Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109009512/bg3094sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109009512/bg3094Isup2.hkl |
CCDC reference: 730084
Fluorenyllithium (Üffing et al., 1998) and Mo(η3-C3H5)Cl(NCMe)2(CO)2 (Ascenso et al., 1995) were synthesized according to reported methods. Solid fluorenyllithium (0.13 g, 0.74 mmol) and Mo(η3-C3H5)Cl(NCMe)2(CO)2 (0.23 g, 0.74 mmol) were cooled in a Schlenk tube to 193 K. Precooled dry THF (40 ml) was added and the temperature raised slowly to room temperature. After 24 h, the mixture was filtered and the solution dried. Recrystallization of the crude product from a mixture of hexane and diethyl ether (2:1) at 277 K yielded orange crystals of the title compound after two months.
H atoms bound to C atoms were placed in idealized positions and allowed to ride on their parent atoms with Uiso(H) values fixed at 1.2Ueq(C). The C—H distances used ranged from 0.95 (for the aromatic and allyl H atoms) to 0.99Å (for the methylene H atoms associated with the THF molecule). Those H atoms associated with the two µ3-OH groups were markedly visible in difference Fourier maps and were included in subsequent least-squares refinement cycles with the O—H distances restrained to 0.95 (1)Å in order to ensure a chemically reasonable geometry for these bridging moieties. These H atoms were also allowed to ride on their parent atoms, with Uiso(H) values fixed at 1.5Ueq(O).
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Mo4(C3H5)4Cl2(OH)2(CO)8]·C4H8O·C13H8O | F(000) = 4464 |
Mr = 1129.33 | Dx = 1.849 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6231 reflections |
a = 46.383 (3) Å | θ = 2.4–25.3° |
b = 10.3975 (6) Å | µ = 1.40 mm−1 |
c = 17.3531 (12) Å | T = 150 K |
β = 104.133 (4)° | Block, brown |
V = 8115.6 (9) Å3 | 0.06 × 0.03 × 0.01 mm |
Z = 8 |
Bruker X8 KappaCCD APEXII diffractometer | 9024 independent reflections |
Radiation source: fine-focus sealed tube | 6026 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
ω and ϕ scans | θmax = 27.5°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −53→59 |
Tmin = 0.918, Tmax = 0.977 | k = −13→12 |
45728 measured reflections | l = −22→22 |
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: mixed |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0279P)2 + 4.2522P] where P = (Fo2 + 2Fc2)/3 |
9024 reflections | (Δ/σ)max = 0.001 |
502 parameters | Δρmax = 0.78 e Å−3 |
2 restraints | Δρmin = −0.69 e Å−3 |
[Mo4(C3H5)4Cl2(OH)2(CO)8]·C4H8O·C13H8O | V = 8115.6 (9) Å3 |
Mr = 1129.33 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 46.383 (3) Å | µ = 1.40 mm−1 |
b = 10.3975 (6) Å | T = 150 K |
c = 17.3531 (12) Å | 0.06 × 0.03 × 0.01 mm |
β = 104.133 (4)° |
Bruker X8 KappaCCD APEXII diffractometer | 9024 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 6026 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.977 | Rint = 0.075 |
45728 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 2 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.78 e Å−3 |
9024 reflections | Δρmin = −0.69 e Å−3 |
502 parameters |
Experimental. The title compound does not crystallize easily and the largest crystal which we were able to isolate (from several crystallization attempts) was as big as 60 x 30 x 10 micrometers. The small size of the crystal allied with a very large unit cell (the a-axis is longer than 46 A) leads to a very poor diffraction at high angle. The reported data collection was performed with 60 seconds per frame with an image width of 1°. Longer exposures times were attempted (120, 180 and 240 seconds) but no extra diffraction spots were noticeable. Nevertheless, a data collection strategy up to 0.73 A of resolution was optimized and crystal data collected. There is also a 1.5% of data missing in the low resolution range, a fact which has to do both with the default APEX-2 setting as well as with the unusually large a cell dimension. |
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 | ||
Mo1 | 0.153906 (9) | 0.27098 (4) | 0.18763 (2) | 0.02183 (11) | |
Mo2 | 0.123257 (8) | 0.46979 (3) | 0.30633 (2) | 0.01708 (10) | |
Mo3 | 0.179712 (9) | 0.24969 (4) | 0.40856 (2) | 0.02084 (10) | |
Mo4 | 0.099568 (9) | 0.12327 (3) | 0.27680 (2) | 0.02027 (10) | |
Cl1 | 0.15639 (2) | 0.08754 (10) | 0.29343 (6) | 0.0243 (3) | |
Cl2 | 0.12293 (2) | 0.27126 (10) | 0.40094 (6) | 0.0214 (2) | |
O9 | 0.16521 (6) | 0.3746 (3) | 0.30538 (16) | 0.0175 (7) | |
H9 | 0.1771 (8) | 0.448 (2) | 0.306 (2) | 0.026* | |
O10 | 0.11234 (6) | 0.2988 (3) | 0.22480 (16) | 0.0182 (7) | |
H10 | 0.0987 (7) | 0.319 (4) | 0.1773 (14) | 0.027* | |
C1 | 0.13179 (12) | 0.1927 (5) | 0.0890 (3) | 0.0403 (14) | |
