Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011103438X/sf3156sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011103438X/sf3156Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S010827011103438X/sf3156Isup4.mol |
CCDC reference: 846632
All reagents and solvents were used as obtained commercially without further purification. A mixture of Lawesson's reagent (202 mg, 0.50 mmol), AgOAc (334 mg, 2.00 mmol) and dppp (412 mg, 1.00 mmol) was dissolved in chloroform (10 ml). The mixture was treated under ultrasonic conditions (323 K, 160 W, 40 KHz, 20 min), during which time the solution changed from colourless to yellow. The mixture was filtered and diffusion of diethyl ether into the reaction mixture produced colourless crystals of (I) after two weeks (yield ca 45% based on AgOAc). Elemental analysis: anal. calc. for AgP3S2C37H39O2Cl3: C 50.10, H 4.43; found: C 49.88, H 4.59 %. Selected IR peaks (ν, cm-1): 3064 (w), 2960 (w), 2936 (w), 1588 (s), 1494 (m), 1481 (m), 1436 (s), 1381 (s), 1244 (w), 1177 (m), 1107 (m), 1030 (s), 933 (m), 747 (m), 695 (s), 625 (s), 545 (m).
All H atoms were generated geometrically and were allowed to ride on their parent atoms in the riding-model approximation, with aromatic C—H = 0.95 Å, methyne C—H = 1.00 Å, methylene C—H = 0.99 Å and methyl C—H = 0.98 Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
[Ag(C27H26P2)(C9H12O2PS2)]·CHCl3 | F(000) = 904 |
Mr = 886.93 | Dx = 1.503 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 28055 reflections |
a = 7.1493 (14) Å | θ = 6.1–55.0° |
b = 16.137 (3) Å | µ = 0.98 mm−1 |
c = 17.010 (3) Å | T = 173 K |
β = 92.95 (3)° | Block, colourless |
V = 1959.8 (7) Å3 | 0.10 × 0.08 × 0.08 mm |
Z = 2 |
Oxford Gemini S Ultra diffractometer | 7381 independent reflections |
Radiation source: sealed tube | 6876 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 16.1903 pixels mm-1 | θmax = 26.0°, θmin = 3.0° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −19→19 |
Tmin = 0.908, Tmax = 0.926 | l = −20→20 |
26211 measured reflections |
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0103P)2 + 2.4402P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
7381 reflections | Δρmax = 0.64 e Å−3 |
433 parameters | Δρmin = −0.78 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (2) |
[Ag(C27H26P2)(C9H12O2PS2)]·CHCl3 | V = 1959.8 (7) Å3 |
Mr = 886.93 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.1493 (14) Å | µ = 0.98 mm−1 |
b = 16.137 (3) Å | T = 173 K |
c = 17.010 (3) Å | 0.10 × 0.08 × 0.08 mm |
β = 92.95 (3)° |
Oxford Gemini S Ultra diffractometer | 7381 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 6876 reflections with I > 2σ(I) |
Tmin = 0.908, Tmax = 0.926 | Rint = 0.053 |
26211 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.074 | Δρmax = 0.64 e Å−3 |
S = 1.01 | Δρmin = −0.78 e Å−3 |
