Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014125/cv6136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014125/cv6136Isup2.hkl |
CCDC reference: 197447
Key indicators
- Single-crystal X-ray study
- T = 178 K
- Mean (C-C) = 0.005 Å
- R factor = 0.040
- wR factor = 0.108
- Data-to-parameter ratio = 13.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.884 Tmax scaled 0.877 Tmin scaled 0.708
The reaction between (norbornadiene)Cr(CO)4 and N,N'-bis(diphenylphosphino)-N,N'-dimethylthiourea in dichloromethane led to a complex mixture of products. The mixture was dissolved in diethyl ether, from which the title compound crystallized in 13% yield (Farkens, 1991). The decomposition of the thiourea to tetraphenyldiphosphine monosulfide has been observed before in our laboratory (Gruber, 1989).
H atoms were included using a riding model with fixed C—H bond lengths of 0.95 Å; Uiso(H) values were fixed at 1.2 times the Ueq of the parent atom.
Data collection: P3 (Nicolet, 1987); cell refinement: P3; data reduction: XDISK (Nicolet, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule of compound (I) in the crystal. Displacement ellipsoids represent 30% probability levels. H-atom radii are arbitrary. |
[Cr(C24H20P2S)(CO)5] | Z = 2 |
Mr = 594.45 | F(000) = 608 |
Triclinic, P1 | Dx = 1.466 Mg m−3 |
a = 9.840 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.089 (5) Å | Cell parameters from 50 reflections |
c = 14.967 (6) Å | θ = 10–11.5° |
α = 77.90 (3)° | µ = 0.66 mm−1 |
β = 84.43 (3)° | T = 178 K |
γ = 68.02 (3)° | Tablet, yellow |
V = 1347.0 (10) Å3 | 0.5 × 0.5 × 0.2 mm |
Nicolet R3 diffractometer | 3476 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 25.1°, θmin = 3.1° |
ω scans | h = −11→11 |
Absorption correction: ψ scan (XEMP; Nicolet, 1987) | k = −11→11 |
Tmin = 0.801, Tmax = 0.991 | l = −12→17 |
5120 measured reflections | 3 standard reflections every 147 reflections |
4578 independent reflections | intensity decay: none |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0464P)2 + 1.6663P] where P = (Fo2 + 2Fc2)/3 |
4578 reflections | (Δ/σ)max < 0.001 |
343 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[Cr(C24H20P2S)(CO)5] | γ = 68.02 (3)° |
Mr = 594.45 | V = 1347.0 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.840 (3) Å | Mo Kα radiation |
b = 10.089 (5) Å | µ = 0.66 mm−1 |
c = 14.967 (6) Å | T = 178 K |
α = 77.90 (3)° | 0.5 × 0.5 × 0.2 mm |
