metal-organic compounds
(μ-4-Methylbenzenethiolato-κ2S:S)bis[carbonyl(η5-cyclopentadienyl)molybdenum(II)]
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
The 2(C5H5)2(C7H7S)2(CO)2], consists of two half-molecules, each molecule lying on a centre of symmetry. The thiolate groups function as bridges between the MoII atoms, which adopt a quasi-octahedral geometry. In the octahedral environment the two ligating S atoms are in a cis arrangement.
of the title compound, [MoRelated literature
For related literature on unsubstituted [MoCp(CO)(μ-SC6H5)]2, see: Song et al. (1997). The 4-methyl-substituted compound was characterized spectroscopically, see: Benson et al. (1980).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).
Supporting information
10.1107/S1600536808010751/ci2579sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808010751/ci2579Isup2.hkl
A reddish-brown suspension of [(η5-C5H5)Mo(CO)2]2 (100 mg, 0.23 mmol) and an equivalent quantity of the deuterated phosphine, o-P(PhSCD3)3 (94 mg, 0.23 mol), was heated at 383 K for 14.5 h under argon. The mixture was filtered and then absorbed onto Celite (1.5 g). The slurry was evacuated to dryness and loaded onto a silica gel column (9.5 cm x 2.0 cm) in n-hexane. The title compound was eluted with n-hexane-toluene (1:4, 50 ml) as a greenish-brown fraction (60.0 mg, 0.096 mmol, 40% yield). The dichroic compound was recrystallized from an n-hexane-toluene mixture and crystals were isolated after 2 d.
H-atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and were included in the
in the riding-model approximation, with Uiso(H) = 1.2–1.5Ueq(C). The final difference Fourier map had a peak at 0.80 Å and a deep hole at 0.68 Å from Mo2.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).[Mo2(C5H5)2(C7H7S)2(CO)2] | F(000) = 1248 |
Mr = 624.45 | Dx = 1.772 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2210 reflections |
a = 13.245 (2) Å | θ = 2.3–24.8° |
b = 10.135 (1) Å | µ = 1.27 mm−1 |
c = 18.042 (2) Å | T = 100 K |
β = 104.901 (2)° | Cube, green–brown |
V = 2340.4 (5) Å3 | 0.06 × 0.06 × 0.06 mm |
Z = 4 |
Bruker APEXII diffractometer | 5374 independent reflections |
Radiation source: fine-focus sealed tube | 3915 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→16 |
Tmin = 0.758, Tmax = 0.928 | k = −7→13 |
14384 measured reflections | l = −23→23 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0453P)2 + 1.5589P] where P = (Fo2 + 2Fc2)/3 |
5374 reflections | (Δ/σ)max = 0.001 |
291 parameters | Δρmax = 2.60 e Å−3 |
0 restraints | Δρmin = −1.78 e Å−3 |
[Mo2(C5H5)2(C7H7S)2(CO)2] | V = 2340.4 (5) Å3 |
Mr = 624.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.245 (2) Å | µ = 1.27 mm−1 |
b = 10.135 (1) Å | T = 100 K |
c = 18.042 (2) Å | 0.06 × 0.06 × 0.06 mm |
β = 104.901 (2)° |
Bruker APEXII diffractometer | 5374 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3915 reflections with I > 2σ(I) |
