metal-organic compounds
In the crystal structure of the title heterothiolate cluster, [MoCu2S4(C19H17P)4]·4H2O, the Mo atom lies on a postion of crystallographic site symmetry , coordinated by four S atoms in a tetrahedral environment; each pair of S atoms bis-chelates two Cu atoms which are, in addition, coordinated by two phosphine ligands each. The tetrahedrally coordinated Cu atoms lie on positions of site symmetry 2.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806011111/lh2030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806011111/lh2030Isup2.hkl |
CCDC reference: 608441
Computing details top
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Crystal data top
[MoCu2S4(C19H17P)4]·4H2O | Dx = 1.163 Mg m−3 |
Mr = 1528.51 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 3407 reflections |
Hall symbol: I -4 | θ = 2.7–25.7° |
a = 13.777 (1) Å | µ = 0.83 mm−1 |
c = 22.995 (2) Å | T = 291 K |
V = 4364.3 (4) Å3 | Plate, red |
Z = 2 | 0.39 × 0.28 × 0.06 mm |
F(000) = 1576 |
Data collection top
Bruker APEX-II area-detector diffractometer | 4886 independent reflections |
Radiation source: fine-focus sealed tube | 3959 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→15 |
Tmin = 0.831, Tmax = 0.952 | k = −17→7 |
9215 measured reflections | l = −25→29 |
Refinement top
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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.148 | w = 1/[σ2(Fo2) + (0.0923P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
4886 reflections | Δρmax = 0.79 e Å−3 |
180 parameters | Δρmin = −0.25 e Å−3 |
49 restraints | Absolute structure: Flack (1983), 2328 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (2) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mo1 | 1.0000 | 0.5000 | 0.2500 | 0.0440 (2) | |
Cu1 | 1.0000 | 0.5000 | 0.12961 (2) | 0.0482 (2) | |
S1 | 1.0529 (1) | 0.3822 (1) | 0.19337 (5) | 0.0592 (3) | |
P1 | 0.8803 (1) | 0.4323 (1) | 0.07304 (5) | 0.0556 (3) | |
O1w | 1.161 (1) | 0.111 (1) | −0.2339 (6) | 0.177 (4) | 0.50 |
O1w' | 1.068 (1) | 0.215 (1) | −0.2229 (6) | 0.177 (4) | 0.50 |
C1 | 0.938 (1) | 0.3502 (7) | 0.0211 (3) | 0.063 (2) | 0.50 |
C2 | 0.947 (1) | 0.3740 (6) | −0.0374 (3) | 0.085 (3) | 0.50 |
C3 | 0.993 (1) | 0.3103 (7) | −0.0754 (3) | 0.092 (3) | 0.50 |
C4 | 1.029 (1) | 0.2228 (7) | −0.0550 (4) | 0.100 (4) | 0.50 |
C5 | 1.021 (1) | 0.1990 (6) | 0.0035 (4) | 0.096 (3) | 0.50 |