β = 84.43 (3)° |
Nicolet R3 diffractometer | 3476 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XEMP; Nicolet, 1987) | Rint = 0.038 |
Tmin = 0.801, Tmax = 0.991 | 3 standard reflections every 147 reflections |
5120 measured reflections | intensity decay: none |
4578 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.48 e Å−3 |
4578 reflections | Δρmin = −0.47 e Å−3 |
343 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 | ||
Cr | 0.12119 (5) | 0.22328 (5) | 0.40722 (3) | 0.02628 (15) | |
S | 0.06062 (9) | 0.57737 (10) | 0.15723 (6) | 0.0382 (2) | |
P1 | 0.23659 (8) | 0.21117 (8) | 0.25938 (5) | 0.02230 (19) | |
P2 | 0.25228 (8) | 0.42161 (8) | 0.17823 (5) | 0.02327 (19) | |
O1 | 0.3039 (3) | −0.0945 (3) | 0.47601 (17) | 0.0481 (7) | |
O2 | 0.3385 (3) | 0.3212 (3) | 0.48080 (17) | 0.0508 (7) | |
O3 | −0.0302 (3) | 0.2233 (3) | 0.59188 (18) | 0.0514 (7) | |
O4 | −0.1003 (3) | 0.1140 (3) | 0.35052 (18) | 0.0489 (7) | |
O5 | −0.0987 (3) | 0.5345 (3) | 0.3672 (2) | 0.0626 (8) | |
C1 | 0.4255 (3) | 0.0849 (3) | 0.2502 (2) | 0.0240 (6) | |
C2 | 0.4827 (3) | 0.0388 (3) | 0.1683 (2) | 0.0299 (7) | |
H2 | 0.4217 | 0.0691 | 0.1168 | 0.036* | |
C3 | 0.6278 (4) | −0.0508 (4) | 0.1620 (3) | 0.0378 (8) | |
H3 | 0.6666 | −0.0801 | 0.1056 | 0.045* | |
C4 | 0.7171 (4) | −0.0983 (4) | 0.2370 (3) | 0.0425 (9) | |
H4 | 0.8160 | −0.1620 | 0.2327 | 0.051* | |
C5 | 0.6619 (4) | −0.0527 (4) | 0.3175 (2) | 0.0400 (9) | |
H5 | 0.7235 | −0.0837 | 0.3688 | 0.048* | |
C6 | 0.5170 (3) | 0.0381 (4) | 0.3248 (2) | 0.0321 (7) | |
H6 | 0.4799 | 0.0687 | 0.3810 | 0.038* | |
C7 | 0.1355 (3) | 0.1573 (3) | 0.1860 (2) | 0.0237 (6) | |
C8 | 0.0092 (4) | 0.2571 (4) | 0.1432 (2) | 0.0365 (8) | |
H8 | −0.0171 | 0.3576 | 0.1435 | 0.044* | |
C9 | −0.0793 (4) | 0.2120 (4) | 0.0998 (3) | 0.0450 (9) | |
H9 | −0.1650 | 0.2815 | 0.0699 | 0.054* | |
C10 | −0.0430 (4) | 0.0660 (4) | 0.1002 (2) | 0.0407 (9) | |
H10 | −0.1036 | 0.0350 | 0.0704 | 0.049* | |
C11 | 0.0804 (4) | −0.0344 (4) | 0.1435 (2) | 0.0405 (9) | |
H11 | 0.1046 | −0.1350 | 0.1442 | 0.049* | |
C12 | 0.1698 (3) | 0.0107 (4) | 0.1862 (2) | 0.0322 (7) | |
H12 | 0.2554 | −0.0594 | 0.2159 | 0.039* | |
C13 | 0.3465 (3) | 0.3827 (3) | 0.0705 (2) | 0.0245 (6) | |
C14 | 0.2578 (4) | 0.3983 (4) | −0.0014 (2) | 0.0325 (7) | |
H14 | 0.1543 | 0.4310 | 0.0070 | 0.039* | |
C15 | 0.3201 (4) | 0.3664 (4) | −0.0847 (2) | 0.0397 (8) | |
H15 | 0.2593 | 0.3772 | −0.1334 | 0.048* | |