Tmin = 0.758, Tmax = 0.928 | Rint = 0.048 |
14384 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.03 | Δρmax = 2.60 e Å−3 |
5374 reflections | Δρmin = −1.78 e Å−3 |
291 parameters |
x | y | z | Uiso*/Ueq | ||
Mo1 | 0.53951 (3) | 0.10457 (4) | 0.53870 (2) | 0.01595 (11) | |
Mo2 | −0.01435 (3) | 0.62084 (4) | 0.47776 (2) | 0.02086 (11) | |
S1 | 0.49151 (8) | 0.09871 (11) | 0.39974 (6) | 0.0174 (2) | |
S2 | 0.00847 (9) | 0.55650 (11) | 0.61079 (6) | 0.0195 (2) | |
O1 | 0.7457 (2) | −0.0389 (3) | 0.53895 (18) | 0.0277 (8) | |
O2 | −0.2474 (2) | 0.5238 (4) | 0.4399 (2) | 0.0345 (9) | |
C1 | 0.4768 (4) | 0.2943 (4) | 0.5899 (3) | 0.0261 (11) | |
H1 | 0.4026 | 0.3118 | 0.5901 | 0.031* | |
C2 | 0.5256 (4) | 0.3337 (4) | 0.5324 (3) | 0.0262 (11) | |
H2 | 0.4922 | 0.3862 | 0.4856 | 0.031* | |
C3 | 0.6331 (4) | 0.2982 (4) | 0.5566 (3) | 0.0235 (10) | |
H3 | 0.6886 | 0.3237 | 0.5309 | 0.028* | |
C4 | 0.6493 (3) | 0.2359 (4) | 0.6296 (2) | 0.0209 (10) | |
H4 | 0.7183 | 0.2086 | 0.6636 | 0.025* | |
C5 | 0.5531 (4) | 0.2342 (4) | 0.6494 (2) | 0.0223 (10) | |
H5 | 0.5420 | 0.2022 | 0.6991 | 0.027* | |
C6 | 0.6654 (4) | 0.0091 (4) | 0.5356 (2) | 0.0212 (10) | |
C7 | 0.6066 (3) | 0.1070 (5) | 0.3651 (2) | 0.0188 (9) | |
C8 | 0.6512 (4) | −0.0029 (5) | 0.3415 (3) | 0.0253 (10) | |
H8 | 0.6245 | −0.0882 | 0.3471 | 0.030* | |
C9 | 0.7354 (4) | 0.0111 (5) | 0.3093 (3) | 0.0261 (11) | |
H9 | 0.7648 | −0.0653 | 0.2926 | 0.031* | |
C10 | 0.7776 (4) | 0.1338 (5) | 0.3010 (3) | 0.0247 (10) | |
C11 | 0.7337 (4) | 0.2431 (5) | 0.3263 (3) | 0.0272 (11) | |
H11 | 0.7625 | 0.3279 | 0.3226 | 0.033* | |
C12 | 0.6477 (3) | 0.2307 (5) | 0.3573 (2) | 0.0213 (10) | |
H12 | 0.6173 | 0.3072 | 0.3730 | 0.026* | |
C13 | 0.8678 (4) | 0.1468 (6) | 0.2643 (3) | 0.0355 (13) | |
H13A | 0.9059 | 0.2287 | 0.2817 | 0.053* | |
H13B | 0.8410 | 0.1486 | 0.2084 | 0.053* | |
H13C | 0.9150 | 0.0714 | 0.2792 | 0.053* | |
C14 | 0.0611 (4) | 0.7759 (5) | 0.4160 (3) | 0.0269 (11) | |
H14 | 0.1135 | 0.7584 | 0.3860 | 0.032* | |
C15 | −0.0495 (4) | 0.7844 (5) | 0.3857 (3) | 0.0258 (11) | |
H15 | −0.0881 | 0.7726 | 0.3307 | 0.031* | |
C16 | −0.0927 (4) | 0.8291 (5) | 0.4449 (3) | 0.0279 (11) | |
H16 | −0.1679 | 0.8510 | 0.4395 | 0.033* | |
C17 | −0.0100 (4) | 0.8469 (4) | 0.5119 (3) | 0.0302 (12) | |
H17 | −0.0172 | 0.8827 | 0.5619 | 0.036* | |
C18 | 0.0835 (4) | 0.8158 (5) | 0.4944 (3) | 0.0276 (11) | |
H18 | 0.1549 | 0.8274 | 0.5295 | 0.033* | |
C19 | −0.1602 (4) | 0.5542 (5) | 0.4557 (3) | 0.0279 (11) | |
C20 | −0.1100 (3) | 0.5593 (4) | 0.6420 (2) | 0.0178 (9) | |
C21 | −0.1885 (3) | 0.6503 (4) | 0.6146 (3) | 0.0225 (10) | |
H21 | −0.1827 | 0.7113 | 0.5759 | 0.027* | |
C22 | −0.2757 (4) | 0.6521 (5) | 0.6437 (3) | 0.0232 (10) | |
H22 | −0.3293 | 0.7148 | 0.6242 | 0.028* | |
C23 | −0.2869 (3) | 0.5659 (5) | 0.6999 (3) | 0.0217 (10) | |
C24 | −0.2062 (3) | 0.4753 (4) | 0.7287 (2) | 0.0206 (10) | |
H24 | −0.2118 | 0.4152 | 0.7678 | 0.025* | |