C2 | 0.14788 (10) | 0.4143 (5) | 0.1148 (3) | 0.0295 (12) | |
C3 | 0.18215 (11) | 0.1257 (5) | 0.1350 (3) | 0.0412 (14) | |
H3A | 0.1716 | 0.1592 | 0.0851 | 0.049* | |
H3B | 0.1810 | 0.0366 | 0.1461 | 0.049* | |
C4 | 0.19964 (12) | 0.2090 (5) | 0.1931 (3) | 0.0414 (14) | |
H4 | 0.2103 | 0.1768 | 0.2432 | 0.050* | |
C5 | 0.20070 (11) | 0.3367 (5) | 0.1750 (3) | 0.0374 (13) | |
H5A | 0.1899 | 0.3676 | 0.1246 | 0.045* | |
H5B | 0.2122 | 0.3944 | 0.2127 | 0.045* | |
C6 | 0.12641 (10) | 0.6008 (4) | 0.2309 (3) | 0.0265 (11) | |
C7 | 0.14481 (10) | 0.6037 (4) | 0.3762 (3) | 0.0245 (11) | |
C8 | 0.07536 (10) | 0.5381 (4) | 0.2451 (3) | 0.0288 (12) | |
H8A | 0.0851 | 0.6155 | 0.2368 | 0.035* | |
H8B | 0.0639 | 0.4918 | 0.2009 | 0.035* | |
C9 | 0.07787 (10) | 0.4926 (4) | 0.3218 (3) | 0.0259 (11) | |
H9A | 0.0683 | 0.4154 | 0.3311 | 0.031* | |
C10 | 0.09501 (10) | 0.5647 (4) | 0.3849 (3) | 0.0283 (12) | |
H10A | 0.1044 | 0.6417 | 0.3744 | 0.034* | |
H10B | 0.0972 | 0.5365 | 0.4381 | 0.034* | |
C11 | 0.21999 (12) | 0.2549 (5) | 0.3974 (3) | 0.0327 (12) | |
C12 | 0.19569 (10) | 0.3896 (5) | 0.4799 (3) | 0.0283 (12) | |
C13 | 0.20513 (14) | 0.0655 (5) | 0.4617 (3) | 0.0524 (17) | |
H13A | 0.2219 | 0.1207 | 0.4762 | 0.063* | |
H13B | 0.2055 | −0.0059 | 0.4278 | 0.063* | |
C14 | 0.17986 (14) | 0.0893 (5) | 0.4903 (3) | 0.0452 (15) | |
H14 | 0.1628 | 0.0353 | 0.4765 | 0.054* | |
C15 | 0.18079 (12) | 0.1957 (5) | 0.5398 (3) | 0.0382 (14) | |
H15A | 0.1980 | 0.2484 | 0.5527 | 0.046* | |
H15B | 0.1642 | 0.2156 | 0.5606 | 0.046* | |
C16 | 0.08570 (11) | 0.0388 (4) | 0.1750 (3) | 0.0301 (12) | |
C17 | 0.05839 (11) | 0.1727 (4) | 0.2490 (3) | 0.0286 (12) | |
C18 | 0.10047 (11) | −0.0997 (4) | 0.2899 (3) | 0.0359 (13) | |
H18A | 0.0833 | −0.0962 | 0.2469 | 0.043* | |
H18B | 0.1175 | −0.1465 | 0.2844 | 0.043* | |
C19 | 0.10079 (11) | −0.0360 (4) | 0.3611 (3) | 0.0312 (12) | |
H19 | 0.1177 | −0.0381 | 0.4048 | 0.037* | |
C20 | 0.07531 (11) | 0.0303 (5) | 0.3649 (3) | 0.0357 (13) | |
H20A | 0.0586 | 0.0311 | 0.3204 | 0.043* | |
H20B | 0.0745 | 0.0751 | 0.4121 | 0.043* | |
O1 | 0.11840 (9) | 0.1534 (4) | 0.0291 (2) | 0.0661 (13) | |
O2 | 0.14398 (8) | 0.4973 (3) | 0.0676 (2) | 0.0410 (9) | |
O3 | 0.12818 (8) | 0.6852 (3) | 0.1875 (2) | 0.0401 (9) | |
O4 | 0.15803 (7) | 0.6861 (3) | 0.4147 (2) | 0.0364 (9) | |
O5 | 0.24443 (8) | 0.2638 (4) | 0.3922 (2) | 0.0531 (11) | |
O6 | 0.20698 (8) | 0.4704 (3) | 0.5225 (2) | 0.0413 (9) | |
O7 | 0.07622 (8) | −0.0127 (3) | 0.1146 (2) | 0.0442 (10) | |
O8 | 0.03293 (8) | 0.1972 (3) | 0.2287 (2) | 0.0441 (10) | |
O11 | 0.20647 (7) | 0.5680 (3) | 0.3076 (2) | 0.0381 (9) | |
C21 | 0.20499 (14) | 0.6589 (6) | 0.2445 (4) | 0.0601 (18) | |
H21A | 0.1848 | 0.6598 | 0.2085 | 0.072* | |
H21B | 0.2195 | 0.6363 | 0.2132 | 0.072* | |
C22 | 0.21233 (17) | 0.7883 (6) | 0.2837 (5) | 0.087 (3) | |
H22A | 0.1941 | 0.8396 | 0.2804 | 0.105* | |
H22B | 0.2260 | 0.8372 | 0.2587 | 0.105* | |
C23 | 0.22757 (16) | 0.7545 (6) | 0.3712 (5) | 0.077 (2) | |
H23A | 0.2473 | 0.7959 | 0.3882 | 0.093* | |
H23B | 0.2152 | 0.7815 | 0.4074 | 0.093* | |
C24 | 0.23038 (13) | 0.6110 (6) | 0.3697 (3) | 0.0557 (17) | |
H24A | 0.2497 | 0.5860 | 0.3592 | 0.067* | |
H24B | 0.2290 | 0.5735 | 0.4211 | 0.067* | |
O12 | 0.06712 (8) | 0.3163 (3) | 0.0882 (2) | 0.0468 (10) | |
C25 | 0.01314 (10) | 0.3510 (4) | −0.0922 (3) | 0.0230 (11) | |
C26 | −0.00749 (10) | 0.2984 (5) | −0.1559 (3) | 0.0329 (12) | |
H26 | −0.0183 | 0.3511 | −0.1978 | 0.039* | |
C27 | −0.01189 (11) | 0.1665 (5) | −0.1566 (3) | 0.0399 (14) | |
H27 | −0.0262 | 0.1289 | −0.1993 | 0.048* | |
C28 | 0.00396 (11) | 0.0883 (5) | −0.0969 (3) | 0.0395 (14) | |
H28 | 0.0003 | −0.0017 | −0.0987 | 0.047* | |
C29 | 0.02499 (11) | 0.1401 (5) | −0.0349 (3) | 0.0343 (13) | |
H29 | 0.0363 | 0.0863 | 0.0056 | 0.041* | |
C30 | 0.02939 (10) | 0.2717 (4) | −0.0324 (3) | 0.0267 (11) | |
C31 | 0.05013 (11) | 0.3536 (5) | 0.0271 (3) | 0.0308 (12) | |
C32 | 0.04478 (11) | 0.4884 (4) | −0.0023 (3) | 0.0283 (12) | |
C33 | 0.05795 (12) | 0.6009 (5) | 0.0291 (3) | 0.0363 (13) | |
H33 | 0.0733 | 0.6007 | 0.0767 | 0.044* | |
C34 | 0.04843 (13) | 0.7148 (5) | −0.0103 (3) | 0.0416 (14) | |
H34 | 0.0571 | 0.7941 | 0.0105 | 0.050* | |
C35 | 0.02618 (12) | 0.7130 (5) | −0.0802 (3) | 0.0416 (14) | |
H35 | 0.0199 | 0.7919 | −0.1065 | 0.050* | |
C36 | 0.01282 (11) | 0.5987 (5) | −0.1128 (3) | 0.0353 (13) | |
H36 | −0.0025 | 0.5988 | −0.1606 | 0.042* | |
C37 | 0.02246 (10) | 0.4857 (4) | −0.0735 (3) | 0.0264 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0260 (2) | 0.0235 (2) | 0.0155 (2) | 0.00310 (17) | 0.00423 (18) | −0.00270 (17) |
Mo2 | 0.0193 (2) | 0.0138 (2) | 0.0177 (2) | 0.00146 (16) | 0.00363 (17) | −0.00048 (16) |
