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In the present redetermination of the complex cis-tetra­carbonyl­bis­(tri­cyclo­hexyl­phosphine)molybdenum(0), (I), [Mo(C18H33P)2(CO)4] or cis-{η1-[P(C6H11)3]2}Mo(CO)4, the Mo atom has a distorted octahedral geometry with a large P—Mo—P angle of 104.8 (1)°. A strong trans influence on the carbonyls in (I) is seen in a shortening of the Mo—C and a lengthening of the C—O distances opposite the phosphines compared with those that are cis. This influence is greatly diminished in the complex penta­carbonyl­(tri­cyclo­hexyl­phosphine)­molyb­denum(0), (II), [Mo(C18H33P)(CO)5] or {η1-[P(C6H11)3]}­Mo(CO)5, the core of which has a slightly distorted C4v geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013111/fr1291sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013111/fr1291Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013111/fr1291IIsup3.hkl
Contains datablock II

CCDC references: 156148; 156149

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular view of complex (I) showing the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level and H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The molecular view of the major conformer of complex (II) showing the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level and H atoms have been omitted for clarity.
(I) cis-Tetracarbonyl[bis(tricyclohexylphosphine)]molybdenum(0) top
Crystal data top
[Mo(C18H33P)2(CO)4]F(000) = 1640
Mr = 768.81Dx = 1.260 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.856 (3) ÅCell parameters from 50 reflections
b = 25.323 (8) Åθ = 7.5–18.0°
c = 14.795 (7) ŵ = 0.44 mm1
β = 94.68 (3)°T = 293 K
V = 4054 (3) Å3Prism, light yellow
Z = 40.40 × 0.20 × 0.05 mm
Data collection top
Siemens P3
diffractometer
9302 independent reflections
Radiation source: normal-focus sealed tube3635 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: not applicable pixels mm-1θmax = 27.5°, θmin = 2.1°
ω scansh = 014
Absorption correction: ψ-scans
semi-empirical (using intensity measurements) (XEMP; Siemens, 1989)
k = 032
Tmin = 0.844, Tmax = 0.978l = 1919
12628 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 0.93Calculated w = 1/[σ2(Fo2) + (0.048P)2]
where P = (Fo2 + 2Fc2)/3
9302 reflections(Δ/σ)max = 0.001
424 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.70 e Å3
Crystal data top
[Mo(C18H33P)2(CO)4]V = 4054 (3) Å3
Mr = 768.81Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.856 (3) ŵ = 0.44 mm1
b = 25.323 (8) ÅT = 293 K
c = 14.795 (7) Å0.40 × 0.20 × 0.05 mm
β = 94.68 (3)°
Data collection top
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 = 0.978Rint = 0.092
12628 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 0.93Δρmax = 0.59 e Å3
9302 reflectionsΔρmin = 0.70 e Å3
