Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015152/na1446sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015152/na1446Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015152/na1446IIsup3.hkl |
CCDC references: 142739; 142740
Preparation of (I): Re2(CO)10 (200 mg, 0.307 mmol) and 4-methoxy-thiophenol (75 µl, 0.612 mmol) were heated at 443 K in a sealed glass tube in the presence of xylene (1.5 ml) for 10 h. Subsequent thin-layer chromatography (TLC) separation (eluant: dichloromethane/n-hexane 1/5) gave (I) in 10% yield. Single crystals were grown from chloroform/n-pentane. Preparation of (II): trimethylamine N-oxide (17 mg, 0.226 mmol) were added to a solution of Re2[µ-S(2- naphthyl)]2(CO)8 (100 mg, 0.109 mmol) and PHCy2 (44 µl, 0.218 mmol) in tetra-hydrofuran. The Re educt was prepared according to Treichel & Tegen (1988). After stirring for 2 h (II) was isolated by TLC separation (eluant: dichloromethane/n-hexane 1/2) in 60% yield. Single crystals were grown from dichloromethane/n-pentane.
Data collection: XSCANS (Siemens, 1995a) for (I); XSCANS (Siemens, 1995b) for (II). For both compounds, cell refinement: XSCANS; data reduction: XSCANS. Program(s) used to solve structure: SHELXTL (Siemens 1995b) for (I); SHELXTL (Siemens, 1995a) for (II). For both compounds, program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Re2(C7H7OS)2(CO)8] | F(000) = 816 |
Mr = 874.85 | Dx = 2.361 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.731 (2) Å | Cell parameters from 30 reflections |
b = 9.638 (1) Å | θ = 7.3–22.1° |
c = 13.772 (1) Å | µ = 10.05 mm−1 |
β = 107.66 (1)° | T = 203 K |
V = 1230.8 (3) Å3 | Block, pale yellow |
Z = 2 | 0.44 × 0.24 × 0.18 mm |
Siemens P4 diffractometer | 2448 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
2θ/ω scans | h = −12→1 |
Absorption correction: ψ scan North et al. (1968) | k = −1→12 |
Tmin = 0.080, Tmax = 0.164 | l = −17→17 |
3716 measured reflections | 3 standard reflections every 397 reflections |
2832 independent reflections | intensity decay: <1% |
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0352P)2 + 1.1289P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2832 reflections | Δρmax = 0.99 e Å−3 |
165 parameters | Δρmin = −1.00 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Siemens 1995a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00201 (18) |
[Re2(C7H7OS)2(CO)8] | V = 1230.8 (3) Å3 |
Mr = 874.85 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.731 (2) Å | µ = 10.05 mm−1 |
b = 9.638 (1) Å | T = 203 K |
c = 13.772 (1) Å | 0.44 × 0.24 × 0.18 mm |
β = 107.66 (1)° |
Siemens P4 diffractometer | 2448 reflections with I > 2σ(I) |