Mo3 | 0.0210 (2) | 0.0217 (2) | 0.0170 (2) | 0.00357 (17) | −0.00075 (17) | 0.00064 (17) |
Mo4 | 0.0231 (2) | 0.0141 (2) | 0.0211 (2) | −0.00070 (16) | 0.00063 (18) | 0.00037 (17) |
Cl1 | 0.0271 (7) | 0.0183 (6) | 0.0252 (6) | 0.0033 (5) | 0.0017 (5) | −0.0008 (5) |
Cl2 | 0.0248 (6) | 0.0201 (6) | 0.0186 (6) | −0.0007 (5) | 0.0041 (5) | 0.0015 (5) |
O9 | 0.0197 (18) | 0.0174 (16) | 0.0153 (15) | −0.0007 (13) | 0.0039 (13) | −0.0006 (13) |
O10 | 0.0188 (18) | 0.0184 (17) | 0.0138 (16) | 0.0042 (12) | −0.0033 (13) | 0.0007 (13) |
C1 | 0.040 (4) | 0.047 (4) | 0.034 (3) | −0.005 (3) | 0.011 (3) | −0.015 (3) |
C2 | 0.031 (3) | 0.038 (3) | 0.020 (3) | 0.004 (2) | 0.008 (2) | −0.003 (2) |
C3 | 0.042 (4) | 0.037 (3) | 0.044 (3) | 0.014 (3) | 0.010 (3) | −0.010 (3) |
C4 | 0.039 (4) | 0.055 (4) | 0.032 (3) | 0.009 (3) | 0.014 (3) | −0.006 (3) |
C5 | 0.041 (3) | 0.034 (3) | 0.038 (3) | 0.010 (3) | 0.011 (3) | −0.003 (3) |
C6 | 0.030 (3) | 0.022 (3) | 0.030 (3) | 0.004 (2) | 0.011 (2) | −0.004 (2) |
C7 | 0.021 (3) | 0.027 (3) | 0.028 (3) | 0.005 (2) | 0.010 (2) | −0.002 (2) |
C8 | 0.019 (3) | 0.029 (3) | 0.036 (3) | −0.001 (2) | 0.002 (2) | −0.001 (2) |
C9 | 0.019 (3) | 0.023 (3) | 0.039 (3) | 0.003 (2) | 0.012 (2) | 0.001 (2) |
C10 | 0.026 (3) | 0.035 (3) | 0.031 (3) | −0.004 (2) | 0.021 (2) | −0.004 (2) |
C11 | 0.036 (3) | 0.033 (3) | 0.027 (3) | 0.009 (2) | 0.004 (3) | −0.002 (2) |
C12 | 0.021 (3) | 0.037 (3) | 0.026 (3) | 0.004 (2) | 0.006 (2) | 0.000 (2) |
C13 | 0.070 (5) | 0.022 (3) | 0.051 (4) | 0.012 (3) | −0.012 (3) | 0.002 (3) |
C14 | 0.055 (4) | 0.033 (3) | 0.035 (3) | −0.005 (3) | −0.013 (3) | 0.021 (3) |
C15 | 0.041 (3) | 0.050 (4) | 0.023 (3) | −0.006 (3) | 0.007 (2) | 0.015 (3) |
C16 | 0.030 (3) | 0.023 (3) | 0.034 (3) | −0.004 (2) | 0.000 (2) | 0.001 (2) |
C17 | 0.028 (3) | 0.020 (3) | 0.035 (3) | −0.007 (2) | 0.003 (2) | −0.001 (2) |
C18 | 0.040 (3) | 0.016 (3) | 0.047 (3) | 0.003 (2) | 0.000 (3) | 0.009 (2) |
C19 | 0.038 (3) | 0.019 (3) | 0.034 (3) | −0.002 (2) | 0.003 (3) | 0.014 (2) |
C20 | 0.045 (4) | 0.037 (3) | 0.026 (3) | −0.003 (3) | 0.010 (3) | 0.004 (2) |
O1 | 0.075 (3) | 0.083 (3) | 0.036 (3) | −0.014 (3) | 0.005 (2) | −0.022 (2) |
O2 | 0.052 (3) | 0.046 (2) | 0.027 (2) | 0.0087 (18) | 0.0123 (18) | 0.0120 (18) |
O3 | 0.057 (3) | 0.026 (2) | 0.042 (2) | 0.0067 (18) | 0.0227 (19) | 0.0116 (18) |
O4 | 0.037 (2) | 0.029 (2) | 0.041 (2) | −0.0041 (17) | 0.0064 (18) | −0.0153 (17) |
O5 | 0.025 (2) | 0.086 (3) | 0.047 (2) | 0.011 (2) | 0.006 (2) | −0.015 (2) |
O6 | 0.042 (2) | 0.044 (2) | 0.034 (2) | −0.0094 (18) | 0.0035 (18) | −0.0170 (18) |
O7 | 0.054 (3) | 0.034 (2) | 0.035 (2) | −0.0098 (18) | −0.0080 (19) | −0.0115 (18) |
O8 | 0.022 (2) | 0.044 (2) | 0.061 (3) | 0.0018 (17) | −0.0010 (19) | 0.0065 (19) |
O11 | 0.034 (2) | 0.035 (2) | 0.043 (2) | −0.0105 (16) | 0.0056 (18) | 0.0048 (18) |
C21 | 0.050 (4) | 0.058 (4) | 0.068 (5) | −0.005 (3) | 0.006 (3) | 0.022 (4) |
C22 | 0.089 (6) | 0.037 (4) | 0.144 (8) | 0.013 (4) | 0.044 (6) | 0.019 (5) |
C23 | 0.085 (6) | 0.053 (5) | 0.114 (7) | −0.031 (4) | 0.062 (5) | −0.035 (5) |
C24 | 0.048 (4) | 0.063 (4) | 0.053 (4) | −0.021 (3) | 0.008 (3) | 0.006 (3) |
O12 | 0.051 (3) | 0.043 (2) | 0.032 (2) | 0.0034 (18) | −0.0174 (19) | 0.0015 (18) |
C25 | 0.014 (3) | 0.032 (3) | 0.023 (3) | 0.001 (2) | 0.006 (2) | −0.002 (2) |
C26 | 0.018 (3) | 0.051 (4) | 0.026 (3) | 0.005 (2) | 0.000 (2) | 0.003 (2) |
C27 | 0.029 (3) | 0.050 (4) | 0.038 (3) | −0.010 (3) | 0.004 (3) | −0.014 (3) |
C28 | 0.038 (3) | 0.030 (3) | 0.050 (4) | −0.007 (3) | 0.010 (3) | −0.007 (3) |
C29 | 0.032 (3) | 0.031 (3) | 0.035 (3) | 0.004 (2) | 0.000 (3) | 0.002 (2) |
C30 | 0.023 (3) | 0.031 (3) | 0.026 (3) | −0.001 (2) | 0.004 (2) | −0.003 (2) |
C31 | 0.030 (3) | 0.037 (3) | 0.021 (3) | 0.000 (2) | −0.001 (2) | 0.004 (2) |
C32 | 0.030 (3) | 0.032 (3) | 0.026 (3) | 0.003 (2) | 0.014 (2) | 0.002 (2) |
C33 | 0.043 (4) | 0.039 (3) | 0.030 (3) | −0.013 (3) | 0.016 (3) | −0.008 (3) |
C34 | 0.066 (4) | 0.024 (3) | 0.044 (4) | −0.006 (3) | 0.031 (3) | −0.003 (3) |
C35 | 0.048 (4) | 0.030 (3) | 0.052 (4) | 0.010 (3) | 0.022 (3) | 0.011 (3) |
C36 | 0.031 (3) | 0.040 (3) | 0.036 (3) | 0.013 (2) | 0.011 (3) | 0.006 (3) |
C37 | 0.023 (3) | 0.031 (3) | 0.028 (3) | 0.007 (2) | 0.011 (2) | 0.006 (2) |
Mo1—C1 | 1.947 (5) | C13—C14 | 1.402 (7) |
Mo1—C2 | 1.930 (5) | C13—H13A | 0.9500 |
Mo1—C3 | 2.327 (5) | C13—H13B | 0.9500 |
Mo1—C4 | 2.197 (5) | C14—C15 | 1.396 (7) |
Mo1—C5 | 2.337 (5) | C14—H14 | 0.9500 |
Mo1—O9 | 2.255 (3) | C15—H15A | 0.9500 |
Mo1—O10 | 2.196 (3) | C15—H15B | 0.9500 |
Mo1—Cl1 | 2.6302 (11) | C16—O7 | 1.163 (5) |
Mo2—C6 | 1.919 (5) | C17—O8 | 1.175 (5) |
