Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030218/lh2438sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030218/lh2438Isup2.hkl |
CCDC reference: 654818
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.006 Å
- Disorder in solvent or counterion
- R factor = 0.028
- wR factor = 0.068
- Data-to-parameter ratio = 20.3
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT431_ALERT_2_A Short Inter HL..A Contact Cl .. Cl .. 2.81 Ang.
Author Response: This is a consequence of imperfectly modelled disorder, as described in the paper. |
PLAT432_ALERT_2_A Short Inter X...Y Contact C55 .. C55 .. 2.42 Ang.
Author Response: These two atoms are alternative disorder sites, so the short distance is an artefact and not genuine. |
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.61 Ratio PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 67.00 Perc.
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
This compound is an unexpected product in the attempted preparation of [WS4Ag(PPh3)IZn(Diap)2] (Diap = 1,3-diazepane-2-thione). An aqueous solution of (Diap)2Zn(OAc)2.H2O (0.05 mmol, 0.023 g) was added to an aqueous solution of (NH4)2[WS4] (0.05 mmol, 0.017 g) in a total volume of 5 ml of water and the mixture was stirred for 2 min. The yellow precipitate was separated by centrifugation and washed with EtOH (2 × 5 ml) and Et2O (2 × 5 ml). The yellow product, which is soluble in all common organic solvents, was dissolved in CH2Cl2 (10 ml) and solid AgI (0.05 mmol, 0.011 g) and PPh3 (0.05 mmol, 0.013 g) were added. The mixture was stirred for 30 min and then filtered. The filtrate was evaporated under vacuum. The residue was washed with diethyl ether (2 × 5 ml) and dried in vacuo to give a yellow powder. Single crystals were obtained by slow diffusion of diethyl ether into an acetone solution of the complex. On leaving the solution to stand in a refrigerator overnight, air-stable yellow crystals were deposited.
The FT—IR spectrum in the range 4000–400 cm-1 shows all the expected strong phosphine bands, which remain practically unshifted from those of the uncomplexed ligand. The spectrum also displays a doublet at 419.4 and 438.8 cm-1, which is attributed to ν(W—µ3-S) vibrations. A strong band at 510 cm-1 is due to the δ(C—H) vibrations of the PPh3 ligands It is difficult to identify features due to the W—S(terminal) and Ag—P absorptions, because the PPh3 ligands give rise to a strong band in the same positions as expected for these features. The electronic absorption spectrum of the complex in DMF solution appears to be mainly of intraligand character, presenting two broad bands with maxima at 291 and 401.5 nm. These absorptions can be assigned as charge-transfer bands of the type (π)S→ (d)W arising from the WS4 group; these are red-shifted compared to the free [WS4]2- anion.
Hydrogen atoms were positioned geometrically and refined with a riding model, with C—H = 0.95 or 0.99 Å and with Uiso = 1.2Ueq(C). The dichloromethane solvent molecule is disordered equally over two positions close to an inversion centre, sharing the Cl atom sites; no restraints were used, and the anisotropic displacement parameters indicate that the disorder is actually more complicated. The largest residual electron density peaks are close to W and Cl atoms.
The title complex was obtained as an unexpected decomposition product in an attempt to prepare a WS4/Ag/Zn mixed-metal complex containing phosphine and heterocyclic thione ligands. It features a pseudo-cubane WS3Ag3I core with a typical geometry involving wide angles at the metal corners and narrow angles at the S and I atoms, giving short W···Ag distances [2.9737 (5)–3.0310 (8) Å] that do not represent formal direct metal-metal bonds.
The W atom has an almost regular tetrahedral coordination geometry, with the terminal W?S bond significantly shorter than the bonds to triply-bridging S atoms. The coordination of the Ag atoms is rather distorted tetrahedral, with the smallest angle in each case between the two Ag—S bonds and the largest angles between Ag—S and Ag—P bonds, as a consequence of the steric demands of the triphenylphosphine ligands.
Very similar structures have been found for related complexes in which one or more of the following substitutions are made: Mo for W, O for the terminal S, Cl or Br for I, pyridyl for one of the phenyl rings on each phosphine ligand (Jin et al., 1999, 2000; Sakane et al., 1996; Wang et al., 2003; Lang et al., 1992, 1993; Zhu et al., 1992; Wu et al., 1992). Some of these are actually isomorphous and probably isostructural with the title complex, although the solvent is water rather than dichloromethane in one case, but coordinates are not available for all of the structures.