Absorption correction: ψ scan North et al. (1968) | Rint = 0.019 |
Tmin = 0.080, Tmax = 0.164 | 3 standard reflections every 397 reflections |
3716 measured reflections | intensity decay: <1% |
2832 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.99 e Å−3 |
2832 reflections | Δρmin = −1.00 e Å−3 |
165 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 | ||
Re1 | −0.563075 (18) | 0.313838 (19) | −0.034644 (13) | 0.02253 (8) | |
S1 | −0.35250 (12) | 0.46876 (12) | −0.03121 (8) | 0.0230 (2) | |
O1 | −0.6890 (5) | 0.4452 (5) | −0.2516 (3) | 0.0484 (10) | |
C1 | −0.6459 (5) | 0.3910 (6) | −0.1762 (4) | 0.0304 (11) | |
O2 | −0.4286 (5) | 0.2426 (5) | 0.1961 (3) | 0.0464 (10) | |
C2 | −0.4753 (5) | 0.2655 (5) | 0.1123 (4) | 0.0293 (11) | |
O3 | −0.4467 (4) | 0.0480 (4) | −0.1051 (3) | 0.0427 (9) | |
C3 | −0.4876 (5) | 0.1499 (6) | −0.0804 (4) | 0.0303 (11) | |
O4 | −0.8242 (4) | 0.1285 (5) | −0.0439 (3) | 0.0462 (10) | |
C4 | −0.7316 (5) | 0.2021 (6) | −0.0410 (4) | 0.0329 (12) | |
C11 | −0.1824 (5) | 0.4096 (5) | 0.0519 (3) | 0.0230 (9) | |
C12 | −0.1485 (6) | 0.2702 (6) | 0.0607 (5) | 0.0389 (13) | |
H12 | −0.2182 | 0.2044 | 0.0273 | 0.047* | |
C13 | −0.0125 (6) | 0.2266 (7) | 0.1183 (5) | 0.0470 (16) | |
H13 | 0.0095 | 0.1314 | 0.1222 | 0.056* | |
C14 | 0.0907 (5) | 0.3195 (6) | 0.1699 (4) | 0.0336 (12) | |
C15 | 0.0589 (5) | 0.4582 (6) | 0.1600 (4) | 0.0353 (12) | |
H15 | 0.1290 | 0.5238 | 0.1928 | 0.042* | |
C16 | −0.0768 (5) | 0.5018 (6) | 0.1014 (4) | 0.0354 (12) | |
H16 | −0.0972 | 0.5974 | 0.0955 | 0.042* | |
O5 | 0.2208 (4) | 0.2662 (5) | 0.2275 (4) | 0.0526 (12) | |
C17 | 0.3234 (6) | 0.3616 (8) | 0.2884 (5) | 0.0480 (16) | |
H17A | 0.3576 | 0.4223 | 0.2445 | 0.072* | |
H17B | 0.4041 | 0.3107 | 0.3329 | 0.072* | |
H17C | 0.2781 | 0.4166 | 0.3292 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.01726 (11) | 0.02045 (11) | 0.02749 (11) | −0.00094 (8) | 0.00321 (7) | −0.00102 (8) |
S1 | 0.0170 (5) | 0.0232 (6) | 0.0267 (5) | 0.0002 (4) | 0.0038 (4) | 0.0002 (4) |
O1 | 0.051 (2) | 0.057 (3) | 0.0302 (19) | −0.006 (2) | 0.0008 (17) | 0.007 (2) |
C1 | 0.025 (2) | 0.033 (3) | 0.031 (3) | 0.001 (2) | 0.004 (2) | −0.006 (2) |
O2 | 0.051 (3) | 0.045 (2) | 0.037 (2) | 0.012 (2) | 0.0045 (19) | 0.0060 (19) |
C2 | 0.024 (2) | 0.025 (2) | 0.038 (3) | 0.007 (2) | 0.008 (2) | 0.002 (2) |
O3 | 0.047 (2) | 0.031 (2) | 0.055 (2) | 0.0033 (19) | 0.0231 (19) | −0.0091 (18) |
C3 | 0.022 (2) | 0.030 (3) | 0.036 (3) | −0.003 (2) | 0.006 (2) | −0.002 (2) |
O4 | 0.029 (2) | 0.042 (2) | 0.067 (3) | −0.0107 (19) | 0.0124 (19) | 0.000 (2) |