C16 | 0.4705 (4) | 0.3189 (4) | −0.0978 (2) | 0.0358 (8) | |
H16 | 0.5133 | 0.2968 | −0.1551 | 0.043* | |
C17 | 0.5573 (4) | 0.3040 (4) | −0.0273 (2) | 0.0378 (8) | |
H17 | 0.6607 | 0.2715 | −0.0362 | 0.045* | |
C18 | 0.4972 (3) | 0.3354 (4) | 0.0562 (2) | 0.0324 (7) | |
H18 | 0.5592 | 0.3245 | 0.1042 | 0.039* | |
C19 | 0.3649 (3) | 0.4636 (3) | 0.2496 (2) | 0.0265 (7) | |
C20 | 0.5115 (3) | 0.3782 (4) | 0.2695 (2) | 0.0311 (7) | |
H20 | 0.5586 | 0.2917 | 0.2455 | 0.037* | |
C21 | 0.5876 (4) | 0.4198 (4) | 0.3243 (3) | 0.0435 (9) | |
H21 | 0.6875 | 0.3623 | 0.3370 | 0.052* | |
C22 | 0.5201 (4) | 0.5442 (4) | 0.3606 (3) | 0.0466 (10) | |
H22 | 0.5737 | 0.5726 | 0.3976 | 0.056* | |
C23 | 0.3750 (4) | 0.6270 (4) | 0.3433 (2) | 0.0412 (9) | |
H23 | 0.3280 | 0.7119 | 0.3689 | 0.049* | |
C24 | 0.2971 (4) | 0.5864 (4) | 0.2883 (2) | 0.0336 (8) | |
H24 | 0.1966 | 0.6432 | 0.2771 | 0.040* | |
C25 | 0.2382 (4) | 0.0257 (4) | 0.4483 (2) | 0.0333 (8) | |
C26 | 0.2590 (4) | 0.2869 (4) | 0.4496 (2) | 0.0346 (8) | |
C27 | 0.0275 (4) | 0.2238 (4) | 0.5217 (2) | 0.0365 (8) | |
C28 | −0.0164 (4) | 0.1567 (4) | 0.3695 (2) | 0.0334 (8) | |
C29 | −0.0118 (4) | 0.4205 (4) | 0.3756 (2) | 0.0376 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr | 0.0250 (3) | 0.0285 (3) | 0.0259 (3) | −0.0090 (2) | 0.0015 (2) | −0.0087 (2) |
S | 0.0323 (5) | 0.0326 (5) | 0.0487 (5) | −0.0077 (4) | −0.0059 (4) | −0.0106 (4) |
P1 | 0.0210 (4) | 0.0235 (4) | 0.0235 (4) | −0.0079 (3) | −0.0023 (3) | −0.0061 (3) |
P2 | 0.0222 (4) | 0.0219 (4) | 0.0263 (4) | −0.0072 (3) | −0.0029 (3) | −0.0064 (3) |
O1 | 0.0527 (16) | 0.0344 (15) | 0.0443 (15) | −0.0035 (13) | 0.0030 (12) | −0.0054 (12) |
O2 | 0.0583 (17) | 0.076 (2) | 0.0383 (14) | −0.0420 (16) | 0.0004 (12) | −0.0207 (14) |
O3 | 0.0471 (16) | 0.0629 (18) | 0.0383 (15) | −0.0131 (14) | 0.0133 (13) | −0.0162 (13) |
O4 | 0.0420 (15) | 0.0630 (18) | 0.0549 (17) | −0.0323 (14) | 0.0076 (12) | −0.0182 (14) |
O5 | 0.0576 (18) | 0.0338 (16) | 0.078 (2) | −0.0006 (14) | 0.0144 (15) | −0.0092 (14) |
C1 | 0.0206 (15) | 0.0214 (16) | 0.0314 (17) | −0.0087 (13) | −0.0002 (12) | −0.0059 (13) |
C2 | 0.0304 (17) | 0.0277 (17) | 0.0353 (18) | −0.0139 (14) | 0.0006 (14) | −0.0077 (14) |
C3 | 0.038 (2) | 0.0325 (19) | 0.045 (2) | −0.0148 (16) | 0.0101 (16) | −0.0133 (16) |
C4 | 0.0242 (17) | 0.0287 (19) | 0.065 (3) | −0.0028 (15) | 0.0035 (17) | −0.0037 (18) |