For similar structures, see: Jin et al. (1999, 2000); Sakane et al. (1996); Wang et al. (2003); Lang et al. (1992, 1993); Zhu et al. (1992); Wu et al. (1992).
Data collection: COLLECT (Nonius, 1998); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD; program(s) used to solve structure: SHELXTL (Sheldrick, 2005); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Fig. 1. The molecular structure with atom labels and 40% probability ellipsoids for non-H atoms. H atoms and the solvent molecule have been omitted. |
[WAg3IS4(C18H15P)3]·0.45CH2Cl2 | Z = 2 |
Mr = 1587.63 | F(000) = 1530 |
Triclinic, P1 | Dx = 1.894 Mg m−3 |
a = 12.113 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.3231 (14) Å | Cell parameters from 643 reflections |
c = 20.0301 (14) Å | θ = 2.5–27.5° |
α = 74.671 (8)° | µ = 3.97 mm−1 |
β = 87.659 (11)° | T = 150 K |
γ = 63.692 (10)° | Block, yellow |
V = 2783.7 (8) Å3 | 0.37 × 0.22 × 0.18 mm |
Nonius KappaCCD diffractometer | 12444 independent reflections |
Radiation source: fine-focus sealed tube | 10245 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
φ and ω scans | θmax = 27.5°, θmin = 4.4° |
Absorption correction: numerical (SHELXTL; Sheldrick, 2005) | h = −15→15 |
Tmin = 0.321, Tmax = 0.545 | k = −16→17 |
38642 measured reflections | l = −25→26 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0275P)2 + 1.8123P] where P = (Fo2 + 2Fc2)/3 |
12444 reflections | (Δ/σ)max = 0.001 |
614 parameters | Δρmax = 1.21 e Å−3 |
0 restraints | Δρmin = −0.98 e Å−3 |
[WAg3IS4(C18H15P)3]·0.45CH2Cl2 | γ = 63.692 (10)° |
Mr = 1587.63 | V = 2783.7 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.113 (3) Å | Mo Kα radiation |
b = 13.3231 (14) Å | µ = 3.97 mm−1 |
c = 20.0301 (14) Å | T = 150 K |
α = 74.671 (8)° | 0.37 × 0.22 × 0.18 mm |
β = 87.659 (11)° |
Nonius KappaCCD diffractometer | 12444 independent reflections |
Absorption correction: numerical (SHELXTL; Sheldrick, 2005) | 10245 reflections with I > 2σ(I) |
Tmin = 0.321, Tmax = 0.545 | Rint = 0.049 |
38642 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.21 e Å−3 |
12444 reflections | Δρmin = −0.98 e Å−3 |
614 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
W | 0.105460 (12) | 0.535347 (11) | 0.148656 (7) | 0.01491 (4) | |
Ag1 | 0.25207 (3) | 0.58341 (3) | 0.240876 (15) | 0.02614 (7) | |
Ag2 | 0.17124 (3) | 0.35043 (2) | 0.282604 (15) | 0.03036 (8) | |
Ag3 | 0.37164 (3) | 0.35425 (2) | 0.156496 (17) | 0.02844 (7) | |
S1 | 0.04814 (8) | 0.57272 (8) | 0.25178 (5) | 0.01983 (18) | |
S2 | 0.16114 (9) | 0.34801 (8) | 0.15507 (5) | 0.02232 (19) | |
S3 | 0.25794 (8) | 0.58312 (7) | 0.11261 (5) | 0.01902 (18) | |
S4 | −0.05180 (9) | 0.63984 (9) | 0.07374 (5) | 0.0313 (2) | |
I | 0.43103 (2) | 0.326826 (19) | 0.307325 (12) | 0.02289 (6) | |
P1 | 0.32368 (8) | 0.68707 (8) | 0.29432 (5) | 0.01763 (19) | |
C1 | 0.3168 (3) | 0.6609 (3) | 0.38846 (19) | 0.0203 (7) | |
C2 | 0.3521 (3) | 0.5466 (3) | 0.42839 (19) | 0.0242 (8) | |
H2 | 0.3747 | 0.4864 | 0.4061 | 0.029* | |
C3 | 0.3546 (4) | 0.5203 (3) | 0.5001 (2) | 0.0300 (9) | |
H3 | 0.3802 | 0.4419 | 0.5266 | 0.036* | |
C4 | 0.3204 (4) | 0.6067 (4) | 0.5335 (2) | 0.0315 (9) | |
H4 | 0.3211 | 0.5884 | 0.5827 | 0.038* | |
C5 | 0.2849 (4) | 0.7202 (4) | 0.4944 (2) | 0.0335 (10) | |
H5 | 0.2612 | 0.7803 | 0.5169 | 0.040* | |
C6 | 0.2836 (4) | 0.7473 (3) | 0.4220 (2) | 0.0268 (8) | |
H6 | 0.2599 | 0.8255 | 0.3957 | 0.032* | |
C7 | 0.2375 (3) | 0.8447 (3) | 0.26030 (19) | 0.0227 (8) | |
C8 | 0.1089 (4) | 0.8910 (4) | 0.2542 (2) | 0.0358 (10) | |
H8 | 0.0708 | 0.8406 | 0.2657 | 0.043* | |
C9 | 0.0363 (4) | 1.0109 (4) | 0.2313 (2) | 0.0454 (12) | |
H9 | −0.0513 | 1.0423 | 0.2284 | 0.054* | |
C10 | 0.0915 (5) | 1.0837 (4) | 0.2129 (2) | 0.0433 (12) | |
H10 | 0.0419 | 1.1657 | 0.1978 | 0.052* | |
C11 | 0.2174 (5) | 1.0387 (3) | 0.2161 (2) | 0.0400 (11) | |
H11 | 0.2547 | 1.0895 | 0.2018 | 0.048* | |
C12 | 0.2914 (4) | 0.9193 (3) | 0.2400 (2) | 0.0299 (9) | |
H12 | 0.3789 | 0.8889 | 0.2424 | 0.036* | |
C13 | 0.4860 (3) | 0.6514 (3) | 0.28289 (18) | 0.0183 (7) | |
C14 | 0.5505 (4) | 0.6868 (3) | 0.32088 (19) | 0.0252 (8) | |
H14 | 0.5108 | 0.7261 | 0.3547 | 0.030* | |
C15 | 0.6706 (4) | 0.6648 (4) | 0.3094 (2) | 0.0336 (10) | |
H15 | 0.7132 | 0.6908 | 0.3341 | 0.040* | |
C16 | 0.7295 (4) | 0.6042 (4) | 0.2612 (2) | 0.0398 (11) | |
H16 | 0.8124 | 0.5893 | 0.2530 | 0.048* | |
C17 | 0.6687 (4) | 0.5656 (4) | 0.2255 (2) | 0.0361 (10) | |
H17 | 0.7103 | 0.5227 | 0.1935 | 0.043* | |