C25 | −0.1182 (3) | 0.4732 (4) | 0.7002 (2) | 0.0199 (9) | |
H25 | −0.0633 | 0.4126 | 0.7206 | 0.024* | |
C26 | −0.3837 (4) | 0.5654 (5) | 0.7300 (3) | 0.0282 (11) | |
H26A | −0.4087 | 0.6561 | 0.7318 | 0.042* | |
H26B | −0.3666 | 0.5276 | 0.7818 | 0.042* | |
H26C | −0.4383 | 0.5124 | 0.6961 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0185 (2) | 0.01103 (19) | 0.01885 (19) | −0.00035 (15) | 0.00568 (15) | −0.00125 (15) |
Mo2 | 0.0320 (2) | 0.01180 (19) | 0.0223 (2) | 0.00178 (17) | 0.01341 (17) | 0.00156 (16) |
S1 | 0.0177 (5) | 0.0141 (5) | 0.0211 (5) | 0.0004 (4) | 0.0062 (4) | −0.0003 (4) |
S2 | 0.0217 (6) | 0.0178 (6) | 0.0203 (5) | −0.0011 (4) | 0.0077 (4) | −0.0015 (4) |
O1 | 0.0218 (18) | 0.0253 (19) | 0.039 (2) | 0.0060 (15) | 0.0126 (15) | 0.0047 (15) |
O2 | 0.0170 (18) | 0.042 (2) | 0.043 (2) | −0.0054 (16) | 0.0061 (15) | −0.0146 (18) |
C1 | 0.031 (3) | 0.014 (2) | 0.035 (3) | 0.004 (2) | 0.011 (2) | −0.011 (2) |
C2 | 0.042 (3) | 0.011 (2) | 0.025 (2) | 0.000 (2) | 0.007 (2) | −0.0026 (19) |
C3 | 0.031 (3) | 0.015 (2) | 0.023 (2) | −0.008 (2) | 0.005 (2) | −0.0039 (18) |
C4 | 0.023 (2) | 0.016 (2) | 0.021 (2) | −0.0067 (19) | 0.0008 (18) | −0.0057 (18) |
C5 | 0.033 (3) | 0.014 (2) | 0.021 (2) | −0.0059 (19) | 0.009 (2) | −0.0046 (18) |
C6 | 0.030 (3) | 0.013 (2) | 0.020 (2) | −0.005 (2) | 0.006 (2) | 0.0012 (18) |
C7 | 0.017 (2) | 0.022 (2) | 0.018 (2) | 0.0009 (19) | 0.0057 (17) | 0.0018 (19) |
C8 | 0.027 (3) | 0.019 (2) | 0.032 (3) | −0.001 (2) | 0.012 (2) | 0.001 (2) |
C9 | 0.024 (3) | 0.028 (3) | 0.028 (3) | −0.001 (2) | 0.009 (2) | −0.003 (2) |
C10 | 0.025 (2) | 0.030 (3) | 0.020 (2) | −0.008 (2) | 0.0079 (19) | −0.003 (2) |
C11 | 0.033 (3) | 0.027 (3) | 0.022 (2) | −0.010 (2) | 0.010 (2) | 0.001 (2) |
C12 | 0.029 (2) | 0.017 (2) | 0.018 (2) | 0.0010 (19) | 0.0062 (19) | 0.0025 (18) |
C13 | 0.037 (3) | 0.040 (3) | 0.035 (3) | −0.011 (2) | 0.019 (2) | −0.009 (2) |
C14 | 0.035 (3) | 0.017 (2) | 0.032 (3) | 0.000 (2) | 0.016 (2) | 0.008 (2) |
C15 | 0.038 (3) | 0.015 (2) | 0.028 (3) | 0.005 (2) | 0.013 (2) | 0.0070 (19) |
C16 | 0.030 (3) | 0.016 (2) | 0.042 (3) | 0.004 (2) | 0.017 (2) | 0.005 (2) |
C17 | 0.062 (4) | 0.008 (2) | 0.030 (3) | −0.002 (2) | 0.027 (3) | 0.0018 (19) |
C18 | 0.039 (3) | 0.015 (2) | 0.030 (3) | −0.006 (2) | 0.010 (2) | 0.004 (2) |
C19 | 0.036 (3) | 0.023 (3) | 0.028 (3) | 0.003 (2) | 0.015 (2) | −0.003 (2) |
C20 | 0.019 (2) | 0.015 (2) | 0.019 (2) | −0.0018 (17) | 0.0052 (18) | −0.0048 (17) |
C21 | 0.030 (3) | 0.017 (2) | 0.023 (2) | 0.0026 (19) | 0.011 (2) | 0.0028 (18) |
C22 | 0.028 (2) | 0.018 (2) | 0.024 (2) | 0.005 (2) | 0.0067 (19) | −0.0032 (19) |
C23 | 0.024 (2) | 0.019 (2) | 0.023 (2) | −0.0015 (19) | 0.0082 (19) | −0.0089 (19) |
C24 | 0.028 (2) | 0.014 (2) | 0.021 (2) | −0.0013 (19) | 0.0070 (19) | 0.0002 (18) |
C25 | 0.022 (2) | 0.016 (2) | 0.021 (2) | 0.0028 (18) | 0.0041 (18) | −0.0015 (18) |
C26 | 0.025 (3) | 0.026 (3) | 0.035 (3) | 0.000 (2) | 0.010 (2) | −0.002 (2) |