C5 | 0.0281 (18) | 0.040 (2) | 0.042 (2) | −0.0064 (16) | −0.0068 (15) | 0.0037 (17) |
C6 | 0.0257 (16) | 0.0367 (19) | 0.0304 (18) | −0.0091 (15) | −0.0002 (13) | −0.0033 (15) |
C7 | 0.0258 (15) | 0.0263 (16) | 0.0232 (15) | −0.0137 (13) | −0.0018 (12) | −0.0049 (13) |
C8 | 0.0358 (19) | 0.0293 (18) | 0.047 (2) | −0.0136 (15) | −0.0133 (16) | −0.0035 (16) |
C9 | 0.044 (2) | 0.049 (2) | 0.048 (2) | −0.0264 (19) | −0.0226 (17) | 0.0054 (18) |
C10 | 0.049 (2) | 0.057 (2) | 0.0329 (19) | −0.036 (2) | −0.0030 (16) | −0.0122 (17) |
C11 | 0.047 (2) | 0.037 (2) | 0.050 (2) | −0.0229 (18) | 0.0062 (17) | −0.0222 (17) |
C12 | 0.0280 (17) | 0.0294 (18) | 0.0408 (19) | −0.0107 (14) | 0.0000 (14) | −0.0102 (15) |
C13 | 0.0306 (16) | 0.0176 (15) | 0.0275 (16) | −0.0090 (13) | −0.0035 (13) | −0.0071 (12) |
C14 | 0.0287 (17) | 0.0345 (19) | 0.0322 (18) | −0.0090 (15) | −0.0038 (14) | −0.0053 (15) |
C15 | 0.048 (2) | 0.044 (2) | 0.0318 (19) | −0.0170 (18) | −0.0074 (16) | −0.0127 (16) |
C16 | 0.046 (2) | 0.0350 (19) | 0.0299 (18) | −0.0184 (17) | 0.0071 (15) | −0.0095 (15) |
C17 | 0.0317 (18) | 0.044 (2) | 0.043 (2) | −0.0179 (16) | 0.0079 (15) | −0.0153 (17) |
C18 | 0.0284 (17) | 0.041 (2) | 0.0309 (18) | −0.0162 (15) | −0.0004 (14) | −0.0076 (15) |
C19 | 0.0298 (16) | 0.0250 (16) | 0.0279 (17) | −0.0120 (14) | −0.0020 (13) | −0.0078 (13) |
C20 | 0.0294 (17) | 0.0322 (18) | 0.0329 (18) | −0.0104 (14) | −0.0046 (14) | −0.0088 (14) |
C21 | 0.0330 (19) | 0.051 (2) | 0.048 (2) | −0.0134 (17) | −0.0117 (16) | −0.0115 (18) |
C22 | 0.051 (2) | 0.061 (3) | 0.043 (2) | −0.029 (2) | −0.0081 (18) | −0.0207 (19) |
C23 | 0.049 (2) | 0.048 (2) | 0.038 (2) | −0.0228 (19) | 0.0023 (17) | −0.0228 (17) |
C24 | 0.0311 (17) | 0.0357 (19) | 0.0377 (19) | −0.0140 (15) | 0.0016 (14) | −0.0123 (15) |
C25 | 0.0331 (18) | 0.041 (2) | 0.0270 (17) | −0.0135 (17) | 0.0063 (14) | −0.0108 (16) |
C26 | 0.0401 (19) | 0.042 (2) | 0.0236 (17) | −0.0165 (17) | 0.0037 (14) | −0.0099 (15) |
C27 | 0.0307 (18) | 0.036 (2) | 0.040 (2) | −0.0062 (15) | 0.0007 (16) | −0.0128 (16) |
C28 | 0.0320 (18) | 0.037 (2) | 0.0316 (18) | −0.0138 (16) | 0.0048 (14) | −0.0075 (15) |
C29 | 0.0373 (19) | 0.032 (2) | 0.042 (2) | −0.0111 (17) | 0.0073 (16) | −0.0123 (16) |
Cr—C27 | 1.865 (4) | C8—H8 | 0.9500 |
Cr—C25 | 1.893 (4) | C9—C10 | 1.378 (5) |
Cr—C28 | 1.895 (4) | C9—H9 | 0.9500 |
Cr—C26 | 1.909 (4) | C10—C11 | 1.369 (5) |
Cr—C29 | 1.916 (4) | C10—H10 | 0.9500 |