C18 | 0.5467 (3) | 0.5893 (3) | 0.2362 (2) | 0.0270 (8) | |
H18 | 0.5047 | 0.5628 | 0.2114 | 0.032* | |
P2 | 0.14681 (9) | 0.22050 (8) | 0.38378 (5) | 0.02021 (19) | |
C19 | 0.1090 (3) | 0.2784 (3) | 0.45942 (18) | 0.0209 (8) | |
C20 | 0.1687 (3) | 0.3413 (3) | 0.47205 (19) | 0.0242 (8) | |
H20 | 0.2253 | 0.3547 | 0.4410 | 0.029* | |
C21 | 0.1456 (4) | 0.3843 (3) | 0.5299 (2) | 0.0290 (9) | |
H21 | 0.1859 | 0.4275 | 0.5381 | 0.035* | |
C22 | 0.0646 (4) | 0.3645 (3) | 0.5754 (2) | 0.0294 (9) | |
H22 | 0.0499 | 0.3934 | 0.6151 | 0.035* | |
C23 | 0.0042 (4) | 0.3028 (3) | 0.5636 (2) | 0.0306 (9) | |
H23 | −0.0519 | 0.2896 | 0.5950 | 0.037* | |
C24 | 0.0260 (4) | 0.2599 (3) | 0.5053 (2) | 0.0272 (8) | |
H24 | −0.0159 | 0.2180 | 0.4970 | 0.033* | |
C25 | 0.0217 (3) | 0.1831 (3) | 0.37216 (18) | 0.0208 (8) | |
C26 | −0.0861 (4) | 0.2707 (3) | 0.3318 (2) | 0.0302 (9) | |
H26 | −0.0904 | 0.3449 | 0.3095 | 0.036* | |
C27 | −0.1862 (4) | 0.2500 (4) | 0.3242 (2) | 0.0349 (10) | |
H27 | −0.2592 | 0.3101 | 0.2969 | 0.042* | |
C28 | −0.1806 (4) | 0.1417 (4) | 0.3563 (2) | 0.0331 (10) | |
H28 | −0.2500 | 0.1278 | 0.3515 | 0.040* | |
C29 | −0.0741 (4) | 0.0546 (4) | 0.3949 (2) | 0.0336 (10) | |
H29 | −0.0697 | −0.0200 | 0.4160 | 0.040* | |
C30 | 0.0277 (4) | 0.0744 (3) | 0.4037 (2) | 0.0263 (8) | |
H30 | 0.1004 | 0.0139 | 0.4310 | 0.032* | |
C31 | 0.2853 (3) | 0.0832 (3) | 0.4146 (2) | 0.0222 (8) | |
C32 | 0.3116 (4) | 0.0162 (3) | 0.4846 (2) | 0.0302 (9) | |
H32 | 0.2557 | 0.0424 | 0.5179 | 0.036* | |
C33 | 0.4182 (4) | −0.0872 (4) | 0.5048 (2) | 0.0388 (11) | |
H33 | 0.4352 | −0.1327 | 0.5519 | 0.047* | |
C34 | 0.4995 (4) | −0.1242 (4) | 0.4570 (3) | 0.0440 (12) | |
H34 | 0.5724 | −0.1959 | 0.4713 | 0.053* | |
C35 | 0.4775 (4) | −0.0600 (4) | 0.3889 (3) | 0.0406 (11) | |
H35 | 0.5354 | −0.0868 | 0.3565 | 0.049* | |
C36 | 0.3702 (4) | 0.0449 (3) | 0.3669 (2) | 0.0289 (9) | |
H36 | 0.3551 | 0.0899 | 0.3198 | 0.035* | |
P3 | 0.55628 (8) | 0.23800 (8) | 0.10917 (5) | 0.02003 (19) | |
C37 | 0.6526 (3) | 0.0897 (3) | 0.16250 (19) | 0.0194 (7) | |
C38 | 0.6651 (4) | 0.0684 (3) | 0.2341 (2) | 0.0330 (10) | |
H38 | 0.6211 | 0.1305 | 0.2544 | 0.040* | |
C39 | 0.7405 (4) | −0.0420 (3) | 0.2768 (2) | 0.0363 (10) | |
H39 | 0.7479 | −0.0551 | 0.3258 | 0.044* | |
C40 | 0.8041 (4) | −0.1317 (3) | 0.2475 (2) | 0.0289 (9) | |
H40 | 0.8568 | −0.2070 | 0.2763 | 0.035* | |
C41 | 0.7920 (4) | −0.1133 (3) | 0.1771 (2) | 0.0432 (12) | |
H41 | 0.8357 | −0.1761 | 0.1573 | 0.052* | |
C42 | 0.7158 (4) | −0.0028 (3) | 0.1343 (2) | 0.0387 (11) | |
H42 | 0.7072 | 0.0091 | 0.0855 | 0.046* | |
C43 | 0.5242 (3) | 0.2135 (3) | 0.02780 (19) | 0.0227 (8) | |
C44 | 0.4232 (4) | 0.1924 (3) | 0.0225 (2) | 0.0329 (9) | |
H44 | 0.3703 | 0.1959 | 0.0591 | 0.039* | |
C45 | 0.3990 (4) | 0.1662 (4) | −0.0364 (3) | 0.0433 (11) | |
H45 | 0.3303 | 0.1508 | −0.0398 | 0.052* | |
C46 | 0.4756 (5) | 0.1626 (4) | −0.0901 (3) | 0.0478 (12) | |
H46 | 0.4595 | 0.1440 | −0.1301 | 0.057* | |
C47 | 0.5745 (5) | 0.1857 (4) | −0.0858 (2) | 0.0435 (11) | |
H47 | 0.6257 | 0.1843 | −0.1231 | 0.052* | |
C48 | 0.5998 (4) | 0.2113 (3) | −0.0268 (2) | 0.0307 (9) | |
H48 | 0.6683 | 0.2271 | −0.0237 | 0.037* | |
C49 | 0.6616 (3) | 0.3046 (3) | 0.09070 (18) | 0.0217 (8) | |
C50 | 0.6130 (4) | 0.4248 (3) | 0.0786 (2) | 0.0274 (8) | |
H50 | 0.5268 | 0.4701 | 0.0800 | 0.033* | |
C51 | 0.6905 (4) | 0.4789 (3) | 0.0644 (2) | 0.0331 (9) | |
H51 | 0.6564 | 0.5610 | 0.0559 | 0.040* | |
C52 | 0.8155 (4) | 0.4147 (4) | 0.0625 (2) | 0.0326 (9) | |
H52 | 0.8677 | 0.4521 | 0.0535 | 0.039* | |
C53 | 0.8652 (4) | 0.2947 (4) | 0.0739 (2) | 0.0312 (9) | |
H53 | 0.9513 | 0.2500 | 0.0718 | 0.037* | |
C54 | 0.7887 (3) | 0.2403 (3) | 0.0882 (2) | 0.0280 (9) | |
H54 | 0.8232 | 0.1582 | 0.0965 | 0.034* | |
Cl | 1.0901 (3) | 0.0109 (3) | 0.0356 (2) | 0.182 (3) | 0.898 (9) |
C55 | 0.9850 (12) | 0.0868 (12) | −0.0452 (9) | 0.092 (6) | 0.449 (4) |
H55A | 0.9249 | 0.1672 | −0.0459 | 0.111* | 0.449 (4) |
H55B | 1.0308 | 0.0882 | −0.0873 | 0.111* | 0.449 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
W | 0.01416 (8) | 0.01395 (7) | 0.01676 (7) | −0.00668 (6) | 0.00146 (5) | −0.00376 (5) |
Ag1 | 0.02735 (16) | 0.03518 (17) | 0.02890 (16) | −0.02200 (14) | 0.00552 (12) | −0.01526 (13) |
Ag2 | 0.04511 (19) | 0.02228 (15) | 0.02184 (15) | −0.01689 (14) | 0.00866 (13) | −0.00086 (12) |
Ag3 | 0.02171 (16) | 0.02078 (15) | 0.03969 (18) | −0.00569 (12) | 0.01081 (13) | −0.01155 (13) |
S1 | 0.0169 (4) | 0.0212 (4) | 0.0242 (5) | −0.0092 (4) | 0.0078 (3) | −0.0104 (4) |
S2 | 0.0280 (5) | 0.0185 (4) | 0.0258 (5) | −0.0137 (4) | 0.0043 (4) | −0.0089 (4) |