7381 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
433 parameters | Absolute structure parameter: −0.01 (2) |
1 restraint |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.93558 (4) | 0.267458 (16) | 0.277491 (16) | 0.03018 (7) | |
Cl1 | −0.1357 (2) | 0.19776 (9) | −0.03697 (11) | 0.0711 (5) | |
Cl2 | −0.3657 (2) | 0.33509 (9) | −0.08913 (8) | 0.0602 (4) | |
Cl3 | 0.0353 (2) | 0.34327 (9) | −0.09900 (8) | 0.0585 (3) | |
S1 | 1.06916 (17) | 0.41944 (7) | 0.28743 (6) | 0.0378 (3) | |
S2 | 0.74536 (17) | 0.34191 (7) | 0.15887 (6) | 0.0373 (3) | |
P1 | 0.77758 (15) | 0.23400 (6) | 0.39844 (6) | 0.0252 (2) | |
P2 | 0.10029 (15) | 0.14039 (6) | 0.24491 (6) | 0.0251 (2) | |
P3 | 0.89644 (17) | 0.44060 (6) | 0.19358 (6) | 0.0324 (2) | |
C1 | 0.6657 (6) | 0.3153 (2) | 0.4529 (2) | 0.0291 (9) | |
C2 | 0.5576 (7) | 0.3740 (3) | 0.4110 (3) | 0.0393 (11) | |
H2A | 0.5513 | 0.3729 | 0.3550 | 0.047* | |
C3 | 0.4599 (8) | 0.4336 (3) | 0.4498 (3) | 0.0495 (13) | |
H3A | 0.3831 | 0.4721 | 0.4207 | 0.059* | |
C4 | 0.4735 (8) | 0.4375 (3) | 0.5301 (3) | 0.0508 (13) | |
H4A | 0.4045 | 0.4782 | 0.5567 | 0.061* | |
C5 | 0.5867 (8) | 0.3827 (3) | 0.5729 (3) | 0.0505 (13) | |
H5A | 0.6006 | 0.3875 | 0.6286 | 0.061* | |
C6 | 0.6790 (7) | 0.3214 (3) | 0.5347 (2) | 0.0408 (11) | |
H6A | 0.7531 | 0.2826 | 0.5645 | 0.049* | |
C11 | 0.9449 (6) | 0.1878 (3) | 0.4702 (2) | 0.0291 (8) | |
C12 | 0.9285 (7) | 0.1090 (3) | 0.4999 (3) | 0.0499 (13) | |
H12A | 0.8208 | 0.0769 | 0.4855 | 0.060* | |
C13 | 1.0680 (8) | 0.0754 (4) | 0.5510 (3) | 0.0633 (16) | |
H13A | 1.0567 | 0.0203 | 0.5697 | 0.076* | |
C14 | 1.2194 (8) | 0.1217 (4) | 0.5739 (3) | 0.0555 (14) | |
H14A | 1.3128 | 0.0994 | 0.6096 | 0.067* | |
C15 | 1.2378 (7) | 0.2005 (4) | 0.5454 (3) | 0.0571 (15) | |
H15A | 1.3440 | 0.2327 | 0.5618 | 0.069* | |
C16 | 1.1040 (6) | 0.2336 (3) | 0.4934 (3) | 0.0411 (11) | |
H16A | 1.1201 | 0.2878 | 0.4731 | 0.049* | |
C21 | 0.2016 (6) | 0.1364 (2) | 0.1496 (2) | 0.0277 (8) | |
C22 | 0.2914 (6) | 0.2072 (3) | 0.1246 (2) | 0.0369 (10) | |
H22A | 0.2956 | 0.2549 | 0.1574 | 0.044* | |
C23 | 0.3751 (7) | 0.2099 (3) | 0.0527 (3) | 0.0427 (11) | |
H23A | 0.4388 | 0.2582 | 0.0369 | 0.051* | |
C24 | 0.3638 (6) | 0.1407 (3) | 0.0048 (3) | 0.0422 (11) | |
H24A | 0.4201 | 0.1418 | −0.0445 | 0.051* | |
C26 | 0.1931 (6) | 0.0673 (3) | 0.1003 (2) | 0.0349 (10) | |
H26A | 0.1332 | 0.0180 | 0.1163 | 0.042* | |
C27 | 0.2730 (7) | 0.0709 (3) | 0.0274 (3) | 0.0426 (12) | |
H27A | 0.2643 | 0.0244 | −0.0069 | 0.051* | |
C31 | −0.0589 (5) | 0.0526 (2) | 0.2446 (2) | 0.0265 (8) | |
C32 | −0.2186 (6) | 0.0556 (3) | 0.1934 (2) | 0.0328 (9) | |
H32A | −0.2370 | 0.1017 | 0.1591 | 0.039* | |
C33 | −0.3494 (7) | −0.0070 (3) | 0.1918 (3) | 0.0396 (11) | |
H33A | −0.4560 | −0.0041 | 0.1562 | 0.047* | |
C34 | −0.3262 (7) | −0.0743 (3) | 0.2420 (3) | 0.0409 (11) | |