Cr—P1 | 2.3921 (13) | C11—C12 | 1.386 (5) |
S—P2 | 1.9531 (15) | C11—H11 | 0.9500 |
P1—C1 | 1.830 (3) | C12—H12 | 0.9500 |
P1—C7 | 1.833 (3) | C13—C18 | 1.387 (4) |
P1—P2 | 2.2659 (15) | C13—C14 | 1.399 (4) |
P2—C13 | 1.821 (3) | C14—C15 | 1.381 (5) |
P2—C19 | 1.822 (3) | C14—H14 | 0.9500 |
O1—C25 | 1.146 (4) | C15—C16 | 1.382 (5) |
O2—C26 | 1.135 (4) | C15—H15 | 0.9500 |
O3—C27 | 1.144 (4) | C16—C17 | 1.371 (5) |
O4—C28 | 1.144 (4) | C16—H16 | 0.9500 |
O5—C29 | 1.138 (4) | C17—C18 | 1.376 (5) |
C1—C6 | 1.391 (4) | C17—H17 | 0.9500 |
C1—C2 | 1.394 (4) | C18—H18 | 0.9500 |
C2—C3 | 1.382 (5) | C19—C24 | 1.387 (4) |
C2—H2 | 0.9500 | C19—C20 | 1.399 (4) |
C3—C4 | 1.383 (5) | C20—C21 | 1.381 (5) |
C3—H3 | 0.9500 | C20—H20 | 0.9500 |
C4—C5 | 1.371 (5) | C21—C22 | 1.380 (5) |
C4—H4 | 0.9500 | C21—H21 | 0.9500 |
C5—C6 | 1.384 (5) | C22—C23 | 1.376 (5) |
C5—H5 | 0.9500 | C22—H22 | 0.9500 |
C6—H6 | 0.9500 | C23—C24 | 1.389 (5) |
C7—C8 | 1.384 (4) | C23—H23 | 0.9500 |
C7—C12 | 1.388 (4) | C24—H24 | 0.9500 |
C8—C9 | 1.384 (5) | ||
C27—Cr—C25 | 88.48 (15) | C10—C9—H9 | 120.1 |
C27—Cr—C28 | 88.55 (15) | C8—C9—H9 | 120.1 |
C25—Cr—C28 | 87.44 (15) | C11—C10—C9 | 120.1 (3) |
C27—Cr—C26 | 89.65 (15) | C11—C10—H10 | 119.9 |
C25—Cr—C26 | 91.50 (15) | C9—C10—H10 | 119.9 |
C28—Cr—C26 | 177.94 (14) | C10—C11—C12 | 120.0 (3) |
C27—Cr—C29 | 85.89 (15) | C10—C11—H11 | 120.0 |
C25—Cr—C29 | 173.94 (14) | C12—C11—H11 | 120.0 |
C28—Cr—C29 | 90.19 (15) | C11—C12—C7 | 120.6 (3) |
C26—Cr—C29 | 90.69 (16) | C11—C12—H12 | 119.7 |
C27—Cr—P1 | 176.55 (11) | C7—C12—H12 | 119.7 |
C25—Cr—P1 | 89.77 (10) | C18—C13—C14 | 118.7 (3) |
C28—Cr—P1 | 88.40 (10) | C18—C13—P2 | 125.1 (2) |
C26—Cr—P1 | 93.36 (10) | C14—C13—P2 | 116.2 (2) |
C29—Cr—P1 | 95.75 (11) | C15—C14—C13 | 120.2 (3) |
C1—P1—C7 | 103.54 (14) | C15—C14—H14 | 119.9 |
C1—P1—P2 | 101.21 (10) | C13—C14—H14 | 119.9 |
C7—P1—P2 | 104.56 (10) | C14—C15—C16 | 120.4 (3) |
C1—P1—Cr | 119.02 (11) | C14—C15—H15 | 119.8 |
C7—P1—Cr | 110.78 (10) | C16—C15—H15 | 119.8 |
P2—P1—Cr | 116.02 (5) | C17—C16—C15 | 119.3 (3) |
C13—P2—C19 | 110.90 (14) | C17—C16—H16 | 120.3 |
C13—P2—S | 111.01 (11) | C15—C16—H16 | 120.3 |
C19—P2—S | 111.67 (11) | C16—C17—C18 | 121.1 (3) |
C13—P2—P1 | 107.35 (10) | C16—C17—H17 | 119.4 |
C19—P2—P1 | 103.03 (11) | C18—C17—H17 | 119.4 |
S—P2—P1 | 112.55 (6) | C17—C18—C13 | 120.2 (3) |
C6—C1—C2 | 118.7 (3) | C17—C18—H18 | 119.9 |