S3 | 0.0196 (5) | 0.0173 (4) | 0.0197 (4) | −0.0094 (4) | 0.0049 (3) | −0.0029 (3) |
S4 | 0.0236 (5) | 0.0308 (5) | 0.0320 (6) | −0.0084 (4) | −0.0086 (4) | −0.0021 (4) |
I | 0.02200 (13) | 0.01956 (12) | 0.02312 (13) | −0.00603 (10) | 0.00018 (9) | −0.00527 (9) |
P1 | 0.0166 (5) | 0.0186 (5) | 0.0205 (5) | −0.0101 (4) | 0.0028 (3) | −0.0061 (4) |
C1 | 0.0201 (19) | 0.0212 (18) | 0.0222 (19) | −0.0111 (15) | 0.0039 (14) | −0.0070 (15) |
C2 | 0.026 (2) | 0.0240 (19) | 0.024 (2) | −0.0136 (16) | 0.0041 (15) | −0.0056 (16) |
C3 | 0.028 (2) | 0.030 (2) | 0.027 (2) | −0.0133 (18) | 0.0026 (16) | 0.0009 (17) |
C4 | 0.030 (2) | 0.045 (3) | 0.021 (2) | −0.018 (2) | 0.0048 (16) | −0.0080 (18) |
C5 | 0.039 (2) | 0.041 (2) | 0.028 (2) | −0.020 (2) | 0.0113 (18) | −0.0184 (19) |
C6 | 0.031 (2) | 0.025 (2) | 0.027 (2) | −0.0135 (17) | 0.0047 (16) | −0.0111 (16) |
C7 | 0.026 (2) | 0.0211 (19) | 0.0200 (19) | −0.0088 (16) | 0.0016 (15) | −0.0069 (15) |
C8 | 0.024 (2) | 0.037 (2) | 0.034 (2) | −0.0096 (19) | 0.0050 (17) | 0.0030 (19) |
C9 | 0.029 (2) | 0.041 (3) | 0.037 (3) | 0.005 (2) | 0.0020 (19) | −0.002 (2) |
C10 | 0.052 (3) | 0.021 (2) | 0.036 (3) | 0.002 (2) | −0.008 (2) | −0.0063 (19) |
C11 | 0.059 (3) | 0.021 (2) | 0.038 (3) | −0.018 (2) | −0.010 (2) | −0.0034 (18) |
C12 | 0.034 (2) | 0.023 (2) | 0.034 (2) | −0.0143 (18) | −0.0036 (18) | −0.0066 (17) |
C13 | 0.0166 (18) | 0.0184 (17) | 0.0188 (18) | −0.0097 (15) | 0.0005 (13) | 0.0001 (14) |
C14 | 0.028 (2) | 0.028 (2) | 0.0212 (19) | −0.0157 (17) | −0.0014 (15) | −0.0048 (16) |
C15 | 0.028 (2) | 0.039 (2) | 0.036 (2) | −0.022 (2) | −0.0080 (18) | −0.0006 (19) |
C16 | 0.018 (2) | 0.044 (3) | 0.050 (3) | −0.014 (2) | 0.0038 (19) | −0.001 (2) |
C17 | 0.027 (2) | 0.039 (2) | 0.042 (3) | −0.014 (2) | 0.0114 (19) | −0.014 (2) |
C18 | 0.025 (2) | 0.031 (2) | 0.027 (2) | −0.0131 (18) | 0.0035 (16) | −0.0107 (17) |
P2 | 0.0224 (5) | 0.0175 (5) | 0.0189 (5) | −0.0093 (4) | 0.0024 (4) | −0.0016 (4) |
C19 | 0.0211 (19) | 0.0179 (18) | 0.0204 (19) | −0.0075 (15) | 0.0013 (14) | −0.0025 (14) |
C20 | 0.023 (2) | 0.026 (2) | 0.023 (2) | −0.0125 (17) | 0.0043 (15) | −0.0042 (16) |
C21 | 0.028 (2) | 0.027 (2) | 0.031 (2) | −0.0122 (18) | −0.0014 (17) | −0.0075 (17) |
C22 | 0.028 (2) | 0.028 (2) | 0.022 (2) | −0.0044 (17) | 0.0003 (16) | −0.0069 (16) |
C23 | 0.026 (2) | 0.036 (2) | 0.027 (2) | −0.0132 (18) | 0.0099 (16) | −0.0074 (18) |
C24 | 0.026 (2) | 0.029 (2) | 0.030 (2) | −0.0164 (18) | 0.0043 (16) | −0.0064 (17) |
C25 | 0.025 (2) | 0.0205 (18) | 0.0159 (18) | −0.0101 (16) | −0.0001 (14) | −0.0042 (14) |
C26 | 0.030 (2) | 0.023 (2) | 0.031 (2) | −0.0094 (17) | −0.0072 (17) | 0.0006 (17) |
C27 | 0.029 (2) | 0.033 (2) | 0.037 (3) | −0.0099 (19) | −0.0058 (18) | −0.0071 (19) |
C28 | 0.029 (2) | 0.043 (3) | 0.037 (2) | −0.021 (2) | 0.0017 (18) | −0.017 (2) |
C29 | 0.041 (3) | 0.032 (2) | 0.037 (2) | −0.026 (2) | 0.0030 (19) | −0.0072 (19) |
C30 | 0.026 (2) | 0.022 (2) | 0.027 (2) | −0.0113 (17) | −0.0017 (16) | −0.0003 (16) |
C31 | 0.0197 (19) | 0.0176 (18) | 0.028 (2) | −0.0093 (15) | −0.0018 (15) | −0.0025 (15) |
C32 | 0.030 (2) | 0.027 (2) | 0.030 (2) | −0.0143 (18) | −0.0019 (17) | 0.0007 (17) |
C33 | 0.037 (3) | 0.026 (2) | 0.045 (3) | −0.012 (2) | −0.019 (2) | 0.0029 (19) |
C34 | 0.027 (2) | 0.021 (2) | 0.078 (4) | −0.0050 (19) | −0.012 (2) | −0.012 (2) |
C35 | 0.031 (2) | 0.036 (2) | 0.067 (3) | −0.017 (2) | 0.012 (2) | −0.030 (2) |
C36 | 0.027 (2) | 0.024 (2) | 0.037 (2) | −0.0119 (17) | 0.0080 (17) | −0.0120 (17) |
P3 | 0.0187 (5) | 0.0153 (4) | 0.0220 (5) | −0.0040 (4) | 0.0030 (4) | −0.0053 (4) |
C37 | 0.0191 (18) | 0.0171 (17) | 0.0217 (19) | −0.0083 (15) | 0.0048 (14) | −0.0052 (14) |
C38 | 0.038 (2) | 0.0189 (19) | 0.028 (2) | 0.0028 (17) | −0.0044 (18) | −0.0102 (17) |
C39 | 0.042 (3) | 0.030 (2) | 0.021 (2) | −0.0032 (19) | −0.0021 (18) | −0.0040 (17) |
C40 | 0.029 (2) | 0.0180 (19) | 0.034 (2) | −0.0092 (17) | −0.0018 (17) | −0.0004 (16) |
C41 | 0.056 (3) | 0.018 (2) | 0.040 (3) | 0.001 (2) | −0.002 (2) | −0.0139 (19) |
C42 | 0.056 (3) | 0.021 (2) | 0.027 (2) | −0.004 (2) | 0.003 (2) | −0.0098 (17) |
C43 | 0.0198 (19) | 0.0166 (18) | 0.023 (2) | −0.0013 (15) | −0.0009 (15) | −0.0047 (15) |
C44 | 0.031 (2) | 0.027 (2) | 0.038 (2) | −0.0101 (18) | 0.0007 (18) | −0.0077 (18) |
C45 | 0.039 (3) | 0.045 (3) | 0.049 (3) | −0.018 (2) | −0.006 (2) | −0.018 (2) |
C46 | 0.059 (3) | 0.048 (3) | 0.031 (3) | −0.017 (3) | −0.010 (2) | −0.013 (2) |
C47 | 0.053 (3) | 0.052 (3) | 0.023 (2) | −0.021 (2) | 0.005 (2) | −0.011 (2) |
C48 | 0.034 (2) | 0.034 (2) | 0.023 (2) | −0.0154 (19) | 0.0020 (17) | −0.0057 (17) |