H34A | −0.4162 | −0.1176 | 0.2408 | 0.049* | |
C35 | −0.1717 (7) | −0.0778 (3) | 0.2935 (3) | 0.0417 (11) | |
H35A | −0.1560 | −0.1236 | 0.3284 | 0.050* | |
C36 | −0.0380 (6) | −0.0148 (3) | 0.2950 (3) | 0.0347 (10) | |
H36A | 0.0681 | −0.0181 | 0.3309 | 0.042* | |
C41 | 1.1751 (7) | 0.4315 (3) | 0.0975 (3) | 0.0404 (11) | |
H41A | 1.1344 | 0.3794 | 0.0711 | 0.048* | |
H41B | 1.2597 | 0.4174 | 0.1435 | 0.048* | |
C42 | 1.2751 (8) | 0.4856 (4) | 0.0414 (3) | 0.0530 (14) | |
H42A | 1.3846 | 0.4561 | 0.0231 | 0.079* | |
H42B | 1.3159 | 0.5367 | 0.0683 | 0.079* | |
H42C | 1.1902 | 0.4993 | −0.0038 | 0.079* | |
C51 | 0.7469 (6) | 0.5282 (3) | 0.2090 (2) | 0.0325 (9) | |
C52 | 0.5653 (7) | 0.5178 (3) | 0.2302 (2) | 0.0358 (10) | |
H52A | 0.5160 | 0.4633 | 0.2330 | 0.043* | |
C53 | 0.4509 (7) | 0.5847 (3) | 0.2476 (2) | 0.0372 (10) | |
H53A | 0.3251 | 0.5760 | 0.2610 | 0.045* | |
C54 | 0.5245 (6) | 0.6645 (3) | 0.2449 (2) | 0.0362 (10) | |
C55 | 0.7067 (7) | 0.6760 (3) | 0.2225 (3) | 0.0420 (11) | |
H55A | 0.7564 | 0.7304 | 0.2196 | 0.050* | |
C56 | 0.8154 (7) | 0.6092 (3) | 0.2046 (3) | 0.0417 (11) | |
H56A | 0.9394 | 0.6181 | 0.1889 | 0.050* | |
C100 | 0.5942 (6) | 0.1550 (3) | 0.3855 (2) | 0.0280 (9) | |
H10A | 0.6516 | 0.1025 | 0.3687 | 0.034* | |
H10B | 0.5388 | 0.1449 | 0.4368 | 0.034* | |
C101 | 0.4398 (6) | 0.1793 (2) | 0.3256 (2) | 0.0289 (9) | |
H10C | 0.4948 | 0.1912 | 0.2746 | 0.035* | |
H10D | 0.3780 | 0.2304 | 0.3433 | 0.035* | |
C102 | 0.2939 (5) | 0.1103 (2) | 0.3145 (2) | 0.0277 (8) | |
H10E | 0.2431 | 0.0968 | 0.3661 | 0.033* | |
H10F | 0.3551 | 0.0599 | 0.2948 | 0.033* | |
C200 | 0.2363 (7) | 0.7284 (3) | 0.2725 (3) | 0.0508 (13) | |
H20A | 0.1866 | 0.7826 | 0.2867 | 0.076* | |
H20D | 0.2107 | 0.6881 | 0.3137 | 0.076* | |
H20B | 0.1761 | 0.7102 | 0.2224 | 0.076* | |
C201 | −0.1503 (8) | 0.3042 (3) | −0.0446 (3) | 0.0482 (13) | |
H20C | −0.1390 | 0.3283 | 0.0096 | 0.058* | |
O1 | 1.0128 (4) | 0.47708 (19) | 0.12311 (17) | 0.0389 (7) | |
O2 | 0.4314 (5) | 0.73445 (19) | 0.26493 (19) | 0.0460 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.03697 (17) | 0.02438 (14) | 0.02935 (14) | 0.00030 (15) | 0.00336 (10) | 0.00300 (13) |
Cl1 | 0.0694 (11) | 0.0505 (9) | 0.0944 (12) | 0.0067 (7) | 0.0130 (8) | 0.0195 (8) |
Cl2 | 0.0545 (9) | 0.0716 (9) | 0.0544 (8) | 0.0093 (7) | 0.0008 (6) | 0.0141 (6) |
Cl3 | 0.0596 (9) | 0.0586 (8) | 0.0587 (8) | −0.0128 (6) | 0.0159 (6) | −0.0031 (6) |
S1 | 0.0480 (7) | 0.0292 (6) | 0.0345 (6) | −0.0116 (5) | −0.0139 (5) | 0.0056 (4) |
S2 | 0.0486 (7) | 0.0309 (6) | 0.0308 (5) | −0.0058 (5) | −0.0131 (5) | 0.0010 (4) |
P1 | 0.0286 (6) | 0.0237 (5) | 0.0232 (5) | −0.0026 (4) | 0.0003 (4) | 0.0017 (4) |
P2 | 0.0255 (6) | 0.0231 (5) | 0.0266 (5) | −0.0001 (4) | 0.0002 (4) | −0.0012 (4) |
P3 | 0.0407 (7) | 0.0269 (6) | 0.0290 (5) | −0.0062 (5) | −0.0058 (4) | 0.0056 (4) |