C4 | 0.024 (2) | 0.033 (3) | 0.040 (3) | 0.002 (2) | 0.007 (2) | 0.001 (2) |
C11 | 0.0159 (19) | 0.026 (2) | 0.028 (2) | 0.0014 (19) | 0.0067 (17) | 0.0010 (19) |
C12 | 0.020 (2) | 0.031 (3) | 0.058 (4) | 0.000 (2) | 0.002 (2) | 0.000 (3) |
C13 | 0.029 (3) | 0.031 (3) | 0.074 (4) | 0.005 (2) | 0.005 (3) | 0.005 (3) |
C14 | 0.018 (2) | 0.039 (3) | 0.039 (3) | 0.003 (2) | 0.001 (2) | 0.005 (2) |
C15 | 0.024 (2) | 0.035 (3) | 0.042 (3) | 0.000 (2) | 0.003 (2) | −0.006 (2) |
C16 | 0.024 (2) | 0.027 (3) | 0.050 (3) | 0.008 (2) | 0.003 (2) | −0.002 (2) |
O5 | 0.0246 (19) | 0.050 (3) | 0.071 (3) | 0.0094 (19) | −0.0040 (19) | 0.015 (2) |
C17 | 0.020 (2) | 0.070 (4) | 0.046 (3) | 0.005 (3) | −0.003 (2) | 0.002 (3) |
Re1—C3 | 1.927 (5) | O3—C3 | 1.150 (6) |
Re1—C4 | 1.941 (5) | O4—C4 | 1.138 (6) |
Re1—C2 | 1.998 (5) | C11—C16 | 1.373 (7) |
Re1—C1 | 2.012 (5) | C11—C12 | 1.379 (7) |
Re1—S1i | 2.5179 (12) | C12—C13 | 1.387 (7) |
Re1—S1 | 2.5243 (12) | C13—C14 | 1.372 (8) |
S1—C11 | 1.796 (4) | C14—C15 | 1.370 (8) |
S1—Re1i | 2.5179 (12) | C14—O5 | 1.373 (6) |
O1—C1 | 1.123 (6) | C15—C16 | 1.388 (6) |
O2—C2 | 1.126 (6) | O5—C17 | 1.428 (7) |
C3—Re1—C4 | 86.0 (2) | Re1i—S1—Re1 | 98.47 (4) |
C3—Re1—C2 | 93.0 (2) | O1—C1—Re1 | 173.9 (5) |
C4—Re1—C2 | 90.7 (2) | O2—C2—Re1 | 177.3 (5) |
C3—Re1—C1 | 93.8 (2) | O3—C3—Re1 | 176.3 (5) |
C4—Re1—C1 | 94.4 (2) | O4—C4—Re1 | 175.1 (5) |
C2—Re1—C1 | 171.8 (2) | C16—C11—C12 | 117.7 (4) |
C3—Re1—S1i | 176.78 (15) | C16—C11—S1 | 121.1 (4) |
C4—Re1—S1i | 96.58 (16) | C12—C11—S1 | 121.0 (4) |
C2—Re1—S1i | 85.13 (15) | C11—C12—C13 | 120.4 (5) |
C1—Re1—S1i | 87.88 (15) | C14—C13—C12 | 121.4 (6) |
C3—Re1—S1 | 95.93 (16) | C15—C14—C13 | 118.5 (5) |
C4—Re1—S1 | 177.08 (16) | C15—C14—O5 | 124.3 (5) |
C2—Re1—S1 | 91.36 (15) | C13—C14—O5 | 117.2 (5) |
C1—Re1—S1 | 83.32 (15) | C14—C15—C16 | 120.0 (5) |
S1i—Re1—S1 | 81.53 (4) | C11—C16—C15 | 121.9 (5) |
C11—S1—Re1i | 111.92 (16) | C14—O5—C17 | 117.1 (5) |
C11—S1—Re1 | 114.20 (16) |
Symmetry code: (i) −x−1, −y+1, −z. |
[Re2(C12H23P)2(C10H7S)2(CO)6] | F(000) = 2480 |
Mr = 1255.44 | Dx = 1.653 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.561 (3) Å | Cell parameters from 35 reflections |
b = 9.378 (3) Å | θ = 8.7–15.6° |
c = 23.722 (3) Å | µ = 4.99 mm−1 |
β = 112.63 (1)° | T = 293 K |
V = 5043.3 (18) Å3 | Prism, colorless |
Z = 4 | 0.41 × 0.10 × 0.08 mm |
Siemens P4 diffractometer | 2766 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω scans | h = −31→1 |
Absorption correction: ψ scan North et al. (1968) | k = −1→12 |
Tmin = 0.482, Tmax = 0.671 | l = −28→30 |
6948 measured reflections | 3 standard reflections every 397 reflections |