C6 | 0.975 (1) | 0.2627 (7) | 0.0416 (3) | 0.089 (3) | 0.50 |
C1' | 0.928 (1) | 0.3281 (7) | 0.0300 (3) | 0.063 (2) | 0.50 |
C2' | 0.942 (1) | 0.3371 (6) | −0.0296 (3) | 0.085 (3) | 0.50 |
C3' | 0.994 (1) | 0.2666 (7) | −0.0596 (3) | 0.092 (3) | 0.50 |
C4' | 1.031 (1) | 0.1871 (7) | −0.0300 (4) | 0.100 (4) | 0.50 |
C5' | 1.017 (1) | 0.1781 (7) | 0.0296 (4) | 0.096 (3) | 0.50 |
C6' | 0.965 (1) | 0.2486 (7) | 0.0596 (3) | 0.089 (3) | 0.50 |
C7 | 0.7842 (2) | 0.3672 (2) | 0.11048 (13) | 0.057 (1) | |
C8 | 0.7335 (3) | 0.2914 (3) | 0.08459 (14) | 0.076 (2) | |
C9 | 0.6601 (3) | 0.2444 (2) | 0.11500 (19) | 0.090 (2) | |
C10 | 0.6373 (3) | 0.2732 (3) | 0.17131 (18) | 0.094 (2) | |
C11 | 0.6880 (3) | 0.3489 (3) | 0.19720 (13) | 0.089 (2) | |
C12 | 0.7614 (2) | 0.3960 (2) | 0.16679 (13) | 0.069 (1) | |
C13 | 0.8094 (4) | 0.5088 (5) | 0.0231 (2) | 0.080 (2) | |
C14 | 0.7433 (2) | 0.5778 (3) | 0.0544 (2) | 0.070 (1) | |
C15 | 0.6457 (2) | 0.5549 (3) | 0.0615 (2) | 0.084 (2) | |
C16 | 0.5850 (2) | 0.6177 (3) | 0.0918 (2) | 0.093 (2) | |
C17 | 0.6219 (3) | 0.7032 (3) | 0.1151 (2) | 0.104 (2) | |
C18 | 0.7195 (4) | 0.7260 (3) | 0.1080 (2) | 0.118 (3) | |
C19 | 0.7802 (2) | 0.6633 (3) | 0.0777 (2) | 0.099 (2) | |
H2 | 0.9221 | 0.4325 | −0.0511 | 0.102* | 0.50 |
H3 | 0.9984 | 0.3262 | −0.1146 | 0.111* | 0.50 |
H4 | 1.0600 | 0.1802 | −0.0804 | 0.120* | 0.50 |
H5 | 1.0453 | 0.1405 | 0.0172 | 0.115* | 0.50 |
H6 | 0.9690 | 0.2468 | 0.0807 | 0.106* | 0.50 |
H2' | 0.9165 | 0.3903 | −0.0494 | 0.102* | 0.50 |
H3' | 1.0032 | 0.2726 | −0.0995 | 0.111* | 0.50 |
H4' | 1.0662 | 0.1399 | −0.0501 | 0.120* | 0.50 |
H5' | 1.0425 | 0.1249 | 0.0493 | 0.115* | 0.50 |
H6' | 0.9557 | 0.2425 | 0.0995 | 0.106* | 0.50 |
H8 | 0.7488 | 0.2721 | 0.0469 | 0.091* | |
H9 | 0.6262 | 0.1937 | 0.0977 | 0.107* | |
H10 | 0.5882 | 0.2417 | 0.1917 | 0.112* | |
H11 | 0.6728 | 0.3682 | 0.2349 | 0.107* | |
H12 | 0.7953 | 0.4467 | 0.1841 | 0.082* | |
H13a | 0.8536 | 0.5456 | −0.0012 | 0.096* | |
H13b | 0.7709 | 0.4675 | −0.0021 | 0.096* | |
H15 | 0.6211 | 0.4977 | 0.0460 | 0.100* | |
H16 | 0.5198 | 0.6024 | 0.0966 | 0.112* | |
H17 | 0.5813 | 0.7452 | 0.1353 | 0.124* | |
H18 | 0.7442 | 0.7833 | 0.1235 | 0.141* | |
H19 | 0.8455 | 0.6786 | 0.0729 | 0.118* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0484 (2) | 0.0484 (2) | 0.0353 (3) | 0.000 | 0.000 | 0.000 |