C1 | 0.031 (2) | 0.028 (2) | 0.028 (2) | −0.0052 (17) | −0.0009 (16) | 0.0004 (15) |
C2 | 0.057 (3) | 0.026 (2) | 0.034 (2) | 0.003 (2) | −0.004 (2) | −0.0016 (17) |
C3 | 0.064 (4) | 0.031 (3) | 0.052 (3) | 0.010 (2) | −0.005 (2) | −0.001 (2) |
C4 | 0.062 (4) | 0.035 (3) | 0.055 (3) | 0.013 (2) | 0.005 (2) | −0.014 (2) |
C5 | 0.066 (4) | 0.051 (3) | 0.035 (3) | 0.011 (2) | 0.004 (2) | −0.009 (2) |
C6 | 0.053 (3) | 0.038 (3) | 0.031 (2) | 0.013 (2) | 0.0005 (19) | −0.0012 (18) |
C11 | 0.026 (2) | 0.036 (2) | 0.025 (2) | −0.0024 (17) | −0.0008 (15) | −0.0031 (16) |
C12 | 0.049 (3) | 0.042 (3) | 0.056 (3) | −0.010 (2) | −0.018 (2) | 0.022 (2) |
C13 | 0.068 (4) | 0.057 (4) | 0.063 (4) | −0.004 (3) | −0.021 (3) | 0.021 (3) |
C14 | 0.054 (4) | 0.075 (4) | 0.035 (3) | 0.019 (3) | −0.015 (2) | 0.001 (2) |
C15 | 0.035 (3) | 0.082 (4) | 0.053 (3) | 0.000 (3) | −0.014 (2) | −0.019 (3) |
C16 | 0.031 (3) | 0.045 (3) | 0.047 (3) | −0.0074 (19) | −0.005 (2) | −0.0025 (19) |
C21 | 0.029 (2) | 0.030 (2) | 0.0235 (19) | −0.0007 (16) | −0.0025 (15) | 0.0043 (15) |
C22 | 0.045 (3) | 0.034 (2) | 0.032 (2) | −0.0060 (19) | −0.0013 (19) | −0.0003 (17) |
C23 | 0.044 (3) | 0.049 (3) | 0.035 (2) | −0.008 (2) | 0.004 (2) | 0.0069 (19) |
C24 | 0.034 (3) | 0.061 (3) | 0.031 (2) | 0.005 (2) | 0.0053 (18) | 0.005 (2) |
C26 | 0.040 (3) | 0.036 (3) | 0.029 (2) | 0.0003 (19) | −0.0003 (18) | −0.0038 (17) |
C27 | 0.044 (3) | 0.050 (3) | 0.034 (2) | 0.006 (2) | 0.004 (2) | −0.012 (2) |
C31 | 0.024 (2) | 0.025 (2) | 0.030 (2) | 0.0009 (15) | 0.0017 (15) | −0.0046 (15) |
C32 | 0.029 (2) | 0.036 (2) | 0.033 (2) | −0.0020 (18) | −0.0014 (17) | −0.0018 (17) |
C33 | 0.028 (3) | 0.045 (3) | 0.046 (3) | −0.005 (2) | 0.001 (2) | −0.010 (2) |
C34 | 0.035 (3) | 0.041 (3) | 0.047 (3) | −0.014 (2) | 0.011 (2) | −0.012 (2) |
C35 | 0.050 (3) | 0.031 (2) | 0.045 (3) | −0.010 (2) | 0.009 (2) | 0.0033 (18) |
C36 | 0.033 (3) | 0.032 (2) | 0.039 (2) | −0.0022 (18) | −0.0016 (18) | 0.0014 (17) |
C41 | 0.035 (3) | 0.040 (3) | 0.046 (3) | 0.001 (2) | 0.001 (2) | 0.000 (2) |
C42 | 0.043 (3) | 0.057 (3) | 0.059 (3) | 0.001 (3) | 0.012 (3) | 0.004 (3) |
C51 | 0.035 (3) | 0.032 (2) | 0.030 (2) | −0.0042 (18) | −0.0051 (17) | 0.0071 (17) |
C52 | 0.044 (3) | 0.029 (2) | 0.033 (2) | −0.0117 (19) | −0.0086 (19) | 0.0064 (16) |
C53 | 0.038 (3) | 0.040 (3) | 0.033 (2) | −0.0078 (19) | −0.0054 (18) | 0.0033 (18) |
C54 | 0.039 (3) | 0.035 (2) | 0.033 (2) | −0.0021 (19) | −0.0069 (18) | 0.0019 (17) |
C55 | 0.048 (3) | 0.028 (2) | 0.049 (3) | −0.008 (2) | 0.003 (2) | 0.0045 (19) |
C56 | 0.042 (3) | 0.034 (2) | 0.050 (3) | −0.010 (2) | 0.004 (2) | 0.0049 (19) |
C100 | 0.028 (2) | 0.028 (2) | 0.028 (2) | −0.0046 (16) | −0.0020 (16) | 0.0027 (15) |
C101 | 0.030 (2) | 0.027 (2) | 0.030 (2) | −0.0026 (16) | −0.0002 (16) | 0.0004 (15) |
C102 | 0.025 (2) | 0.030 (2) | 0.028 (2) | −0.0042 (16) | −0.0005 (15) | −0.0028 (15) |