Mo1—C6 | 1.941 (5) | C8—C9 | 1.390 (6) |
Mo1—C3 | 2.299 (4) | C8—H8 | 0.95 |
Mo1—C4 | 2.312 (4) | C9—C10 | 1.388 (7) |
Mo1—C2 | 2.330 (5) | C9—H9 | 0.95 |
Mo1—C5 | 2.359 (4) | C10—C11 | 1.381 (7) |
Mo1—C1 | 2.374 (4) | C10—C13 | 1.513 (6) |
Mo1—S1 | 2.424 (1) | C11—C12 | 1.398 (6) |
Mo1—S1i | 2.425 (1) | C11—H11 | 0.95 |
Mo1—Mo1i | 2.6052 (8) | C12—H12 | 0.95 |
Mo2—C19 | 1.988 (5) | C13—H13A | 0.98 |
Mo2—C14 | 2.298 (5) | C13—H13B | 0.98 |
Mo2—C15 | 2.308 (4) | C13—H13C | 0.98 |
Mo2—C18 | 2.340 (5) | C14—C15 | 1.428 (7) |
Mo2—C16 | 2.359 (5) | C14—C18 | 1.428 (7) |
Mo2—C17 | 2.370 (5) | C14—H14 | 1.00 |
Mo2—S2 | 2.430 (1) | C15—C16 | 1.410 (6) |
Mo2—S2ii | 2.419 (1) | C15—H15 | 1.00 |
Mo2—Mo2ii | 2.5751 (8) | C16—C17 | 1.419 (7) |
S1—C7 | 1.792 (4) | C16—H16 | 1.00 |
S1—Mo1i | 2.4252 (12) | C17—C18 | 1.391 (7) |
S2—C20 | 1.799 (4) | C17—H17 | 1.00 |
S2—Mo2ii | 2.4192 (12) | C18—H18 | 1.00 |
O1—C6 | 1.157 (5) | C20—C21 | 1.382 (6) |
O2—C19 | 1.159 (6) | C20—C25 | 1.391 (6) |
C1—C5 | 1.409 (6) | C21—C22 | 1.387 (6) |
C1—C2 | 1.414 (7) | C21—H21 | 0.95 |
C1—H1 | 1.00 | C22—C23 | 1.376 (6) |
C2—C3 | 1.423 (6) | C22—H22 | 0.95 |
C2—H2 | 1.00 | C23—C24 | 1.403 (6) |
C3—C4 | 1.426 (6) | C23—C26 | 1.516 (6) |
C3—H3 | 1.00 | C24—C25 | 1.390 (6) |
C4—C5 | 1.410 (6) | C24—H24 | 0.95 |
C4—H4 | 1.00 | C25—H25 | 0.95 |
C5—H5 | 1.00 | C26—H26A | 0.98 |
C7—C8 | 1.380 (6) | C26—H26B | 0.98 |
C7—C12 | 1.388 (6) | C26—H26C | 0.98 |
C6—Mo1—C3 | 89.65 (18) | C4—C3—H3 | 126.1 |
C6—Mo1—C4 | 85.36 (17) | Mo1—C3—H3 | 126.1 |
C3—Mo1—C4 | 36.02 (15) | C5—C4—C3 | 107.9 (4) |
C6—Mo1—C2 | 123.59 (18) | C5—C4—Mo1 | 74.2 (2) |
C3—Mo1—C2 | 35.81 (16) | C3—C4—Mo1 | 71.5 (2) |
C4—Mo1—C2 | 59.25 (16) | C5—C4—H4 | 125.8 |
C6—Mo1—C5 | 115.04 (17) | C3—C4—H4 | 125.8 |
C3—Mo1—C5 | 58.96 (16) | Mo1—C4—H4 | 125.8 |
C4—Mo1—C5 | 35.11 (15) | C1—C5—C4 | 108.6 (4) |
C2—Mo1—C5 | 58.27 (16) | C1—C5—Mo1 | 73.3 (2) |
C6—Mo1—C1 | 143.52 (17) | C4—C5—Mo1 | 70.6 (2) |
C3—Mo1—C1 | 58.91 (17) | C1—C5—H5 | 125.6 |
C4—Mo1—C1 | 58.47 (16) | C4—C5—H5 | 125.6 |
C2—Mo1—C1 | 34.99 (16) | Mo1—C5—H5 | 125.6 |
C5—Mo1—C1 | 34.63 (16) | O1—C6—Mo1 | 173.3 (4) |
C6—Mo1—S1 | 87.53 (13) | C8—C7—C12 | 119.1 (4) |
C3—Mo1—S1 | 98.92 (11) | C8—C7—S1 | 122.7 (4) |
C4—Mo1—S1 | 134.23 (11) | C12—C7—S1 | 118.0 (3) |
C2—Mo1—S1 | 88.70 (12) | C7—C8—C9 | 120.0 (4) |
C5—Mo1—S1 | 146.32 (12) | C7—C8—H8 | 120.0 |
C1—Mo1—S1 | 113.43 (12) | C9—C8—H8 | 120.0 |
C6—Mo1—S1i | 80.65 (13) | C10—C9—C8 | 121.7 (5) |
C3—Mo1—S1i | 144.04 (11) | C10—C9—H9 | 119.2 |
C4—Mo1—S1i | 108.29 (11) | C8—C9—H9 | 119.2 |
C2—Mo1—S1i | 148.06 (12) | C11—C10—C9 | 117.9 (4) |
C5—Mo1—S1i | 94.04 (11) | C11—C10—C13 | 121.4 (4) |
C1—Mo1—S1i | 113.10 (12) | C9—C10—C13 | 120.7 (4) |
S1—Mo1—S1i | 115.00 (3) | C10—C11—C12 | 121.0 (5) |
C6—Mo1—Mo1i | 78.96 (13) | C10—C11—H11 | 119.5 |
C3—Mo1—Mo1i | 153.86 (12) | C12—C11—H11 | 119.5 |
C4—Mo1—Mo1i | 160.22 (12) | C7—C12—C11 | 120.2 (4) |