5783 independent reflections | intensity decay: 3% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom and difmap |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0328P)2 + 11.0195P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
5783 reflections | Δρmax = 0.99 e Å−3 |
284 parameters | Δρmin = −0.50 e Å−3 |
67 restraints | Extinction correction: SHELXTL (Siemens, 1995a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00016 (3) |
[Re2(C12H23P)2(C10H7S)2(CO)6] | V = 5043.3 (18) Å3 |
Mr = 1255.44 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.561 (3) Å | µ = 4.99 mm−1 |
b = 9.378 (3) Å | T = 293 K |
c = 23.722 (3) Å | 0.41 × 0.10 × 0.08 mm |
β = 112.63 (1)° |
Siemens P4 diffractometer | 2766 reflections with I > 2σ(I) |
Absorption correction: ψ scan North et al. (1968) | Rint = 0.037 |
Tmin = 0.482, Tmax = 0.671 | 3 standard reflections every 397 reflections |
6948 measured reflections | intensity decay: 3% |
5783 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 67 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0328P)2 + 11.0195P] where P = (Fo2 + 2Fc2)/3 |
5783 reflections | Δρmax = 0.99 e Å−3 |
284 parameters | Δρmin = −0.50 e Å−3 |
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 | ||
Re1 | 0.018345 (16) | 0.43684 (5) | 0.178340 (17) | 0.05035 (16) | |
S1 | 0.06590 (9) | 0.4999 (3) | 0.29032 (10) | 0.0484 (6) | |
P1 | 0.03091 (10) | 0.6969 (3) | 0.16728 (11) | 0.0511 (7) | |
H1 | 0.025 (4) | 0.773 (10) | 0.217 (4) | 0.080* | |
O1 | 0.1296 (3) | 0.3655 (10) | 0.1552 (4) | 0.097 (3) | |
C1 | 0.0873 (5) | 0.3964 (12) | 0.1640 (5) | 0.067 (3) | |
O2 | 0.0028 (4) | 0.1162 (10) | 0.1881 (4) | 0.101 (3) | |
C2 | 0.0084 (5) | 0.2456 (13) | 0.1855 (5) | 0.075 (4) | |
C3 | −0.0287 (4) | 0.4116 (13) | 0.0952 (5) | 0.075 (4) | |
O3 | −0.0577 (4) | 0.3863 (10) | 0.0442 (3) | 0.101 (3) | |
C11 | −0.0210 (3) | 0.7929 (12) | 0.1011 (4) | 0.058 (3) | |
H11 | −0.0119 | 0.8943 | 0.1094 | 0.069* | |
C12 | −0.0842 (4) | 0.7750 (13) | 0.0947 (4) | 0.079 (4) | |
H12A | −0.0878 | 0.8072 | 0.1320 | 0.095* | |
H12B | −0.0943 | 0.6745 | 0.0897 | 0.095* | |
C13 | −0.1278 (4) | 0.8573 (15) | 0.0409 (5) | 0.098 (4) | |
H13A | −0.1678 | 0.8349 | 0.0368 | 0.118* | |
H13B | −0.1217 | 0.9588 | 0.0485 | 0.118* | |
C14 | −0.1204 (4) | 0.8198 (16) | −0.0176 (5) | 0.108 (5) | |
H14A | −0.1302 | 0.7201 | −0.0273 | 0.129* | |
H14B | −0.1472 | 0.8768 | −0.0509 | 0.129* | |
C15 | −0.0579 (4) | 0.8465 (13) | −0.0116 (4) | 0.087 (4) | |
H15A | −0.0491 | 0.9474 | −0.0048 | 0.104* | |
H15B | −0.0539 | 0.8200 | −0.0493 | 0.104* | |
C16 | −0.0143 (4) | 0.7617 (12) | 0.0409 (4) | 0.071 (3) | |