C6—C1—P1 | 119.9 (2) | C13—C18—H18 | 119.9 |
C2—C1—P1 | 121.3 (2) | C24—C19—C20 | 118.9 (3) |
C3—C2—C1 | 120.1 (3) | C24—C19—P2 | 116.7 (2) |
C3—C2—H2 | 119.9 | C20—C19—P2 | 124.4 (2) |
C1—C2—H2 | 119.9 | C21—C20—C19 | 119.9 (3) |
C2—C3—C4 | 120.6 (3) | C21—C20—H20 | 120.0 |
C2—C3—H3 | 119.7 | C19—C20—H20 | 120.0 |
C4—C3—H3 | 119.7 | C22—C21—C20 | 120.7 (3) |
C5—C4—C3 | 119.6 (3) | C22—C21—H21 | 119.7 |
C5—C4—H4 | 120.2 | C20—C21—H21 | 119.7 |
C3—C4—H4 | 120.2 | C23—C22—C21 | 119.9 (3) |
C4—C5—C6 | 120.5 (3) | C23—C22—H22 | 120.1 |
C4—C5—H5 | 119.7 | C21—C22—H22 | 120.1 |
C6—C5—H5 | 119.7 | C22—C23—C24 | 120.0 (3) |
C5—C6—C1 | 120.5 (3) | C22—C23—H23 | 120.0 |
C5—C6—H6 | 119.8 | C24—C23—H23 | 120.0 |
C1—C6—H6 | 119.8 | C19—C24—C23 | 120.5 (3) |
C8—C7—C12 | 118.5 (3) | C19—C24—H24 | 119.7 |
C8—C7—P1 | 121.0 (2) | C23—C24—H24 | 119.7 |
C12—C7—P1 | 119.4 (2) | O1—C25—Cr | 176.9 (3) |
C9—C8—C7 | 120.8 (3) | O2—C26—Cr | 175.3 (3) |
C9—C8—H8 | 119.6 | O3—C27—Cr | 179.6 (3) |
C7—C8—H8 | 119.6 | O4—C28—Cr | 177.1 (3) |
C10—C9—C8 | 119.9 (3) | O5—C29—Cr | 171.5 (3) |
C25—Cr—P1—C1 | −29.32 (15) | P2—P1—C7—C12 | 145.4 (2) |
C28—Cr—P1—C1 | −116.76 (15) | Cr—P1—C7—C12 | −88.9 (2) |
C26—Cr—P1—C1 | 62.17 (16) | C12—C7—C8—C9 | −1.4 (5) |
C29—Cr—P1—C1 | 153.20 (15) | P1—C7—C8—C9 | −169.7 (3) |
C25—Cr—P1—C7 | 90.49 (15) | C7—C8—C9—C10 | 1.0 (6) |
C28—Cr—P1—C7 | 3.04 (15) | C8—C9—C10—C11 | 0.1 (6) |
C26—Cr—P1—C7 | −178.02 (15) | C9—C10—C11—C12 | −0.7 (5) |
C29—Cr—P1—C7 | −86.99 (15) | C10—C11—C12—C7 | 0.2 (5) |
C25—Cr—P1—P2 | −150.53 (11) | C8—C7—C12—C11 | 0.8 (5) |
C28—Cr—P1—P2 | 122.02 (11) | P1—C7—C12—C11 | 169.3 (3) |
C26—Cr—P1—P2 | −59.04 (12) | C19—P2—C13—C18 | 23.4 (3) |
C29—Cr—P1—P2 | 31.99 (12) | S—P2—C13—C18 | 148.1 (3) |
C1—P1—P2—C13 | 48.63 (15) | P1—P2—C13—C18 | −88.5 (3) |
C7—P1—P2—C13 | −58.72 (15) | C19—P2—C13—C14 | −158.7 (2) |
Cr—P1—P2—C13 | 178.96 (10) | S—P2—C13—C14 | −33.9 (3) |
C1—P1—P2—C19 | −68.50 (15) | P1—P2—C13—C14 | 89.5 (2) |
C7—P1—P2—C19 | −175.85 (14) | C18—C13—C14—C15 | 0.2 (5) |
Cr—P1—P2—C19 | 61.83 (11) | P2—C13—C14—C15 | −177.8 (3) |
C1—P1—P2—S | 171.07 (11) | C13—C14—C15—C16 | 0.0 (5) |
C7—P1—P2—S | 63.72 (11) | C14—C15—C16—C17 | −0.1 (5) |
Cr—P1—P2—S | −58.60 (7) | C15—C16—C17—C18 | 0.1 (5) |
C7—P1—C1—C6 | −146.8 (3) | C16—C17—C18—C13 | 0.1 (5) |
P2—P1—C1—C6 | 105.1 (2) | C14—C13—C18—C17 | −0.3 (5) |
Cr—P1—C1—C6 | −23.3 (3) | P2—C13—C18—C17 | 177.6 (3) |