C2—Mo1—Mo1i | 140.25 (12) | C7—C12—H12 | 119.9 |
C5—Mo1—Mo1i | 147.12 (11) | C11—C12—H12 | 119.9 |
C1—Mo1—Mo1i | 137.32 (12) | C10—C13—H13A | 109.5 |
S1—Mo1—Mo1i | 57.53 (3) | C10—C13—H13B | 109.5 |
S1i—Mo1—Mo1i | 57.47 (3) | H13A—C13—H13B | 109.5 |
C19—Mo2—C14 | 131.04 (19) | C10—C13—H13C | 109.5 |
C19—Mo2—C15 | 95.41 (19) | H13A—C13—H13C | 109.5 |
C14—Mo2—C15 | 36.11 (16) | H13B—C13—H13C | 109.5 |
C19—Mo2—C18 | 142.23 (19) | C15—C14—C18 | 107.1 (4) |
C14—Mo2—C18 | 35.85 (16) | C15—C14—Mo2 | 72.3 (3) |
C15—Mo2—C18 | 59.24 (17) | C18—C14—Mo2 | 73.7 (3) |
C19—Mo2—C16 | 84.92 (19) | C15—C14—H14 | 126.2 |
C14—Mo2—C16 | 58.97 (17) | C18—C14—H14 | 126.2 |
C15—Mo2—C16 | 35.15 (16) | Mo2—C14—H14 | 126.2 |
C18—Mo2—C16 | 58.02 (17) | C16—C15—C14 | 107.8 (4) |
C19—Mo2—C17 | 109.75 (19) | C16—C15—Mo2 | 74.4 (3) |
C14—Mo2—C17 | 58.68 (17) | C14—C15—Mo2 | 71.6 (3) |
C15—Mo2—C17 | 58.62 (16) | C16—C15—H15 | 125.9 |
C18—Mo2—C17 | 34.35 (17) | C14—C15—H15 | 125.9 |
C16—Mo2—C17 | 34.91 (17) | Mo2—C15—H15 | 125.9 |
C19—Mo2—S2ii | 79.05 (14) | C15—C16—C17 | 108.1 (4) |
C14—Mo2—S2ii | 95.51 (13) | C15—C16—Mo2 | 70.4 (3) |
C15—Mo2—S2ii | 95.34 (12) | C17—C16—Mo2 | 72.9 (3) |
C18—Mo2—S2ii | 126.98 (12) | C15—C16—H16 | 125.9 |
C16—Mo2—S2ii | 125.83 (13) | C17—C16—H16 | 125.9 |
C17—Mo2—S2ii | 152.53 (11) | Mo2—C16—H16 | 125.9 |
C19—Mo2—S2 | 88.51 (14) | C18—C17—C16 | 108.4 (4) |
C14—Mo2—S2 | 134.69 (13) | C18—C17—Mo2 | 71.7 (3) |
C15—Mo2—S2 | 148.71 (12) | C16—C17—Mo2 | 72.2 (3) |
C18—Mo2—S2 | 100.11 (12) | C18—C17—H17 | 125.7 |
C16—Mo2—S2 | 115.04 (12) | C16—C17—H17 | 125.7 |
C17—Mo2—S2 | 90.83 (12) | Mo2—C17—H17 | 125.7 |
S2ii—Mo2—S2 | 115.85 (3) | C17—C18—C14 | 108.5 (4) |
C19—Mo2—Mo2ii | 78.29 (15) | C17—C18—Mo2 | 74.0 (3) |
C14—Mo2—Mo2ii | 138.92 (12) | C14—C18—Mo2 | 70.5 (3) |
C15—Mo2—Mo2ii | 153.36 (12) | C17—C18—H18 | 125.6 |
C18—Mo2—Mo2ii | 136.94 (13) | C14—C18—H18 | 125.6 |
C16—Mo2—Mo2ii | 161.67 (12) | Mo2—C18—H18 | 125.6 |
C17—Mo2—Mo2ii | 147.90 (12) | O2—C19—Mo2 | 175.0 (4) |
S2ii—Mo2—Mo2ii | 58.12 (3) | C21—C20—C25 | 119.4 (4) |
S2—Mo2—Mo2ii | 57.72 (3) | C21—C20—S2 | 122.3 (3) |
C7—S1—Mo1 | 109.82 (14) | C25—C20—S2 | 118.0 (3) |
C7—S1—Mo1i | 117.34 (15) | C20—C21—C22 | 119.8 (4) |
Mo1—S1—Mo1i | 65.00 (3) | C20—C21—H21 | 120.1 |
C20—S2—Mo2ii | 113.39 (14) | C22—C21—H21 | 120.1 |
C20—S2—Mo2 | 114.07 (14) | C23—C22—C21 | 121.9 (4) |
Mo2ii—S2—Mo2 | 64.15 (3) | C23—C22—H22 | 119.0 |
C5—C1—C2 | 107.9 (4) | C21—C22—H22 | 119.0 |
C5—C1—Mo1 | 72.1 (3) | C22—C23—C24 | 118.2 (4) |
C2—C1—Mo1 | 70.8 (3) | C22—C23—C26 | 121.8 (4) |
C5—C1—H1 | 126.0 | C24—C23—C26 | 120.0 (4) |
C2—C1—H1 | 126.0 | C25—C24—C23 | 120.3 (4) |
Mo1—C1—H1 | 126.0 | C25—C24—H24 | 119.8 |
C1—C2—C3 | 108.2 (4) | C23—C24—H24 | 119.8 |
C1—C2—Mo1 | 74.2 (3) | C24—C25—C20 | 120.3 (4) |
C3—C2—Mo1 | 70.9 (3) | C24—C25—H25 | 119.8 |
C1—C2—H2 | 125.7 | C20—C25—H25 | 119.8 |
C3—C2—H2 | 125.7 | C23—C26—H26A | 109.5 |