H16A | 0.0255 | 0.7851 | 0.0450 | 0.085* | |
H16B | −0.0205 | 0.6607 | 0.0319 | 0.085* | |
C21 | 0.1053 (3) | 0.7552 (9) | 0.1727 (4) | 0.049 (2) | |
H21 | 0.1118 | 0.7089 | 0.1387 | 0.059* | |
C22 | 0.1111 (4) | 0.9132 (9) | 0.1647 (4) | 0.059 (3) | |
H22A | 0.1052 | 0.9637 | 0.1976 | 0.071* | |
H22B | 0.0805 | 0.9434 | 0.1265 | 0.071* | |
C23 | 0.1710 (4) | 0.9533 (11) | 0.1644 (5) | 0.071 (3) | |
H23A | 0.1738 | 1.0563 | 0.1627 | 0.085* | |
H23B | 0.1747 | 0.9140 | 0.1282 | 0.085* | |
C24 | 0.2215 (4) | 0.8974 (10) | 0.2215 (5) | 0.069 (3) | |
H24A | 0.2587 | 0.9129 | 0.2171 | 0.083* | |
H24B | 0.2224 | 0.9504 | 0.2569 | 0.083* | |
C25 | 0.2146 (3) | 0.7398 (10) | 0.2315 (5) | 0.064 (3) | |
H25A | 0.2211 | 0.6858 | 0.1998 | 0.077* | |
H25B | 0.2445 | 0.7116 | 0.2704 | 0.077* | |
C26 | 0.1544 (3) | 0.7025 (11) | 0.2309 (4) | 0.061 (3) | |
H26A | 0.1499 | 0.7454 | 0.2661 | 0.074* | |
H26B | 0.1514 | 0.6000 | 0.2340 | 0.074* | |
C31 | 0.1300 (4) | 0.4001 (12) | 0.3338 (4) | 0.056 (3) | |
C32 | 0.1368 (5) | 0.2595 (13) | 0.3277 (5) | 0.071 (3) | |
H32 | 0.1070 | 0.2072 | 0.2986 | 0.085* | |
C33 | 0.1920 (5) | 0.1884 (15) | 0.3673 (5) | 0.071 (3) | |
C34 | 0.1971 (7) | 0.0470 (18) | 0.3613 (7) | 0.110 (5) | |
H34 | 0.1667 | −0.0067 | 0.3336 | 0.132* | |
C35 | 0.2516 (7) | −0.0159 (19) | 0.3996 (7) | 0.129 (7) | |
H35 | 0.2574 | −0.1130 | 0.3963 | 0.154* | |
C36 | 0.2969 (7) | 0.066 (2) | 0.4424 (7) | 0.131 (7) | |
H36 | 0.3321 | 0.0224 | 0.4665 | 0.157* | |
C37 | 0.2903 (7) | 0.204 (2) | 0.4490 (7) | 0.127 (7) | |
H37 | 0.3201 | 0.2568 | 0.4779 | 0.152* | |
C38 | 0.2345 (6) | 0.2720 (16) | 0.4096 (5) | 0.074 (3) | |
C39 | 0.2281 (6) | 0.4125 (16) | 0.4163 (5) | 0.093 (4) | |
H39 | 0.2575 | 0.4648 | 0.4458 | 0.111* | |
C40 | 0.1762 (4) | 0.4775 (14) | 0.3778 (4) | 0.072 (4) | |
H40 | 0.1718 | 0.5752 | 0.3811 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.0413 (2) | 0.0581 (3) | 0.0530 (2) | −0.0043 (2) | 0.01959 (16) | −0.0070 (3) |
S1 | 0.0366 (11) | 0.0596 (15) | 0.0483 (13) | 0.0025 (11) | 0.0154 (10) | 0.0016 (12) |
P1 | 0.0421 (13) | 0.0569 (17) | 0.0463 (14) | 0.0057 (13) | 0.0080 (11) | −0.0010 (13) |
O1 | 0.063 (5) | 0.120 (7) | 0.124 (7) | −0.008 (5) | 0.055 (5) | −0.030 (6) |
C1 | 0.057 (6) | 0.072 (9) | 0.065 (7) | −0.018 (6) | 0.014 (5) | −0.014 (6) |
O2 | 0.107 (7) | 0.069 (6) | 0.148 (8) | −0.001 (5) | 0.071 (6) | −0.010 (6) |
C2 | 0.073 (8) | 0.069 (8) | 0.096 (9) | 0.025 (7) | 0.046 (7) | −0.028 (7) |
C3 | 0.061 (6) | 0.102 (10) | 0.072 (7) | −0.014 (7) | 0.035 (6) | −0.025 (8) |
O3 | 0.090 (6) | 0.135 (9) | 0.066 (5) | −0.017 (6) | 0.017 (5) | −0.035 (5) |