C200 | 0.043 (3) | 0.055 (3) | 0.054 (3) | 0.002 (2) | 0.000 (2) | −0.005 (2) |
C201 | 0.055 (3) | 0.055 (3) | 0.035 (3) | −0.001 (2) | 0.007 (2) | 0.006 (2) |
O1 | 0.042 (2) | 0.0379 (17) | 0.0370 (17) | 0.0015 (14) | 0.0019 (13) | 0.0153 (13) |
O2 | 0.047 (2) | 0.0360 (17) | 0.055 (2) | 0.0019 (14) | −0.0026 (15) | −0.0072 (14) |
Ag1—P2i | 2.4424 (11) | C24—H24A | 0.9500 |
Ag1—P1 | 2.4575 (12) | C26—C27 | 1.393 (6) |
Ag1—S1 | 2.6343 (12) | C26—H26A | 0.9500 |
Ag1—S2 | 2.6610 (12) | C27—H27A | 0.9500 |
Cl1—C201 | 1.725 (5) | C31—C36 | 1.389 (6) |
Cl2—C201 | 1.753 (6) | C31—C32 | 1.401 (5) |
Cl3—C201 | 1.773 (5) | C32—C33 | 1.375 (6) |
S1—P3 | 1.9968 (16) | C32—H32A | 0.9500 |
S2—P3 | 1.9964 (15) | C33—C34 | 1.385 (7) |
P1—C1 | 1.815 (4) | C33—H33A | 0.9500 |
P1—C11 | 1.824 (4) | C34—C35 | 1.375 (6) |
P1—C100 | 1.834 (4) | C34—H34A | 0.9500 |
P2—C21 | 1.811 (4) | C35—C36 | 1.395 (6) |
P2—C31 | 1.818 (4) | C35—H35A | 0.9500 |
P2—C102 | 1.840 (4) | C36—H36A | 0.9500 |
P2—Ag1ii | 2.4424 (11) | C41—O1 | 1.459 (6) |
P3—O1 | 1.605 (3) | C41—C42 | 1.502 (7) |
P3—C51 | 1.800 (5) | C41—H41A | 0.9900 |
C1—C6 | 1.393 (6) | C41—H41B | 0.9900 |
C1—C2 | 1.396 (6) | C42—H42A | 0.9800 |
C2—C3 | 1.377 (7) | C42—H42B | 0.9800 |
C2—H2A | 0.9500 | C42—H42C | 0.9800 |
C3—C4 | 1.366 (7) | C51—C52 | 1.376 (6) |
C3—H3A | 0.9500 | C51—C56 | 1.399 (6) |
C4—C5 | 1.380 (7) | C52—C53 | 1.395 (6) |
C4—H4A | 0.9500 | C52—H52A | 0.9500 |
C5—C6 | 1.372 (6) | C53—C54 | 1.392 (6) |
C5—H5A | 0.9500 | C53—H53A | 0.9500 |
C6—H6A | 0.9500 | C54—O2 | 1.363 (5) |
C11—C12 | 1.376 (6) | C54—C55 | 1.388 (6) |
C11—C16 | 1.396 (6) | C55—C56 | 1.372 (6) |
C12—C13 | 1.398 (6) | C55—H55A | 0.9500 |
C12—H12A | 0.9500 | C56—H56A | 0.9500 |
C13—C14 | 1.355 (8) | C100—C101 | 1.515 (5) |
C13—H13A | 0.9500 | C100—H10A | 0.9900 |
C14—C15 | 1.370 (8) | C100—H10B | 0.9900 |
C14—H14A | 0.9500 | C101—C102 | 1.531 (5) |
C15—C16 | 1.377 (7) | C101—H10C | 0.9900 |
C15—H15A | 0.9500 | C101—H10D | 0.9900 |
C16—H16A | 0.9500 | C102—H10E | 0.9900 |
C21—C22 | 1.389 (6) | C102—H10F | 0.9900 |
C21—C26 | 1.394 (5) | C200—O2 | 1.410 (6) |
C22—C23 | 1.389 (6) | C200—H20A | 0.9800 |
C22—H22A | 0.9500 | C200—H20D | 0.9800 |
C23—C24 | 1.381 (7) | C200—H20B | 0.9800 |
C23—H23A | 0.9500 | C201—H20C | 1.0000 |
C24—C27 | 1.366 (7) | ||
P2i—Ag1—P1 | 104.67 (4) | C36—C31—C32 | 118.0 (4) |
P2i—Ag1—S1 | 128.23 (4) | C36—C31—P2 | 124.2 (3) |
P1—Ag1—S1 | 109.36 (4) | C32—C31—P2 | 117.7 (3) |
P2i—Ag1—S2 | 116.14 (4) | C33—C32—C31 | 121.2 (4) |
P1—Ag1—S2 | 119.67 (4) | C33—C32—H32A | 119.4 |
S1—Ag1—S2 | 78.33 (4) | C31—C32—H32A | 119.4 |
P3—S1—Ag1 | 84.30 (5) | C32—C33—C34 | 120.2 (4) |
P3—S2—Ag1 | 83.59 (5) | C32—C33—H33A | 119.9 |
C1—P1—C11 | 104.17 (18) | C34—C33—H33A | 119.9 |
C1—P1—C100 | 103.43 (19) | C35—C34—C33 | 119.5 (4) |