C7—P1—C1—C2 | 36.1 (3) | C13—P2—C19—C24 | 132.2 (3) |
P2—P1—C1—C2 | −72.0 (2) | S—P2—C19—C24 | 7.9 (3) |
Cr—P1—C1—C2 | 159.5 (2) | P1—P2—C19—C24 | −113.2 (2) |
C6—C1—C2—C3 | −0.4 (4) | C13—P2—C19—C20 | −49.9 (3) |
P1—C1—C2—C3 | 176.8 (2) | S—P2—C19—C20 | −174.3 (2) |
C1—C2—C3—C4 | 1.3 (5) | P1—P2—C19—C20 | 64.7 (3) |
C2—C3—C4—C5 | −1.7 (5) | C24—C19—C20—C21 | −2.4 (5) |
C3—C4—C5—C6 | 1.2 (5) | P2—C19—C20—C21 | 179.8 (3) |
C4—C5—C6—C1 | −0.2 (5) | C19—C20—C21—C22 | 0.8 (5) |
C2—C1—C6—C5 | −0.2 (5) | C20—C21—C22—C23 | 0.8 (6) |
P1—C1—C6—C5 | −177.3 (3) | C21—C22—C23—C24 | −0.8 (6) |
C1—P1—C7—C8 | −152.0 (3) | C20—C19—C24—C23 | 2.4 (5) |
P2—P1—C7—C8 | −46.4 (3) | P2—C19—C24—C23 | −179.7 (3) |
Cr—P1—C7—C8 | 79.3 (3) | C22—C23—C24—C19 | −0.8 (5) |
C1—P1—C7—C12 | 39.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O2i | 0.95 | 2.65 | 3.581 (4) | 166 |
C21—H21···O4ii | 0.95 | 2.57 | 3.426 (5) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cr(C24H20P2S)(CO)5] |
Mr | 594.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 178 |
a, b, c (Å) | 9.840 (3), 10.089 (5), 14.967 (6) |
α, β, γ (°) | 77.90 (3), 84.43 (3), 68.02 (3) |
V (Å3) | 1347.0 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.66 |
Crystal size (mm) | 0.5 × 0.5 × 0.2 |
Data collection | |
Diffractometer | Nicolet R3 diffractometer |
Absorption correction | ψ scan (XEMP; Nicolet, 1987) |
Tmin, Tmax | 0.801, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5120, 4578, 3476 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.108, 1.03 |
No. of reflections | 4578 |
No. of parameters | 343 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.47 |
Computer programs: P3 (Nicolet, 1987), P3, XDISK (Nicolet, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Cr—C27 | 1.865 (4) | S—P2 | 1.9531 (15) |
Cr—C25 | 1.893 (4) | P1—C1 | 1.830 (3) |
Cr—C28 | 1.895 (4) | P1—C7 | 1.833 (3) |
Cr—C26 | 1.909 (4) | P1—P2 | 2.2659 (15) |
Cr—C29 | 1.916 (4) | P2—C13 | 1.821 (3) |
Cr—P1 | 2.3921 (13) | P2—C19 | 1.822 (3) |
C27—Cr—C25 | 88.48 (15) | C29—Cr—P1 | 95.75 (11) |
C27—Cr—C28 | 88.55 (15) | C1—P1—C7 | 103.54 (14) |
C25—Cr—C28 | 87.44 (15) | C1—P1—P2 | 101.21 (10) |
C27—Cr—C26 | 89.65 (15) | C7—P1—P2 | 104.56 (10) |
C25—Cr—C26 | 91.50 (15) | C1—P1—Cr | 119.02 (11) |
C28—Cr—C26 | 177.94 (14) | C7—P1—Cr | 110.78 (10) |
C27—Cr—C29 | 85.89 (15) | P2—P1—Cr | 116.02 (5) |
C25—Cr—C29 | 173.94 (14) | C13—P2—C19 | 110.90 (14) |
