C36 | 120.8 (2) |
C12—C11—H11 | 119.7 | C34—C35—H35 | 119.6 |
C10—C11—H11 | 119.7 | C36—C35—H35 | 119.6 |
C13—C12—C11 | 120.3 (2) | C37—C36—C35 | 119.8 (2) |
C13—C12—H12 | 119.9 | C37—C36—H36 | 120.1 |
C11—C12—H12 | 119.9 | C35—C36—H36 | 120.1 |
C12—C13—C14 | 119.5 (2) | C38—C37—C36 | 119.6 (3) |
C12—C13—H13 | 120.3 | C38—C37—H37 | 120.2 |
C14—C13—H13 | 120.3 | C36—C37—H37 | 120.2 |
C15—C14—C13 | 120.6 (2) | C39—C38—C37 | 120.8 (2) |
C15—C14—H14 | 119.7 | C39—C38—H38 | 119.6 |
C13—C14—H14 | 119.7 | C37—C38—H38 | 119.6 |
C14—C15—C10 | 120.6 (2) | C38—C39—C34 | 120.0 (2) |
C14—C15—H15 | 119.7 | C38—C39—H39 | 120.0 |
C10—C15—H15 | 119.7 | C34—C39—H39 | 120.0 |
P1—Ag1—S1—C1 | 112.92 (9) | P1—C10—C15—C14 | 174.6 (2) |
P2—Ag1—S1—C1 | −110.46 (9) | C4—P1—C16—C21 | 73.5 (2) |
S2—Ag1—S1—C1 | 2.80 (9) | C10—P1—C16—C21 | −34.5 (2) |
P1—Ag1—S2—C1 | −122.23 (9) | Ag1—P1—C16—C21 | −157.06 (18) |
P2—Ag1—S2—C1 | 82.07 (9) | C4—P1—C16—C17 | −108.3 (2) |
S1—Ag1—S2—C1 | −2.74 (9) | C10—P1—C16—C17 | 143.7 (2) |
P2—Ag1—P1—C16 | 168.55 (9) | Ag1—P1—C16—C17 | 21.2 (2) |
S2—Ag1—P1—C16 | 15.40 (9) | C21—C16—C17—C18 | 0.3 (4) |
S1—Ag1—P1—C16 | −66.23 (9) | P1—C16—C17—C18 | −178.02 (19) |
P2—Ag1—P1—C4 | −64.95 (9) | C16—C17—C18—C19 | 1.1 (4) |
S2—Ag1—P1—C4 | 141.90 (8) | C17—C18—C19—C20 | −1.5 (4) |
S1—Ag1—P1—C4 | 60.27 (9) | C18—C19—C20—C21 | 0.4 (4) |
P2—Ag1—P1—C10 | 49.92 (9) | C19—C20—C21—C16 | 1.0 (4) |
S2—Ag1—P1—C10 | −103.24 (8) | C17—C16—C21—C20 | −1.3 (4) |
S1—Ag1—P1—C10 | 175.13 (8) | P1—C16—C21—C20 | 176.93 (19) |
P1—Ag1—P2—C34 | −177.95 (9) | C34—P2—C22—C23 | −10.1 (2) |
S2—Ag1—P2—C34 | −23.41 (9) | C28—P2—C22—C23 | 97.6 (2) |
S1—Ag1—P2—C34 | 43.75 (9) | Ag1—P2—C22—C23 | −137.93 (18) |
P1—Ag1—P2—C28 | 64.07 (9) | C34—P2—C22—C27 | 169.28 (19) |
S2—Ag1—P2—C28 | −141.40 (8) | C28—P2—C22—C27 | −83.0 (2) |
S1—Ag1—P2—C28 | −74.24 (9) | Ag1—P2—C22—C27 | 41.4 (2) |
P1—Ag1—P2—C22 | −56.04 (10) | C27—C22—C23—C24 | 0.1 (4) |
S2—Ag1—P2—C22 | 98.50 (9) | P2—C22—C23—C24 | 179.46 (19) |
S1—Ag1—P2—C22 | 165.66 (9) | C22—C23—C24—C25 | 0.6 (4) |
C2—O1—C1—S1 | 0.1 (3) | C23—C24—C25—C26 | 0.0 (4) |
C2—O1—C1—S2 | −178.61 (19) | C24—C25—C26—C27 | −1.3 (4) |
Ag1—S1—C1—O1 | 176.8 (2) | C25—C26—C27—C22 | 1.9 (4) |
Ag1—S1—C1—S2 | −4.69 (15) | C23—C22—C27—C26 | −1.3 (4) |
Ag1—S2—C1—O1 | −176.26 (18) | P2—C22—C27—C26 | 179.27 (19) |
Ag1—S2—C1—S1 | 5.09 (16) | C34—P2—C28—C33 | 92.1 (2) |
C1—O1—C2—C3 | 171.7 (2) | C22—P2—C28—C33 | −14.9 (2) |
C16—P1—C4—C5 | −8.0 (2) | Ag1—P2—C28—C33 | −143.4 (2) |