Cu1 | 0.0513 (5) | 0.0535 (5) | 0.0400 (4) | −0.0006 (4) | 0.000 | 0.000 |
S1 | 0.0778 (7) | 0.0526 (5) | 0.0472 (5) | 0.0123 (5) | −0.0001 (6) | 0.0008 (5) |
P1 | 0.0490 (6) | 0.0742 (8) | 0.0436 (6) | 0.0004 (6) | −0.0038 (5) | −0.0082 (5) |
O1w | 0.211 (8) | 0.204 (8) | 0.117 (6) | −0.042 (6) | −0.041 (6) | −0.007 (6) |
O1w' | 0.211 (8) | 0.204 (8) | 0.117 (6) | −0.042 (6) | −0.041 (6) | −0.007 (6) |
C1 | 0.042 (4) | 0.087 (5) | 0.060 (3) | −0.017 (4) | 0.008 (3) | −0.024 (3) |
C2 | 0.081 (4) | 0.105 (8) | 0.069 (4) | −0.021 (6) | 0.016 (3) | −0.021 (5) |
C3 | 0.096 (5) | 0.112 (8) | 0.067 (5) | −0.001 (6) | 0.023 (5) | −0.012 (5) |
C4 | 0.099 (5) | 0.118 (8) | 0.083 (7) | −0.002 (5) | 0.017 (6) | −0.040 (6) |
C5 | 0.084 (4) | 0.097 (5) | 0.105 (8) | 0.003 (4) | 0.015 (6) | −0.039 (6) |
C6 | 0.076 (5) | 0.108 (5) | 0.082 (6) | 0.013 (4) | 0.008 (5) | −0.037 (5) |
C1' | 0.042 (4) | 0.087 (5) | 0.060 (3) | −0.017 (4) | 0.008 (3) | −0.024 (3) |
C2' | 0.081 (4) | 0.105 (8) | 0.069 (4) | −0.021 (6) | 0.016 (3) | −0.021 (5) |
C3' | 0.096 (5) | 0.112 (8) | 0.067 (5) | −0.001 (6) | 0.023 (5) | −0.012 (5) |
C4' | 0.099 (5) | 0.118 (8) | 0.083 (7) | −0.002 (5) | 0.017 (6) | −0.040 (6) |
C5' | 0.084 (4) | 0.097 (5) | 0.105 (8) | 0.003 (4) | 0.015 (6) | −0.039 (6) |
C6' | 0.076 (5) | 0.108 (5) | 0.082 (6) | 0.013 (4) | 0.008 (5) | −0.037 (5) |
C7 | 0.049 (2) | 0.063 (3) | 0.060 (3) | 0.001 (2) | −0.012 (2) | −0.002 (2) |
C8 | 0.066 (3) | 0.077 (3) | 0.085 (4) | −0.008 (2) | −0.009 (3) | −0.021 (3) |
C9 | 0.076 (4) | 0.090 (4) | 0.102 (5) | −0.027 (3) | −0.006 (4) | −0.015 (4) |
C10 | 0.061 (3) | 0.100 (4) | 0.120 (6) | −0.022 (3) | −0.002 (3) | 0.027 (4) |
C11 | 0.080 (3) | 0.127 (5) | 0.060 (3) | −0.023 (3) | 0.009 (3) | −0.004 (3) |
C12 | 0.061 (3) | 0.082 (3) | 0.063 (3) | −0.012 (2) | 0.001 (2) | −0.009 (2) |
C13 | 0.075 (3) | 0.116 (4) | 0.048 (3) | −0.001 (3) | −0.009 (2) | 0.018 (3) |
C14 | 0.056 (3) | 0.089 (4) | 0.066 (3) | −0.003 (3) | −0.012 (2) | 0.031 (3) |
C15 | 0.060 (3) | 0.093 (4) | 0.098 (4) | −0.003 (3) | −0.015 (3) | 0.019 (3) |
C16 | 0.063 (3) | 0.096 (5) | 0.121 (5) | 0.006 (3) | −0.006 (3) | 0.022 (4) |
C17 | 0.090 (5) | 0.096 (5) | 0.125 (6) | 0.036 (4) | −0.020 (4) | 0.009 (4) |
C18 | 0.121 (6) | 0.080 (4) | 0.152 (8) | 0.004 (4) | −0.050 (6) | 0.016 (5) |
C19 | 0.073 (4) | 0.087 (4) | 0.136 (6) | 0.000 (3) | −0.034 (4) | 0.037 (4) |