C11—P1—C100 | 103.66 (18) | C35—C34—H34A | 120.3 |
C1—P1—Ag1 | 120.16 (13) | C33—C34—H34A | 120.3 |
C11—P1—Ag1 | 109.63 (14) | C34—C35—C36 | 120.6 (4) |
C100—P1—Ag1 | 114.16 (13) | C34—C35—H35A | 119.7 |
C21—P2—C31 | 104.37 (18) | C36—C35—H35A | 119.7 |
C21—P2—C102 | 104.16 (19) | C31—C36—C35 | 120.5 (4) |
C31—P2—C102 | 104.26 (18) | C31—C36—H36A | 119.7 |
C21—P2—Ag1ii | 116.94 (13) | C35—C36—H36A | 119.7 |
C31—P2—Ag1ii | 110.26 (13) | O1—C41—C42 | 108.0 (4) |
C102—P2—Ag1ii | 115.54 (13) | O1—C41—H41A | 110.1 |
O1—P3—C51 | 98.94 (18) | C42—C41—H41A | 110.1 |
O1—P3—S2 | 111.41 (13) | O1—C41—H41B | 110.1 |
C51—P3—S2 | 110.69 (15) | C42—C41—H41B | 110.1 |
O1—P3—S1 | 109.68 (13) | H41A—C41—H41B | 108.4 |
C51—P3—S1 | 111.41 (14) | C41—C42—H42A | 109.5 |
S2—P3—S1 | 113.76 (7) | C41—C42—H42B | 109.5 |
C6—C1—C2 | 118.0 (4) | H42A—C42—H42B | 109.5 |
C6—C1—P1 | 123.5 (3) | C41—C42—H42C | 109.5 |
C2—C1—P1 | 118.4 (3) | H42A—C42—H42C | 109.5 |
C3—C2—C1 | 120.7 (4) | H42B—C42—H42C | 109.5 |
C3—C2—H2A | 119.7 | C52—C51—C56 | 117.8 (4) |
C1—C2—H2A | 119.7 | C52—C51—P3 | 121.2 (3) |
C4—C3—C2 | 120.0 (5) | C56—C51—P3 | 120.9 (4) |
C4—C3—H3A | 120.0 | C51—C52—C53 | 122.2 (4) |
C2—C3—H3A | 120.0 | C51—C52—H52A | 118.9 |
C3—C4—C5 | 120.5 (4) | C53—C52—H52A | 118.9 |
C3—C4—H4A | 119.8 | C52—C53—C54 | 118.8 (4) |
C5—C4—H4A | 119.8 | C52—C53—H53A | 120.6 |
C6—C5—C4 | 119.7 (4) | C54—C53—H53A | 120.6 |
C6—C5—H5A | 120.2 | O2—C54—C55 | 115.8 (4) |
C4—C5—H5A | 120.2 | O2—C54—C53 | 124.6 (4) |
C5—C6—C1 | 121.0 (4) | C55—C54—C53 | 119.6 (4) |
C5—C6—H6A | 119.5 | C56—C55—C54 | 120.4 (4) |
C1—C6—H6A | 119.5 | C56—C55—H55A | 119.8 |
C12—C11—C16 | 118.0 (4) | C54—C55—H55A | 119.8 |
C12—C11—P1 | 123.9 (3) | C55—C56—C51 | 121.2 (5) |
C16—C11—P1 | 118.0 (3) | C55—C56—H56A | 119.4 |
C11—C12—C13 | 121.0 (5) | C51—C56—H56A | 119.4 |
C11—C12—H12A | 119.5 | C101—C100—P1 | 113.1 (3) |
C13—C12—H12A | 119.5 | C101—C100—H10A | 109.0 |
C14—C13—C12 | 119.9 (5) | P1—C100—H10A | 109.0 |
C14—C13—H13A | 120.0 | C101—C100—H10B | 109.0 |
C12—C13—H13A | 120.0 | P1—C100—H10B | 109.0 |
C13—C14—C15 | 120.0 (5) | H10A—C100—H10B | 107.8 |
C13—C14—H14A | 120.0 | C100—C101—C102 | 111.2 (3) |
C15—C14—H14A | 120.0 | C100—C101—H10C | 109.4 |
C14—C15—C16 | 120.7 (5) | C102—C101—H10C | 109.4 |
C14—C15—H15A | 119.6 | C100—C101—H10D | 109.4 |
C16—C15—H15A | 119.6 | C102—C101—H10D | 109.4 |
C15—C16—C11 | 120.4 (5) | H10C—C101—H10D | 108.0 |
C15—C16—H16A | 119.8 | C101—C102—P2 | 111.8 (3) |
C11—C16—H16A | 119.8 | C101—C102—H10E | 109.2 |
C22—C21—C26 | 118.7 (4) | P2—C102—H10E | 109.2 |
C22—C21—P2 | 117.2 (3) | C101—C102—H10F | 109.2 |
C26—C21—P2 | 124.1 (3) | P2—C102—H10F | 109.2 |
C21—C22—C23 | 121.4 (4) | H10E—C102—H10F | 107.9 |
C21—C22—H22A | 119.3 | O2—C200—H20A | 109.5 |
C23—C22—H22A | 119.3 | O2—C200—H20D | 109.5 |
C24—C23—C22 | 118.7 (4) | H20A—C200—H20D | 109.5 |