Mo2—C7 | 1.953 (5) | C18—C19 | 1.399 (6) |
Mo2—C8 | 2.327 (4) | C18—H18A | 0.9500 |
Mo2—C9 | 2.199 (4) | C18—H18B | 0.9500 |
Mo2—C10 | 2.328 (4) | C19—C20 | 1.384 (6) |
Mo2—O9 | 2.187 (3) | C19—H19 | 0.9500 |
Mo2—O10 | 2.252 (3) | C20—H20A | 0.9500 |
Mo2—Cl2 | 2.6399 (11) | C20—H20B | 0.9500 |
Mo3—C11 | 1.926 (6) | O11—C24 | 1.417 (6) |
Mo3—C12 | 1.937 (5) | O11—C21 | 1.435 (6) |
Mo3—C13 | 2.319 (5) | C21—C22 | 1.509 (8) |
Mo3—C14 | 2.188 (5) | C21—H21A | 0.9900 |
Mo3—C15 | 2.334 (4) | C21—H21B | 0.9900 |
Mo3—O9 | 2.181 (3) | C22—C23 | 1.551 (9) |
Mo3—Cl2 | 2.6142 (12) | C22—H22A | 0.9900 |
Mo3—Cl1 | 2.6361 (11) | C22—H22B | 0.9900 |
Mo4—C16 | 1.937 (5) | C23—C24 | 1.499 (8) |
Mo4—C17 | 1.922 (5) | C23—H23A | 0.9900 |
Mo4—C18 | 2.329 (4) | C23—H23B | 0.9900 |
Mo4—C19 | 2.200 (4) | C24—H24A | 0.9900 |
Mo4—C20 | 2.319 (5) | C24—H24B | 0.9900 |
Mo4—O10 | 2.181 (3) | O12—C31 | 1.219 (5) |
Mo4—Cl1 | 2.6068 (12) | C25—C26 | 1.385 (6) |
Mo4—Cl2 | 2.6538 (11) | C25—C30 | 1.393 (6) |
O9—H9 | 0.94 (3) | C25—C37 | 1.478 (6) |
O10—H10 | 0.93 (3) | C26—C27 | 1.386 (7) |
C1—O1 | 1.147 (5) | C26—H26 | 0.9500 |
C2—O2 | 1.172 (5) | C27—C28 | 1.379 (7) |
C3—C4 | 1.424 (7) | C27—H27 | 0.9500 |
C3—H3A | 0.9500 | C28—C29 | 1.373 (6) |
C3—H3B | 0.9500 | C28—H28 | 0.9500 |
C4—C5 | 1.368 (7) | C29—C30 | 1.383 (6) |
C4—H4 | 0.9500 | C29—H29 | 0.9500 |
C5—H5A | 0.9500 | C30—C31 | 1.494 (6) |
C5—H5B | 0.9500 | C31—C32 | 1.492 (6) |
C6—O3 | 1.172 (5) | C32—C33 | 1.369 (6) |
C7—O4 | 1.164 (5) | C32—C37 | 1.405 (6) |
C8—C9 | 1.390 (6) | C33—C34 | 1.385 (7) |
C8—H8A | 0.9500 | C33—H33 | 0.9500 |
C8—H8B | 0.9500 | C34—C35 | 1.387 (7) |
C9—C10 | 1.403 (6) | C34—H34 | 0.9500 |
C9—H9A | 0.9500 | C35—C36 | 1.395 (7) |
C10—H10A | 0.9500 | C35—H35 | 0.9500 |
C10—H10B | 0.9500 | C36—C37 | 1.377 (6) |
C11—O5 | 1.162 (6) | C36—H36 | 0.9500 |
C12—O6 | 1.156 (5) | ||
C2—Mo1—C1 | 77.6 (2) | H3A—C3—H3B | 120.0 |
C2—Mo1—O10 | 95.38 (16) | C5—C4—C3 | 118.3 (5) |
C1—Mo1—O10 | 90.08 (17) | C5—C4—Mo1 | 78.1 (3) |
C2—Mo1—C4 | 103.8 (2) | C3—C4—Mo1 | 76.7 (3) |
C1—Mo1—C4 | 102.2 (2) | C5—C4—H4 | 120.9 |
O10—Mo1—C4 | 158.98 (16) | C3—C4—H4 | 120.9 |
C2—Mo1—O9 | 100.90 (15) | Mo1—C4—H4 | 115.1 |
C1—Mo1—O9 | 162.30 (17) | C4—C5—Mo1 | 66.9 (3) |
O10—Mo1—O9 | 72.41 (10) | C4—C5—H5A | 120.0 |
C4—Mo1—O9 | 95.29 (15) | Mo1—C5—H5A | 83.9 |
C2—Mo1—C3 | 104.43 (19) | C4—C5—H5B | 120.0 |
C1—Mo1—C3 | 67.0 (2) | Mo1—C5—H5B | 119.9 |
O10—Mo1—C3 | 145.01 (15) | H5A—C5—H5B | 120.0 |
C4—Mo1—C3 | 36.54 (17) | O3—C6—Mo2 | 176.7 (4) |
O9—Mo1—C3 | 129.56 (15) | O4—C7—Mo2 | 176.7 (4) |
C2—Mo1—C5 | 72.66 (19) | C9—C8—Mo2 | 67.1 (2) |
C1—Mo1—C5 | 110.0 (2) | C9—C8—H8A | 120.0 |
O10—Mo1—C5 | 153.06 (14) | Mo2—C8—H8A | 83.8 |
C4—Mo1—C5 | 34.95 (17) | C9—C8—H8B | 120.0 |
O9—Mo1—C5 | 85.97 (14) | Mo2—C8—H8B | 119.7 |
C3—Mo1—C5 | 61.82 (18) | H8A—C8—H8B | 120.0 |
C2—Mo1—Cl1 | 172.66 (14) | C8—C9—C10 | 117.7 (4) |
C1—Mo1—Cl1 | 103.57 (16) | C8—C9—Mo2 | 77.2 (3) |
O10—Mo1—Cl1 | 77.42 (8) | C10—C9—Mo2 | 77.1 (3) |
C4—Mo1—Cl1 | 83.10 (15) | C8—C9—H9A | 121.2 |
O9—Mo1—Cl1 | 75.71 (7) | C10—C9—H9A | 121.2 |
C3—Mo1—Cl1 | 82.56 (14) | Mo2—C9—H9A | 115.5 |
C5—Mo1—Cl1 | 113.22 (13) | C9—C10—Mo2 | 67.0 (2) |
C6—Mo2—C7 | 78.72 (19) | C9—C10—H10A | 120.0 |
C6—Mo2—O9 | 95.74 (15) | Mo2—C10—H10A | 84.0 |
C7—Mo2—O9 | 90.32 (15) | C9—C10—H10B | 120.0 |
C6—Mo2—C9 | 103.96 (18) | Mo2—C10—H10B | 119.7 |
C7—Mo2—C9 | 101.99 (18) | H10A—C10—H10B | 120.0 |
O9—Mo2—C9 | 158.42 (14) | O5—C11—Mo3 | 176.7 (4) |
C6—Mo2—O10 | 100.08 (15) | O6—C12—Mo3 | 175.7 (4) |
C7—Mo2—O10 | 162.79 (15) | C14—C13—Mo3 | 66.9 (3) |
O9—Mo2—O10 | 72.65 (10) | C14—C13—H13A | 120.0 |
C9—Mo2—O10 | 94.98 (14) | Mo3—C13—H13A | 84.8 |
C6—Mo2—C8 | 72.25 (18) | C14—C13—H13B | 120.0 |
C7—Mo2—C8 | 110.66 (17) | Mo3—C13—H13B | 118.9 |
O9—Mo2—C8 | 152.45 (14) | H13A—C13—H13B | 120.0 |
C9—Mo2—C8 | 35.63 (15) | C15—C14—C13 | 117.1 (5) |
O10—Mo2—C8 | 84.90 (13) | C15—C14—Mo3 | 77.8 (3) |
C6—Mo2—C10 | 104.24 (18) | C13—C14—Mo3 | 77.1 (3) |
C7—Mo2—C10 | 67.09 (17) | C15—C14—H14 | 121.5 |
O9—Mo2—C10 | 145.62 (14) | C13—C14—H14 | 121.5 |
C9—Mo2—C10 | 35.96 (15) | Mo3—C14—H14 | 114.6 |
O10—Mo2—C10 | 129.07 (14) | C14—C15—Mo3 | 66.4 (3) |
C8—Mo2—C10 | 61.78 (16) | C14—C15—H15A | 120.0 |
C6—Mo2—Cl2 | 172.78 (13) | Mo3—C15—H15A | 84.7 |
C7—Mo2—Cl2 | 104.56 (13) | C14—C15—H15B | 120.0 |
O9—Mo2—Cl2 | 77.94 (8) | Mo3—C15—H15B | 119.5 |
C9—Mo2—Cl2 | 81.81 (12) | H15A—C15—H15B | 120.0 |
O10—Mo2—Cl2 | 74.85 (7) | O7—C16—Mo4 | 177.1 (4) |
C8—Mo2—Cl2 | 111.89 (12) | O8—C17—Mo4 | 176.1 (4) |
C10—Mo2—Cl2 | 82.98 (12) | C19—C18—Mo4 | 67.1 (2) |
C11—Mo3—C12 | 79.3 (2) | C19—C18—H18A | 120.0 |
C11—Mo3—O9 | 90.72 (16) | Mo4—C18—H18A | 83.9 |