C10—P1—C4—C5 | 100.4 (2) | C34—P2—C28—C29 | −89.8 (2) |
Ag1—P1—C4—C5 | −140.01 (19) | C22—P2—C28—C29 | 163.1 (2) |
C16—P1—C4—C9 | 172.58 (18) | Ag1—P2—C28—C29 | 34.6 (2) |
C10—P1—C4—C9 | −79.0 (2) | C33—C28—C29—C30 | −1.0 (4) |
Ag1—P1—C4—C9 | 40.6 (2) | P2—C28—C29—C30 | −179.1 (2) |
C9—C4—C5—C6 | 1.1 (4) | C28—C29—C30—C31 | 0.6 (4) |
P1—C4—C5—C6 | −178.27 (19) | C29—C30—C31—C32 | 0.1 (4) |
C4—C5—C6—C7 | 0.5 (4) | C30—C31—C32—C33 | −0.5 (4) |
C5—C6—C7—C8 | −1.2 (4) | C31—C32—C33—C28 | 0.2 (4) |
C6—C7—C8—C9 | 0.3 (4) | C29—C28—C33—C32 | 0.6 (4) |
C7—C8—C9—C4 | 1.3 (4) | P2—C28—C33—C32 | 178.6 (2) |
C5—C4—C9—C8 | −2.0 (4) | C28—P2—C34—C35 | −5.8 (2) |
P1—C4—C9—C8 | 177.41 (19) | C22—P2—C34—C35 | 101.6 (2) |
C16—P1—C10—C11 | −62.6 (2) | Ag1—P2—C34—C35 | −128.4 (2) |
C4—P1—C10—C11 | −173.9 (2) | C28—P2—C34—C39 | 175.62 (19) |
Ag1—P1—C10—C11 | 64.7 (2) | C22—P2—C34—C39 | −76.9 (2) |
C16—P1—C10—C15 | 123.0 (2) | Ag1—P2—C34—C39 | 53.1 (2) |
C4—P1—C10—C15 | 11.7 (2) | C39—C34—C35—C36 | 2.7 (4) |
Ag1—P1—C10—C15 | −109.8 (2) | P2—C34—C35—C36 | −175.81 (19) |
C15—C10—C11—C12 | −0.6 (4) | C34—C35—C36—C37 | 0.1 (4) |
P1—C10—C11—C12 | −175.3 (2) | C35—C36—C37—C38 | −2.4 (4) |
C10—C11—C12—C13 | 0.5 (4) | C36—C37—C38—C39 | 1.7 (4) |
C11—C12—C13—C14 | 0.0 (4) | C37—C38—C39—C34 | 1.2 (4) |
C12—C13—C14—C15 | −0.4 (4) | C35—C34—C39—C38 | −3.4 (4) |
C13—C14—C15—C10 | 0.3 (4) | P2—C34—C39—C38 | 175.2 (2) |
C11—C10—C15—C14 | 0.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···S2i | 0.95 | 2.76 | 3.568 (3) | 144 |
C13—H13···S2ii | 0.95 | 2.79 | 3.632 (3) | 148 |
C31—H31···S2i | 0.95 | 3.14 | 3.625 (3) | 113 |
C5—H5···S1iii | 0.95 | 3.08 | 3.943 (3) | 152 |
C2—H2A···S1 | 0.99 | 2.76 | 2.963 (3) | 92 |
C29—H29···S1 | 0.95 | 2.97 | 3.856 (3) | 156 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C3H5OS2)(C18H15P)2] |
Mr | 753.60 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 10.3302 (6), 12.8582 (7), 13.8270 (8) |
α, β, γ (°) | 87.432 (1), 74.956 (1), 76.067 (1) |
V (Å3) | 1721.17 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.25 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan SADABS (Bruker, 1999) |
Tmin, Tmax | 0.819, 0.879 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10445, 6873, 5720 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.067, 0.94 |
No. of reflections | 6873 |
No. of parameters | 406 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −0.49 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP, SHELXTL (Bruker, 2000), XCIF, SHELXTL (Bruker, 2000).