C49 | 0.0218 (19) | 0.0220 (19) | 0.0184 (18) | −0.0079 (16) | 0.0012 (14) | −0.0043 (15) |
C50 | 0.027 (2) | 0.0207 (19) | 0.031 (2) | −0.0076 (17) | 0.0029 (16) | −0.0066 (16) |
C51 | 0.042 (3) | 0.023 (2) | 0.035 (2) | −0.0167 (19) | 0.0056 (19) | −0.0067 (17) |
C52 | 0.045 (3) | 0.042 (2) | 0.022 (2) | −0.030 (2) | 0.0044 (18) | −0.0062 (18) |
C53 | 0.023 (2) | 0.037 (2) | 0.030 (2) | −0.0130 (18) | −0.0003 (16) | −0.0020 (18) |
C54 | 0.024 (2) | 0.025 (2) | 0.033 (2) | −0.0100 (17) | 0.0039 (16) | −0.0072 (17) |
Cl | 0.096 (2) | 0.203 (4) | 0.203 (4) | 0.028 (2) | −0.019 (2) | −0.152 (3) |
C55 | 0.042 (8) | 0.072 (10) | 0.119 (14) | −0.006 (7) | 0.044 (9) | 0.001 (9) |
W—S1 | 2.2621 (9) | C24—H24 | 0.950 |
W—S2 | 2.2464 (9) | C25—C26 | 1.399 (5) |
W—S3 | 2.2423 (10) | C25—C30 | 1.389 (5) |
W—S4 | 2.1440 (11) | C26—H26 | 0.950 |
Ag1—S1 | 2.5341 (11) | C26—C27 | 1.380 (6) |
Ag1—S3 | 2.5683 (9) | C27—H27 | 0.950 |
Ag1—I | 3.0689 (7) | C27—C28 | 1.388 (6) |
Ag1—P1 | 2.3927 (9) | C28—H28 | 0.950 |
Ag2—S1 | 2.5631 (10) | C28—C29 | 1.375 (6) |
Ag2—S2 | 2.5718 (10) | C29—H29 | 0.950 |
Ag2—I | 3.0683 (9) | C29—C30 | 1.396 (5) |
Ag2—P2 | 2.3961 (10) | C30—H30 | 0.950 |
Ag3—S2 | 2.5892 (11) | C31—C32 | 1.410 (5) |
Ag3—S3 | 2.6319 (10) | C31—C36 | 1.394 (5) |
Ag3—I | 3.0231 (5) | C32—H32 | 0.950 |
Ag3—P3 | 2.4150 (10) | C32—C33 | 1.378 (6) |
P1—C1 | 1.830 (4) | C33—H33 | 0.950 |
P1—C7 | 1.823 (4) | C33—C34 | 1.368 (7) |
P1—C13 | 1.827 (4) | C34—H34 | 0.950 |
C1—C2 | 1.396 (5) | C34—C35 | 1.370 (7) |
C1—C6 | 1.385 (5) | C35—H35 | 0.950 |
C2—H2 | 0.950 | C35—C36 | 1.395 (6) |
C2—C3 | 1.383 (5) | C36—H36 | 0.950 |
C3—H3 | 0.950 | P3—C37 | 1.830 (4) |
C3—C4 | 1.381 (5) | P3—C43 | 1.833 (4) |
C4—H4 | 0.950 | P3—C49 | 1.829 (4) |
C4—C5 | 1.382 (6) | C37—C38 | 1.387 (5) |
C5—H5 | 0.950 | C37—C42 | 1.386 (5) |
C5—C6 | 1.396 (5) | C38—H38 | 0.950 |
C6—H6 | 0.950 | C38—C39 | 1.392 (5) |
C7—C8 | 1.395 (5) | C39—H39 | 0.950 |
C7—C12 | 1.386 (5) | C39—C40 | 1.373 (5) |
C8—H8 | 0.950 | C40—H40 | 0.950 |
C8—C9 | 1.390 (6) | C40—C41 | 1.368 (6) |
C9—H9 | 0.950 | C41—H41 | 0.950 |
C9—C10 | 1.375 (7) | C41—C42 | 1.397 (6) |
C10—H10 | 0.950 | C42—H42 | 0.950 |
C10—C11 | 1.366 (7) | C43—C44 | 1.385 (5) |
C11—H11 | 0.950 | C43—C48 | 1.395 (5) |
C11—C12 | 1.389 (5) | C44—H44 | 0.950 |
C12—H12 | 0.950 | C44—C45 | 1.391 (6) |
C13—C14 | 1.405 (5) | C45—H45 | 0.950 |
C13—C18 | 1.384 (5) | C45—C46 | 1.387 (7) |
C14—H14 | 0.950 | C46—H46 | 0.950 |
C14—C15 | 1.373 (5) | C46—C47 | 1.374 (7) |
C15—H15 | 0.950 | C47—H47 | 0.950 |
C15—C16 | 1.392 (6) | C47—C48 | 1.394 (6) |
C16—H16 | 0.950 | C48—H48 | 0.950 |
C16—C17 | 1.376 (6) | C49—C50 | 1.393 (5) |
C17—H17 | 0.950 | C49—C54 | 1.397 (5) |
C17—C18 | 1.389 (5) | C50—H50 | 0.950 |
C18—H18 | 0.950 | C50—C51 | 1.397 (5) |
P2—C19 | 1.830 (4) | C51—H51 | 0.950 |
P2—C25 | 1.833 (4) | C51—C52 | 1.375 (6) |
P2—C31 | 1.819 (4) | C52—H52 | 0.950 |
C19—C20 | 1.397 (5) | C52—C53 | 1.392 (6) |
C19—C24 | 1.393 (5) | C53—H53 | 0.950 |
C20—H20 | 0.950 | C53—C54 | 1.390 (5) |
C20—C21 | 1.390 (5) | C54—H54 | 0.950 |
C21—H21 | 0.950 | Cl—C55 | 1.851 (17) |
C21—C22 | 1.375 (5) | Cl—C55i | 1.862 (16) |
C22—H22 | 0.950 | C55—Cli | 1.862 (16) |
C22—C23 | 1.384 (6) | C55—H55A | 0.990 |
C23—H23 | 0.950 | C55—H55B | 0.990 |
C23—C24 | 1.397 (5) | ||
S1—W—S2 | 111.00 (3) | C21—C22—C23 | 120.4 (4) |
S1—W—S3 | 110.99 (3) | H22—C22—C23 | 119.8 |
S1—W—S4 | 107.87 (4) | C22—C23—H23 | 120.0 |
S2—W—S3 | 110.95 (3) | C22—C23—C24 | 119.9 (4) |
S2—W—S4 | 107.43 (4) | H23—C23—C24 | 120.0 |
S3—W—S4 | 108.45 (4) | C19—C24—C23 | 120.1 (3) |
S1—Ag1—S3 | 93.35 (3) | C19—C24—H24 | 120.0 |
S1—Ag1—I | 99.88 (3) | C23—C24—H24 | 120.0 |
S1—Ag1—P1 | 128.00 (3) | P2—C25—C26 | 117.6 (3) |
S3—Ag1—I | 99.25 (2) | P2—C25—C30 | 123.1 (3) |
S3—Ag1—P1 | 126.77 (3) | C26—C25—C30 | 119.3 (3) |
I—Ag1—P1 | 103.73 (3) | C25—C26—H26 | 119.8 |
S1—Ag2—S2 | 92.71 (3) | C25—C26—C27 | 120.4 (4) |
S1—Ag2—I | 99.23 (3) | H26—C26—C27 | 119.8 |
S1—Ag2—P2 | 123.93 (3) | C26—C27—H27 | 119.9 |
S2—Ag2—I | 103.11 (3) | C26—C27—C28 | 120.2 (4) |
S2—Ag2—P2 | 128.24 (3) | H27—C27—C28 | 119.9 |
I—Ag2—P2 | 104.95 (3) | C27—C28—H28 | 120.2 |
S2—Ag3—S3 | 90.19 (3) | C27—C28—C29 | 119.6 (4) |
S2—Ag3—I | 103.92 (3) | H28—C28—C29 | 120.2 |
S2—Ag3—P3 | 126.86 (3) | C28—C29—H29 | 119.6 |
S3—Ag3—I | 98.97 (2) | C28—C29—C30 | 120.9 (4) |
S3—Ag3—P3 | 122.69 (3) | H29—C29—C30 | 119.6 |
I—Ag3—P3 | 109.54 (3) | C25—C30—C29 | 119.5 (4) |
W—S1—Ag1 | 76.58 (3) | C25—C30—H30 | 120.2 |
W—S1—Ag2 | 75.80 (3) | C29—C30—H30 | 120.2 |
Ag1—S1—Ag2 | 88.04 (3) | P2—C31—C32 | 122.9 (3) |
W—S2—Ag2 | 75.89 (3) | P2—C31—C36 | 118.2 (3) |