C11 | 0.047 (5) | 0.073 (8) | 0.054 (6) | −0.003 (6) | 0.020 (5) | −0.003 (6) |
C12 | 0.061 (7) | 0.100 (10) | 0.075 (7) | 0.020 (7) | 0.025 (6) | 0.025 (7) |
C13 | 0.063 (7) | 0.141 (13) | 0.083 (9) | 0.031 (8) | 0.018 (7) | 0.051 (9) |
C14 | 0.069 (8) | 0.138 (14) | 0.090 (10) | −0.007 (9) | 0.002 (7) | 0.033 (10) |
C15 | 0.087 (9) | 0.102 (10) | 0.053 (7) | 0.011 (8) | 0.008 (6) | 0.020 (7) |
C16 | 0.073 (7) | 0.083 (9) | 0.059 (6) | 0.002 (7) | 0.028 (6) | 0.004 (6) |
C21 | 0.043 (5) | 0.049 (6) | 0.051 (6) | −0.001 (5) | 0.014 (5) | −0.002 (5) |
C22 | 0.050 (5) | 0.063 (8) | 0.061 (6) | −0.002 (5) | 0.019 (5) | 0.007 (6) |
C23 | 0.066 (6) | 0.054 (7) | 0.088 (8) | −0.004 (6) | 0.026 (6) | 0.013 (7) |
C24 | 0.048 (6) | 0.066 (8) | 0.083 (8) | 0.000 (5) | 0.015 (6) | 0.007 (6) |
C25 | 0.045 (6) | 0.061 (7) | 0.077 (7) | 0.004 (5) | 0.014 (5) | 0.017 (6) |
C26 | 0.049 (5) | 0.068 (7) | 0.066 (6) | 0.003 (6) | 0.022 (5) | 0.019 (6) |
C31 | 0.040 (5) | 0.076 (9) | 0.058 (6) | 0.011 (5) | 0.027 (5) | 0.011 (6) |
C32 | 0.062 (7) | 0.084 (9) | 0.080 (8) | 0.010 (7) | 0.041 (6) | 0.012 (7) |
C33 | 0.086 (9) | 0.074 (9) | 0.075 (8) | 0.018 (8) | 0.055 (7) | 0.012 (7) |
C34 | 0.121 (12) | 0.111 (14) | 0.119 (12) | 0.019 (11) | 0.071 (10) | 0.012 (11) |
C35 | 0.116 (12) | 0.155 (17) | 0.112 (12) | 0.082 (13) | 0.040 (10) | 0.038 (12) |
C36 | 0.097 (11) | 0.20 (2) | 0.084 (11) | 0.083 (15) | 0.024 (9) | 0.050 (14) |
C37 | 0.094 (11) | 0.19 (2) | 0.101 (11) | 0.062 (13) | 0.047 (9) | 0.055 (14) |
C38 | 0.072 (8) | 0.097 (11) | 0.060 (7) | 0.015 (8) | 0.035 (6) | −0.003 (8) |
C39 | 0.082 (9) | 0.118 (13) | 0.077 (8) | −0.011 (9) | 0.031 (7) | −0.036 (9) |
C40 | 0.031 (5) | 0.117 (11) | 0.061 (6) | 0.009 (6) | 0.010 (5) | −0.002 (7) |
Re1—C2 | 1.827 (13) | C15—C16 | 1.518 (10) |
Re1—C3 | 1.878 (11) | C21—C22 | 1.508 (9) |
Re1—C1 | 1.889 (11) | C21—C26 | 1.526 (9) |
Re1—P1 | 2.484 (3) | C22—C23 | 1.519 (9) |
Re1—S1i | 2.523 (2) | C23—C24 | 1.535 (10) |
Re1—S1 | 2.526 (2) | C24—C25 | 1.517 (10) |
S1—C31 | 1.780 (10) | C25—C26 | 1.512 (9) |
S1—Re1i | 2.523 (2) | C31—C32 | 1.343 (14) |
P1—C11 | 1.834 (9) | C31—C40 | 1.412 (13) |
P1—C21 | 1.864 (8) | C32—C33 | 1.478 (14) |
O1—C1 | 1.173 (11) | C33—C34 | 1.345 (17) |
O2—C2 | 1.225 (13) | C33—C38 | 1.380 (16) |
C3—O3 | 1.169 (11) | C34—C35 | 1.424 (17) |
C11—C12 | 1.509 (9) | C35—C36 | 1.41 (2) |
C11—C16 | 1.527 (9) | C36—C37 | 1.32 (2) |
C12—C13 | 1.524 (10) | C37—C38 | 1.473 (17) |
C13—C14 | 1.510 (11) | C38—C39 | 1.344 (16) |
C14—C15 | 1.506 (10) | C39—C40 | 1.391 (15) |
C2—Re1—C3 | 85.7 (5) | C14—C13—C12 | 111.0 (9) |
C2—Re1—C1 | 88.9 (5) | C15—C14—C13 | 110.7 (9) |