C24—C23—H23A | 120.7 | O2—C200—H20B | 109.5 |
C22—C23—H23A | 120.7 | H20A—C200—H20B | 109.5 |
C27—C24—C23 | 121.0 (4) | H20D—C200—H20B | 109.5 |
C27—C24—H24A | 119.5 | Cl1—C201—Cl2 | 111.4 (3) |
C23—C24—H24A | 119.5 | Cl1—C201—Cl3 | 110.4 (3) |
C27—C26—C21 | 119.7 (4) | Cl2—C201—Cl3 | 109.7 (3) |
C27—C26—H26A | 120.1 | Cl1—C201—H20C | 108.4 |
C21—C26—H26A | 120.1 | Cl2—C201—H20C | 108.4 |
C24—C27—C26 | 120.4 (4) | Cl3—C201—H20C | 108.4 |
C24—C27—H27A | 119.8 | C41—O1—P3 | 119.2 (3) |
C26—C27—H27A | 119.8 | C54—O2—C200 | 117.6 (4) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C27H26P2)(C9H12O2PS2)]·CHCl3 |
Mr | 886.93 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 7.1493 (14), 16.137 (3), 17.010 (3) |
β (°) | 92.95 (3) |
V (Å3) | 1959.8 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.98 |
Crystal size (mm) | 0.10 × 0.08 × 0.08 |
Data collection | |
Diffractometer | Oxford Gemini S Ultra diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.908, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26211, 7381, 6876 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.074, 1.01 |
No. of reflections | 7381 |
No. of parameters | 433 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.78 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | −0.01 (2) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008) and SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Ag1—P2i | 2.4424 (11) | Ag1—S1 | 2.6343 (12) |
Ag1—P1 | 2.4575 (12) | Ag1—S2 | 2.6610 (12) |
P2i—Ag1—P1 | 104.67 (4) | P2i—Ag1—S2 | 116.14 (4) |
P2i—Ag1—S1 | 128.23 (4) | P1—Ag1—S2 | 119.67 (4) |
P1—Ag1—S1 | 109.36 (4) | S1—Ag1—S2 | 78.33 (4) |
Symmetry code: (i) x+1, y, z. |
The design and construction of coordination structures is one of the most attractive areas of crystal engineering, due to their intriguing structural motifs and functional properties (Chen et al., 2010; Blake, Brooks et al., 1999; Blake, Champness et al., 1999; Evans & Lin, 2002; Kitagawa et al., 2004; Yaghi et al., 2003; Sun et al., 2011). Organophosphorus sulfide reagents like P4S10, Lawesson's reagent [2,4-bis(4-methoxyphenyl)-1,3-dithiadiphosphetane-2,4-disulfide, LR; see first scheme], and modified LRs such as Davy's reagent, Japanese reagent and Belleau's reagent have been successfully employed as thionation agents for organic substrates to give thiolactones and thiocarbonyls (Scheibye et al., 1981; Jesberger et al., 2003; Foreman & Woollins, 2000; Ozturk et al., 2007). The LR containing a four-membered P2S2 ring with alternating P and S atoms can be in equilibrium with a highly reactive dithiophosphine ylide [ArPS2]- (Ar = 4-methoxyphenyl), which reacts with carbonyl-containing compounds to form P/S-containing anionic ligands. Subsequent assembly of anionic ligands into large CuI or AgI aggregates has been reported as an efficient synthetic route to a broader variety