W—S2—Ag3 | 77.27 (3) | C32—C31—C36 | 119.0 (3) |
Ag2—S2—Ag3 | 83.52 (3) | C31—C32—H32 | 119.9 |
W—S3—Ag1 | 76.20 (3) | C31—C32—C33 | 120.1 (4) |
W—S3—Ag3 | 76.44 (3) | H32—C32—C33 | 119.9 |
Ag1—S3—Ag3 | 87.30 (3) | C32—C33—H33 | 120.0 |
Ag1—I—Ag2 | 70.505 (16) | C32—C33—C34 | 120.0 (4) |
Ag1—I—Ag3 | 72.199 (14) | H33—C33—C34 | 120.0 |
Ag2—I—Ag3 | 68.704 (14) | C33—C34—H34 | 119.4 |
Ag1—P1—C1 | 116.19 (11) | C33—C34—C35 | 121.2 (4) |
Ag1—P1—C7 | 113.08 (12) | H34—C34—C35 | 119.4 |
Ag1—P1—C13 | 112.69 (12) | C34—C35—H35 | 120.0 |
C1—P1—C7 | 104.13 (16) | C34—C35—C36 | 120.1 (4) |
C1—P1—C13 | 103.49 (16) | H35—C35—C36 | 120.0 |
C7—P1—C13 | 106.22 (16) | C31—C36—C35 | 119.6 (4) |
P1—C1—C2 | 117.8 (3) | C31—C36—H36 | 120.2 |
P1—C1—C6 | 123.5 (3) | C35—C36—H36 | 120.2 |
C2—C1—C6 | 118.6 (3) | Ag3—P3—C37 | 117.03 (12) |
C1—C2—H2 | 119.7 | Ag3—P3—C43 | 113.15 (12) |
C1—C2—C3 | 120.6 (4) | Ag3—P3—C49 | 112.36 (12) |
H2—C2—C3 | 119.7 | C37—P3—C43 | 102.27 (16) |
C2—C3—H3 | 119.6 | C37—P3—C49 | 104.46 (16) |
C2—C3—C4 | 120.7 (4) | C43—P3—C49 | 106.46 (17) |
H3—C3—C4 | 119.6 | P3—C37—C38 | 119.1 (3) |
C3—C4—H4 | 120.4 | P3—C37—C42 | 122.7 (3) |
C3—C4—C5 | 119.2 (4) | C38—C37—C42 | 118.2 (3) |
H4—C4—C5 | 120.4 | C37—C38—H38 | 119.3 |
C4—C5—H5 | 119.7 | C37—C38—C39 | 121.4 (4) |
C4—C5—C6 | 120.5 (4) | H38—C38—C39 | 119.3 |
H5—C5—C6 | 119.7 | C38—C39—H39 | 120.4 |
C1—C6—C5 | 120.4 (4) | C38—C39—C40 | 119.3 (4) |
C1—C6—H6 | 119.8 | H39—C39—C40 | 120.4 |
C5—C6—H6 | 119.8 | C39—C40—H40 | 119.8 |
P1—C7—C8 | 116.6 (3) | C39—C40—C41 | 120.4 (4) |
P1—C7—C12 | 124.4 (3) | H40—C40—C41 | 119.8 |
C8—C7—C12 | 119.0 (4) | C40—C41—H41 | 119.9 |
C7—C8—H8 | 119.9 | C40—C41—C42 | 120.3 (4) |
C7—C8—C9 | 120.2 (4) | H41—C41—C42 | 119.9 |
H8—C8—C9 | 119.9 | C37—C42—C41 | 120.3 (4) |
C8—C9—H9 | 120.0 | C37—C42—H42 | 119.8 |
C8—C9—C10 | 119.9 (4) | C41—C42—H42 | 119.8 |
H9—C9—C10 | 120.0 | P3—C43—C44 | 117.7 (3) |
C9—C10—H10 | 119.9 | P3—C43—C48 | 122.4 (3) |
C9—C10—C11 | 120.2 (4) | C44—C43—C48 | 119.8 (4) |
H10—C10—C11 | 119.9 | C43—C44—H44 | 120.0 |
C10—C11—H11 | 119.6 | C43—C44—C45 | 120.1 (4) |
C10—C11—C12 | 120.7 (4) | H44—C44—C45 | 120.0 |
H11—C11—C12 | 119.6 | C44—C45—H45 | 120.1 |
C7—C12—C11 | 119.9 (4) | C44—C45—C46 | 119.7 (4) |
C7—C12—H12 | 120.0 | H45—C45—C46 | 120.1 |
C11—C12—H12 | 120.0 | C45—C46—H46 | 119.7 |
P1—C13—C14 | 120.8 (3) | C45—C46—C47 | 120.5 (4) |
P1—C13—C18 | 119.9 (3) | H46—C46—C47 | 119.7 |
C14—C13—C18 | 119.3 (3) | C46—C47—H47 | 120.0 |
C13—C14—H14 | 119.8 | C46—C47—C48 | 120.0 (4) |
C13—C14—C15 | 120.3 (4) | H47—C47—C48 | 120.0 |
H14—C14—C15 | 119.8 | C43—C48—C47 | 119.8 (4) |
C14—C15—H15 | 120.2 | C43—C48—H48 | 120.1 |
C14—C15—C16 | 119.6 (4) | C47—C48—H48 | 120.1 |
H15—C15—C16 | 120.2 | P3—C49—C50 | 118.5 (3) |
C15—C16—H16 | 119.7 | P3—C49—C54 | 122.9 (3) |
C15—C16—C17 | 120.6 (4) | C50—C49—C54 | 118.6 (3) |
H16—C16—C17 | 119.7 | C49—C50—H50 | 119.9 |
C16—C17—H17 | 120.0 | C49—C50—C51 | 120.2 (4) |
C16—C17—C18 | 120.0 (4) | H50—C50—C51 | 119.9 |
H17—C17—C18 | 120.0 | C50—C51—H51 | 119.6 |
C13—C18—C17 | 120.2 (4) | C50—C51—C52 | 120.8 (4) |
C13—C18—H18 | 119.9 | H51—C51—C52 | 119.6 |
C17—C18—H18 | 119.9 | C51—C52—H52 | 120.2 |
Ag2—P2—C19 | 114.01 (12) | C51—C52—C53 | 119.7 (4) |
Ag2—P2—C25 | 113.98 (12) | H52—C52—C53 | 120.2 |
Ag2—P2—C31 | 113.57 (12) | C52—C53—H53 | 120.1 |
C19—P2—C25 | 103.73 (16) | C52—C53—C54 | 119.9 (4) |
C19—P2—C31 | 104.17 (17) | H53—C53—C54 | 120.1 |
C25—P2—C31 | 106.36 (16) | C49—C54—C53 | 120.9 (4) |
P2—C19—C20 | 118.0 (3) | C49—C54—H54 | 119.6 |
P2—C19—C24 | 122.7 (3) | C53—C54—H54 | 119.6 |
C20—C19—C24 | 119.2 (3) | C55—Cl—C55i | 81.4 (7) |
C19—C20—H20 | 119.9 | Cl—C55—Cli | 98.6 (7) |
C19—C20—C21 | 120.2 (3) | Cl—C55—H55A | 112.1 |
H20—C20—C21 | 119.9 | Cli—C55—H55A | 112.1 |
C20—C21—H21 | 119.9 | Cl—C55—H55B | 112.1 |
C20—C21—C22 | 120.3 (4) | Cli—C55—H55B | 112.1 |
H21—C21—C22 | 119.9 | H55A—C55—H55B | 109.7 |
C21—C22—H22 | 119.8 | ||
S2—W—S1—Ag1 | 109.50 (3) | C7—P1—C13—C14 | 67.3 (3) |
S2—W—S1—Ag2 | 18.11 (4) | C7—P1—C13—C18 | −112.4 (3) |
S3—W—S1—Ag1 | −14.38 (3) | P1—C13—C14—C15 | −176.7 (3) |
S3—W—S1—Ag2 | −105.76 (3) | C18—C13—C14—C15 | 3.1 (5) |
S4—W—S1—Ag1 | −133.06 (3) | C13—C14—C15—C16 | −1.8 (6) |
S4—W—S1—Ag2 | 135.56 (3) | C14—C15—C16—C17 | −0.4 (6) |
S3—Ag1—S1—W | 11.70 (3) | C15—C16—C17—C18 | 1.5 (7) |
S3—Ag1—S1—Ag2 | 87.57 (3) | P1—C13—C18—C17 | 177.7 (3) |
I—Ag1—S1—W | −88.30 (2) | C14—C13—C18—C17 | −2.1 (6) |
I—Ag1—S1—Ag2 | −12.43 (2) | C16—C17—C18—C13 | −0.2 (6) |
P1—Ag1—S1—W | 155.48 (3) | S1—Ag2—P2—C19 | −33.44 (14) |
P1—Ag1—S1—Ag2 | −128.65 (4) | S1—Ag2—P2—C25 | 85.41 (13) |