C12—Mo3—O9 | 94.06 (16) | C19—C18—H18B | 120.0 |
C11—Mo3—C14 | 103.7 (2) | Mo4—C18—H18B | 119.7 |
C12—Mo3—C14 | 102.6 (2) | H18A—C18—H18B | 120.0 |
O9—Mo3—C14 | 159.63 (16) | C20—C19—C18 | 117.0 (5) |
C11—Mo3—C13 | 69.6 (2) | C20—C19—Mo4 | 76.9 (3) |
C12—Mo3—C13 | 106.7 (2) | C18—C19—Mo4 | 77.1 (3) |
O9—Mo3—C13 | 147.47 (17) | C20—C19—H19 | 121.5 |
C14—Mo3—C13 | 36.09 (19) | C18—C19—H19 | 121.5 |
C11—Mo3—C15 | 108.37 (19) | Mo4—C19—H19 | 115.5 |
C12—Mo3—C15 | 69.08 (19) | C19—C20—Mo4 | 67.5 (3) |
O9—Mo3—C15 | 150.81 (15) | C19—C20—H20A | 120.0 |
C14—Mo3—C15 | 35.77 (18) | Mo4—C20—H20A | 83.7 |
C13—Mo3—C15 | 61.7 (2) | C19—C20—H20B | 120.0 |
C11—Mo3—Cl2 | 169.32 (15) | Mo4—C20—H20B | 119.4 |
C12—Mo3—Cl2 | 101.04 (14) | H20A—C20—H20B | 120.0 |
O9—Mo3—Cl2 | 78.61 (8) | C24—O11—C21 | 104.8 (4) |
C14—Mo3—Cl2 | 86.67 (17) | O11—C21—C22 | 106.2 (5) |
C13—Mo3—Cl2 | 119.94 (17) | O11—C21—H21A | 110.5 |
C15—Mo3—Cl2 | 81.45 (13) | C22—C21—H21A | 110.5 |
C11—Mo3—Cl1 | 99.80 (14) | O11—C21—H21B | 110.5 |
C12—Mo3—Cl1 | 170.81 (14) | C22—C21—H21B | 110.5 |
O9—Mo3—Cl1 | 76.78 (8) | H21A—C21—H21B | 108.7 |
C14—Mo3—Cl1 | 86.53 (15) | C21—C22—C23 | 103.8 (5) |
C13—Mo3—Cl1 | 81.25 (14) | C21—C22—H22A | 111.0 |
C15—Mo3—Cl1 | 119.53 (13) | C23—C22—H22A | 111.0 |
Cl2—Mo3—Cl1 | 78.14 (4) | C21—C22—H22B | 111.0 |
C17—Mo4—C16 | 78.7 (2) | C23—C22—H22B | 111.0 |
C17—Mo4—O10 | 91.50 (15) | H22A—C22—H22B | 109.0 |
C16—Mo4—O10 | 93.75 (15) | C24—C23—C22 | 103.2 (5) |
C17—Mo4—C19 | 103.35 (19) | C24—C23—H23A | 111.1 |
C16—Mo4—C19 | 102.35 (19) | C22—C23—H23A | 111.1 |
O10—Mo4—C19 | 159.88 (15) | C24—C23—H23B | 111.1 |
C17—Mo4—C20 | 70.41 (19) | C22—C23—H23B | 111.1 |
C16—Mo4—C20 | 107.82 (19) | H23A—C23—H23B | 109.1 |
O10—Mo4—C20 | 147.78 (14) | O11—C24—C23 | 105.8 (5) |
C19—Mo4—C20 | 35.54 (16) | O11—C24—H24A | 110.6 |
C17—Mo4—C18 | 106.47 (18) | C23—C24—H24A | 110.6 |
C16—Mo4—C18 | 68.37 (18) | O11—C24—H24B | 110.6 |
O10—Mo4—C18 | 150.80 (15) | C23—C24—H24B | 110.6 |
C19—Mo4—C18 | 35.84 (16) | H24A—C24—H24B | 108.7 |
C20—Mo4—C18 | 61.39 (17) | C26—C25—C30 | 120.2 (4) |
C17—Mo4—Cl1 | 168.99 (14) | C26—C25—C37 | 131.1 (4) |
C16—Mo4—Cl1 | 97.93 (14) | C30—C25—C37 | 108.7 (4) |
O10—Mo4—Cl1 | 78.20 (8) | C25—C26—C27 | 118.0 (5) |
C19—Mo4—Cl1 | 87.59 (13) | C25—C26—H26 | 121.0 |
C20—Mo4—Cl1 | 120.52 (13) | C27—C26—H26 | 121.0 |
C18—Mo4—Cl1 | 81.59 (13) | C28—C27—C26 | 121.7 (5) |
C17—Mo4—Cl2 | 103.47 (14) | C28—C27—H27 | 119.1 |
C16—Mo4—Cl2 | 169.18 (14) | C26—C27—H27 | 119.1 |
O10—Mo4—Cl2 | 75.66 (8) | C29—C28—C27 | 120.3 (5) |
C19—Mo4—Cl2 | 87.58 (13) | C29—C28—H28 | 119.9 |
C20—Mo4—Cl2 | 82.76 (13) | C27—C28—H28 | 119.9 |
C18—Mo4—Cl2 | 120.28 (13) | C28—C29—C30 | 118.9 (5) |
Cl1—Mo4—Cl2 | 77.96 (3) | C28—C29—H29 | 120.6 |
Mo4—Cl1—Mo1 | 87.06 (3) | C30—C29—H29 | 120.6 |
Mo4—Cl1—Mo3 | 102.09 (4) | C29—C30—C25 | 120.9 (4) |
Mo1—Cl1—Mo3 | 90.30 (4) | C29—C30—C31 | 130.6 (4) |
Mo3—Cl2—Mo2 | 86.55 (3) | C25—C30—C31 | 108.5 (4) |
Mo3—Cl2—Mo4 | 101.42 (4) | O12—C31—C32 | 127.9 (5) |
Mo2—Cl2—Mo4 | 90.68 (3) | O12—C31—C30 | 126.2 (4) |
Mo3—O9—Mo2 | 111.09 (12) | C32—C31—C30 | 105.9 (4) |
Mo3—O9—Mo1 | 114.60 (12) | C33—C32—C37 | 121.9 (5) |
Mo2—O9—Mo1 | 102.27 (11) | C33—C32—C31 | 130.2 (5) |
Mo3—O9—H9 | 115 (3) | C37—C32—C31 | 107.9 (4) |
Mo2—O9—H9 | 99 (3) | C32—C33—C34 | 118.5 (5) |
Mo1—O9—H9 | 113 (3) | C32—C33—H33 | 120.8 |
Mo4—O10—Mo1 | 110.99 (12) | C34—C33—H33 | 120.8 |
Mo4—O10—Mo2 | 116.29 (12) | C33—C34—C35 | 119.9 (5) |
Mo1—O10—Mo2 | 102.10 (11) | C33—C34—H34 | 120.0 |
Mo4—O10—H10 | 111 (3) | C35—C34—H34 | 120.0 |
Mo1—O10—H10 | 103 (3) | C34—C35—C36 | 121.9 (5) |
Mo2—O10—H10 | 112 (3) | C34—C35—H35 | 119.1 |
O1—C1—Mo1 | 176.2 (5) | C36—C35—H35 | 119.1 |
O2—C2—Mo1 | 176.9 (4) | C37—C36—C35 | 117.9 (5) |
C4—C3—Mo1 | 66.7 (3) | C37—C36—H36 | 121.1 |
C4—C3—H3A | 120.0 | C35—C36—H36 | 121.1 |
Mo1—C3—H3A | 84.6 | C36—C37—C32 | 119.9 (5) |
C4—C3—H3B | 120.0 | C36—C37—C25 | 131.1 (5) |
Mo1—C3—H3B | 119.3 | C32—C37—C25 | 109.0 (4) |
C17—Mo4—Cl1—Mo1 | 4.2 (7) | C10—Mo2—O10—Mo4 | −53.4 (2) |
C16—Mo4—Cl1—Mo1 | 75.43 (14) | Cl2—Mo2—O10—Mo4 | 14.13 (10) |
O10—Mo4—Cl1—Mo1 | −16.77 (8) | C6—Mo2—O10—Mo1 | 67.90 (17) |
C19—Mo4—Cl1—Mo1 | 177.56 (13) | C7—Mo2—O10—Mo1 | −16.5 (5) |
C20—Mo4—Cl1—Mo1 | −168.42 (14) | O9—Mo2—O10—Mo1 | −25.01 (10) |
C18—Mo4—Cl1—Mo1 | 142.04 (13) | C9—Mo2—O10—Mo1 | 173.05 (15) |
Cl2—Mo4—Cl1—Mo1 | −94.40 (3) | C8—Mo2—O10—Mo1 | 138.83 (15) |
C17—Mo4—Cl1—Mo3 | 93.9 (7) | C10—Mo2—O10—Mo1 | −174.33 (16) |
C16—Mo4—Cl1—Mo3 | 165.10 (14) | Cl2—Mo2—O10—Mo1 | −106.84 (10) |
O10—Mo4—Cl1—Mo3 | 72.91 (8) | C2—Mo1—C3—C4 | 93.8 (3) |
C19—Mo4—Cl1—Mo3 | −92.77 (14) | C1—Mo1—C3—C4 | 163.4 (4) |
C20—Mo4—Cl1—Mo3 | −78.75 (15) | O10—Mo1—C3—C4 | −143.7 (3) |