Geometric parameters (Å, º) top
Mo1—S1 | 2.205 (1) | C13—C14 | 1.501 (7) |
Mo1—S1i | 2.205 (1) | C14—C15 | 1.39 |
Mo1—S1ii | 2.205 (1) | C14—C19 | 1.39 |
Mo1—S1iii | 2.205 (1) | C15—C16 | 1.39 |
Cu1—P1 | 2.298 (1) | C16—C17 | 1.39 |
Cu1—P1i | 2.298 (1) | C17—C18 | 1.39 |
Cu1—S1 | 2.306 (1) | C18—C19 | 1.39 |
Cu1—S1i | 2.306 (1) | C2—H2 | 0.93 |
P1—C7 | 1.817 (3) | C3—H3 | 0.93 |
P1—C1 | 1.826 (5) | C4—H4 | 0.93 |
P1—C13 | 1.840 (5) | C5—H5 | 0.93 |
P1—C1' | 1.861 (5) | C6—H6 | 0.93 |
C1—C2 | 1.39 | C2'—H2' | 0.93 |
C1—C6 | 1.39 | C3'—H3' | 0.93 |
C2—C3 | 1.39 | C4'—H4' | 0.93 |
C3—C4 | 1.39 | C5'—H5' | 0.93 |
C4—C5 | 1.39 | C6'—H6' | 0.93 |
C5—C6 | 1.39 | C8—H8 | 0.93 |
C1'—C2' | 1.39 | C9—H9 | 0.93 |
C1'—C6' | 1.39 | C10—H10 | 0.93 |
C2'—C3' | 1.39 | C11—H11 | 0.93 |
C3'—C4' | 1.39 | C12—H12 | 0.93 |
C4'—C5' | 1.39 | C13—H13a | 0.97 |
C5'—C6' | 1.39 | C13—H13b | 0.97 |
C7—C8 | 1.39 | C15—H15 | 0.93 |
C7—C12 | 1.39 | C16—H16 | 0.93 |
C8—C9 | 1.39 | C17—H17 | 0.93 |
C9—C10 | 1.39 | C18—H18 | 0.93 |
C10—C11 | 1.39 | C19—H19 | 0.93 |
C11—C12 | 1.39 | ||
S1—Mo1—S1i | 107.62 (6) | C19—C18—C17 | 120.0 |
S1—Mo1—S1ii | 110.40 (3) | C18—C19—C14 | 120.0 |
S1—Mo1—S1iii | 110.40 (3) | C1—C2—H2 | 120.0 |
P1—Cu1—P1i | 111.05 (6) | C3—C2—H2 | 120.0 |
P1—Cu1—S1 | 107.51 (5) | C4—C3—H3 | 120.0 |
P1—Cu1—S1i | 114.77 (4) | C2—C3—H3 | 120.0 |
S1—Cu1—S1i | 101.04 (6) | C3—C4—H4 | 120.0 |
Mo1—S1—Cu1 | 75.67 (3) | C5—C4—H4 | 120.0 |
C7—P1—C1 | 108.7 (5) | C4—C5—H5 | 120.0 |
C7—P1—C13 | 101.0 (2) | C6—C5—H5 | 120.0 |
C1—P1—C13 | 100.2 (3) | C5—C6—H6 | 120.0 |
C7—P1—C1' | 97.2 (5) | C1—C6—H6 | 120.0 |
C13—P1—C1' | 107.2 (4) | C1'—C2'—H2' | 120.0 |
C7—P1—Cu1 | 117.1 (1) | C3'—C2'—H2' | 120.0 |
C1—P1—Cu1 | 108.0 (6) | C4'—C3'—H3' | 120.0 |
C13—P1—Cu1 | 120.1 (2) | C2'—C3'—H3' | 120.0 |
C1'—P1—Cu1 | 111.3 (5) | C3'—C4'—H4' | 120.0 |
C2—C1—C6 | 120.0 | C5'—C4'—H4' | 120.0 |
C2—C1—P1 | 121.6 (3) | C4'—C5'—H5' | 120.0 |
C6—C1—P1 | 118.3 (3) | C6'—C5'—H5' | 120.0 |
C1—C2—C3 | 120.0 | C5'—C6'—H6' | 120.0 |
C4—C3—C2 | 120.0 | C1'—C6'—H6' | 120.0 |
C3—C4—C5 | 120.0 | C7—C8—H8 | 120.0 |
C4—C5—C6 | 120.0 | C9—C8—H8 | 120.0 |
C5—C6—C1 | 120.0 | C8—C9—H9 | 120.0 |
C2'—C1'—C6' | 120.0 | C10—C9—H9 | 120.0 |
C2'—C1'—P1 | 120.3 (3) | C11—C10—H10 | 120.0 |
C6'—C1'—P1 | 118.6 (3) | C9—C10—H10 | 120.0 |
C1'—C2'—C3' | 120.0 | C12—C11—H11 | 120.0 |
C4'—C3'—C2' | 120.0 | C10—C11—H11 | 120.0 |