Ag1—P1 | 2.4196 (7) | S1—C1 | 1.680 (2) |
Ag1—P2 | 2.4612 (7) | S2—C1 | 1.693 (3) |
Ag1—S2 | 2.5489 (6) | O1—C1 | 1.347 (3) |
Ag1—S1 | 2.8055 (7) | ||
P1—Ag1—P2 | 123.04 (2) | C1—S1—Ag1 | 80.29 (9) |
P1—Ag1—S2 | 118.85 (2) | C1—S2—Ag1 | 88.26 (9) |
P2—Ag1—S2 | 113.08 (2) | O1—C1—S1 | 122.45 (18) |
P1—Ag1—S1 | 125.71 (2) | O1—C1—S2 | 113.66 (17) |
P2—Ag1—S1 | 94.25 (2) | S1—C1—S2 | 123.87 (15) |
S2—Ag1—S1 | 67.345 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···S2i | 0.95 | 2.76 | 3.568 (3) | 143.5 |
C13—H13···S2ii | 0.95 | 2.79 | 3.632 (3) | 148.2 |
C2—H2A···S1 | 0.99 | 2.76 | 2.963 (3) | 91.9 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z. |
In chemistry, the term polymorphism refers to the existence of more than one crystal structure for a chemical substance. In recent years, there has been a growing interest in the preparation and study of polymorphs, not only because they are an intrinsically interesting phenomenon that involve diverse scientific branches (mineralogy, material science, supramolecular chemistry, thermodynamics), but also because polymorphism has become a major issue in the pharmaceutical, optoelectronic, and dyes and pigments industries.
The addition of various ligands to suspensions of polymeric metal xanthates (dithiocarbonates) often results in the formation of monomeric adducts of different stoichiometries and structures. For instance, [Cu(S2COEt)(PPh3)2] is tetracoordinated, with a chelating xanthate ligand (Bianchini et al., 1985); [Hg(S2COEt)2(PPh3)] is five-coordinated (Watanabe, 1981); and the linear system [Au(S2COMe)(PPh3)] features a monodentate mode of coordination for the xanthate ligand (Tiekink, 1985). Complex [Ag(S2COEt)(PPh3)2] was first prepared by the addition of PPh3 to a suspension of Ag(S2COEt) (Kowala & Swan, 1966), although the crystal structure was determined later (Tiekink, 1988). The complex crystallizes in the orthorhombic system, with the Ag atom in a distorted tetrahedral environment formed by two S atoms derived from the chelating S2COEt ligand and by two PPh3 groups, as in [Cu(S2COEt)(PPh3)2] (Bianchini et al., 1985). The Ag—P distances [2.4193 (6) and 2.4614 (6) Å] are very similar and lie in the range expected for Ag-PPh3 bonds (2.363–2.529 Å). The two Ag—S distances are also similar [2.686 (4) and 2.601 (4) Å], although they are a little longer than the distances found in other comparable Ag coordination compounds (Müller et al., 1979). Planes S1—Ag1—S2 and P1—Ag1—P2 are almost perpendicular (89.81 °).
We report here a new polymorph of [Ag(S2COEt)(PPh3)2], (I), that crystallizes in the triclinic system. Compound (I) has the same general molecular shape as the orthorhombic polymorph, i.e. the Ag atom has a distorted tetrahedral environment, the distortion being due in part to the restricted bite angle of the chelating xanthate ligand [67.345 (19) °]. The Ag—P distances (Table 1) are comparable in both cases. The main difference between the two polymorphs is that (I) features an asymmetrically chelating xanthate ligand, with Ag—S distances of 2.5489 (6) and 2.8055 (7) Å. The latter is a very long Ag—S bond, although similar values have been found in other complexes (Drew et al., 1987). This difference cannot be attibuted to packing forces. The bite distance of the xanthate is 2.9764 (9) Å. The angle between planes S1—Ag1—S2 and P1—Ag1—P2 is 75.55 (2) °. Thus, the coordination sphere of the Ag atom in (I) is highly irregular, with a wide variation in bond lengths and angles. There are also some differences in the orientation of the phenyl groups between the two forms. The dihedral angles between the planes of the phenyl rings bonded to P1 and P2 and the plane P1—Ag1—P2 are 86.96 (6), 54.51 (6), 20.76 (8), 53.84 (5), 79.96 (6) and 47.38 (6)°, respectively, in (I). These angles are 69.39, 79.38, 38.47, 31.08, 59.22 and 74.79° for the orthorhombic polymorph.
There is no clear evidence of intermolecular hydrogen bonding; the shortest potential hydrogen-bond interaction involves atoms C8 and S2 at a separation of 3.568 (3) Å, with the corresponding H···S distance being 2.76 Å. This contact could be considered as a weak electrostatic interaction, since the separation is some 0.3 Å shorter than the sum of the Van der Waals radii for H (1.2 Å) and S (1.85 Å) (Whuler et al., 1980). In addition there is a weak intramolecular interaction S1···H2A of 2.76 Å that may be associated with the long distance Ag1—S1.