Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013111/fr1291sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013111/fr1291Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013111/fr1291IIsup3.hkl |
CCDC references: 156148; 156149
Complex (I) was prepared from cis-[bis(piperidine)]tetracarbonylmolybdenum(0) following the procedure of Darensbourg & Kump (1978); a 2.5 mol excess of tricyclohexylphosphine to the piperidine complex was used, in dichloromethane. Light-yellow crystals of (I) were obtained by recrystallization from dichloromethane-methanol solution. Complex (II) was prepared by refluxing Mo(CO)6 and P(cy)3 in bis(2-methoxyethyl)ether under dinitrogen. Upon cooling to 277 K, colorless crystals of (II) formed in low yield.
H atoms were treated as riding, with Uiso(H) = 1.2Ueq(C) and C—H distances in the range 0.97–0.98 Å. Query.
For both compounds, data collection: P3/PC Diffractometer Program (Siemens, 1989); cell refinement: P3/PC Diffractometer Program; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS93 (Sheldrick, 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
[Mo(C18H33P)2(CO)4] | F(000) = 1640 |
Mr = 768.81 | Dx = 1.260 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.856 (3) Å | Cell parameters from 50 reflections |
b = 25.323 (8) Å | θ = 7.5–18.0° |
c = 14.795 (7) Å | µ = 0.44 mm−1 |
β = 94.68 (3)° | T = 293 K |
V = 4054 (3) Å3 | Prism, light yellow |
Z = 4 | 0.40 × 0.20 × 0.05 mm |
Siemens P3 diffractometer | 9302 independent reflections |
Radiation source: normal-focus sealed tube | 3635 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
Detector resolution: not applicable pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = 0→14 |
Absorption correction: ψ-scans semi-empirical (using intensity measurements) (XEMP; Siemens, 1989) | k = 0→32 |
Tmin = 0.844, Tmax = 0.978 | l = −19→19 |
12628 measured reflections |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 0.93 | Calculated w = 1/[σ2(Fo2) + (0.048P)2] where P = (Fo2 + 2Fc2)/3 |
9302 reflections | (Δ/σ)max = 0.001 |
424 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
[Mo(C18H33P)2(CO)4] | V = 4054 (3) Å3 |
Mr = 768.81 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.856 (3) Å | µ = 0.44 mm−1 |
b = 25.323 (8) Å | T = 293 K |
c = 14.795 (7) Å | 0.40 × 0.20 × 0.05 mm |
β = 94.68 (3)° |
Siemens P3 diffractometer | 9302 independent reflections |
Absorption correction: ψ-scans semi-empirical (using intensity measurements) (XEMP; Siemens, 1989) | 3635 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.978 | Rint = 0.092 |
12628 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.59 e Å−3 |
9302 reflections | Δρmin = −0.70 e Å−3 |
424 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 | ||
Mo | 0.15100 (4) | 0.840978 (19) | 0.81155 (3) | 0.03624 (12) | |
P1 | 0.02248 (11) | 0.78943 (5) | 0.67883 (10) | 0.0345 (4) | |
P2 | 0.25599 (12) | 0.92050 (5) | 0.72991 (10) | 0.0388 (4) | |
O1 | −0.0887 (4) | 0.90010 (17) | 0.8648 (3) | 0.0918 (16) | |
O2 | 0.2704 (4) | 0.88954 (19) | 0.9927 (3) | 0.0945 (17) | |
O3 | 0.0826 (4) | 0.75176 (18) | 0.9403 (3) | 0.0767 (13) | |
O4 | 0.4016 (3) | 0.77648 (15) | 0.8048 (3) | 0.0697 (14) | |
C1 | −0.0056 (5) | 0.8798 (2) | 0.8406 (4) | 0.0514 (16) | |
C2 | 0.2256 (5) | 0.8718 (2) | 0.9214 (4) | 0.0516 (17) | |
C3 | 0.1040 (5) | 0.7852 (2) | 0.8904 (4) | 0.0468 (15) | |
C4 | 0.3116 (5) | 0.8001 (2) | 0.8020 (4) | 0.0554 (17) | |
C11 | 0.1082 (4) | 0.73550 (19) | 0.6268 (3) | 0.0357 (13) | |
H11A | 0.0523 | 0.7207 | 0.5779 | 0.043* | |
C12 | 0.1436 (4) | 0.69024 (19) | 0.6917 (4) | 0.0457 (15) | |
H12A | 0.0696 | 0.6759 | 0.7149 | 0.055* | |
H12B | 0.1964 | 0.7035 | 0.7427 | 0.055* | |
C13 | 0.2111 (5) | 0.6465 (2) | 0.6446 (4) | 0.0609 (18) | |
H13A | 0.2372 | 0.6196 | 0.6888 | 0.073* | |
H13B | 0.1543 | 0.6302 | 0.5989 | 0.073* | |
C14 | 0.3225 (5) | 0.6662 (2) | 0.6004 (4) | 0.0698 (19) | |
H14A | 0.3571 | 0.6376 | 0.5669 | 0.084* | |
H14B | 0.3850 | 0.6778 | 0.6467 | 0.084* | |
C15 | 0.2881 (5) | 0.7112 (2) | 0.5369 (4) | 0.0544 (17) | |
H15A | 0.3623 | 0.7251 | 0.5133 | 0.065* | |
H15B | 0.2346 | 0.6982 | 0.4861 | 0.065* | |
C16 | 0.2234 (4) | 0.75491 (19) | 0.5829 (3) | 0.0423 (14) | |
H16A | 0.1993 | 0.7821 | 0.5387 | 0.051* | |
H16B | 0.2804 | 0.7706 | 0.6292 | 0.051* | |
C21 | −0.1101 (4) | 0.74977 (19) | 0.7175 (3) | 0.0416 (14) | |
H21A | −0.0693 | 0.7241 | 0.7595 | 0.050* | |
C22 | −0.1800 (4) | 0.7151 (2) | 0.6462 (4) | 0.0523 (16) | |
H22A | −0.2301 | 0.7372 | 0.6041 | 0.063* | |
H22B | −0.1215 | 0.6961 | 0.6122 | 0.063* | |
C23 | −0.2624 (5) | 0.6759 (2) | 0.6904 (4) | 0.087 (2) | |
H23A | −0.3075 | 0.6550 | 0.6438 | 0.105* | |
H23B | −0.2117 | 0.6522 | 0.7291 | 0.105* | |
C24 | −0.3525 (5) | 0.7040 (3) | 0.7459 (4) | 0.082 (2) | |
H24A | −0.4068 | 0.7261 | 0.7066 | 0.098* | |
H24B | −0.4031 | 0.6782 | 0.7743 | 0.098* | |
C25 | −0.2852 (4) | 0.7373 (2) | 0.8172 (4) | 0.0652 (19) | |
H25A | −0.2370 | 0.7148 | 0.8596 | 0.078* | |
H25B | −0.3446 | 0.7563 | 0.8505 | 0.078* | |
C26 | −0.1978 (4) | 0.7777 (2) | 0.7748 (4) | 0.0566 (17) | |
H26A | −0.2467 | 0.8029 | 0.7378 | 0.068* | |
H26B | −0.1512 | 0.7971 | 0.8228 | 0.068* | |
C31 | −0.0412 (4) | 0.82737 (18) | 0.5769 (3) | 0.0313 (13) | |
H31A | 0.0213 | 0.8543 | 0.5677 | 0.038* | |
C32 | −0.1573 (4) | 0.85854 (18) | 0.5947 (3) | 0.0427 (15) | |
H32A | −0.2249 | 0.8340 | 0.6006 | 0.051* | |
H32B | −0.1429 | 0.8774 | 0.6516 | 0.051* | |
C33 | −0.1943 (4) | 0.8974 (2) | 0.5206 (3) | 0.0459 (15) | |
H33A | −0.1310 | 0.9243 | 0.5190 | 0.055* | |
H33B | −0.2706 | 0.9147 | 0.5338 | 0.055* | |
C34 | −0.2123 (4) | 0.8710 (2) | 0.4292 (3) | 0.0487 (16) | |
H34A | −0.2281 | 0.8976 | 0.3824 | 0.058* | |
H34B | −0.2833 | 0.8477 | 0.4276 | 0.058* | |
C35 | −0.0978 (4) | 0.8395 (2) | 0.4107 (3) | 0.0479 (14) | |
H35A | −0.1129 | 0.8209 | 0.3534 | 0.057* | |
H35B | −0.0292 | 0.8635 | 0.4053 | 0.057* | |
C36 | −0.0633 (4) | 0.79987 (18) | 0.4851 (3) | 0.0394 (14) | |