Mo1—C2—H2 | 125.7 | C23—C26—H26B | 109.5 |
C2—C3—C4 | 107.3 (4) | H26A—C26—H26B | 109.5 |
C2—C3—Mo1 | 73.3 (3) | C23—C26—H26C | 109.5 |
C4—C3—Mo1 | 72.5 (2) | H26A—C26—H26C | 109.5 |
C2—C3—H3 | 126.1 | H26B—C26—H26C | 109.5 |
C6—Mo1—S1—C7 | −33.3 (2) | Mo1i—Mo1—C5—C4 | 144.4 (2) |
C3—Mo1—S1—C7 | 56.0 (2) | Mo1—S1—C7—C8 | 100.0 (4) |
C4—Mo1—S1—C7 | 47.8 (2) | Mo1i—S1—C7—C8 | 28.6 (4) |
C2—Mo1—S1—C7 | 90.4 (2) | Mo1—S1—C7—C12 | −84.4 (3) |
C5—Mo1—S1—C7 | 101.1 (3) | Mo1i—S1—C7—C12 | −155.8 (3) |
C1—Mo1—S1—C7 | 115.9 (2) | C12—C7—C8—C9 | −0.8 (7) |
S1i—Mo1—S1—C7 | −111.75 (17) | S1—C7—C8—C9 | 174.7 (3) |
Mo1i—Mo1—S1—C7 | −111.75 (17) | C7—C8—C9—C10 | 0.8 (7) |
C6—Mo1—S1—Mo1i | 78.49 (13) | C8—C9—C10—C11 | 0.5 (7) |
C3—Mo1—S1—Mo1i | 167.74 (12) | C8—C9—C10—C13 | −178.8 (4) |
C4—Mo1—S1—Mo1i | 159.57 (16) | C9—C10—C11—C12 | −1.8 (7) |
C2—Mo1—S1—Mo1i | −157.81 (13) | C13—C10—C11—C12 | 177.4 (4) |
C5—Mo1—S1—Mo1i | −147.2 (2) | C8—C7—C12—C11 | −0.5 (6) |
C1—Mo1—S1—Mo1i | −132.37 (13) | S1—C7—C12—C11 | −176.3 (3) |
S1i—Mo1—S1—Mo1i | 0.0 | C10—C11—C12—C7 | 1.9 (7) |
C19—Mo2—S2—C20 | −28.4 (2) | C19—Mo2—C14—C15 | 11.2 (4) |
C14—Mo2—S2—C20 | 125.5 (2) | C18—Mo2—C14—C15 | −114.5 (4) |
C15—Mo2—S2—C20 | 69.6 (3) | C16—Mo2—C14—C15 | −37.4 (3) |
C18—Mo2—S2—C20 | 114.6 (2) | C17—Mo2—C14—C15 | −78.4 (3) |
C16—Mo2—S2—C20 | 55.3 (2) | S2ii—Mo2—C14—C15 | 91.5 (3) |
C17—Mo2—S2—C20 | 81.3 (2) | S2—Mo2—C14—C15 | −133.1 (2) |
S2ii—Mo2—S2—C20 | −105.47 (16) | Mo2ii—Mo2—C14—C15 | 137.3 (2) |
Mo2ii—Mo2—S2—C20 | −105.47 (16) | C19—Mo2—C14—C18 | 125.8 (3) |
C19—Mo2—S2—Mo2ii | 77.08 (14) | C15—Mo2—C14—C18 | 114.5 (4) |
C14—Mo2—S2—Mo2ii | −129.00 (17) | C16—Mo2—C14—C18 | 77.1 (3) |
C15—Mo2—S2—Mo2ii | 175.1 (2) | C17—Mo2—C14—C18 | 36.1 (3) |
C18—Mo2—S2—Mo2ii | −139.93 (13) | S2ii—Mo2—C14—C18 | −153.9 (3) |
C16—Mo2—S2—Mo2ii | 160.76 (14) | S2—Mo2—C14—C18 | −18.6 (4) |
C17—Mo2—S2—Mo2ii | −173.19 (13) | Mo2ii—Mo2—C14—C18 | −108.1 (3) |
S2ii—Mo2—S2—Mo2ii | 0.0 | C18—C14—C15—C16 | 0.2 (5) |
C6—Mo1—C1—C5 | −45.1 (4) | Mo2—C14—C15—C16 | 66.2 (3) |
C3—Mo1—C1—C5 | −79.2 (3) | C18—C14—C15—Mo2 | −66.0 (3) |
C4—Mo1—C1—C5 | −36.8 (3) | C19—Mo2—C15—C16 | 73.2 (3) |
C2—Mo1—C1—C5 | −117.1 (4) | C14—Mo2—C15—C16 | −115.3 (4) |
S1—Mo1—C1—C5 | −165.6 (2) | C18—Mo2—C15—C16 | −77.0 (3) |
S1i—Mo1—C1—C5 | 61.1 (3) | C17—Mo2—C15—C16 | −36.7 (3) |
Mo1i—Mo1—C1—C5 | 127.6 (2) | S2ii—Mo2—C15—C16 | 152.7 (3) |
C6—Mo1—C1—C2 | 72.0 (4) | S2—Mo2—C15—C16 | −22.9 (4) |
C3—Mo1—C1—C2 | 37.8 (3) | Mo2ii—Mo2—C15—C16 | 147.8 (3) |
C4—Mo1—C1—C2 | 80.2 (3) | C19—Mo2—C15—C14 | −171.5 (3) |
C5—Mo1—C1—C2 | 117.1 (4) | C18—Mo2—C15—C14 | 38.3 (3) |
S1—Mo1—C1—C2 | −48.5 (3) | C16—Mo2—C15—C14 | 115.3 (4) |
S1i—Mo1—C1—C2 | 178.2 (2) | C17—Mo2—C15—C14 | 78.6 (3) |
Mo1i—Mo1—C1—C2 | −115.4 (3) | S2ii—Mo2—C15—C14 | −92.0 (3) |
C5—C1—C2—C3 | −0.3 (5) | S2—Mo2—C15—C14 | 92.4 (3) |
Mo1—C1—C2—C3 | −63.2 (3) | Mo2ii—Mo2—C15—C14 | −96.9 (4) |
C5—C1—C2—Mo1 | 63.0 (3) | C14—C15—C16—C17 | −0.6 (5) |