S2—Ag2—S1—W | −14.70 (3) | S1—Ag2—P2—C31 | −152.55 (13) |
S2—Ag2—S1—Ag1 | −91.35 (3) | S2—Ag2—P2—C19 | −160.48 (13) |
I—Ag2—S1—W | 89.05 (2) | S2—Ag2—P2—C25 | −41.64 (14) |
I—Ag2—S1—Ag1 | 12.41 (3) | S2—Ag2—P2—C31 | 80.40 (14) |
P2—Ag2—S1—W | −155.83 (3) | I—Ag2—P2—C19 | 78.89 (13) |
P2—Ag2—S1—Ag1 | 127.52 (4) | I—Ag2—P2—C25 | −162.27 (13) |
S1—W—S2—Ag2 | −18.04 (4) | I—Ag2—P2—C31 | −40.23 (13) |
S1—W—S2—Ag3 | −104.46 (3) | Ag2—P2—C19—C20 | −40.0 (3) |
S3—W—S2—Ag2 | 105.85 (3) | Ag2—P2—C19—C24 | 141.6 (3) |
S3—W—S2—Ag3 | 19.43 (4) | C25—P2—C19—C20 | −164.6 (3) |
S4—W—S2—Ag2 | −135.76 (4) | C25—P2—C19—C24 | 17.1 (3) |
S4—W—S2—Ag3 | 137.82 (4) | C31—P2—C19—C20 | 84.3 (3) |
S1—Ag2—S2—W | 14.80 (3) | C31—P2—C19—C24 | −94.1 (3) |
S1—Ag2—S2—Ag3 | 93.26 (3) | P2—C19—C20—C21 | −178.2 (3) |
I—Ag2—S2—W | −85.33 (3) | C24—C19—C20—C21 | 0.2 (5) |
I—Ag2—S2—Ag3 | −6.87 (2) | C19—C20—C21—C22 | 0.5 (6) |
P2—Ag2—S2—W | 153.28 (4) | C20—C21—C22—C23 | −0.7 (6) |
P2—Ag2—S2—Ag3 | −128.27 (4) | C21—C22—C23—C24 | 0.2 (6) |
S3—Ag3—S2—W | −15.35 (3) | P2—C19—C24—C23 | 177.7 (3) |
S3—Ag3—S2—Ag2 | −92.29 (3) | C20—C19—C24—C23 | −0.7 (6) |
I—Ag3—S2—W | 83.94 (3) | C22—C23—C24—C19 | 0.5 (6) |
I—Ag3—S2—Ag2 | 7.00 (2) | Ag2—P2—C25—C26 | −37.4 (3) |
P3—Ag3—S2—W | −148.00 (3) | Ag2—P2—C25—C30 | 145.3 (3) |
P3—Ag3—S2—Ag2 | 135.06 (4) | C19—P2—C25—C26 | 87.2 (3) |
S1—W—S3—Ag1 | 14.20 (3) | C19—P2—C25—C30 | −90.1 (3) |
S1—W—S3—Ag3 | 104.73 (3) | C31—P2—C25—C26 | −163.3 (3) |
S2—W—S3—Ag1 | −109.70 (3) | C31—P2—C25—C30 | 19.4 (4) |
S2—W—S3—Ag3 | −19.17 (4) | P2—C25—C26—C27 | −176.4 (3) |
S4—W—S3—Ag1 | 132.53 (3) | C30—C25—C26—C27 | 1.0 (6) |
S4—W—S3—Ag3 | −136.94 (3) | C25—C26—C27—C28 | −0.4 (6) |
S1—Ag1—S3—W | −11.82 (3) | C26—C27—C28—C29 | −0.8 (6) |
S1—Ag1—S3—Ag3 | −88.52 (3) | C27—C28—C29—C30 | 1.4 (6) |
I—Ag1—S3—W | 88.76 (3) | P2—C25—C30—C29 | 176.9 (3) |
I—Ag1—S3—Ag3 | 12.06 (2) | C26—C25—C30—C29 | −0.4 (6) |
P1—Ag1—S3—W | −156.29 (3) | C28—C29—C30—C25 | −0.8 (6) |
P1—Ag1—S3—Ag3 | 127.02 (4) | Ag2—P2—C31—C32 | 153.2 (3) |
S2—Ag3—S3—W | 15.43 (3) | Ag2—P2—C31—C36 | −24.9 (3) |
S2—Ag3—S3—Ag1 | 91.89 (3) | C19—P2—C31—C32 | 28.6 (3) |
I—Ag3—S3—W | −88.69 (2) | C19—P2—C31—C36 | −149.5 (3) |
I—Ag3—S3—Ag1 | −12.24 (2) | C25—P2—C31—C32 | −80.6 (3) |
P3—Ag3—S3—W | 151.06 (3) | C25—P2—C31—C36 | 101.2 (3) |
P3—Ag3—S3—Ag1 | −132.48 (3) | P2—C31—C32—C33 | −180.0 (3) |
S2—Ag3—I—Ag1 | −81.71 (3) | C36—C31—C32—C33 | −1.8 (5) |
S2—Ag3—I—Ag2 | −6.25 (2) | C31—C32—C33—C34 | 0.8 (6) |
S3—Ag3—I—Ag1 | 10.72 (2) | C32—C33—C34—C35 | 0.4 (6) |
S3—Ag3—I—Ag2 | 86.19 (2) | C33—C34—C35—C36 | −0.6 (6) |
P3—Ag3—I—Ag1 | 140.24 (3) | P2—C31—C36—C35 | 179.9 (3) |
P3—Ag3—I—Ag2 | −144.30 (3) | C32—C31—C36—C35 | 1.7 (5) |
S1—Ag2—I—Ag1 | −10.84 (2) | C34—C35—C36—C31 | −0.5 (6) |
S1—Ag2—I—Ag3 | −88.71 (2) | S2—Ag3—P3—C37 | −81.18 (13) |
S2—Ag2—I—Ag1 | 84.15 (2) | S2—Ag3—P3—C43 | 37.35 (14) |
S2—Ag2—I—Ag3 | 6.27 (2) | S2—Ag3—P3—C49 | 157.96 (13) |
P2—Ag2—I—Ag1 | −139.79 (3) | S3—Ag3—P3—C37 | 159.75 (13) |
P2—Ag2—I—Ag3 | 142.33 (3) | S3—Ag3—P3—C43 | −81.72 (13) |
S1—Ag1—I—Ag2 | 10.99 (2) | S3—Ag3—P3—C49 | 38.89 (13) |
S1—Ag1—I—Ag3 | 84.07 (2) | I—Ag3—P3—C37 | 44.64 (13) |
S3—Ag1—I—Ag2 | −84.09 (2) | I—Ag3—P3—C43 | 163.17 (13) |
S3—Ag1—I—Ag3 | −11.00 (2) | I—Ag3—P3—C49 | −76.23 (13) |
P1—Ag1—I—Ag2 | 144.30 (3) | Ag3—P3—C37—C38 | −36.4 (4) |
P1—Ag1—I—Ag3 | −142.62 (3) | Ag3—P3—C37—C42 | 144.7 (3) |
S1—Ag1—P1—C1 | 51.69 (14) | C43—P3—C37—C38 | −160.6 (3) |
S1—Ag1—P1—C7 | −68.66 (14) | C43—P3—C37—C42 | 20.4 (4) |
S1—Ag1—P1—C13 | 170.85 (12) | C49—P3—C37—C38 | 88.6 (3) |
S3—Ag1—P1—C1 | −175.74 (13) | C49—P3—C37—C42 | −90.4 (4) |
S3—Ag1—P1—C7 | 63.92 (14) | P3—C37—C38—C39 | −177.8 (3) |
S3—Ag1—P1—C13 | −56.57 (13) | C42—C37—C38—C39 | 1.2 (6) |
I—Ag1—P1—C1 | −62.83 (13) | C37—C38—C39—C40 | 0.1 (7) |
I—Ag1—P1—C7 | 176.82 (13) | C38—C39—C40—C41 | −1.0 (7) |
I—Ag1—P1—C13 | 56.33 (12) | C39—C40—C41—C42 | 0.6 (7) |
Ag1—P1—C1—C2 | 41.8 (3) | P3—C37—C42—C41 | 177.4 (4) |
Ag1—P1—C1—C6 | −141.1 (3) | C38—C37—C42—C41 | −1.6 (7) |
C7—P1—C1—C2 | 166.8 (3) | C40—C41—C42—C37 | 0.7 (7) |
C7—P1—C1—C6 | −16.1 (4) | Ag3—P3—C43—C44 | −39.6 (3) |
C13—P1—C1—C2 | −82.3 (3) | Ag3—P3—C43—C48 | 142.8 (3) |
C13—P1—C1—C6 | 94.8 (3) | C37—P3—C43—C44 | 87.2 (3) |
P1—C1—C2—C3 | 176.9 (3) | C37—P3—C43—C48 | −90.4 (3) |
C6—C1—C2—C3 | −0.4 (6) | C49—P3—C43—C44 | −163.5 (3) |
C1—C2—C3—C4 | 1.0 (6) | C49—P3—C43—C48 | 18.9 (3) |
C2—C3—C4—C5 | −0.8 (6) | P3—C43—C44—C45 | −176.1 (3) |
C3—C4—C5—C6 | 0.0 (6) | C48—C43—C44—C45 | 1.7 (6) |
P1—C1—C6—C5 | −177.6 (3) | C43—C44—C45—C46 | −0.8 (6) |
C2—C1—C6—C5 | −0.5 (6) | C44—C45—C46—C47 | −0.5 (7) |