H36A | 0.0109 | 0.7812 | 0.4715 | 0.047* | |
H36B | −0.1293 | 0.7742 | 0.4877 | 0.047* | |
C41 | 0.1546 (4) | 0.98033 (19) | 0.7141 (3) | 0.0406 (14) | |
H41A | 0.1998 | 1.0071 | 0.6822 | 0.049* | |
C42 | 0.1246 (4) | 1.00403 (18) | 0.8066 (4) | 0.0475 (15) | |
H42A | 0.0894 | 0.9769 | 0.8429 | 0.057* | |
H42B | 0.2001 | 1.0165 | 0.8393 | 0.057* | |
C43 | 0.0320 (5) | 1.0505 (2) | 0.7923 (4) | 0.0675 (19) | |
H43A | 0.0074 | 1.0621 | 0.8506 | 0.081* | |
H43B | 0.0723 | 1.0799 | 0.7647 | 0.081* | |
C44 | −0.0817 (5) | 1.0348 (2) | 0.7325 (4) | 0.071 (2) | |
H44A | −0.1266 | 1.0080 | 0.7632 | 0.085* | |
H44B | −0.1352 | 1.0653 | 0.7228 | 0.085* | |
C45 | −0.0507 (5) | 1.0138 (2) | 0.6424 (4) | 0.0584 (17) | |
H45A | −0.0134 | 1.0415 | 0.6086 | 0.070* | |
H45B | −0.1257 | 1.0024 | 0.6078 | 0.070* | |
C46 | 0.0400 (4) | 0.96656 (18) | 0.6555 (4) | 0.0468 (15) | |
H46A | −0.0014 | 0.9374 | 0.6828 | 0.056* | |
H46B | 0.0630 | 0.9550 | 0.5966 | 0.056* | |
C51 | 0.3940 (4) | 0.94834 (19) | 0.7992 (4) | 0.0453 (15) | |
H51A | 0.3586 | 0.9624 | 0.8532 | 0.054* | |
C52 | 0.4917 (4) | 0.9098 (2) | 0.8381 (4) | 0.0618 (18) | |
H52A | 0.5377 | 0.8964 | 0.7895 | 0.074* | |
H52B | 0.4515 | 0.8801 | 0.8649 | 0.074* | |
C53 | 0.5823 (5) | 0.9357 (2) | 0.9108 (4) | 0.075 (2) | |
H53A | 0.5383 | 0.9457 | 0.9626 | 0.090* | |
H53B | 0.6461 | 0.9106 | 0.9311 | 0.090* | |
C54 | 0.6400 (5) | 0.9832 (3) | 0.8734 (5) | 0.084 (2) | |
H54A | 0.6927 | 0.9723 | 0.8268 | 0.101* | |
H54B | 0.6916 | 1.0003 | 0.9213 | 0.101* | |
C55 | 0.5461 (5) | 1.0220 (2) | 0.8335 (4) | 0.080 (2) | |
H55A | 0.5885 | 1.0512 | 0.8069 | 0.096* | |
H55B | 0.4998 | 1.0361 | 0.8814 | 0.096* | |
C56 | 0.4549 (4) | 0.9965 (2) | 0.7597 (4) | 0.0534 (17) | |
H56A | 0.3921 | 1.0219 | 0.7388 | 0.064* | |
H56B | 0.4991 | 0.9859 | 0.7082 | 0.064* | |
C61 | 0.3020 (4) | 0.90969 (19) | 0.6140 (3) | 0.0400 (14) | |
H61A | 0.2361 | 0.8879 | 0.5840 | 0.048* | |
C62 | 0.3142 (5) | 0.9565 (2) | 0.5515 (4) | 0.0559 (18) | |
H62A | 0.3821 | 0.9787 | 0.5755 | 0.067* | |
H62B | 0.2391 | 0.9774 | 0.5493 | 0.067* | |
C63 | 0.3380 (4) | 0.9385 (2) | 0.4537 (4) | 0.0588 (18) | |
H63A | 0.2671 | 0.9187 | 0.4279 | 0.071* | |
H63B | 0.3477 | 0.9693 | 0.4161 | 0.071* | |
C64 | 0.4523 (5) | 0.9044 (2) | 0.4537 (4) | 0.0595 (18) | |
H64A | 0.5247 | 0.9256 | 0.4717 | 0.071* | |
H64B | 0.4605 | 0.8915 | 0.3928 | 0.071* | |
C65 | 0.4465 (5) | 0.8581 (2) | 0.5177 (4) | 0.0556 (17) | |
H65A | 0.3813 | 0.8343 | 0.4948 | 0.067* | |
H65B | 0.5240 | 0.8390 | 0.5202 | 0.067* | |
C66 | 0.4222 (4) | 0.8757 (2) | 0.6119 (3) | 0.0494 (16) | |
H66A | 0.4922 | 0.8962 | 0.6373 | 0.059* | |
H66B | 0.4150 | 0.8448 | 0.6499 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo | 0.0288 (2) | 0.0359 (2) | 0.0443 (3) | −0.0014 (3) | 0.00473 (19) | 0.0030 (3) |
P1 | 0.0262 (7) | 0.0346 (8) | 0.0436 (9) | −0.0002 (7) | 0.0072 (7) | 0.0019 (7) |
P2 | 0.0323 (8) | 0.0343 (9) | 0.0501 (10) | 0.0008 (7) | 0.0044 (7) | 0.0014 (8) |
O1 | 0.068 (3) | 0.072 (3) | 0.143 (5) | 0.016 (3) | 0.052 (3) | −0.010 (3) |
O2 | 0.106 (4) | 0.116 (4) | 0.060 (3) | −0.029 (3) | −0.001 (3) | −0.016 (3) |
O3 | 0.081 (3) | 0.073 (3) | 0.078 (3) | −0.009 (3) | 0.020 (3) | 0.025 (3) |
O4 | 0.037 (2) | 0.062 (3) | 0.111 (4) | 0.010 (2) | 0.008 (2) | 0.012 (3) |
C1 | 0.038 (3) | 0.040 (4) | 0.077 (5) | 0.000 (3) | 0.005 (3) | −0.009 (3) |
C2 | 0.039 (3) | 0.063 (4) | 0.054 (4) | 0.009 (3) | 0.013 (3) | 0.016 (4) |
C3 | 0.048 (4) | 0.055 (4) | 0.038 (4) | 0.005 (3) | 0.008 (3) | 0.005 (3) |
C4 | 0.046 (4) | 0.031 (4) | 0.089 (5) | −0.013 (3) | 0.007 (4) | −0.005 (3) |
C11 | 0.027 (3) | 0.042 (3) | 0.039 (3) | 0.002 (2) | 0.010 (2) | 0.010 (3) |
C12 | 0.034 (3) | 0.040 (3) | 0.063 (4) | −0.004 (3) | 0.007 (3) | 0.006 (3) |
C13 | 0.076 (4) | 0.039 (4) | 0.066 (4) | 0.006 (3) | 0.000 (4) | 0.007 (3) |
C14 | 0.062 (4) | 0.070 (5) | 0.078 (5) | 0.025 (4) | 0.015 (4) | 0.007 (4) |
C15 | 0.052 (4) | 0.053 (4) | 0.061 (4) | 0.017 (3) | 0.025 (3) | 0.015 (3) |
C16 | 0.032 (3) | 0.049 (4) | 0.046 (4) | −0.001 (3) | 0.004 (3) | 0.014 (3) |
C21 | 0.038 (3) | 0.041 (3) | 0.046 (4) | −0.005 (3) | 0.009 (3) | −0.002 (3) |
C22 | 0.037 (3) | 0.060 (4) | 0.062 (4) | −0.016 (3) | 0.018 (3) | −0.006 (3) |
C23 | 0.077 (5) | 0.075 (5) | 0.117 (6) | −0.041 (4) | 0.055 (4) | −0.039 (5) |
C24 | 0.054 (4) | 0.105 (6) | 0.090 (6) | −0.049 (4) | 0.029 (4) | −0.030 (5) |
C25 | 0.049 (4) | 0.089 (5) | 0.061 (4) | −0.024 (4) | 0.025 (3) | −0.014 (4) |
C26 | 0.043 (3) | 0.068 (4) | 0.062 (4) | −0.016 (3) | 0.021 (3) | −0.007 (4) |
C31 | 0.024 (3) | 0.031 (3) | 0.039 (3) | −0.004 (2) | 0.003 (2) | 0.001 (2) |
C32 | 0.033 (3) | 0.041 (4) | 0.054 (4) | −0.003 (3) | 0.003 (3) | −0.003 (3) |
C33 | 0.036 (3) | 0.043 (4) | 0.058 (4) | 0.014 (3) | 0.003 (3) | 0.002 (3) |
C34 | 0.037 (3) | 0.048 (4) | 0.060 (4) | 0.004 (3) | −0.006 (3) | 0.009 (3) |
C35 | 0.047 (3) | 0.048 (3) | 0.048 (4) | 0.001 (3) | −0.003 (3) | −0.019 (3) |
C36 | 0.037 (3) | 0.036 (3) | 0.047 (4) | 0.009 (3) | 0.010 (3) | 0.012 (3) |
C41 | 0.031 (3) | 0.036 (3) | 0.054 (4) | −0.006 (3) | −0.002 (3) | 0.003 (3) |
C42 | 0.035 (3) | 0.036 (3) | 0.072 (4) | −0.001 (3) | 0.007 (3) | −0.004 (3) |
C43 | 0.074 (5) | 0.036 (4) | 0.093 (6) | 0.005 (3) | 0.011 (4) | −0.012 (4) |
C44 | 0.053 (4) | 0.042 (4) | 0.117 (6) | 0.009 (3) | 0.010 (4) | −0.011 (4) |
C45 | 0.050 (4) | 0.047 (4) | 0.078 (5) | 0.014 (3) | 0.004 (3) | −0.009 (4) |
C46 | 0.042 (3) | 0.029 (3) | 0.068 (4) | 0.001 (3) | −0.006 (3) | −0.004 (3) |
C51 | 0.046 (3) | 0.035 (3) | 0.054 (4) | 0.006 (3) | −0.007 (3) | 0.001 (3) |
C52 | 0.034 (3) | 0.058 (4) | 0.093 (5) | −0.002 (3) | 0.002 (3) | 0.013 (4) |
C53 | 0.043 (4) | 0.091 (6) | 0.087 (5) | −0.006 (4) | −0.016 (4) | 0.009 (5) |
C54 | 0.057 (4) | 0.082 (5) | 0.112 (7) | −0.034 (4) | −0.008 (4) | −0.003 (5) |
C55 | 0.055 (4) | 0.055 (5) | 0.126 (7) | −0.029 (4) | −0.021 (4) | 0.002 (4) |
C56 | 0.029 (3) | 0.059 (4) | 0.072 (5) | −0.006 (3) | 0.004 (3) | 0.000 (4) |
C61 | 0.033 (3) | 0.037 (3) | 0.051 (4) | −0.006 (3) | 0.004 (3) | 0.002 (3) |