C3'—C4'—C5' | 120.0 | C11—C12—H12 | 120.0 |
C4'—C5'—C6' | 120.0 | C7—C12—H12 | 120.0 |
C5'—C6'—C1' | 120.0 | C14—C13—H13a | 109.1 |
C8—C7—C12 | 120.0 | P1—C13—H13a | 109.1 |
C8—C7—P1 | 122.3 (2) | C14—C13—H13b | 109.1 |
C12—C7—P1 | 117.7 (2) | P1—C13—H13b | 109.1 |
C7—C8—C9 | 120.0 | H13a—C13—H13b | 107.8 |
C8—C9—C10 | 120.0 | C16—C15—H15 | 120.0 |
C11—C10—C9 | 120.0 | C14—C15—H15 | 120.0 |
C12—C11—C10 | 120.0 | C15—C16—H16 | 120.0 |
C11—C12—C7 | 120.0 | C17—C16—H16 | 120.0 |
C14—C13—P1 | 112.6 (3) | C18—C17—H17 | 120.0 |
C15—C14—C19 | 120.0 | C16—C17—H17 | 120.0 |
C15—C14—C13 | 120.0 (4) | C19—C18—H18 | 120.0 |
C19—C14—C13 | 120.0 (4) | C17—C18—H18 | 120.0 |
C16—C15—C14 | 120.0 | C18—C19—H19 | 120.0 |
C15—C16—C17 | 120.0 | C14—C19—H19 | 120.0 |
C18—C17—C16 | 120.0 | ||
S1iii—Mo1—S1—Cu1 | −120.56 (2) | C1—P1—C1'—C2' | −31 (4) |
S1ii—Mo1—S1—Cu1 | 120.56 (2) | C13—P1—C1'—C2' | 26 (1) |
Cu1ii—Mo1—S1—Cu1 | 180 | Cu1—P1—C1'—C2' | −107.2 (8) |
P1—Cu1—S1—Mo1 | −120.61 (4) | C7—P1—C1'—C6' | −62.0 (8) |
P1i—Cu1—S1—Mo1 | 115.32 (5) | C1—P1—C1'—C6' | 137 (5) |
P1i—Cu1—P1—C7 | 175.5 (2) | C13—P1—C1'—C6' | −166.0 (7) |
S1i—Cu1—P1—C7 | −62.4 (2) | Cu1—P1—C1'—C6' | 60.8 (8) |
S1—Cu1—P1—C7 | 49.2 (2) | P1—C1'—C2'—C3' | 168 (1) |
P1i—Cu1—P1—C1 | 52.4 (3) | P1—C1'—C6'—C5' | −168 (1) |
S1i—Cu1—P1—C1 | 174.6 (3) | C1—P1—C7—C8 | −29.3 (5) |
S1—Cu1—P1—C1 | −73.9 (3) | C13—P1—C7—C8 | 75.6 (3) |
P1i—Cu1—P1—C13 | −61.5 (2) | C1'—P1—C7—C8 | −33.5 (4) |
S1i—Cu1—P1—C13 | 60.7 (2) | Cu1—P1—C7—C8 | −152.0 (2) |
S1—Cu1—P1—C13 | 172.2 (2) | C1—P1—C7—C12 | 151.2 (5) |
P1i—Cu1—P1—C1' | 64.9 (3) | C13—P1—C7—C12 | −103.9 (3) |
S1i—Cu1—P1—C1' | −172.9 (3) | C1'—P1—C7—C12 | 146.9 (4) |
S1—Cu1—P1—C1' | −61.4 (3) | Cu1—P1—C7—C12 | 28.4 (3) |
C7—P1—C1—C2 | 125.7 (8) | P1—C7—C8—C9 | −179.5 (3) |
C13—P1—C1—C2 | 20 (1) | P1—C7—C12—C11 | 179.6 (3) |
C1'—P1—C1—C2 | 146 (5) | C7—P1—C13—C14 | 61.6 (4) |
Cu1—P1—C1—C2 | −106.3 (9) | C1—P1—C13—C14 | 173.1 (7) |
C7—P1—C1—C6 | −55.3 (8) | C1'—P1—C13—C14 | 162.8 (6) |
C13—P1—C1—C6 | −160.8 (7) | Cu1—P1—C13—C14 | −69.0 (4) |
C1'—P1—C1—C6 | −35 (4) | P1—C13—C14—C15 | −98.5 (4) |
Cu1—P1—C1—C6 | 72.7 (8) | P1—C13—C14—C19 | 79.9 (4) |
P1—C1—C2—C3 | 179 (1) | C13—C14—C15—C16 | 178.4 (4) |
P1—C1—C6—C5 | −179 (1) | C13—C14—C19—C18 | −178.4 (4) |
C7—P1—C1'—C2' | 130.0 (9) |
Symmetry codes: (i) −x+2, −y+1, z; (ii) y+1/2, −x+3/2, −z+1/2; (iii) −y+3/2, x−1/2, −z+1/2. |