C28—Cr—C29 | 90.19 (15) | C13—P2—S | 111.01 (11) |
C26—Cr—C29 | 90.69 (16) | C19—P2—S | 111.67 (11) |
C27—Cr—P1 | 176.55 (11) | C13—P2—P1 | 107.35 (10) |
C25—Cr—P1 | 89.77 (10) | C19—P2—P1 | 103.03 (11) |
C28—Cr—P1 | 88.40 (10) | S—P2—P1 | 112.55 (6) |
C26—Cr—P1 | 93.36 (10) | ||
C1—P1—P2—C13 | 48.63 (15) | Cr—P1—P2—C19 | 61.83 (11) |
C7—P1—P2—C13 | −58.72 (15) | C1—P1—P2—S | 171.07 (11) |
Cr—P1—P2—C13 | 178.96 (10) | C7—P1—P2—S | 63.72 (11) |
C1—P1—P2—C19 | −68.50 (15) | Cr—P1—P2—S | −58.60 (7) |
C7—P1—P2—C19 | −175.85 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···O2i | 0.95 | 2.65 | 3.581 (4) | 166.4 |
C21—H21···O4ii | 0.95 | 2.57 | 3.426 (5) | 149.3 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z. |
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The title compound, (I), arose during studies (see Experimental) of thioureas substituted with phosphorus-containing groups (Farkens, 1991). It was characterized by this structure determination.
The molecule of (I) is shown in Fig. 1. A search of the Cambridge Structural Database (CSD, Version of April 2002; Allen & Kennard, 1993) revealed no other complexes of any tetra(organyl)diphosphine monosulfide (in the strict sense of a compound containing a P—P bond). The key bond lengths are P1—P2 2.2659 (15), P2—S 1.9531 (15), P1—C 1.830, 1.833 (3) and P2—C 1.821 1.822 (3) Å. These may be compared, although the two systems clearly differ chemically in many respects, with values for uncomplexed tetramethyldiphosphane monosulfide (Gruber et al., 1990): P—P 2.201 (1), P—S 1.970 (1), PIII—C 1.830 and 1.834 (1), and P(S)—C 1.803 and 1.803 (1) Å. The P—P bond in (I) may be regarded as long, and it is reasonable to propose steric effects as the cause. A CSD search revealed 57 structures with (C)2P—P(C)2 single bonds, involving 69 bonds in the range 2.104–2.310 Å (average 2.216 Å).
The P—Cr distance is 2.3921 (13) Å, and the Cr—C bond trans to Cr—P is by far the shortest at 1.865 (4) Å, cf. average 1.903 Å for the other four Cr—C bonds. The conformation about the P—P bond is defined by the torsion angle S—P2—P1—Cr of −58.60 (7)° (in the above-mentioned diphosphine monosulfide, the S atom is trans to the lone pair at the other phosphorus). As expected, the largest angles at phosphorus are those involving the Cr atom at P1 and the S atom at P2.
Two short H···O contacts could reasonably be interpreted as weak hydrogen bonds (Table 2).