C62 | 0.046 (4) | 0.055 (4) | 0.066 (5) | 0.013 (3) | 0.004 (3) | 0.017 (4) |
C63 | 0.044 (4) | 0.078 (5) | 0.054 (4) | 0.015 (3) | 0.007 (3) | 0.007 (4) |
C64 | 0.048 (4) | 0.074 (5) | 0.058 (4) | 0.017 (3) | 0.010 (3) | −0.007 (4) |
C65 | 0.048 (4) | 0.063 (5) | 0.058 (4) | 0.001 (3) | 0.019 (3) | −0.008 (3) |
C66 | 0.045 (3) | 0.042 (4) | 0.063 (4) | 0.005 (3) | 0.013 (3) | 0.011 (3) |
Mo—C2 | 1.921 (6) | C15—H15A | 0.9700 |
Mo—C3 | 1.927 (6) | C15—H15B | 0.9700 |
Mo—C1 | 2.039 (5) | C16—H16A | 0.9700 |
Mo—C4 | 2.042 (6) | C16—H16B | 0.9700 |
Mo—P2 | 2.6529 (16) | C21—H21A | 0.9800 |
Mo—P1 | 2.6569 (17) | C22—H22A | 0.9700 |
P1—C11 | 1.855 (5) | C22—H22B | 0.9700 |
P1—C31 | 1.872 (4) | C23—H23A | 0.9700 |
P1—C21 | 1.882 (5) | C23—H23B | 0.9700 |
P2—C61 | 1.845 (5) | C24—H24A | 0.9700 |
P2—C41 | 1.876 (5) | C24—H24B | 0.9700 |
P2—C51 | 1.882 (5) | C25—H25A | 0.9700 |
O1—C1 | 1.123 (6) | C25—H25B | 0.9700 |
O2—C2 | 1.211 (6) | C26—H26A | 0.9700 |
O3—C3 | 1.159 (6) | C26—H26B | 0.9700 |
O4—C4 | 1.143 (6) | C31—H31A | 0.9800 |
C11—C12 | 1.524 (6) | C32—H32A | 0.9700 |
C11—C16 | 1.537 (6) | C32—H32B | 0.9700 |
C12—C13 | 1.528 (6) | C33—H33A | 0.9700 |
C13—C14 | 1.505 (6) | C33—H33B | 0.9700 |
C14—C15 | 1.506 (6) | C34—H34A | 0.9700 |
C15—C16 | 1.502 (6) | C34—H34B | 0.9700 |
C21—C26 | 1.502 (6) | C35—H35A | 0.9700 |
C21—C22 | 1.526 (6) | C35—H35B | 0.9700 |
C22—C23 | 1.518 (6) | C36—H36A | 0.9700 |
C23—C24 | 1.505 (7) | C36—H36B | 0.9700 |
C24—C25 | 1.495 (6) | C41—H41A | 0.9800 |
C25—C26 | 1.562 (6) | C42—H42A | 0.9700 |
C31—C36 | 1.528 (6) | C42—H42B | 0.9700 |
C31—C32 | 1.528 (5) | C43—H43A | 0.9700 |
C32—C33 | 1.503 (6) | C43—H43B | 0.9700 |
C33—C34 | 1.507 (6) | C44—H44A | 0.9700 |
C34—C35 | 1.522 (6) | C44—H44B | 0.9700 |
C35—C36 | 1.513 (6) | C45—H45A | 0.9700 |
C41—C46 | 1.499 (5) | C45—H45B | 0.9700 |
C41—C42 | 1.553 (6) | C46—H46A | 0.9700 |
C42—C43 | 1.551 (6) | C46—H46B | 0.9700 |
C43—C44 | 1.512 (6) | C51—H51A | 0.9800 |
C44—C45 | 1.498 (7) | C52—H52A | 0.9700 |
C45—C46 | 1.550 (6) | C52—H52B | 0.9700 |
C51—C52 | 1.520 (6) | C53—H53A | 0.9700 |
C51—C56 | 1.525 (6) | C53—H53B | 0.9700 |
C52—C53 | 1.543 (6) | C54—H54A | 0.9700 |
C53—C54 | 1.482 (7) | C54—H54B | 0.9700 |
C54—C55 | 1.502 (7) | C55—H55A | 0.9700 |
C55—C56 | 1.554 (6) | C55—H55B | 0.9700 |
C61—C62 | 1.516 (6) | C56—H56A | 0.9700 |
C61—C66 | 1.566 (6) | C56—H56B | 0.9700 |
C62—C63 | 1.559 (6) | C61—H61A | 0.9800 |
C63—C64 | 1.511 (6) | C62—H62A | 0.9700 |
C64—C65 | 1.512 (6) | C62—H62B | 0.9700 |
C65—C66 | 1.507 (6) | C63—H63A | 0.9700 |
C11—H11A | 0.9800 | C63—H63B | 0.9700 |
C12—H12A | 0.9700 | C64—H64A | 0.9700 |
C12—H12B | 0.9700 | C64—H64B | 0.9700 |
C13—H13A | 0.9700 | C65—H65A | 0.9700 |
C13—H13B | 0.9700 | C65—H65B | 0.9700 |
C14—H14A | 0.9700 | C66—H66A | 0.9700 |
C14—H14B | 0.9700 | C66—H66B | 0.9700 |
C2—Mo—C3 | 84.2 (2) | H35A—C35—H35B | 107.9 |
C2—Mo—C1 | 85.8 (2) | C35—C36—H36A | 109.5 |
C3—Mo—C1 | 87.7 (2) | C31—C36—H36A | 109.5 |
C2—Mo—C4 | 87.8 (2) | C35—C36—H36B | 109.5 |
C3—Mo—C4 | 86.6 (2) | C31—C36—H36B | 109.5 |
C1—Mo—C4 | 171.8 (3) | H36A—C36—H36B | 108.1 |
C2—Mo—P2 | 84.81 (17) | C46—C41—H41A | 107.9 |
C3—Mo—P2 | 167.64 (16) | C42—C41—H41A | 107.9 |
C1—Mo—P2 | 97.26 (16) | P2—C41—H41A | 107.9 |
C4—Mo—P2 | 87.27 (16) | C43—C42—H42A | 109.5 |
C2—Mo—P1 | 169.87 (16) | C41—C42—H42A | 109.5 |
C3—Mo—P1 | 86.47 (17) | C43—C42—H42B | 109.5 |
C1—Mo—P1 | 89.77 (16) | C41—C42—H42B | 109.5 |
C4—Mo—P1 | 95.73 (16) | H42A—C42—H42B | 108.1 |
P2—Mo—P1 | 104.81 (5) | C44—C43—H43A | 109.3 |
C11—P1—C31 | 102.0 (2) | C42—C43—H43A | 109.3 |
C11—P1—C21 | 98.9 (2) | C44—C43—H43B | 109.3 |
C31—P1—C21 | 106.1 (2) | C42—C43—H43B | 109.3 |
C11—P1—Mo | 114.67 (16) | H43A—C43—H43B | 108.0 |
C31—P1—Mo | 118.71 (15) | C45—C44—H44A | 109.1 |
C21—P1—Mo | 113.96 (17) | C43—C44—H44A | 109.1 |
C61—P2—C41 | 101.8 (2) | C45—C44—H44B | 109.1 |
C61—P2—C51 | 107.4 (2) | C43—C44—H44B | 109.1 |
C41—P2—C51 | 101.4 (2) | H44A—C44—H44B | 107.8 |
C61—P2—Mo | 118.00 (17) | C44—C45—H45A | 109.6 |
C41—P2—Mo | 113.60 (16) | C46—C45—H45A | 109.6 |
C51—P2—Mo | 112.87 (17) | C44—C45—H45B | 109.6 |
O1—C1—Mo | 173.5 (6) | C46—C45—H45B | 109.6 |
O2—C2—Mo | 177.2 (5) | H45A—C45—H45B | 108.1 |
O3—C3—Mo | 176.0 (5) | C41—C46—H46A | 109.1 |
O4—C4—Mo | 174.0 (6) | C45—C46—H46A | 109.1 |
C12—C11—C16 | 109.5 (4) | C41—C46—H46B | 109.1 |
C12—C11—P1 | 113.7 (3) | C45—C46—H46B | 109.1 |
C16—C11—P1 | 113.2 (3) | H46A—C46—H46B | 107.8 |
C11—C12—C13 | 111.3 (4) | C52—C51—H51A | 103.5 |
C14—C13—C12 | 113.0 (4) | C56—C51—H51A | 103.5 |
C13—C14—C15 | 110.8 (5) | P2—C51—H51A | 103.5 |
C16—C15—C14 | 112.1 (5) | C51—C52—H52A | 109.2 |
C15—C16—C11 | 112.5 (4) | C53—C52—H52A | 109.2 |
C26—C21—C22 | 111.0 (4) | C51—C52—H52B | 109.2 |
C26—C21—P1 | 117.1 (4) | C53—C52—H52B | 109.2 |
C22—C21—P1 | 116.5 (3) | H52A—C52—H52B | 107.9 |
C23—C22—C21 | 110.8 (5) | C54—C53—H53A | 109.6 |
C24—C23—C22 | 111.0 (5) | C52—C53—H53A | 109.6 |
C25—C24—C23 | 110.5 (5) | C54—C53—H53B | 109.6 |
C24—C25—C26 | 111.4 (5) | C52—C53—H53B | 109.6 |
C21—C26—C25 | 110.6 (4) | H53A—C53—H53B | 108.1 |
C36—C31—C32 | 108.4 (4) | C53—C54—H54A | 109.1 |
C36—C31—P1 | 120.2 (3) | C55—C54—H54A | 109.1 |
C32—C31—P1 | 112.5 (3) | C53—C54—H54B | 109.1 |
C33—C32—C31 | 112.8 (4) | C55—C54—H54B | 109.1 |
C32—C33—C34 | 111.8 (4) | H54A—C54—H54B | 107.8 |
C33—C34—C35 | 110.3 (4) | C54—C55—H55A | 109.2 |
C36—C35—C34 | 112.0 (4) | C56—C55—H55A | 109.2 |
C35—C36—C31 | 110.9 (4) | C54—C55—H55B | 109.2 |
C46—C41—C42 | 112.1 (4) | C56—C55—H55B | 109.2 |
C46—C41—P2 | 109.6 (3) | H55A—C55—H55B | 107.9 |
C42—C41—P2 | 111.4 (3) | C51—C56—H56A | 109.8 |
C43—C42—C41 | 110.7 (4) | C55—C56—H56A | 109.8 |
C44—C43—C42 | 111.7 (4) | C51—C56—H56B | 109.8 |
C45—C44—C43 | 112.5 (5) | C55—C56—H56B | 109.8 |
C44—C45—C46 | 110.5 (5) | H56A—C56—H56B | 108.2 |
C41—C46—C45 | 112.4 (4) | C62—C61—H61A | 105.1 |
C52—C51—C56 | 110.3 (4) | C66—C61—H61A | 105.1 |
C52—C51—P2 | 117.8 (4) | P2—C61—H61A | 105.1 |