C6—Mo1—C2—C1 | −137.3 (3) | Mo2—C15—C16—C17 | 63.6 (3) |
C3—Mo1—C2—C1 | −116.2 (4) | C14—C15—C16—Mo2 | −64.3 (3) |
C4—Mo1—C2—C1 | −77.8 (3) | C19—Mo2—C16—C15 | −106.9 (3) |
C5—Mo1—C2—C1 | −36.5 (3) | C14—Mo2—C16—C15 | 38.4 (3) |
S1—Mo1—C2—C1 | 136.6 (3) | C18—Mo2—C16—C15 | 80.7 (3) |
S1i—Mo1—C2—C1 | −3.1 (4) | C17—Mo2—C16—C15 | 117.0 (4) |
Mo1i—Mo1—C2—C1 | 106.7 (3) | S2ii—Mo2—C16—C15 | −34.3 (3) |
C6—Mo1—C2—C3 | −21.1 (3) | S2—Mo2—C16—C15 | 167.1 (3) |
C4—Mo1—C2—C3 | 38.4 (3) | Mo2ii—Mo2—C16—C15 | −130.5 (4) |
C5—Mo1—C2—C3 | 79.7 (3) | C19—Mo2—C16—C17 | 136.1 (3) |
C1—Mo1—C2—C3 | 116.2 (4) | C14—Mo2—C16—C17 | −78.6 (3) |
S1—Mo1—C2—C3 | −107.2 (3) | C15—Mo2—C16—C17 | −117.0 (4) |
S1i—Mo1—C2—C3 | 113.1 (3) | C18—Mo2—C16—C17 | −36.3 (3) |
Mo1i—Mo1—C2—C3 | −137.1 (2) | S2ii—Mo2—C16—C17 | −151.4 (2) |
C1—C2—C3—C4 | 0.4 (5) | S2—Mo2—C16—C17 | 50.1 (3) |
Mo1—C2—C3—C4 | −65.0 (3) | Mo2ii—Mo2—C16—C17 | 112.4 (4) |
C1—C2—C3—Mo1 | 65.4 (3) | C15—C16—C17—C18 | 0.9 (5) |
C6—Mo1—C3—C2 | 162.6 (3) | Mo2—C16—C17—C18 | 62.9 (3) |
C4—Mo1—C3—C2 | −114.9 (4) | C15—C16—C17—Mo2 | −62.0 (3) |
C5—Mo1—C3—C2 | −77.6 (3) | C19—Mo2—C17—C18 | −164.4 (3) |
C1—Mo1—C3—C2 | −36.9 (3) | C14—Mo2—C17—C18 | −37.7 (3) |
S1—Mo1—C3—C2 | 75.1 (3) | C15—Mo2—C17—C18 | −80.3 (3) |
S1i—Mo1—C3—C2 | −124.0 (2) | C16—Mo2—C17—C18 | −117.2 (4) |
Mo1i—Mo1—C3—C2 | 99.1 (3) | S2ii—Mo2—C17—C18 | −59.8 (4) |
C6—Mo1—C3—C4 | −82.6 (3) | S2—Mo2—C17—C18 | 106.9 (3) |
C2—Mo1—C3—C4 | 114.9 (4) | Mo2ii—Mo2—C17—C18 | 96.0 (3) |
C5—Mo1—C3—C4 | 37.3 (3) | C19—Mo2—C17—C16 | −47.2 (3) |
C1—Mo1—C3—C4 | 77.9 (3) | C14—Mo2—C17—C16 | 79.5 (3) |
S1—Mo1—C3—C4 | −170.0 (2) | C15—Mo2—C17—C16 | 36.9 (3) |
S1i—Mo1—C3—C4 | −9.1 (4) | C18—Mo2—C17—C16 | 117.2 (4) |
Mo1i—Mo1—C3—C4 | −146.0 (2) | S2ii—Mo2—C17—C16 | 57.4 (4) |
C2—C3—C4—C5 | −0.3 (5) | S2—Mo2—C17—C16 | −136.0 (3) |
Mo1—C3—C4—C5 | −65.8 (3) | Mo2ii—Mo2—C17—C16 | −146.8 (2) |
C2—C3—C4—Mo1 | 65.5 (3) | C16—C17—C18—C14 | −0.8 (5) |
C6—Mo1—C4—C5 | −148.6 (3) | Mo2—C17—C18—C14 | 62.4 (3) |
C3—Mo1—C4—C5 | 115.6 (4) | C16—C17—C18—Mo2 | −63.2 (3) |
C2—Mo1—C4—C5 | 77.4 (3) | C15—C14—C18—C17 | 0.4 (5) |
C1—Mo1—C4—C5 | 36.3 (3) | Mo2—C14—C18—C17 | −64.7 (3) |
S1—Mo1—C4—C5 | 129.4 (2) | C15—C14—C18—Mo2 | 65.1 (3) |
S1i—Mo1—C4—C5 | −70.1 (3) | C19—Mo2—C18—C17 | 24.4 (4) |
Mo1i—Mo1—C4—C5 | −111.1 (4) | C14—Mo2—C18—C17 | 116.9 (4) |
C6—Mo1—C4—C3 | 95.8 (3) | C15—Mo2—C18—C17 | 78.3 (3) |
C2—Mo1—C4—C3 | −38.1 (3) | C16—Mo2—C18—C17 | 36.9 (3) |
C5—Mo1—C4—C3 | −115.6 (4) | S2ii—Mo2—C18—C17 | 150.1 (2) |
C1—Mo1—C4—C3 | −79.3 (3) | S2—Mo2—C18—C17 | −76.4 (3) |
S1—Mo1—C4—C3 | 13.8 (3) | Mo2ii—Mo2—C18—C17 | −129.3 (3) |
S1i—Mo1—C4—C3 | 174.4 (2) | C19—Mo2—C18—C14 | −92.5 (4) |
Mo1i—Mo1—C4—C3 | 133.3 (3) | C15—Mo2—C18—C14 | −38.6 (3) |
C2—C1—C5—C4 | 0.1 (5) | C16—Mo2—C18—C14 | −80.0 (3) |
Mo1—C1—C5—C4 | 62.2 (3) | C17—Mo2—C18—C14 | −116.9 (4) |
C2—C1—C5—Mo1 | −62.1 (3) | S2ii—Mo2—C18—C14 | 33.2 (3) |