424 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mo0.15100 (4)0.840978 (19)0.81155 (3)0.03624 (12)
P10.02248 (11)0.78943 (5)0.67883 (10)0.0345 (4)
P20.25599 (12)0.92050 (5)0.72991 (10)0.0388 (4)
O10.0887 (4)0.90010 (17)0.8648 (3)0.0918 (16)
O20.2704 (4)0.88954 (19)0.9927 (3)0.0945 (17)
O30.0826 (4)0.75176 (18)0.9403 (3)0.0767 (13)
O40.4016 (3)0.77648 (15)0.8048 (3)0.0697 (14)
C10.0056 (5)0.8798 (2)0.8406 (4)0.0514 (16)
C20.2256 (5)0.8718 (2)0.9214 (4)0.0516 (17)
C30.1040 (5)0.7852 (2)0.8904 (4)0.0468 (15)
C40.3116 (5)0.8001 (2)0.8020 (4)0.0554 (17)
C110.1082 (4)0.73550 (19)0.6268 (3)0.0357 (13)
H11A0.05230.72070.57790.043*
C120.1436 (4)0.69024 (19)0.6917 (4)0.0457 (15)
H12A0.06960.67590.71490.055*
H12B0.19640.70350.74270.055*
C130.2111 (5)0.6465 (2)0.6446 (4)0.0609 (18)
H13A0.23720.61960.68880.073*
H13B0.15430.63020.59890.073*
C140.3225 (5)0.6662 (2)0.6004 (4)0.0698 (19)
H14A0.35710.63760.56690.084*
H14B0.38500.67780.64670.084*
C150.2881 (5)0.7112 (2)0.5369 (4)0.0544 (17)
H15A0.36230.72510.51330.065*
H15B0.23460.69820.48610.065*
C160.2234 (4)0.75491 (19)0.5829 (3)0.0423 (14)
H16A0.19930.78210.53870.051*
H16B0.28040.77060.62920.051*
C210.1101 (4)0.74977 (19)0.7175 (3)0.0416 (14)
H21A0.06930.72410.75950.050*
C220.1800 (4)0.7151 (2)0.6462 (4)0.0523 (16)
H22A0.23010.73720.60410.063*
H22B0.12150.69610.61220.063*
C230.2624 (5)0.6759 (2)0.6904 (4)0.087 (2)
H23A0.30750.65500.64380.105*
H23B0.21170.65220.72910.105*
C240.3525 (5)0.7040 (3)0.7459 (4)0.082 (2)
H24A0.40680.72610.70660.098*
H24B0.40310.67820.77430.098*
C250.2852 (4)0.7373 (2)0.8172 (4)0.0652 (19)
H25A0.23700.71480.85960.078*
H25B0.34460.75630.85050.078*
C260.1978 (4)0.7777 (2)0.7748 (4)0.0566 (17)
H26A0.24670.80290.73780.068*
H26B0.15120.79710.82280.068*
C310.0412 (4)0.82737 (18)0.5769 (3)0.0313 (13)
H31A0.02130.85430.56770.038*
C320.1573 (4)0.85854 (18)0.5947 (3)0.0427 (15)
H32A0.22490.83400.60060.051*
H32B0.14290.87740.65160.051*
C330.1943 (4)0.8974 (2)0.5206 (3)0.0459 (15)
H33A0.13100.92430.51900.055*
H33B0.27060.91470.53380.055*
C340.2123 (4)0.8710 (2)0.4292 (3)0.0487 (16)
H34A0.22810.89760.38240.058*
H34B0.28330.84770.42760.058*
C350.0978 (4)0.8395 (2)0.4107 (3)0.0479 (14)
H35A0.11290.82090.35340.057*
H35B0.02920.86350.40530.057*
C360.0633 (4)0.79987 (18)0.4851 (3)0.0394 (14)
H36A0.01090.78120.47150.047*
H36B0.12930.77420.48770.047*
C410.1546 (4)0.98033 (19)0.7141 (3)0.0406 (14)
H41A0.19981.00710.68220.049*
C420.1246 (4)1.00403 (18)0.8066 (4)0.0475 (15)
H42A0.08940.97690.84290.057*
H42B0.20011.01650.83930.057*
C430.0320 (5)1.0505 (2)0.7923 (4)0.0675 (19)
H43A0.00741.06210.85060.081*
H43B0.07231.07990.76470.081*
C440.0817 (5)1.0348 (2)0.7325 (4)0.071 (2)
H44A0.12661.00800.76320.085*
H44B0.13521.06530.72280.085*
C450.0507 (5)1.0138 (2)0.6424 (4)0.0584 (17)
H45A0.01341.04150.60860.070*
H45B0.12571.00240.60780.070*