C56—C51—P2 | 116.1 (4) | C61—C62—H62A | 109.3 |
C51—C52—C53 | 112.0 (5) | C63—C62—H62A | 109.3 |
C54—C53—C52 | 110.5 (5) | C61—C62—H62B | 109.3 |
C53—C54—C55 | 112.6 (5) | C63—C62—H62B | 109.3 |
C54—C55—C56 | 112.1 (5) | H62A—C62—H62B | 108.0 |
C51—C56—C55 | 109.5 (4) | C64—C63—H63A | 109.3 |
C62—C61—C66 | 107.7 (4) | C62—C63—H63A | 109.3 |
C62—C61—P2 | 119.6 (4) | C64—C63—H63B | 109.3 |
C66—C61—P2 | 112.9 (3) | C62—C63—H63B | 109.3 |
C61—C62—C63 | 111.4 (5) | H63A—C63—H63B | 108.0 |
C64—C63—C62 | 111.5 (4) | C63—C64—H64A | 109.3 |
C63—C64—C65 | 111.4 (5) | C65—C64—H64A | 109.3 |
C66—C65—C64 | 111.7 (5) | C63—C64—H64B | 109.3 |
C65—C66—C61 | 112.9 (4) | C65—C64—H64B | 109.3 |
C12—C11—H11A | 106.7 | H64A—C64—H64B | 108.0 |
C16—C11—H11A | 106.7 | C66—C65—H65A | 109.3 |
P1—C11—H11A | 106.7 | C64—C65—H65A | 109.3 |
C33—C34—H34A | 109.6 | C66—C65—H65B | 109.3 |
C35—C34—H34A | 109.6 | C64—C65—H65B | 109.3 |
C33—C34—H34B | 109.6 | H65A—C65—H65B | 107.9 |
C35—C34—H34B | 109.6 | C65—C66—H66A | 109.0 |
H34A—C34—H34B | 108.1 | C61—C66—H66A | 109.0 |
C36—C35—H35A | 109.2 | C65—C66—H66B | 109.0 |
C34—C35—H35A | 109.2 | C61—C66—H66B | 109.0 |
C36—C35—H35B | 109.2 | H66A—C66—H66B | 107.8 |
C34—C35—H35B | 109.2 | ||
C2—Mo—P1—C11 | −107.6 (9) | C11—P1—C21—C22 | −52.2 (4) |
C3—Mo—P1—C11 | −83.9 (2) | C31—P1—C21—C22 | 53.2 (4) |
C1—Mo—P1—C11 | −171.6 (2) | Mo—P1—C21—C22 | −174.4 (3) |
C4—Mo—P1—C11 | 2.3 (2) | C26—C21—C22—C23 | −56.2 (6) |
P2—Mo—P1—C11 | 90.95 (17) | P1—C21—C22—C23 | 166.3 (4) |
C2—Mo—P1—C31 | 131.5 (10) | C21—C22—C23—C24 | 57.6 (7) |
C3—Mo—P1—C31 | 155.2 (2) | C22—C23—C24—C25 | −58.2 (7) |
C1—Mo—P1—C31 | 67.5 (2) | C23—C24—C25—C26 | 56.5 (7) |
C4—Mo—P1—C31 | −118.6 (2) | C22—C21—C26—C25 | 54.3 (6) |
P2—Mo—P1—C31 | −29.92 (16) | P1—C21—C26—C25 | −168.5 (4) |
C2—Mo—P1—C21 | 5.4 (10) | C24—C25—C26—C21 | −55.2 (7) |
C3—Mo—P1—C21 | 29.1 (2) | C11—P1—C31—C36 | 25.7 (4) |
C1—Mo—P1—C21 | −58.6 (2) | C21—P1—C31—C36 | −77.4 (4) |
C4—Mo—P1—C21 | 115.3 (2) | Mo—P1—C31—C36 | 152.8 (3) |
P2—Mo—P1—C21 | −156.03 (17) | C11—P1—C31—C32 | 155.3 (3) |
C2—Mo—P2—C61 | 150.0 (2) | C21—P1—C31—C32 | 52.1 (4) |
C3—Mo—P2—C61 | 122.2 (8) | Mo—P1—C31—C32 | −77.6 (3) |
C1—Mo—P2—C61 | −124.9 (2) | C36—C31—C32—C33 | −56.3 (5) |
C4—Mo—P2—C61 | 62.0 (2) | P1—C31—C32—C33 | 168.3 (3) |
P1—Mo—P2—C61 | −33.22 (18) | C31—C32—C33—C34 | 56.0 (5) |
C2—Mo—P2—C41 | −91.0 (2) | C32—C33—C34—C35 | −53.7 (6) |
C3—Mo—P2—C41 | −118.7 (8) | C33—C34—C35—C36 | 55.3 (6) |
C1—Mo—P2—C41 | −5.9 (2) | C34—C35—C36—C31 | −57.8 (5) |
C4—Mo—P2—C41 | −179.0 (2) | C32—C31—C36—C35 | 56.6 (5) |
P1—Mo—P2—C41 | 85.80 (18) | P1—C31—C36—C35 | −172.1 (3) |
C2—Mo—P2—C51 | 23.8 (2) | C61—P2—C41—C46 | 66.6 (4) |
C3—Mo—P2—C51 | −4.0 (8) | C51—P2—C41—C46 | 177.3 (4) |
C1—Mo—P2—C51 | 108.9 (2) | Mo—P2—C41—C46 | −61.3 (4) |
C4—Mo—P2—C51 | −64.2 (2) | C61—P2—C41—C42 | −168.8 (3) |
P1—Mo—P2—C51 | −159.45 (18) | C51—P2—C41—C42 | −58.1 (4) |
C2—Mo—C1—O1 | −38 (4) | Mo—P2—C41—C42 | 63.3 (4) |
C3—Mo—C1—O1 | 47 (5) | C46—C41—C42—C43 | −52.0 (6) |
C4—Mo—C1—O1 | 1 (6) | P2—C41—C42—C43 | −175.2 (3) |
P2—Mo—C1—O1 | −122 (4) | C41—C42—C43—C44 | 52.7 (6) |
P1—Mo—C1—O1 | 133 (5) | C42—C43—C44—C45 | −56.1 (7) |
C3—Mo—C2—O2 | −6 (10) | C43—C44—C45—C46 | 56.1 (6) |
C1—Mo—C2—O2 | 82 (10) | C42—C41—C46—C45 | 53.6 (6) |
C4—Mo—C2—O2 | −93 (10) | P2—C41—C46—C45 | 177.9 (4) |
P2—Mo—C2—O2 | −180 (100) | C44—C45—C46—C41 | −55.2 (6) |
P1—Mo—C2—O2 | 18 (11) | C61—P2—C51—C52 | −82.1 (5) |
C2—Mo—C3—O3 | −45 (8) | C41—P2—C51—C52 | 171.5 (4) |
C1—Mo—C3—O3 | −131 (8) | Mo—P2—C51—C52 | 49.6 (5) |
C4—Mo—C3—O3 | 43 (8) | C61—P2—C51—C56 | 52.0 (4) |
P2—Mo—C3—O3 | −18 (8) | C41—P2—C51—C56 | −54.4 (4) |
P1—Mo—C3—O3 | 139 (8) | Mo—P2—C51—C56 | −176.3 (3) |
C2—Mo—C4—O4 | 42 (4) | C56—C51—C52—C53 | 56.9 (6) |
C3—Mo—C4—O4 | −42 (4) | P2—C51—C52—C53 | −166.6 (4) |
C1—Mo—C4—O4 | 3 (6) | C51—C52—C53—C54 | −55.6 (7) |
P2—Mo—C4—O4 | 127 (4) | C52—C53—C54—C55 | 54.5 (8) |
P1—Mo—C4—O4 | −128 (4) | C53—C54—C55—C56 | −55.5 (8) |
C31—P1—C11—C12 | −165.5 (3) | C52—C51—C56—C55 | −55.6 (6) |
C21—P1—C11—C12 | −56.8 (4) | P2—C51—C56—C55 | 167.1 (4) |
Mo—P1—C11—C12 | 64.8 (4) | C54—C55—C56—C51 | 55.2 (7) |
C31—P1—C11—C16 | 68.7 (4) | C41—P2—C61—C62 | 31.0 (4) |
C21—P1—C11—C16 | 177.4 (4) | C51—P2—C61—C62 | −75.1 (4) |
Mo—P1—C11—C16 | −61.0 (4) | Mo—P2—C61—C62 | 156.1 (3) |
C16—C11—C12—C13 | −53.7 (5) | C41—P2—C61—C66 | 159.3 (3) |
P1—C11—C12—C13 | 178.6 (3) | C51—P2—C61—C66 | 53.2 (4) |
C11—C12—C13—C14 | 54.8 (6) | Mo—P2—C61—C66 | −75.7 (4) |
C12—C13—C14—C15 | −53.9 (7) | C66—C61—C62—C63 | 56.3 (5) |
C13—C14—C15—C16 | 54.0 (7) | P2—C61—C62—C63 | −173.1 (3) |
C14—C15—C16—C11 | −55.8 (6) | C61—C62—C63—C64 | −57.4 (6) |
C12—C11—C16—C15 | 55.0 (6) | C62—C63—C64—C65 | 54.2 (6) |
P1—C11—C16—C15 | −177.0 (3) | C63—C64—C65—C66 | −53.9 (6) |
C11—P1—C21—C26 | 172.9 (4) | C64—C65—C66—C61 | 55.9 (6) |
C31—P1—C21—C26 | −81.7 (4) | C62—C61—C66—C65 | −56.7 (6) |
Mo—P1—C21—C26 | 50.8 (4) | P2—C61—C66—C65 | 169.1 (4) |
[Mo(C18H33P)(CO)5] | F(000) = 1072 |
Mr = 516.40 | Dx = 1.360 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.785 (3) Å | Cell parameters from 42 reflections |
b = 16.760 (7) Å | θ = 12–16° |
c = 12.779 (4) Å | µ = 0.61 mm−1 |
β = 92.15 (2)° | T = 293 K |
V = 2522.3 (14) Å3 | Rod, colorless |
Z = 4 | 0.40 × 0.20 × 0.18 mm |
Siemens P3 diffractometer | 2498 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.089 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
Detector resolution: not applicable pixels mm-1 | h = 0→14 |
ω scans | k = 0→19 |
4655 measured reflections | l = −15→15 |
4435 independent reflections |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.90 | Calculated w = 1/[σ2(Fo2) + (0.0499P)2] where P = (Fo2 + 2Fc2)/3 |
4435 reflections | (Δ/σ)max < 0.001 |
308 parameters | Δρmax = 0.77 e Å−3 |
78 restraints | Δρmin = −0.52 e Å−3 |
[Mo(C18H33P)(CO)5] | V = 2522.3 (14) Å3 |
Mr = 516.40 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.785 (3) Å | µ = 0.61 mm−1 |
b = 16.760 (7) Å | T = 293 K |