C3—Re1—C1 | 91.0 (4) | C14—C15—C16 | 111.2 (9) |
C2—Re1—P1 | 179.3 (4) | C15—C16—C11 | 111.8 (8) |
C3—Re1—P1 | 93.7 (4) | C22—C21—C26 | 110.6 (7) |
C1—Re1—P1 | 91.2 (3) | C22—C21—P1 | 114.7 (6) |
C2—Re1—S1i | 92.8 (3) | C26—C21—P1 | 112.3 (6) |
C3—Re1—S1i | 95.5 (3) | C21—C22—C23 | 112.5 (7) |
C1—Re1—S1i | 173.4 (3) | C22—C23—C24 | 111.6 (7) |
P1—Re1—S1i | 87.16 (8) | C25—C24—C23 | 111.7 (8) |
C2—Re1—S1 | 99.0 (4) | C26—C25—C24 | 113.1 (8) |
C3—Re1—S1 | 169.2 (3) | C25—C26—C21 | 111.3 (7) |
C1—Re1—S1 | 98.8 (3) | C32—C31—C40 | 119.1 (10) |
P1—Re1—S1 | 81.69 (8) | C32—C31—S1 | 125.0 (9) |
S1i—Re1—S1 | 74.64 (8) | C40—C31—S1 | 116.0 (9) |
C31—S1—Re1i | 110.4 (3) | C31—C32—C33 | 119.8 (12) |
C31—S1—Re1 | 115.7 (3) | C34—C33—C38 | 124.2 (14) |
Re1i—S1—Re1 | 98.93 (8) | C34—C33—C32 | 118.5 (14) |
C11—P1—C21 | 104.8 (4) | C38—C33—C32 | 117.3 (12) |
C11—P1—Re1 | 119.9 (3) | C33—C34—C35 | 116.3 (16) |
C21—P1—Re1 | 116.1 (3) | C36—C35—C34 | 121.3 (16) |
O1—C1—Re1 | 177.3 (10) | C37—C36—C35 | 121.4 (16) |
O2—C2—Re1 | 176.8 (10) | C36—C37—C38 | 118.5 (18) |
O3—C3—Re1 | 175.5 (12) | C39—C38—C33 | 123.5 (13) |
C12—C11—C16 | 111.2 (7) | C39—C38—C37 | 118.2 (15) |
C12—C11—P1 | 112.4 (6) | C33—C38—C37 | 118.3 (14) |
C16—C11—P1 | 114.6 (6) | C38—C39—C40 | 118.2 (13) |
C11—C12—C13 | 113.1 (8) | C39—C40—C31 | 122.2 (12) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Re2(C7H7OS)2(CO)8] | [Re2(C12H23P)2(C10H7S)2(CO)6] |
Mr | 874.85 | 1255.44 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, C2/c |
Temperature (K) | 203 | 293 |
a, b, c (Å) | 9.731 (2), 9.638 (1), 13.772 (1) | 24.561 (3), 9.378 (3), 23.722 (3) |
β (°) | 107.66 (1) | 112.63 (1) |
V (Å3) | 1230.8 (3) | 5043.3 (18) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 10.05 | 4.99 |
Crystal size (mm) | 0.44 × 0.24 × 0.18 | 0.41 × 0.10 × 0.08 |
Data collection | ||
Diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan North et al. (1968) | ψ scan North et al. (1968) |
Tmin, Tmax | 0.080, 0.164 | 0.482, 0.671 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3716, 2832, 2448 | 6948, 5783, 2766 |
Rint | 0.019 | 0.037 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.063, 1.05 | 0.047, 0.117, 1.02 |
No. of reflections | 2832 | 5783 |
No. of parameters | 165 | 284 |
No. of restraints | 0 | 67 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0352P)2 + 1.1289P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0328P)2 + 11.0195P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.99, −1.00 | 0.99, −0.50 |
Computer programs: XSCANS (Siemens, 1995a), XSCANS (Siemens, 1995b), XSCANS, SHELXTL (Siemens 1995b), SHELXTL (Siemens, 1995a), SHELXTL.