C18—Mo4—Cl1—Mo3 | −128.28 (13) | O9—Mo1—C3—C4 | −23.9 (4) |
Cl2—Mo4—Cl1—Mo3 | −4.73 (4) | C5—Mo1—C3—C4 | 33.0 (3) |
C1—Mo1—Cl1—Mo4 | −70.30 (16) | Cl1—Mo1—C3—C4 | −88.4 (3) |
O10—Mo1—Cl1—Mo4 | 16.70 (8) | Mo1—C3—C4—C5 | −68.5 (4) |
C4—Mo1—Cl1—Mo4 | −171.26 (14) | C2—Mo1—C4—C5 | 27.4 (3) |
O9—Mo1—Cl1—Mo4 | 91.46 (8) | C1—Mo1—C4—C5 | 107.5 (3) |
C3—Mo1—Cl1—Mo4 | −134.43 (13) | O10—Mo1—C4—C5 | −127.9 (4) |
C5—Mo1—Cl1—Mo4 | 170.62 (13) | O9—Mo1—C4—C5 | −75.2 (3) |
C1—Mo1—Cl1—Mo3 | −172.40 (16) | C3—Mo1—C4—C5 | 123.1 (5) |
O10—Mo1—Cl1—Mo3 | −85.40 (8) | Cl1—Mo1—C4—C5 | −150.1 (3) |
C4—Mo1—Cl1—Mo3 | 86.65 (14) | C2—Mo1—C4—C3 | −95.7 (3) |
O9—Mo1—Cl1—Mo3 | −10.63 (8) | C1—Mo1—C4—C3 | −15.6 (4) |
C3—Mo1—Cl1—Mo3 | 123.48 (13) | O10—Mo1—C4—C3 | 108.9 (5) |
C5—Mo1—Cl1—Mo3 | 68.52 (13) | O9—Mo1—C4—C3 | 161.7 (3) |
C11—Mo3—Cl1—Mo4 | −164.53 (15) | C5—Mo1—C4—C3 | −123.1 (5) |
O9—Mo3—Cl1—Mo4 | −76.11 (8) | Cl1—Mo1—C4—C3 | 86.8 (3) |
C14—Mo3—Cl1—Mo4 | 92.12 (17) | C3—C4—C5—Mo1 | 67.7 (4) |
C13—Mo3—Cl1—Mo4 | 128.05 (17) | C2—Mo1—C5—C4 | −152.1 (4) |
C15—Mo3—Cl1—Mo4 | 77.73 (16) | C1—Mo1—C5—C4 | −82.7 (4) |
Cl2—Mo3—Cl1—Mo4 | 4.80 (4) | O10—Mo1—C5—C4 | 141.4 (3) |
C11—Mo3—Cl1—Mo1 | −77.48 (15) | O9—Mo1—C5—C4 | 105.2 (3) |
O9—Mo3—Cl1—Mo1 | 10.94 (8) | C3—Mo1—C5—C4 | −34.4 (3) |
C14—Mo3—Cl1—Mo1 | 179.18 (17) | Cl1—Mo1—C5—C4 | 32.6 (3) |
C13—Mo3—Cl1—Mo1 | −144.89 (17) | C6—Mo2—C8—C9 | −151.8 (3) |
C15—Mo3—Cl1—Mo1 | 164.79 (15) | C7—Mo2—C8—C9 | −81.7 (3) |
Cl2—Mo3—Cl1—Mo1 | 91.86 (4) | O9—Mo2—C8—C9 | 141.0 (3) |
C11—Mo3—Cl2—Mo2 | −14.8 (8) | O10—Mo2—C8—C9 | 105.9 (3) |
C12—Mo3—Cl2—Mo2 | 75.97 (14) | C10—Mo2—C8—C9 | −34.1 (3) |
O9—Mo3—Cl2—Mo2 | −16.00 (7) | Cl2—Mo2—C8—C9 | 34.5 (3) |
C14—Mo3—Cl2—Mo2 | 178.16 (15) | Mo2—C8—C9—C10 | 67.8 (4) |
C13—Mo3—Cl2—Mo2 | −167.22 (16) | C6—Mo2—C9—C8 | 27.6 (3) |
C15—Mo3—Cl2—Mo2 | 142.56 (14) | C7—Mo2—C9—C8 | 108.8 (3) |
Cl1—Mo3—Cl2—Mo2 | −94.70 (3) | O9—Mo2—C9—C8 | −127.6 (4) |
C11—Mo3—Cl2—Mo4 | 75.2 (8) | O10—Mo2—C9—C8 | −74.0 (3) |
C12—Mo3—Cl2—Mo4 | 165.96 (14) | C10—Mo2—C9—C8 | 122.7 (4) |
O9—Mo3—Cl2—Mo4 | 73.99 (8) | Cl2—Mo2—C9—C8 | −147.9 (3) |
C14—Mo3—Cl2—Mo4 | −91.85 (16) | C6—Mo2—C9—C10 | −95.1 (3) |
C13—Mo3—Cl2—Mo4 | −77.23 (17) | C7—Mo2—C9—C10 | −13.9 (3) |
C15—Mo3—Cl2—Mo4 | −127.44 (14) | O9—Mo2—C9—C10 | 109.6 (4) |
Cl1—Mo3—Cl2—Mo4 | −4.70 (3) | O10—Mo2—C9—C10 | 163.2 (3) |
C7—Mo2—Cl2—Mo3 | −71.17 (13) | C8—Mo2—C9—C10 | −122.7 (4) |
O9—Mo2—Cl2—Mo3 | 16.00 (7) | Cl2—Mo2—C9—C10 | 89.3 (3) |
C9—Mo2—Cl2—Mo3 | −171.50 (12) | C8—C9—C10—Mo2 | −67.9 (4) |
O10—Mo2—Cl2—Mo3 | 91.04 (8) | C6—Mo2—C10—C9 | 94.2 (3) |
C8—Mo2—Cl2—Mo3 | 169.02 (13) | C7—Mo2—C10—C9 | 165.2 (3) |
C10—Mo2—Cl2—Mo3 | −135.24 (12) | O9—Mo2—C10—C9 | −142.2 (3) |
C7—Mo2—Cl2—Mo4 | −172.56 (13) | O10—Mo2—C10—C9 | −21.8 (3) |
O9—Mo2—Cl2—Mo4 | −85.40 (8) | C8—Mo2—C10—C9 | 33.8 (3) |
C9—Mo2—Cl2—Mo4 | 87.10 (12) | Cl2—Mo2—C10—C9 | −85.7 (3) |
O10—Mo2—Cl2—Mo4 | −10.36 (8) | C11—Mo3—C13—C14 | 159.9 (4) |
C8—Mo2—Cl2—Mo4 | 67.62 (13) | C12—Mo3—C13—C14 | 88.5 (4) |
C10—Mo2—Cl2—Mo4 | 123.37 (12) | O9—Mo3—C13—C14 | −144.0 (3) |
C17—Mo4—Cl2—Mo3 | −164.04 (14) | C15—Mo3—C13—C14 | 34.3 (3) |
C16—Mo4—Cl2—Mo3 | −63.9 (8) | Cl2—Mo3—C13—C14 | −25.3 (4) |
O10—Mo4—Cl2—Mo3 | −75.96 (8) | Cl1—Mo3—C13—C14 | −96.1 (3) |
C19—Mo4—Cl2—Mo3 | 92.81 (14) | Mo3—C13—C14—C15 | −68.9 (4) |
C20—Mo4—Cl2—Mo3 | 128.16 (13) | C11—Mo3—C14—C15 | 102.5 (4) |
C18—Mo4—Cl2—Mo3 | 77.44 (15) | C12—Mo3—C14—C15 | 20.6 (4) |
Cl1—Mo4—Cl2—Mo3 | 4.76 (4) | O9—Mo3—C14—C15 | −123.5 (5) |
C17—Mo4—Cl2—Mo2 | −77.42 (14) | C13—Mo3—C14—C15 | 121.8 (5) |
C16—Mo4—Cl2—Mo2 | 22.7 (8) | Cl2—Mo3—C14—C15 | −80.0 (3) |
O10—Mo4—Cl2—Mo2 | 10.66 (8) | Cl1—Mo3—C14—C15 | −158.3 (3) |
C19—Mo4—Cl2—Mo2 | 179.43 (14) | C11—Mo3—C14—C13 | −19.3 (4) |
C20—Mo4—Cl2—Mo2 | −145.22 (13) | C12—Mo3—C14—C13 | −101.2 (3) |
C18—Mo4—Cl2—Mo2 | 164.06 (15) | O9—Mo3—C14—C13 | 114.7 (5) |
Cl1—Mo4—Cl2—Mo2 | 91.38 (4) | C15—Mo3—C14—C13 | −121.8 (5) |
C11—Mo3—O9—Mo2 | −158.92 (17) | Cl2—Mo3—C14—C13 | 158.2 (3) |
C12—Mo3—O9—Mo2 | −79.61 (17) | Cl1—Mo3—C14—C13 | 79.9 (3) |
C14—Mo3—O9—Mo2 | 65.4 (6) | C13—C14—C15—Mo3 | 68.4 (4) |
C13—Mo3—O9—Mo2 | 150.0 (3) | C11—Mo3—C15—C14 | −88.1 (4) |
C15—Mo3—O9—Mo2 | −27.0 (4) | C12—Mo3—C15—C14 | −158.4 (4) |
Cl2—Mo3—O9—Mo2 | 20.85 (9) | O9—Mo3—C15—C14 | 143.5 (3) |
Cl1—Mo3—O9—Mo2 | 101.19 (11) | C13—Mo3—C15—C14 | −34.6 (3) |
C11—Mo3—O9—Mo1 | 85.80 (18) | Cl2—Mo3—C15—C14 | 96.2 (3) |
C12—Mo3—O9—Mo1 | 165.12 (17) | Cl1—Mo3—C15—C14 | 25.1 (4) |
C14—Mo3—O9—Mo1 | −49.9 (6) | C17—Mo4—C18—C19 | −90.1 (3) |
C13—Mo3—O9—Mo1 | 34.7 (4) | C16—Mo4—C18—C19 | −160.4 (4) |
C15—Mo3—O9—Mo1 | −142.2 (3) | O10—Mo4—C18—C19 | 144.1 (3) |
Cl2—Mo3—O9—Mo1 | −94.42 (12) | C20—Mo4—C18—C19 | −34.1 (3) |