C4—C5—C6—C1 | 0.6 (6) | C45—C46—C47—C48 | 1.0 (7) |
Ag1—P1—C7—C8 | 46.9 (3) | C46—C47—C48—C43 | −0.1 (7) |
Ag1—P1—C7—C12 | −132.4 (3) | P3—C43—C48—C47 | 176.4 (3) |
C1—P1—C7—C8 | −80.1 (3) | C44—C43—C48—C47 | −1.2 (6) |
C1—P1—C7—C12 | 100.6 (3) | Ag3—P3—C49—C50 | −24.5 (3) |
C13—P1—C7—C8 | 171.0 (3) | Ag3—P3—C49—C54 | 155.5 (3) |
C13—P1—C7—C12 | −8.3 (4) | C37—P3—C49—C50 | −152.3 (3) |
P1—C7—C8—C9 | 177.4 (3) | C37—P3—C49—C54 | 27.6 (4) |
C12—C7—C8—C9 | −3.2 (6) | C43—P3—C49—C50 | 99.9 (3) |
C7—C8—C9—C10 | 1.7 (7) | C43—P3—C49—C54 | −80.1 (3) |
C8—C9—C10—C11 | 0.9 (7) | P3—C49—C50—C51 | 179.9 (3) |
C9—C10—C11—C12 | −2.0 (7) | C54—C49—C50—C51 | 0.0 (6) |
P1—C7—C12—C11 | −178.6 (3) | C49—C50—C51—C52 | −0.4 (6) |
C8—C7—C12—C11 | 2.0 (6) | C50—C51—C52—C53 | 1.0 (6) |
C10—C11—C12—C7 | 0.5 (6) | C51—C52—C53—C54 | −1.2 (6) |
Ag1—P1—C13—C14 | −168.3 (2) | C52—C53—C54—C49 | 0.8 (6) |
Ag1—P1—C13—C18 | 11.9 (3) | P3—C49—C54—C53 | 179.9 (3) |
C1—P1—C13—C14 | −42.0 (3) | C50—C49—C54—C53 | −0.2 (6) |
C1—P1—C13—C18 | 138.2 (3) | C55i—Cl—C55—Cli | 0.0 |
Symmetry code: (i) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [WAg3IS4(C18H15P)3]·0.45CH2Cl2 |
Mr | 1587.63 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 12.113 (3), 13.3231 (14), 20.0301 (14) |
α, β, γ (°) | 74.671 (8), 87.659 (11), 63.692 (10) |
V (Å3) | 2783.7 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.97 |
Crystal size (mm) | 0.37 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Numerical (SHELXTL; Sheldrick, 2005) |
Tmin, Tmax | 0.321, 0.545 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38642, 12444, 10245 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.068, 0.98 |
No. of reflections | 12444 |
No. of parameters | 614 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.21, −0.98 |
Computer programs: COLLECT (Nonius, 1998), EVALCCD (Duisenberg et al., 2003), EVALCCD, SHELXTL (Sheldrick, 2005), SHELXTL and local programs.
W—S1 | 2.2621 (9) | Ag2—S1 | 2.5631 (10) |
W—S2 | 2.2464 (9) | Ag2—S2 | 2.5718 (10) |
W—S3 | 2.2423 (10) | Ag2—I | 3.0683 (9) |
W—S4 | 2.1440 (11) | Ag2—P2 | 2.3961 (10) |
Ag1—S1 | 2.5341 (11) | Ag3—S2 | 2.5892 (11) |
Ag1—S3 | 2.5683 (9) | Ag3—S3 | 2.6319 (10) |
Ag1—I | 3.0689 (7) | Ag3—I | 3.0231 (5) |
Ag1—P1 | 2.3927 (9) | Ag3—P3 | 2.4150 (10) |
S1—W—S2 | 111.00 (3) | S2—Ag3—S3 | 90.19 (3) |
S1—W—S3 | 110.99 (3) | S2—Ag3—I | 103.92 (3) |
S1—W—S4 | 107.87 (4) | S2—Ag3—P3 | 126.86 (3) |
S2—W—S3 | 110.95 (3) | S3—Ag3—I | 98.97 (2) |
S2—W—S4 | 107.43 (4) | S3—Ag3—P3 | 122.69 (3) |
S3—W—S4 | 108.45 (4) | I—Ag3—P3 | 109.54 (3) |
S1—Ag1—S3 | 93.35 (3) | W—S1—Ag1 | 76.58 (3) |
S1—Ag1—I | 99.88 (3) | W—S1—Ag2 | 75.80 (3) |
S1—Ag1—P1 | 128.00 (3) | Ag1—S1—Ag2 | 88.04 (3) |
S3—Ag1—I | 99.25 (2) | W—S2—Ag2 | 75.89 (3) |
S3—Ag1—P1 | 126.77 (3) | W—S2—Ag3 | 77.27 (3) |
I—Ag1—P1 | 103.73 (3) | Ag2—S2—Ag3 | 83.52 (3) |
S1—Ag2—S2 | 92.71 (3) | W—S3—Ag1 | 76.20 (3) |
S1—Ag2—I | 99.23 (3) | W—S3—Ag3 | 76.44 (3) |
S1—Ag2—P2 | 123.93 (3) | Ag1—S3—Ag3 | 87.30 (3) |
S2—Ag2—I | 103.11 (3) | Ag1—I—Ag2 | 70.505 (16) |
S2—Ag2—P2 | 128.24 (3) | Ag1—I—Ag3 | 72.199 (14) |
I—Ag2—P2 | 104.95 (3) | Ag2—I—Ag3 | 68.704 (14) |
The title complex was obtained as an unexpected decomposition product in an attempt to prepare a WS4/Ag/Zn mixed-metal complex containing phosphine and heterocyclic thione ligands. It features a pseudo-cubane WS3Ag3I core with a typical geometry involving wide angles at the metal corners and narrow angles at the S and I atoms, giving short W···Ag distances [2.9737 (5)–3.0310 (8) Å] that do not represent formal direct metal-metal bonds.
The W atom has an almost regular tetrahedral coordination geometry, with the terminal W?S bond significantly shorter than the bonds to triply-bridging S atoms. The coordination of the Ag atoms is rather distorted tetrahedral, with the smallest angle in each case between the two Ag—S bonds and the largest angles between Ag—S and Ag—P bonds, as a consequence of the steric demands of the triphenylphosphine ligands.
Very similar structures have been found for related complexes in which one or more of the following substitutions are made: Mo for W, O for the terminal S, Cl or Br for I, pyridyl for one of the phenyl rings on each phosphine ligand (Jin et al., 1999, 2000; Sakane et al., 1996; Wang et al., 2003; Lang et al., 1992, 1993; Zhu et al., 1992; Wu et al., 1992). Some of these are actually isomorphous and probably isostructural with the title complex, although the solvent is water rather than dichloromethane in one case, but coordinates are not available for all of the structures.