of coordination polymers or clusters (Shi, Shafaei-Fallah et al., 2005 or Shi, Ahlrichs et al., 2005 ?). Recently, we used this versatile precursor to construct an Ag20 cluster based on in situ-generated bipodal [ArP(OEt)S2]- and tripodal [ArPOS2]2- ligands incorporating the auxiliary Ph3P (triphenylphosphane) ligand (Sun et al., 2010). As an extension of our work, we replaced the auxiliary Ph3P by the 1,3-bis(diphenylphosphanyl)propane (dppp) ligand and intended to exploit the influence of an auxiliary P-donor on the structures of the AgOAc–LR system, and the title compound, (I) (see second scheme), was obtained as an infinite chain.
The asymmetric unit of (I) contains one AgI cation, one dppp ligand, one anionic [ArP(OEt)S2]- ligand and one solvent chloroform molecule. As shown in Fig. 1, the AgI cation is in a tetrahedral environment, completed by two P atoms from two dppp ligands and two S atoms from one [ArP(OEt)S2]- ligand, with average Ag—P and Ag—S bond lengths of 2.4500 (11) and 2.6477 (12) Å, respectively. The distortion of the tetrahedron can be indicated by the calculated value of the τ4 parameter (Yang et al., 2007) to describe the geometry of a four-coordinate metal system, which is 0.80 for Ag1 (for perfect tetrahedral geometry, τ4 = 1). The Ag—P and Ag—S bond lengths (Table 1) are comparable with reported values (Shi et al., 2007).
In (I), the [ArP(OEt)S2]- anion is a bidentate chelating ligand which coordinates one AgI centre to form the [Ag(ArP(OEt)S2)] subunit. The bidentate bridging dppp ligands link the [Ag(ArP(OEt)S2)] subunits to form an achiral one-diemsnional infinite chain along the a axis (Fig. 2). There are no obvious hydrogen-bonding or π-stacking interactions between adjacent chains. Therefore, these achiral chains are packed into chiral crystals by virtue of van der Waals interactions. The chloroform molecules minimize the voids in the crystal structure.
The most fascinating feature of (I) is the in situ-generated anionic [ArP(OEt)S2]- ligand. In spite of the disassociation of LRs into S2-, [ArP(O)S2]2-, [ArS2P-O-PS2Ar]2-, [ArPS3]2- and [ArP(O)(OAc)S]- ligands that has been observed (Shi, Shafaei-Fallah et al., 2005), it is noteworthy that the generation of the bipodal [ArP(OEt)S2]- ligand in the course of the reaction between AgOAc and LR is rarely observed. The formation of the bipodal [ArP(OEt)S2]- anion involves P—S and C—O bond cleavages of LR and OAc-, respectively. To the best of our knowledge, the P—O bond is much stronger than the P—S bond, which makes LRs vulnerable to attack by potential nucleophiles, electrophiles and radicals, as demonstrated by Rauchfuss & Zank (1986), whereby the LR underwent reversible cleavage to give ArPS2. radicals. This could be concluded to be one of the important thermodynamic driving forces behind the formation of the P/S ligand.