Re1—S1i | 2.5179 (12) | S1—C11 | 1.796 (4) |
Re1—S1 | 2.5243 (12) | ||
S1i—Re1—S1 | 81.53 (4) | C11—S1—Re1 | 114.20 (16) |
C11—S1—Re1i | 111.92 (16) | Re1i—S1—Re1 | 98.47 (4) |
Symmetry code: (i) −x−1, −y+1, −z. |
Re1—P1 | 2.484 (3) | Re1—S1 | 2.526 (2) |
Re1—S1i | 2.523 (2) | S1—C31 | 1.780 (10) |
S1i—Re1—S1 | 74.64 (8) | C31—S1—Re1 | 115.7 (3) |
C31—S1—Re1i | 110.4 (3) | Re1i—S1—Re1 | 98.93 (8) |
Symmetry code: (i) −x, y, −z+1/2. |
Recently we reported new synthetic routes to hydrido sulfido bridged dirhenium complexes (Egold et al., 1999). In this context the new twice sulfido bridged complexes Re2(µ-SR)2(CO)8, (I) (R = 4-methoxyphenyl), and Re2(µ-SR')2(CO)6(PHCy2)2, (II) (R' = naphthyl; Cy = cyclohexyl), were also prepared. These two compounds differ markedly in their molecular geometries.
In (I) each Re atom is octahedrally coordinated by two axially and two equatorially positioned carbonyl groups and the two bridging sulfur atoms. The CO groups show ecliptic arrangement with torsion angles C4—Re···Rei—C3i and C2—Re···Rei—C1i (i = −1 − x,1 − y,-z) of 0.4 (3) and 1.3 (3)°, respectively. The geometric centre of the molecule lies on a crystallographic inversion centre. Consequently the Re2S2 core is planar and the methoxyphenyl groups attached to the µ-S atoms adopt anti positions. The two Re—S bond lengths of 2.524 (1) and 2.518 (1) Å differ only slightly, but they are significantly elongated compared to those of 2.471 (3) or 2.478 (3) Å, respectively, found in the hydrido sulfido bridged complexes Re2(µ-H)(µ-SR)(CO)8 (R = phenyl or naphthyl), (Egold et al., 1999). The related acetonitrile substituted complex Re2(µ-StBu)2(CO)6(CH3CN)2 (Eremenko et al., 1992) exhibits Re—S bond lengths of 2.522 (2) and 2.534 (2) Å. The enclosed ring angles of (I) are Re—S—Re 98.47 (4) and S—Re—S 81.53 (4)° and the non-bonding Re···Re separation is 3.819 (1) Å. The basic structural elements of (I), the planar M2S2 ring and the anti position of the R residues at the sulfido bridges, are also valid for the above mentioned rhenium acetonitril complex, for the complex Re2(µ-SR)2(CO)8 (R = CS2Re(CO)4) (Thiele et al., 1974) as well as for the two manganese compounds Mn2(µ-S-phenyl)2(CO)8 (Onaka & Katukawa, 1996) and Mn2(µ-S-tolyl)2(CO)8 (Chen et al., 1996).
In contrast to this, the core structure of (II) is entirely different showing a folded Re2S2 ring with a Re2S/SRe2 dihedral angle of 137.8 (1)° and naphthyl residues at both bridging S atoms in syn position. The coordination of Re by the two µ-S atoms, three CO groups and one axially attached PHCy2 ligand is slightly distorted octahedral. These latter terminal ligands show largely ecliptic arrangement with torsion angles 6.4 (7)° for C3—Re···Reii—C1ii, 9.2 (1)° for P1—Re···Reii—P1ii and 10.3 (7)° for C2—Re···Reii—C2ii (ii = −x, y, 0.5 − z). The phosphido ligands at the rhenium atoms are in syn position too, and a crystallographic twofold axis runs through the midpoint of the Re···Re vector. This geometry leads for the axial PHCy2 and CO ligands to intramolecular non-bonding distances of PH···HP 2.32 (15) Å [P—H is 1.44 (8) Å] and O···O 2.994 (15) Å. For a corresponding planar molecule like (I) the carbonyl O···O distances are about 3.2 Å but the calculated PH···HP separation of 0.9 Å and cyclohexyl CH···HC of 1.8 Å would be clearly too short and the resulting repulsive forces give rise to the observed ring distortion. Similar ring folding in order to reduce intramolecular repulsion is also known for µ-P bridged complexes (Flörke & Haupt, 1994). The Re—S bond lengths of 2.523 (2) and 2.526 (2) Å compare well to those of (I), but the Re—S—Re and S—Re—S angles of 98.93 (8) and 74.64 (8)°, respectively, reflect the folding of the ring. The non-bonding Re···Re distance is 3.838 (1) Å.