c = 12.779 (4) Å | 0.40 × 0.20 × 0.18 mm |
β = 92.15 (2)° |
Siemens P3 diffractometer | 2498 reflections with I > 2σ(I) |
4655 measured reflections | Rint = 0.089 |
4435 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 78 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.77 e Å−3 |
4435 reflections | Δρmin = −0.52 e Å−3 |
308 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. H-atoms were placed at calculated locations and allowed to ride on the attached non-H-atoms; their U's were set at 120% of the U(eq) of the attached non-H-atom. Disorder in the cyclohexyl ring (C11 - C16) was modeled with two contributing chair conformations, refining the occupance factor, and restraining the C—C distances to be equal and ring C U's to be similar. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mo | 0.12595 (4) | 0.80324 (3) | 0.93431 (3) | 0.04578 (15) | |
P | 0.13190 (10) | 0.84953 (7) | 0.74092 (9) | 0.0380 (3) | |
O1 | 0.3066 (4) | 0.9354 (3) | 1.0056 (3) | 0.0901 (14) | |
O2 | −0.0694 (4) | 0.6776 (3) | 0.8803 (4) | 0.1133 (18) | |
O3 | −0.0706 (4) | 0.9186 (3) | 1.0032 (3) | 0.0866 (14) | |
O4 | 0.3236 (3) | 0.6769 (2) | 0.9129 (3) | 0.0861 (14) | |
O5 | 0.1302 (5) | 0.7478 (3) | 1.1679 (3) | 0.1119 (17) | |
C1 | 0.2418 (5) | 0.8890 (3) | 0.9781 (4) | 0.0627 (16) | |
C2 | 0.0032 (5) | 0.7212 (3) | 0.8975 (5) | 0.0730 (18) | |
C3 | 0.0018 (5) | 0.8786 (4) | 0.9732 (4) | 0.0642 (17) | |
C4 | 0.2511 (5) | 0.7228 (3) | 0.9147 (4) | 0.0572 (16) | |
C5 | 0.1272 (5) | 0.7669 (3) | 1.0811 (5) | 0.0700 (17) | |
C11 | 0.1080 (12) | 0.7660 (8) | 0.6442 (10) | 0.041 (4) | 0.638 (13) |
H11A | 0.0329 | 0.7432 | 0.6557 | 0.049* | 0.638 (13) |
C12 | 0.1970 (10) | 0.6981 (5) | 0.6598 (6) | 0.053 (3) | 0.638 (13) |
H12A | 0.2055 | 0.6837 | 0.7332 | 0.063* | 0.638 (13) |
H12B | 0.2703 | 0.7149 | 0.6355 | 0.063* | 0.638 (13) |
C13 | 0.1499 (6) | 0.6254 (3) | 0.5931 (4) | 0.087 (2) | |
H13A | 0.1941 | 0.5777 | 0.6084 | 0.105* | 0.638 (13) |
H13B | 0.0712 | 0.6150 | 0.6080 | 0.105* | 0.638 (13) |
H13A' | 0.2322 | 0.6286 | 0.5971 | 0.105* | 0.362 (13) |
H13B' | 0.1275 | 0.5719 | 0.6123 | 0.105* | 0.362 (13) |
C14 | 0.1613 (14) | 0.6509 (10) | 0.4757 (9) | 0.075 (5) | 0.638 (13) |
H14A | 0.2371 | 0.6704 | 0.4632 | 0.090* | 0.638 (13) |
H14B | 0.1442 | 0.6066 | 0.4287 | 0.090* | 0.638 (13) |
C15 | 0.0737 (12) | 0.7169 (6) | 0.4619 (8) | 0.060 (3) | 0.638 (13) |
H15A | 0.0006 | 0.6983 | 0.4843 | 0.072* | 0.638 (13) |
H15B | 0.0657 | 0.7316 | 0.3885 | 0.072* | 0.638 (13) |
C16 | 0.1116 (5) | 0.7903 (3) | 0.5275 (3) | 0.0593 (15) | |
H16A | 0.0609 | 0.8349 | 0.5131 | 0.071* | 0.638 (13) |
H16B | 0.1880 | 0.8061 | 0.5105 | 0.071* | 0.638 (13) |
H16A' | 0.0295 | 0.7938 | 0.5223 | 0.071* | 0.362 (13) |
H16B' | 0.1422 | 0.8420 | 0.5091 | 0.071* | 0.362 (13) |
C11A | 0.1493 (19) | 0.7700 (15) | 0.6414 (15) | 0.032 (6) | 0.362 (13) |
H11A' | 0.2312 | 0.7604 | 0.6399 | 0.038* | 0.362 (13) |
C12A | 0.097 (2) | 0.6890 (9) | 0.6689 (11) | 0.082 (8) | 0.362 (13) |
H12A' | 0.0146 | 0.6908 | 0.6582 | 0.099* | 0.362 (13) |
H12B' | 0.1144 | 0.6755 | 0.7415 | 0.099* | 0.362 (13) |
C14A | 0.104 (2) | 0.6457 (15) | 0.4812 (17) | 0.072 (9) | 0.362 (13) |
H14A' | 0.1276 | 0.6051 | 0.4323 | 0.087* | 0.362 (13) |
H14B' | 0.0218 | 0.6475 | 0.4794 | 0.087* | 0.362 (13) |
C15A | 0.152 (2) | 0.7275 (9) | 0.4500 (13) | 0.073 (7) | 0.362 (13) |
H15A' | 0.2343 | 0.7256 | 0.4517 | 0.088* | 0.362 (13) |
H15B' | 0.1255 | 0.7411 | 0.3795 | 0.088* | 0.362 (13) |
C21 | 0.0165 (4) | 0.9174 (3) | 0.6952 (4) | 0.0418 (12) | |
H21A | 0.0277 | 0.9272 | 0.6207 | 0.050* | |
C22 | −0.1015 (4) | 0.8805 (3) | 0.7029 (4) | 0.0578 (15) | |
H22A | −0.1050 | 0.8311 | 0.6635 | 0.069* | |
H22B | −0.1151 | 0.8681 | 0.7756 | 0.069* | |
C23 | −0.1931 (5) | 0.9370 (4) | 0.6609 (5) | 0.0768 (18) | |
H23A | −0.2670 | 0.9132 | 0.6704 | 0.092* | |
H23B | −0.1843 | 0.9447 | 0.5864 | 0.092* | |
C24 | −0.1876 (5) | 1.0174 (4) | 0.7156 (5) | 0.096 (2) | |
H24A | −0.2442 | 1.0529 | 0.6840 | 0.115* | |
H24B | −0.2042 | 1.0108 | 0.7889 | 0.115* | |
C25 | −0.0715 (5) | 1.0534 (3) | 0.7068 (5) | 0.0788 (19) | |
H25A | −0.0682 | 1.1034 | 0.7450 | 0.095* | |
H25B | −0.0586 | 1.0649 | 0.6338 | 0.095* | |
C26 | 0.0218 (4) | 0.9984 (3) | 0.7494 (4) | 0.0546 (14) | |
H26A | 0.0138 | 0.9912 | 0.8241 | 0.066* | |
H26B | 0.0952 | 1.0228 | 0.7388 | 0.066* | |
C31 | 0.2607 (4) | 0.9091 (3) | 0.7170 (3) | 0.0392 (12) | |
H31A | 0.2610 | 0.9511 | 0.7704 | 0.047* | |
C32 | 0.3713 (4) | 0.8638 (3) | 0.7377 (4) | 0.0506 (14) | |
H32A | 0.3808 | 0.8245 | 0.6830 | 0.061* | |
H32B | 0.3684 | 0.8359 | 0.8040 | 0.061* | |
C33 | 0.4732 (4) | 0.9214 (3) | 0.7409 (4) | 0.0588 (15) | |
H33A | 0.4676 | 0.9574 | 0.7999 | 0.071* | |
H33B | 0.5431 | 0.8912 | 0.7503 | 0.071* | |
C34 | 0.4764 (4) | 0.9698 (3) | 0.6396 (4) | 0.0629 (16) | |
H34A | 0.5382 | 1.0080 | 0.6451 | 0.075* | |
H34B | 0.4909 | 0.9343 | 0.5817 | 0.075* | |
C35 | 0.3670 (4) | 1.0132 (3) | 0.6176 (4) | 0.0594 (15) | |
H35A | 0.3707 | 1.0417 | 0.5518 | 0.071* | |
H35B | 0.3553 | 1.0520 | 0.6726 | 0.071* | |
C36 | 0.2672 (4) | 0.9541 (3) | 0.6120 (4) | 0.0562 (15) | |
H36A | 0.2776 | 0.9163 | 0.5557 | 0.067* | |
H36B | 0.1968 | 0.9827 | 0.5975 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo | 0.0568 (3) | 0.0436 (3) | 0.0369 (2) | −0.0042 (3) | 0.00034 (18) | 0.0040 (3) |
P | 0.0389 (8) | 0.0402 (7) | 0.0345 (7) | 0.0026 (6) | −0.0035 (6) | 0.0023 (6) |
O1 | 0.101 (4) | 0.078 (3) | 0.090 (3) | −0.029 (3) | −0.016 (3) | −0.009 (3) |
O2 | 0.081 (3) | 0.074 (4) | 0.184 (5) | −0.029 (3) | −0.008 (3) | −0.007 (3) |
O3 | 0.079 (3) | 0.093 (3) | 0.088 (3) | 0.012 (3) | 0.017 (3) | −0.017 (3) |
O4 | 0.074 (3) | 0.072 (3) | 0.111 (4) | 0.012 (2) | −0.008 (3) | 0.004 (3) |
O5 | 0.195 (5) | 0.091 (3) | 0.049 (3) | 0.002 (3) | 0.007 (3) | 0.024 (3) |
C1 | 0.083 (5) | 0.056 (4) | 0.049 (3) | 0.001 (4) | −0.007 (3) | 0.012 (3) |
C2 | 0.074 (5) | 0.048 (4) | 0.098 (5) | −0.001 (3) | 0.010 (4) | 0.009 (3) |