Cl1—Mo3—O9—Mo1 | −14.09 (10) | Cl1—Mo4—C18—C19 | 97.6 (3) |
C6—Mo2—O9—Mo3 | 162.83 (16) | Cl2—Mo4—C18—C19 | 26.9 (3) |
C7—Mo2—O9—Mo3 | 84.13 (17) | Mo4—C18—C19—C20 | 67.8 (4) |
C9—Mo2—O9—Mo3 | −41.3 (4) | C17—Mo4—C19—C20 | −22.3 (3) |
O10—Mo2—O9—Mo3 | −98.38 (13) | C16—Mo4—C19—C20 | −103.4 (3) |
C8—Mo2—O9—Mo3 | −135.2 (3) | O10—Mo4—C19—C20 | 114.2 (5) |
C10—Mo2—O9—Mo3 | 37.1 (3) | C18—Mo4—C19—C20 | −122.1 (4) |
Cl2—Mo2—O9—Mo3 | −20.69 (9) | Cl1—Mo4—C19—C20 | 159.0 (3) |
C6—Mo2—O9—Mo1 | −74.46 (16) | Cl2—Mo4—C19—C20 | 80.9 (3) |
C7—Mo2—O9—Mo1 | −153.16 (16) | C17—Mo4—C19—C18 | 99.7 (3) |
C9—Mo2—O9—Mo1 | 81.5 (4) | C16—Mo4—C19—C18 | 18.7 (3) |
O10—Mo2—O9—Mo1 | 24.33 (10) | O10—Mo4—C19—C18 | −123.7 (4) |
C8—Mo2—O9—Mo1 | −12.5 (3) | C20—Mo4—C19—C18 | 122.1 (4) |
C10—Mo2—O9—Mo1 | 159.8 (2) | Cl1—Mo4—C19—C18 | −78.9 (3) |
Cl2—Mo2—O9—Mo1 | 102.02 (9) | Cl2—Mo4—C19—C18 | −157.0 (3) |
C2—Mo1—O9—Mo3 | −172.48 (17) | C18—C19—C20—Mo4 | −67.9 (4) |
C1—Mo1—O9—Mo3 | 104.1 (6) | C17—Mo4—C20—C19 | 156.9 (3) |
O10—Mo1—O9—Mo3 | 95.28 (14) | C16—Mo4—C20—C19 | 86.4 (3) |
C4—Mo1—O9—Mo3 | −67.29 (19) | O10—Mo4—C20—C19 | −144.0 (3) |
C3—Mo1—O9—Mo3 | −53.2 (2) | C18—Mo4—C20—C19 | 34.4 (3) |
C5—Mo1—O9—Mo3 | −101.01 (17) | Cl1—Mo4—C20—C19 | −24.6 (3) |
Cl1—Mo1—O9—Mo3 | 14.19 (10) | Cl2—Mo4—C20—C19 | −96.0 (3) |
C2—Mo1—O9—Mo2 | 67.22 (17) | C24—O11—C21—C22 | −36.7 (6) |
C1—Mo1—O9—Mo2 | −16.2 (6) | O11—C21—C22—C23 | 17.7 (7) |
O10—Mo1—O9—Mo2 | −25.02 (10) | C21—C22—C23—C24 | 6.4 (7) |
C4—Mo1—O9—Mo2 | 172.41 (17) | C21—O11—C24—C23 | 41.2 (6) |
C3—Mo1—O9—Mo2 | −173.55 (18) | C22—C23—C24—O11 | −28.8 (6) |
C5—Mo1—O9—Mo2 | 138.69 (15) | C30—C25—C26—C27 | 1.9 (7) |
Cl1—Mo1—O9—Mo2 | −106.11 (10) | C37—C25—C26—C27 | −178.9 (5) |
C17—Mo4—O10—Mo1 | −154.38 (17) | C25—C26—C27—C28 | −1.1 (7) |
C16—Mo4—O10—Mo1 | −75.64 (18) | C26—C27—C28—C29 | −0.6 (8) |
C19—Mo4—O10—Mo1 | 67.6 (5) | C27—C28—C29—C30 | 1.7 (8) |
C20—Mo4—O10—Mo1 | 151.6 (2) | C28—C29—C30—C25 | −0.9 (7) |
C18—Mo4—O10—Mo1 | −25.4 (3) | C28—C29—C30—C31 | 179.3 (5) |
Cl1—Mo4—O10—Mo1 | 21.69 (9) | C26—C25—C30—C29 | −0.9 (7) |
Cl2—Mo4—O10—Mo1 | 102.10 (11) | C37—C25—C30—C29 | 179.7 (4) |
C17—Mo4—O10—Mo2 | 89.52 (18) | C26—C25—C30—C31 | 179.0 (4) |
C16—Mo4—O10—Mo2 | 168.26 (18) | C37—C25—C30—C31 | −0.5 (5) |
C19—Mo4—O10—Mo2 | −48.5 (5) | C29—C30—C31—O12 | −2.1 (9) |
C20—Mo4—O10—Mo2 | 35.5 (3) | C25—C30—C31—O12 | 178.1 (5) |
C18—Mo4—O10—Mo2 | −141.5 (3) | C29—C30—C31—C32 | 179.9 (5) |
Cl1—Mo4—O10—Mo2 | −94.41 (12) | C25—C30—C31—C32 | 0.1 (5) |
Cl2—Mo4—O10—Mo2 | −14.00 (10) | O12—C31—C32—C33 | 2.8 (9) |
C2—Mo1—O10—Mo4 | 159.91 (17) | C30—C31—C32—C33 | −179.3 (5) |
C1—Mo1—O10—Mo4 | 82.34 (19) | O12—C31—C32—C37 | −177.6 (5) |
C4—Mo1—O10—Mo4 | −44.1 (5) | C30—C31—C32—C37 | 0.3 (5) |
O9—Mo1—O10—Mo4 | −100.33 (13) | C37—C32—C33—C34 | 1.2 (7) |
C3—Mo1—O10—Mo4 | 35.1 (3) | C31—C32—C33—C34 | −179.2 (5) |
C5—Mo1—O10—Mo4 | −138.5 (3) | C32—C33—C34—C35 | −0.4 (8) |
Cl1—Mo1—O10—Mo4 | −21.55 (9) | C33—C34—C35—C36 | 0.0 (8) |
C2—Mo1—O10—Mo2 | −75.52 (16) | C34—C35—C36—C37 | −0.2 (8) |
C1—Mo1—O10—Mo2 | −153.09 (18) | C35—C36—C37—C32 | 0.9 (7) |
C4—Mo1—O10—Mo2 | 80.5 (5) | C35—C36—C37—C25 | −179.7 (5) |
O9—Mo1—O10—Mo2 | 24.24 (10) | C33—C32—C37—C36 | −1.5 (7) |
C3—Mo1—O10—Mo2 | 159.6 (2) | C31—C32—C37—C36 | 178.9 (4) |
C5—Mo1—O10—Mo2 | −13.9 (4) | C33—C32—C37—C25 | 179.1 (4) |
Cl1—Mo1—O10—Mo2 | 103.02 (9) | C31—C32—C37—C25 | −0.6 (5) |
C6—Mo2—O10—Mo4 | −171.13 (17) | C26—C25—C37—C36 | 2.0 (8) |
C7—Mo2—O10—Mo4 | 104.5 (5) | C30—C25—C37—C36 | −178.7 (5) |
O9—Mo2—O10—Mo4 | 95.95 (14) | C26—C25—C37—C32 | −178.7 (5) |
C9—Mo2—O10—Mo4 | −65.98 (17) | C30—C25—C37—C32 | 0.7 (5) |
C8—Mo2—O10—Mo4 | −100.20 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9···O11 | 0.94 (3) | 1.84 (3) | 2.770 (4) | 169 (4) |
O10—H10···O12 | 0.93 (3) | 1.85 (2) | 2.761 (4) | 164 (4) |
Experimental details
Crystal data | |
Chemical formula | [Mo4(C3H5)4Cl2(OH)2(CO)8]·C4H8O·C13H8O |
Mr | 1129.33 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 46.383 (3), 10.3975 (6), 17.3531 (12) |
β (°) | 104.133 (4) |
V (Å3) | 8115.6 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.40 |
Crystal size (mm) | 0.06 × 0.03 × 0.01 |
Data collection | |
Diffractometer | Bruker X8 KappaCCD APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.918, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45728, 9024, 6026 |
Rint | 0.075 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.081, 1.01 |
No. of reflections | 9024 |
No. of parameters | 502 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.78, −0.69 |
Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Bruker, 2001), DIAMOND (Brandenburg, 2008).