C460.0400 (4)0.96656 (18)0.6555 (4)0.0468 (15)
H46A0.00140.93740.68280.056*
H46B0.06300.95500.59660.056*
C510.3940 (4)0.94834 (19)0.7992 (4)0.0453 (15)
H51A0.35860.96240.85320.054*
C520.4917 (4)0.9098 (2)0.8381 (4)0.0618 (18)
H52A0.53770.89640.78950.074*
H52B0.45150.88010.86490.074*
C530.5823 (5)0.9357 (2)0.9108 (4)0.075 (2)
H53A0.53830.94570.96260.090*
H53B0.64610.91060.93110.090*
C540.6400 (5)0.9832 (3)0.8734 (5)0.084 (2)
H54A0.69270.97230.82680.101*
H54B0.69161.00030.92130.101*
C550.5461 (5)1.0220 (2)0.8335 (4)0.080 (2)
H55A0.58851.05120.80690.096*
H55B0.49981.03610.88140.096*
C560.4549 (4)0.9965 (2)0.7597 (4)0.0534 (17)
H56A0.39211.02190.73880.064*
H56B0.49910.98590.70820.064*
C610.3020 (4)0.90969 (19)0.6140 (3)0.0400 (14)
H61A0.23610.88790.58400.048*
C620.3142 (5)0.9565 (2)0.5515 (4)0.0559 (18)
H62A0.38210.97870.57550.067*
H62B0.23910.97740.54930.067*
C630.3380 (4)0.9385 (2)0.4537 (4)0.0588 (18)
H63A0.26710.91870.42790.071*
H63B0.34770.96930.41610.071*
C640.4523 (5)0.9044 (2)0.4537 (4)0.0595 (18)
H64A0.52470.92560.47170.071*
H64B0.46050.89150.39280.071*
C650.4465 (5)0.8581 (2)0.5177 (4)0.0556 (17)
H65A0.38130.83430.49480.067*
H65B0.52400.83900.52020.067*
C660.4222 (4)0.8757 (2)0.6119 (3)0.0494 (16)
H66A0.49220.89620.63730.059*
H66B0.41500.84480.64990.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo0.0288 (2)0.0359 (2)0.0443 (3)0.0014 (3)0.00473 (19)0.0030 (3)
P10.0262 (7)0.0346 (8)0.0436 (9)0.0002 (7)0.0072 (7)0.0019 (7)
P20.0323 (8)0.0343 (9)0.0501 (10)0.0008 (7)0.0044 (7)0.0014 (8)
O10.068 (3)0.072 (3)0.143 (5)0.016 (3)0.052 (3)0.010 (3)
O20.106 (4)0.116 (4)0.060 (3)0.029 (3)0.001 (3)0.016 (3)
O30.081 (3)0.073 (3)0.078 (3)0.009 (3)0.020 (3)0.025 (3)
O40.037 (2)0.062 (3)0.111 (4)0.010 (2)0.008 (2)0.012 (3)
C10.038 (3)0.040 (4)0.077 (5)0.000 (3)0.005 (3)0.009 (3)
C20.039 (3)0.063 (4)0.054 (4)0.009 (3)0.013 (3)0.016 (4)
C30.048 (4)0.055 (4)0.038 (4)0.005 (3)0.008 (3)0.005 (3)
C40.046 (4)0.031 (4)0.089 (5)0.013 (3)0.007 (4)0.005 (3)
C110.027 (3)0.042 (3)0.039 (3)0.002 (2)0.010 (2)0.010 (3)
C120.034 (3)0.040 (3)0.063 (4)0.004 (3)0.007 (3)0.006 (3)
C130.076 (4)0.039 (4)0.066 (4)0.006 (3)0.000 (4)0.007 (3)
C140.062 (4)0.070 (5)0.078 (5)0.025 (4)0.015 (4)0.007 (4)
C150.052 (4)0.053 (4)0.061 (4)0.017 (3)0.025 (3)0.015 (3)
C160.032 (3)0.049 (4)0.046 (4)0.001 (3)0.004 (3)0.014 (3)
C210.038 (3)0.041 (3)0.046 (4)0.005 (3)0.009 (3)0.002 (3)
C220.037 (3)0.060 (4)0.062 (4)0.016 (3)0.018 (3)0.006 (3)
C230.077 (5)0.075 (5)0.117 (6)0.041 (4)0.055 (4)0.039 (5)
C240.054 (4)0.105 (6)0.090 (6)0.049 (4)0.029 (4)0.030 (5)
C250.049 (4)0.089 (5)0.061 (4)0.024 (4)0.025 (3)0.014 (4)
C260.043 (3)0.068 (4)0.062 (4)0.016 (3)0.021 (3)0.007 (4)
C310.024 (3)0.031 (3)0.039 (3)0.004 (2)0.003 (2)0.001 (2)
C320.033 (3)0.041 (4)0.054 (4)0.003 (3)0.003 (3)0.003 (3)