C3—C4—C5—C1 | 0.2 (5) | S2—Mo2—C18—C14 | 166.7 (3) |
Mo1—C4—C5—C1 | −63.9 (3) | Mo2ii—Mo2—C18—C14 | 113.8 (3) |
C3—C4—C5—Mo1 | 64.0 (3) | Mo2ii—S2—C20—C21 | −104.6 (4) |
C6—Mo1—C5—C1 | 152.3 (3) | Mo2—S2—C20—C21 | −33.7 (4) |
C3—Mo1—C5—C1 | 79.1 (3) | Mo2ii—S2—C20—C25 | 80.6 (3) |
C4—Mo1—C5—C1 | 117.3 (4) | Mo2—S2—C20—C25 | 151.6 (3) |
C2—Mo1—C5—C1 | 36.9 (3) | C25—C20—C21—C22 | −2.0 (7) |
S1—Mo1—C5—C1 | 24.3 (4) | S2—C20—C21—C22 | −176.6 (3) |
S1i—Mo1—C5—C1 | −126.1 (3) | C20—C21—C22—C23 | 0.3 (7) |
Mo1i—Mo1—C5—C1 | −98.2 (3) | C21—C22—C23—C24 | 0.9 (7) |
C6—Mo1—C5—C4 | 35.0 (3) | C21—C22—C23—C26 | −178.2 (4) |
C3—Mo1—C5—C4 | −38.2 (3) | C22—C23—C24—C25 | −0.5 (6) |
C2—Mo1—C5—C4 | −80.5 (3) | C26—C23—C24—C25 | 178.6 (4) |
C1—Mo1—C5—C4 | −117.3 (4) | C23—C24—C25—C20 | −1.1 (7) |
S1—Mo1—C5—C4 | −93.0 (3) | C21—C20—C25—C24 | 2.3 (6) |
S1i—Mo1—C5—C4 | 116.5 (3) | S2—C20—C25—C24 | 177.2 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mo2(C5H5)2(C7H7S)2(CO)2] |
Mr | 624.45 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 13.245 (2), 10.135 (1), 18.042 (2) |
β (°) | 104.901 (2) |
V (Å3) | 2340.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.06 × 0.06 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.758, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14384, 5374, 3915 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.104, 1.03 |
No. of reflections | 5374 |
No. of parameters | 291 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.60, −1.78 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
Mo1—S1 | 2.424 (1) | Mo2—S2 | 2.430 (1) |
Mo1—S1i | 2.425 (1) | Mo2—S2ii | 2.419 (1) |
Mo1—Mo1i | 2.6052 (8) | Mo2—Mo2ii | 2.5751 (8) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1. |
Acknowledgements
The authors thank the Science Fund MOSTI (grant No. 03-01-03-SF0209) for funding this study, and the University of Malaya for the purchase of the diffractometer.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Benson, I. B., Killops, S. D., Know, S. A. R. & Welch, A. J. (1980). J. Chem. Soc. Chem. Commun. pp. 1137–1139. CrossRef Web of Science Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, L.-C., Wang, J.-Q., Hu, Q.-M., Wang, R.-J. & Mak, T. C. W. (1997). Inorg. Chim. Acta, 256, 129–135. CSD CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound was characterized spectroscopically in a study on [MoCp(CO)(µ-SAr]2 type of compounds. The compound was synthesized by treating MoClCp(CO)3 with 4-tolyl mercaptan (Benson et al., 1980). We have obtained the title compound (Fig. 1) as the unexpected product in the reaction of [(η5-C5H5)Mo(CO)2]2 with deuterated o-P(PhSCD3)3. Under the conditions of the reaction, the ortho-SD3 groups of the phosphine have been rearranged to the para position. The rearrangement is then followed by an exchange of the deuterium atoms by hydrogen atoms; the absence of deuterium in the compound is confirmed by 1H NMR spectroscopic analysis.