C3 | 0.072 (4) | 0.075 (5) | 0.047 (3) | −0.018 (4) | 0.016 (3) | −0.004 (3) |
C4 | 0.059 (4) | 0.063 (4) | 0.049 (3) | −0.010 (3) | −0.006 (3) | −0.004 (3) |
C5 | 0.097 (5) | 0.055 (4) | 0.058 (4) | 0.006 (3) | 0.009 (3) | 0.007 (3) |
C11 | 0.043 (8) | 0.034 (6) | 0.044 (6) | 0.006 (6) | −0.011 (5) | −0.002 (4) |
C12 | 0.069 (7) | 0.046 (5) | 0.042 (4) | 0.012 (6) | −0.018 (4) | −0.003 (5) |
C13 | 0.164 (7) | 0.044 (4) | 0.050 (4) | 0.011 (4) | −0.023 (4) | −0.008 (3) |
C14 | 0.085 (12) | 0.086 (11) | 0.052 (7) | 0.008 (9) | −0.027 (7) | −0.029 (7) |
C15 | 0.081 (7) | 0.056 (7) | 0.041 (5) | 0.006 (5) | −0.019 (5) | −0.010 (4) |
C16 | 0.089 (4) | 0.052 (3) | 0.035 (3) | 0.009 (3) | −0.020 (3) | −0.001 (3) |
C11A | 0.016 (11) | 0.052 (13) | 0.027 (9) | −0.003 (9) | −0.001 (7) | 0.012 (7) |
C12A | 0.12 (2) | 0.081 (15) | 0.044 (9) | −0.048 (14) | −0.011 (10) | 0.018 (10) |
C14A | 0.069 (18) | 0.068 (17) | 0.077 (15) | −0.021 (16) | −0.028 (13) | −0.010 (11) |
C15A | 0.083 (17) | 0.094 (17) | 0.044 (10) | −0.009 (13) | 0.016 (11) | 0.040 (10) |
C21 | 0.040 (3) | 0.041 (3) | 0.044 (3) | 0.011 (3) | −0.004 (2) | 0.001 (2) |
C22 | 0.034 (3) | 0.066 (4) | 0.073 (4) | 0.006 (3) | −0.007 (3) | −0.003 (3) |
C23 | 0.044 (4) | 0.081 (5) | 0.104 (5) | 0.009 (3) | −0.008 (3) | 0.003 (4) |
C24 | 0.063 (5) | 0.112 (6) | 0.111 (6) | 0.036 (5) | −0.001 (4) | 0.006 (5) |
C25 | 0.082 (5) | 0.051 (4) | 0.103 (5) | 0.026 (4) | −0.004 (4) | −0.001 (3) |
C26 | 0.056 (4) | 0.051 (3) | 0.056 (3) | 0.006 (3) | −0.006 (3) | 0.003 (3) |
C31 | 0.037 (3) | 0.044 (3) | 0.036 (3) | 0.001 (2) | −0.001 (2) | 0.006 (2) |
C32 | 0.039 (3) | 0.057 (3) | 0.056 (3) | 0.006 (3) | 0.006 (2) | 0.021 (3) |
C33 | 0.038 (3) | 0.069 (4) | 0.070 (4) | 0.008 (3) | 0.004 (3) | 0.015 (3) |
C34 | 0.047 (4) | 0.076 (4) | 0.066 (4) | −0.004 (3) | 0.008 (3) | 0.019 (3) |
C35 | 0.047 (3) | 0.064 (4) | 0.067 (4) | −0.006 (3) | −0.003 (3) | 0.026 (3) |
C36 | 0.053 (4) | 0.069 (4) | 0.047 (3) | −0.001 (3) | −0.002 (3) | 0.016 (3) |
Mo—C5 | 1.972 (6) | C12—H12A | 0.97 |
Mo—C3 | 2.009 (7) | C12—H12B | 0.97 |
Mo—C4 | 2.020 (6) | C13—H13A | 0.97 |
Mo—C2 | 2.038 (7) | C13—H13B | 0.97 |
Mo—C1 | 2.046 (7) | C14—H14A | 0.97 |
Mo—P | 2.5938 (14) | C14—H14B | 0.97 |
P—C21 | 1.851 (4) | C15—H15A | 0.97 |
P—C31 | 1.851 (4) | C15—H15B | 0.97 |
P—C11A | 1.86 (3) | C16—H16A | 0.97 |
P—C11 | 1.882 (16) | C16—H16B | 0.97 |
O1—C1 | 1.136 (6) | C11A—H11A' | 0.98 |
O2—C2 | 1.140 (6) | C12A—H12A' | 0.97 |
O3—C3 | 1.163 (6) | C12A—H12B' | 0.97 |
O4—C4 | 1.151 (6) | C14A—H14A' | 0.97 |
O5—C5 | 1.154 (6) | C14A—H14B' | 0.97 |
C11—C16 | 1.548 (12) | C15A—H15A' | 0.97 |
C11—C12 | 1.555 (13) | C15A—H15B' | 0.97 |
C12—C13 | 1.576 (9) | C21—H21A | 0.98 |
C13—C14A | 1.548 (17) | C22—H22A | 0.97 |
C13—C14 | 1.570 (12) | C22—H22B | 0.97 |
C13—C12A | 1.587 (16) | C23—H23A | 0.97 |
C14—C15 | 1.520 (13) | C23—H23B | 0.97 |
C15—C16 | 1.546 (9) | C24—H24A | 0.97 |
C16—C15A | 1.534 (15) | C24—H24B | 0.97 |
C16—C11A | 1.544 (16) | C25—H25A | 0.97 |
C11A—C12A | 1.539 (17) | C25—H25B | 0.97 |
C14A—C15A | 1.539 (17) | C26—H26A | 0.97 |
C21—C26 | 1.525 (6) | C26—H26B | 0.97 |
C21—C22 | 1.528 (6) | C31—H31A | 0.98 |
C22—C23 | 1.518 (7) | C32—H32A | 0.97 |
C23—C24 | 1.520 (8) | C32—H32B | 0.97 |
C24—C25 | 1.503 (8) | C33—H33A | 0.97 |
C25—C26 | 1.520 (7) | C33—H33B | 0.97 |
C31—C32 | 1.524 (6) | C34—H34A | 0.97 |
C31—C36 | 1.543 (6) | C34—H34B | 0.97 |
C32—C33 | 1.540 (6) | C35—H35A | 0.97 |
C33—C34 | 1.529 (6) | C35—H35B | 0.97 |
C34—C35 | 1.498 (6) | C36—H36A | 0.97 |
C35—C36 | 1.538 (6) | C36—H36B | 0.97 |
C11—H11A | 0.98 | ||
C5—Mo—C3 | 86.5 (2) | C13—C12A—H12B' | 110.5 |
C5—Mo—C4 | 86.1 (2) | H12A'—C12A—H12B' | 108.7 |
C3—Mo—C4 | 172.6 (2) | C15A—C14A—H14A' | 110.0 |
C5—Mo—C2 | 89.5 (2) | C13—C14A—H14A' | 110.0 |
C3—Mo—C2 | 87.9 (2) | C15A—C14A—H14B' | 110.0 |
C4—Mo—C2 | 92.1 (2) | C13—C14A—H14B' | 110.0 |
C5—Mo—C1 | 88.6 (2) | H14A'—C14A—H14B' | 108.4 |
C3—Mo—C1 | 88.6 (2) | C16—C15A—H15A' | 110.0 |
C4—Mo—C1 | 91.1 (2) | C14A—C15A—H15A' | 110.0 |
C2—Mo—C1 | 176.2 (2) | C16—C15A—H15B' | 110.0 |
C5—Mo—P | 177.94 (18) | C14A—C15A—H15B' | 110.0 |
C3—Mo—P | 95.38 (16) | H15A'—C15A—H15B' | 108.3 |
C4—Mo—P | 92.04 (15) | C26—C21—H21A | 106.7 |
C2—Mo—P | 91.50 (18) | C22—C21—H21A | 106.7 |
C1—Mo—P | 90.52 (15) | P—C21—H21A | 106.7 |
C21—P—C31 | 102.3 (2) | C14A—C13—C12 | 115.7 (11) |
C21—P—C11A | 108.8 (6) | C14—C13—C12 | 105.4 (8) |
C31—P—C11A | 99.3 (6) | C14A—C13—C12A | 106.5 (15) |
C21—P—C11 | 99.2 (4) | C14—C13—C12A | 116.8 (9) |
C31—P—C11 | 113.3 (5) | C12—C13—C12A | 44.7 (7) |
C11A—P—C11 | 15.2 (8) | C15—C14—C13 | 103.1 (12) |
C21—P—Mo | 116.05 (16) | C14—C15—C16 | 109.6 (10) |
C31—P—Mo | 111.74 (14) | C15A—C16—C11A | 111.9 (14) |
C11A—P—Mo | 116.4 (4) | C15A—C16—C15 | 36.2 (7) |
C11—P—Mo | 113.2 (3) | C11A—C16—C15 | 113.8 (11) |
O1—C1—Mo | 177.7 (5) | C15A—C16—C11 | 117.5 (9) |
O2—C2—Mo | 176.2 (5) | C11A—C16—C11 | 18.4 (10) |
O3—C3—Mo | 174.4 (5) | C15—C16—C11 | 107.2 (8) |
O4—C4—Mo | 174.0 (5) | C12A—C11A—C16 | 107.8 (16) |
O5—C5—Mo | 177.8 (5) | C12A—C11A—P | 114.9 (12) |
C16—C11—C12 | 105.9 (10) | C16—C11A—P | 116.9 (14) |
C16—C11—P | 115.3 (8) | C11A—C12A—C13 | 106.3 (15) |
C12—C11—P | 112.1 (8) | C15A—C14A—C13 | 108.4 (17) |
C11—C12—C13 | 105.9 (9) | C16—C15A—C14A | 108.6 (17) |
C14A—C13—C14 | 25.4 (10) | C26—C21—C22 | 110.6 (4) |
C16—C11—H11A | 107.8 | C26—C21—P | 112.7 (3) |
C12—C11—H11A | 107.8 | C22—C21—P | 113.0 (3) |
P—C11—H11A | 107.8 | C23—C22—C21 | 111.2 (4) |
C11—C12—H12A | 110.6 | C23—C22—H22A | 109.4 |
C13—C12—H12A | 110.6 | C21—C22—H22A | 109.4 |
C11—C12—H12B | 110.6 | C23—C22—H22B | 109.4 |
C13—C12—H12B | 110.6 | C21—C22—H22B | 109.4 |
H12A—C12—H12B | 108.7 | H22A—C22—H22B | 108.0 |
C14A—C13—H13A | 122.3 | C22—C23—H23A | 109.2 |
C14—C13—H13A | 110.7 | C24—C23—H23A | 109.2 |
C12—C13—H13A | 110.7 | C22—C23—H23B | 109.2 |
C12A—C13—H13A | 130.7 | C24—C23—H23B | 109.2 |
C14A—C13—H13B | 85.3 | H23A—C23—H23B | 107.9 |
C14—C13—H13B | 110.7 | C25—C24—H24A | 109.6 |
C12—C13—H13B | 110.7 | C23—C24—H24A | 109.6 |