Mo1—C1 | 1.947 (5) | Mo3—C11 | 1.926 (6) |
Mo1—C2 | 1.930 (5) | Mo3—C12 | 1.937 (5) |
Mo1—C3 | 2.327 (5) | Mo3—C13 | 2.319 (5) |
Mo1—C4 | 2.197 (5) | Mo3—C14 | 2.188 (5) |
Mo1—C5 | 2.337 (5) | Mo3—C15 | 2.334 (4) |
Mo1—O9 | 2.255 (3) | Mo3—O9 | 2.181 (3) |
Mo1—O10 | 2.196 (3) | Mo3—Cl2 | 2.6142 (12) |
Mo1—Cl1 | 2.6302 (11) | Mo3—Cl1 | 2.6361 (11) |
Mo2—C6 | 1.919 (5) | Mo4—C16 | 1.937 (5) |
Mo2—C7 | 1.953 (5) | Mo4—C17 | 1.922 (5) |
Mo2—C8 | 2.327 (4) | Mo4—C18 | 2.329 (4) |
Mo2—C9 | 2.199 (4) | Mo4—C19 | 2.200 (4) |
Mo2—C10 | 2.328 (4) | Mo4—C20 | 2.319 (5) |
Mo2—O9 | 2.187 (3) | Mo4—O10 | 2.181 (3) |
Mo2—O10 | 2.252 (3) | Mo4—Cl1 | 2.6068 (12) |
Mo2—Cl2 | 2.6399 (11) | Mo4—Cl2 | 2.6538 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9···O11 | 0.94 (3) | 1.84 (3) | 2.770 (4) | 169 (4) |
O10—H10···O12 | 0.93 (3) | 1.851 (16) | 2.761 (4) | 164 (4) |
The family of η3-allyldicarbonyl complexes of Mo2+ plays an important role in coordination chemistry and catalytic organic transformations. The reactivity of these complexes depends on the nature of the ligands which compose the first coordination sphere (Saraiva et al., 2008, and references therein). Since the discovery of the complex Mo(η3-allyl)Cl(CH3CN)2(CO)2 in the late 1960s (Hayter, 1968), a series of derivatives containing the [Mo(η3-allyl)(CO)2]+ moiety have been prepared by substitution of the labile nitrile ligands and/or Cl. Our research group has been particularly interested in the preparation of Cp'Mo(η3-allyl)(CO)2 (Cp' is cyclopentadienyl, indenyl or fluorenyl) using Mo(η3-C3H5)Cl(NCMe)2(CO)2 as a starting material (Ascenso et al., 1995). As part of our on-going research, in this paper we report a compound containing the first cubane-type complex of a transition metal (T) exhibiting two pairs of distinct µ3-capping bridges, viz. di-µ3-chlorido-di-µ3-hydroxido-tetrakis[(η3-αllyl)dicarbonylmolybdenum(II)]–9-fluorenone–tetrahydrofuran (1/1/1), Mo4(η3-allyl)4(OH)2Cl2(CO)8.C13H8O.THF, (I). A search in the literature and in the Cambridge Structure Database (Allen, 2002) consolidates the uniqueness of this compound: despite cubane-type structures with four capping oxygen or halogen atoms (X) being common, i.e. T4O4 or T4X4, only a handful of compounds contain the two types of capping ligands; moreover, none of the known structures is an organometallic complex, they are all either Mn or Cu complexes with carboxylates or β-diketonates (Aronica et al., 2007; Hendrickson et al., 1992; Wang et al., 1996; Wemple et al., 1993, 1995).
The neutral Mo4(η3-allyl)4(OH)2Cl2(CO)8 complex depicted in Fig. 1 contains a central cationic [Mo4(µ3-OH)2(µ3-Cl)2]4+ core best described as a trigonal prism of Mo atoms having two of the faces capped by µ3-OH groups and the other two by µ3-Cl anions. This arrangement is reminiscent of a distorted Mo4O2Cl2 cubane. The four crystallographically distinct Mo2+ centres are all coordinated to two carbonyl groups [Mo—C = 1.919 (5)–1.953 (5)Å] and one η3-allyl moiety [Mo—C = 2.188 (5)–2.337 (5)Å] (Table 1). For simplification, in Fig. 1 all the Mo—C bonds to the allyl groups have been replaced by a dashed bond to the respective centre of gravity (Cg) with the four crystallographically distinct Mo—Cg ranging from 2.03 to 2.04Å. The presence of two distinct capping ligands leads to two types of coordination environments: while Mo1 and Mo2 contain two OH- and one Cl- anion completing their coordination spheres, Mo3 and Mo4 have instead one OH- and two Cl- anions. The overall coordination spheres can thus be envisaged as highly distorted octahedra with internal (Cg,Cl,O)—-Mo—(Cg,Cl,O) cis and trans angles of ca 72.4–104.5 and ca 162.3–172.8°, respectively. All η3-allyl groups are trans-coordinated to a µ3-OH group and all the carbonyl groups occupy the equatorial plane of the Mo2+ octahedra. The presence of two pairs of capping ligands leads to a symmetrization of the cubane core with the Mo—Cl and Mo—O distances falling into relatively narrow ranges, viz. 2.6068 (12)–2.6538 (11) and 2.181 (3)–2.255 (3)Å, respectively (Table 1). The internal Mo···Mo distances were between 3.459 (1) and 4.077 (1)Å; while the former concerns the Mo4 tetrahedron edge formed by the two adjacent µ3-OH- groups, the latter is that of the edge having the two µ3-Cl- anions, thus reflecting the steric impediment associated with these large anions (which promotes a larger separation between metallic centres). We note the presence of a number of weak intramolecular C—H···O interactions involving the allyl groups and the neighbouring carbonyl moieties (Fig. 1), with D···A distances ranging from ca 3.09 to 3.28Å (<D—H···A from ca 126 to 139°).
The crystal structure contains two extra organic molecules, one solvent (tetrahydrofuran, THF) molecule and a by-product of the reaction, 9-fluorenone. These two molecular species seem to stabilize the crystal structure of (I) by acting as space-filling entities: individual Mo4(η3-allyl)4(OH)2Cl2(CO)8 complexes close pack in the bc plane of the unit cell forming layers (Fig. 2); available space between layers is alternately occupied by either THF or 9-fluorenone molecules. The latter are further engaged in strong π–π interactions along the [100] direction, as depicted in Fig. 2, with the distance between centres of gravity being of ca 3.61Å. These two organic species are strongly hydrogen bonded to the Mo complex while acting as donors in O—H···O interactions with the two µ3-OH groups (see Table 2 for hydrogen-bonding geometry).