C12A—C13—H13B | 66.2 | C25—C24—H24B | 109.6 |
H13A—C13—H13B | 108.8 | C23—C24—H24B | 109.6 |
C14A—C13—H13A' | 110.4 | H24A—C24—H24B | 108.1 |
C14—C13—H13A' | 85.1 | C24—C25—H25A | 109.2 |
C12—C13—H13A' | 66.3 | C26—C25—H25A | 109.2 |
C12A—C13—H13A' | 110.4 | C24—C25—H25B | 109.2 |
H13A—C13—H13A' | 60.5 | C26—C25—H25B | 109.2 |
H13B—C13—H13A' | 163.9 | H25A—C25—H25B | 107.9 |
C14A—C13—H13B' | 110.4 | C25—C26—H26A | 109.4 |
C14—C13—H13B' | 121.8 | C21—C26—H26A | 109.4 |
C12—C13—H13B' | 132.2 | C25—C26—H26B | 109.4 |
C12A—C13—H13B' | 110.4 | C21—C26—H26B | 109.4 |
H13A—C13—H13B' | 48.3 | H26A—C26—H26B | 108.0 |
H13B—C13—H13B' | 60.8 | C32—C31—H31A | 104.8 |
H13A—C13—H13B' | 108.6 | C36—C31—H31A | 104.8 |
C15—C14—H14A | 111.1 | P—C31—H31A | 104.8 |
C13—C14—H14A | 111.1 | C31—C32—H32A | 109.5 |
C15—C14—H14B | 111.1 | C33—C32—H32A | 109.5 |
C13—C14—H14B | 111.1 | C31—C32—H32B | 109.5 |
H14A—C14—H14B | 109.1 | C33—C32—H32B | 109.5 |
C14—C15—H15A | 109.8 | H32A—C32—H32B | 108.1 |
C16—C15—H15A | 109.8 | C34—C33—H33A | 109.5 |
C14—C15—H15B | 109.8 | C32—C33—H33A | 109.5 |
C16—C15—H15B | 109.8 | C34—C33—H33B | 109.5 |
H15A—C15—H15B | 108.2 | C32—C33—H33B | 109.5 |
C15A—C16—H16A | 127.6 | H33A—C33—H33B | 108.1 |
C11A—C16—H16A | 120.1 | C35—C34—H34A | 109.3 |
C15—C16—H16A | 110.3 | C33—C34—H34A | 109.3 |
C11—C16—H16A | 110.3 | C35—C34—H34B | 109.3 |
C15A—C16—H16B | 74.3 | C33—C34—H34B | 109.3 |
C11A—C16—H16B | 92.0 | H34A—C34—H34B | 108.0 |
C15—C16—H16B | 110.3 | C34—C35—H35A | 109.6 |
C11—C16—H16B | 110.3 | C36—C35—H35A | 109.6 |
H16A—C16—H16B | 108.5 | C34—C35—H35B | 109.6 |
C15A—C16—H16A' | 109.2 | C36—C35—H35B | 109.6 |
C11A—C16—H16A' | 109.2 | H35A—C35—H35B | 108.1 |
C15—C16—H16A' | 75.1 | C35—C36—H36A | 109.7 |
C11—C16—H16A' | 91.1 | C31—C36—H36A | 109.7 |
H16A—C16—H16A' | 48.3 | C35—C36—H36B | 109.7 |
H16B—C16—H16A' | 154.2 | C31—C36—H36B | 109.7 |
C15A—C16—H16B' | 109.2 | H36A—C36—H36B | 108.2 |
C11A—C16—H16B' | 109.2 | C22—C23—C24 | 111.9 (5) |
C15—C16—H16B' | 132.9 | C25—C24—C23 | 110.1 (5) |
C11—C16—H16B' | 119.6 | C24—C25—C26 | 112.3 (5) |
H16A—C16—H16B' | 59.9 | C25—C26—C21 | 111.1 (4) |
H16B—C16—H16B' | 49.3 | C32—C31—C36 | 108.9 (4) |
H16A—C16—H16B' | 107.9 | C32—C31—P | 113.9 (3) |
C12A—C11A—H11A' | 105.4 | C36—C31—P | 118.4 (3) |
C16—C11A—H11A' | 105.4 | C31—C32—C33 | 110.7 (4) |
P—C11A—H11A' | 105.4 | C34—C33—C32 | 110.8 (4) |
C11A—C12A—H12A' | 110.5 | C35—C34—C33 | 111.6 (4) |
C13—C12A—H12A' | 110.5 | C34—C35—C36 | 110.3 (4) |
C11A—C12A—H12B' | 110.5 | C35—C36—C31 | 109.7 (4) |
C5—Mo—P—C21 | −162 (5) | C12—C11—C16—C15A | 26 (2) |
C3—Mo—P—C21 | −9.4 (2) | P—C11—C16—C15A | 150.2 (12) |
C4—Mo—P—C21 | 170.8 (2) | C12—C11—C16—C11A | −51 (4) |
C2—Mo—P—C21 | 78.7 (2) | P—C11—C16—C11A | 74 (5) |
C1—Mo—P—C21 | −98.1 (2) | C12—C11—C16—C15 | 63.3 (13) |
C5—Mo—P—C31 | −45 (5) | P—C11—C16—C15 | −172.2 (7) |
C3—Mo—P—C31 | 107.4 (2) | C15A—C16—C11A—C12A | −61 (2) |
C4—Mo—P—C31 | −72.4 (2) | C15—C16—C11A—C12A | −21 (2) |
C2—Mo—P—C31 | −164.6 (2) | C11—C16—C11A—C12A | 51 (4) |
C1—Mo—P—C31 | 18.7 (2) | C15A—C16—C11A—P | 168.4 (12) |
C5—Mo—P—C11A | 68 (5) | C15—C16—C11A—P | −152.3 (10) |
C3—Mo—P—C11A | −139.5 (8) | C11—C16—C11A—P | −80 (5) |
C4—Mo—P—C11A | 40.7 (8) | C21—P—C11A—C12A | −102.1 (17) |
C2—Mo—P—C11A | −51.4 (8) | C31—P—C11A—C12A | 151.4 (17) |
C1—Mo—P—C11A | 131.8 (8) | C11—P—C11A—C12A | −50 (2) |
C5—Mo—P—C11 | 84 (5) | Mo—P—C11A—C12A | 31 (2) |
C3—Mo—P—C11 | −123.2 (5) | C21—P—C11A—C16 | 25.6 (14) |
C4—Mo—P—C11 | 57.0 (5) | C31—P—C11A—C16 | −80.9 (13) |
C2—Mo—P—C11 | −35.1 (5) | C11—P—C11A—C16 | 78 (3) |
C1—Mo—P—C11 | 148.2 (5) | Mo—P—C11A—C16 | 159.1 (9) |
C5—Mo—C1—O1 | 9 (14) | C16—C11A—C12A—C13 | 64 (2) |
C3—Mo—C1—O1 | 96 (14) | P—C11A—C12A—C13 | −164.2 (10) |
C4—Mo—C1—O1 | −77 (14) | C14A—C13—C12A—C11A | −67 (2) |
C2—Mo—C1—O1 | 70 (15) | C14—C13—C12A—C11A | −42 (2) |
P—Mo—C1—O1 | −169 (14) | C12—C13—C12A—C11A | 42.7 (12) |
C5—Mo—C2—O2 | 66 (9) | C14—C13—C14A—C15A | −52 (3) |
C3—Mo—C2—O2 | −21 (9) | C12—C13—C14A—C15A | 19 (3) |
C4—Mo—C2—O2 | 152 (9) | C12A—C13—C14A—C15A | 66 (3) |
C1—Mo—C2—O2 | 6 (11) | C11A—C16—C15A—C14A | 58 (3) |
P—Mo—C2—O2 | −116 (9) | C15—C16—C15A—C14A | −42.7 (13) |
C5—Mo—C3—O3 | −13 (5) | C11—C16—C15A—C14A | 39 (3) |
C4—Mo—C3—O3 | −14 (7) | C13—C14A—C15A—C16 | −61 (3) |
C2—Mo—C3—O3 | 77 (5) | C31—P—C21—C26 | −55.7 (4) |
C1—Mo—C3—O3 | −102 (5) | C11A—P—C21—C26 | −160.1 (6) |
P—Mo—C3—O3 | 168 (5) | C11—P—C21—C26 | −172.2 (5) |
C5—Mo—C4—O4 | −18 (4) | Mo—P—C21—C26 | 66.2 (4) |
C3—Mo—C4—O4 | −17 (6) | C31—P—C21—C22 | 177.9 (3) |
C2—Mo—C4—O4 | −107 (5) | C11A—P—C21—C22 | 73.5 (7) |
C1—Mo—C4—O4 | 71 (5) | C11—P—C21—C22 | 61.4 (6) |
P—Mo—C4—O4 | 161 (4) | Mo—P—C21—C22 | −60.1 (4) |
C3—Mo—C5—O5 | −82 (15) | C26—C21—C22—C23 | 54.7 (6) |
C4—Mo—C5—O5 | 98 (15) | P—C21—C22—C23 | −177.9 (4) |
C2—Mo—C5—O5 | −170 (15) | C21—C22—C23—C24 | −55.8 (7) |
C1—Mo—C5—O5 | 7 (15) | C22—C23—C24—C25 | 55.9 (7) |
P—Mo—C5—O5 | 70 (17) | C23—C24—C25—C26 | −56.0 (7) |
C21—P—C11—C16 | 56.9 (9) | C24—C25—C26—C21 | 56.1 (6) |
C31—P—C11—C16 | −50.9 (9) | C22—C21—C26—C25 | −54.5 (6) |
C11A—P—C11—C16 | −74 (3) | P—C21—C26—C25 | 177.8 (4) |
Mo—P—C11—C16 | −179.5 (6) | C21—P—C31—C32 | −174.1 (3) |
C21—P—C11—C12 | 178.1 (10) | C11A—P—C31—C32 | −62.3 (6) |
C31—P—C11—C12 | 70.3 (10) | C11—P—C31—C32 | −68.3 (5) |
C11A—P—C11—C12 | 47 (2) | Mo—P—C31—C32 | 61.1 (3) |
Mo—P—C11—C12 | −58.3 (12) | C21—P—C31—C36 | −44.2 (4) |
C16—C11—C12—C13 | −66.4 (12) | C11A—P—C31—C36 | 67.6 (6) |
P—C11—C12—C13 | 167.1 (6) | C11—P—C31—C36 | 61.6 (5) |
C11—C12—C13—C14A | 45.4 (18) | Mo—P—C31—C36 | −169.0 (3) |
C11—C12—C13—C14 | 70.3 (13) | C36—C31—C32—C33 | 58.5 (5) |
C11—C12—C13—C12A | −42.4 (10) | P—C31—C32—C33 | −167.1 (3) |
C14A—C13—C14—C15 | 49 (3) | C31—C32—C33—C34 | −56.0 (5) |
C12—C13—C14—C15 | −69.0 (15) | C32—C33—C34—C35 | 55.3 (6) |
C12A—C13—C14—C15 | −22 (2) | C33—C34—C35—C36 | −57.1 (6) |
C13—C14—C15—C16 | 67.9 (17) | C34—C35—C36—C31 | 59.6 (6) |
C14—C15—C16—C15A | 46.8 (13) | C32—C31—C36—C35 | −60.0 (5) |
C14—C15—C16—C11A | −48.1 (19) | P—C31—C36—C35 | 167.9 (3) |
C14—C15—C16—C11 | −66.4 (17) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Mo(C18H33P)2(CO)4] | [Mo(C18H33P)(CO)5] |
Mr | 768.81 | 516.40 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.856 (3), 25.323 (8), 14.795 (7) | 11.785 (3), 16.760 (7), 12.779 (4) |
α, β, γ (°) | 90, 94.68 (3), 90 | 90, 92.15 (2), 90 |
V (Å3) | 4054 (3) | 2522.3 (14) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.44 | 0.61 |
Crystal size (mm) | 0.40 × 0.20 × 0.05 | 0.40 × 0.20 × 0.18 |
Data collection | ||
Diffractometer | Siemens P3 diffractometer | Siemens P3 diffractometer |
Absorption correction | ψ-scans semi-empirical (using intensity measurements) (XEMP; Siemens, 1989) | – |
Tmin, Tmax | 0.844, 0.978 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12628, 9302, 3635 | 4655, 4435, 2498 |
Rint | 0.092 | 0.089 |
(sin θ/λ)max (Å−1) | 0.650 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.080, 0.93 | 0.045, 0.091, 0.90 |
No. of reflections | 9302 | 4435 |
No. of parameters | 424 | 308 |
No. of restraints | 0 | 78 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.70 | 0.77, −0.52 |
Computer programs: P3/PC Diffractometer Program (Siemens, 1989), P3/PC Diffractometer Program, XDISK (Siemens, 1989), SHELXS93 (Sheldrick, 1993), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Mo—C2 | 1.921 (6) | Mo—P1 | 2.6569 (17) |
Mo—C3 | 1.927 (6) | O1—C1 | 1.123 (6) |
Mo—C1 | 2.039 (5) | O2—C2 | 1.211 (6) |
Mo—C4 | 2.042 (6) | O3—C3 | 1.159 (6) |
Mo—P2 | 2.6529 (16) | O4—C4 | 1.143 (6) |
C2—Mo—C3 | 84.2 (2) | C1—Mo—P2 | 97.26 (16) |
C2—Mo—C1 | 85.8 (2) | C4—Mo—P2 | 87.27 (16) |
C3—Mo—C1 | 87.7 (2) | C2—Mo—P1 | 169.87 (16) |
C2—Mo—C4 | 87.8 (2) | C3—Mo—P1 | 86.47 (17) |
C3—Mo—C4 | 86.6 (2) | C1—Mo—P1 | 89.77 (16) |
C1—Mo—C4 | 171.8 (3) | C4—Mo—P1 | 95.73 (16) |
C2—Mo—P2 | 84.81 (17) | P2—Mo—P1 | 104.81 (5) |
C3—Mo—P2 | 167.64 (16) |
Mo—C5 | 1.972 (6) | Mo—P | 2.5938 (14) |
Mo—C3 | 2.009 (7) | O1—C1 | 1.136 (6) |
Mo—C4 | 2.020 (6) | O2—C2 | 1.140 (6) |
Mo—C2 | 2.038 (7) | O3—C3 | 1.163 (6) |
Mo—C1 | 2.046 (7) | O4—C4 | 1.151 (6) |
C5—Mo—C3 | 86.5 (2) | C4—Mo—C1 | 91.1 (2) |
C5—Mo—C4 | 86.1 (2) | C2—Mo—C1 | 176.2 (2) |
C3—Mo—C4 | 172.6 (2) | C5—Mo—P | 177.94 (18) |
C5—Mo—C2 | 89.5 (2) | C3—Mo—P | 95.38 (16) |
C3—Mo—C2 | 87.9 (2) | C4—Mo—P | 92.04 (15) |
C4—Mo—C2 | 92.1 (2) | C2—Mo—P | 91.50 (18) |
C5—Mo—C1 | 88.6 (2) | C1—Mo—P | 90.52 (15) |
C3—Mo—C1 | 88.6 (2) |
Tricyclohexylphoshine dissociates from cis-{η1-[P(cy)3]2}tetracarbonylmolybdenum(0) (cy is cyclohexyl) to produce a mixture of {η2-[P(cy)3]2}tetracarbonylmolybdenum(0) and [η1-P(cy)3]pentacarbonylmolybdenum(0) (Cortes-Figueroa et al., 1997). Ligand dissociation from cis-(η1-L)(η1-L')Mo(CO)4 produces (η2-L')Mo(CO)4, for L = P(cy)3, triphenylphosphine or piperidine and L' = P(cy)3 or triphenylphosphine, where L and L' have cone angles greater than 45° (Tolman, 1977). The lability of the Mo—P(cy)3 bond in such complexes may arise in part from the ligand cone angle of 170° and may account for the difficulty in preparation of the analogous complex cis-{[η1-P(cy)3]2}W(CO)4 by Boyles et al. (1985). Rates of ligand dissociation reactions from cis-(η1-L)(η1-L')Mo(CO)4 also point to the type of metal ion and the size of the ligand as important kinetic controlling features (Laboy et al., 1995; Cortes-Figueroa et al., 1997). As part of a systematic study testing the relationships between structure and reactivity in these complexes, the synthesis and structures of the title compounds, (I) and (II), are reported. The structure of (I) is a redetermination of that reported by Watson et al. (1994), which was based on a very limited data set. \sch
The structures of (I) and (II) are shown in Figs. 1 and 2, respectively. In (I), the Mo has a considerably distorted octahedral coordination geometry, as indicated by the P1—Mo—P2 bond angle of 104.8 (1)° (ideal value 90°) and the molecular distortion from C2v symmetry. This is accompanied by a contraction of the C2—Mo—C3 angle opposite, to 84.2 (2)°, and of the adjacent P1—Mo—C3 and P2—Mo—C2 angles, to 86.5 (2) and 84.8 (2)°, respectively. The sterically crowded environment at Mo is further indicated by the distortions of the equatorial trans bond angles for P1—Mo—C2 [169.9 (2)°], P2—Mo—C3 [167.6 (2)°] and C4—Mo—C1 [171.8 (3)°] from the 180° ideal. The Mo—Caxial bond lengths, averaging 2.040 (8) Å, are trans to each other and are significantly (about 10 e.s.d.'s) longer than the Mo—Cequatorial distances, which average 1.924 (8) Å and are both trans to P. Both Mo—P bond distances are similar and average 2.655 (2) Å, which is significantly longer than the average Mo—P distance in phosphine-pentacarbonyl-molybdenum complexes such as (II) [2.594 (1) Å], [η1-PPh3]Mo(CO)5 [2.560 (1) Å] and [η1-P(CH2CH2CN)3]Mo(CO)5 [2.506 (1) Å; Cotton et al., 1981], and trans-{bis[η1-P(cy)3]}Mo(CO)4 [2.544 (1) Å; Alyea et al., 1996]. The trans influence extends to the carbonyl groups in (I), such that those opposite the shorter Mo—P distances, C2—O2 and C3—O3, average 1.185 (8) Å, while those cis to P, C1—O1 and C4—O4, average 1.133 (8) Å. This observation is consistent with the larger π-acceptor ability of carbonyls (Cotton & Wilkinson, 1988; Cortes-Figueroa et al., 1998).
In the pentacarbonyl complex, (II), the Mo geometry is only slightly distorted from the octahedral ideal and is nearly C4v. The trans influence is present in (II) but greatly diminished compared with (I). The Mo—C5 distance, trans to P and the shorter Mo—P distance mentioned above, is shorter [1.97 (1) Å] than the average of the remaining Mo—C distances [2.03 (1) Å]. At the carbonyl groups, however, the influence is very weak, with the trans C5—O5 distance of 1.154 (6) Å being larger but not statistically distinguishable from the other four [average 1.149 (12) Å]. Disorder in one cyclohexyl ring, between alternate chair conformers, was modelled with the major conformer having an occupancy of 0.64 (1).