C330.036 (3)0.043 (4)0.058 (4)0.014 (3)0.003 (3)0.002 (3)
C340.037 (3)0.048 (4)0.060 (4)0.004 (3)0.006 (3)0.009 (3)
C350.047 (3)0.048 (3)0.048 (4)0.001 (3)0.003 (3)0.019 (3)
C360.037 (3)0.036 (3)0.047 (4)0.009 (3)0.010 (3)0.012 (3)
C410.031 (3)0.036 (3)0.054 (4)0.006 (3)0.002 (3)0.003 (3)
C420.035 (3)0.036 (3)0.072 (4)0.001 (3)0.007 (3)0.004 (3)
C430.074 (5)0.036 (4)0.093 (6)0.005 (3)0.011 (4)0.012 (4)
C440.053 (4)0.042 (4)0.117 (6)0.009 (3)0.010 (4)0.011 (4)
C450.050 (4)0.047 (4)0.078 (5)0.014 (3)0.004 (3)0.009 (4)
C460.042 (3)0.029 (3)0.068 (4)0.001 (3)0.006 (3)0.004 (3)
C510.046 (3)0.035 (3)0.054 (4)0.006 (3)0.007 (3)0.001 (3)
C520.034 (3)0.058 (4)0.093 (5)0.002 (3)0.002 (3)0.013 (4)
C530.043 (4)0.091 (6)0.087 (5)0.006 (4)0.016 (4)0.009 (5)
C540.057 (4)0.082 (5)0.112 (7)0.034 (4)0.008 (4)0.003 (5)
C550.055 (4)0.055 (5)0.126 (7)0.029 (4)0.021 (4)0.002 (4)
C560.029 (3)0.059 (4)0.072 (5)0.006 (3)0.004 (3)0.000 (4)
C610.033 (3)0.037 (3)0.051 (4)0.006 (3)0.004 (3)0.002 (3)
C620.046 (4)0.055 (4)0.066 (5)0.013 (3)0.004 (3)0.017 (4)
C630.044 (4)0.078 (5)0.054 (4)0.015 (3)0.007 (3)0.007 (4)
C640.048 (4)0.074 (5)0.058 (4)0.017 (3)0.010 (3)0.007 (4)
C650.048 (4)0.063 (5)0.058 (4)0.001 (3)0.019 (3)0.008 (3)
C660.045 (3)0.042 (4)0.063 (4)0.005 (3)0.013 (3)0.011 (3)
Geometric parameters (Å, º) top
Mo—C21.921 (6)C15—H15A0.9700
Mo—C31.927 (6)C15—H15B0.9700
Mo—C12.039 (5)C16—H16A0.9700
Mo—C42.042 (6)C16—H16B0.9700
Mo—P22.6529 (16)C21—H21A0.9800
Mo—P12.6569 (17)C22—H22A0.9700
P1—C111.855 (5)C22—H22B0.9700
P1—C311.872 (4)C23—H23A0.9700
P1—C211.882 (5)C23—H23B0.9700
P2—C611.845 (5)C24—H24A0.9700
P2—C411.876 (5)C24—H24B0.9700
P2—C511.882 (5)C25—H25A0.9700
O1—C11.123 (6)C25—H25B0.9700
O2—C21.211 (6)C26—H26A0.9700
O3—C31.159 (6)C26—H26B0.9700
O4—C41.143 (6)C31—H31A0.9800
C11—C121.524 (6)C32—H32A0.9700
C11—C161.537 (6)C32—H32B0.9700
C12—C131.528 (6)C33—H33A0.9700
C13—C141.505 (6)C33—H33B0.9700
C14—C151.506 (6)C34—H34A0.9700
C15—C161.502 (6)C34—H34B0.9700
C21—C261.502 (6)C35—H35A0.9700
C21—C221.526 (6)C35—H35B0.9700
C22—C231.518 (6)C36—H36A0.9700
C23—C241.505 (7)C36—H36B0.9700
C24—C251.495 (6)C41—H41A0.9800
C25—C261.562 (6)C42—H42A0.9700
C31—C361.528 (6)C42—H42B0.9700
C31—C321.528 (5)C43—H43A0.9700
C32—C331.503 (6)C43—H43B0.9700
C33—C341.507 (6)C44—H44A0.9700
C34—C351.522 (6)C44—H44B0.9700
C35—C361.513 (6)C45—H45A0.9700
C41—C461.499 (5)C45—H45B0.9700
C41—C421.553 (6)C46—H46A0.9700
C42—C431.551 (6)C46—H46B0.9700
C43—C441.512 (6)C51—H51A0.9800
C44—C451.498 (7)C52—H52A0.9700
C45—C461.550 (6)C52—H52B0.9700
C51—C521.520 (6)C53—H53A0.9700
C51—C561.525 (6)C53—H53B0.9700
C52—C531.543 (6)C54—H54A0.9700
C53—C541.482 (7)C54—H54B0.9700
C54—C551.502 (7)C55—H55A0.9700
C55—C561.554 (6)C55—H55B0.9700
C61—C621.516 (6)C56—H56A0.9700
C61—C661.566 (6)C56—H56B0.9700
C62—C631.559 (6)C61—H61A0.9800
C63—C641.511 (6)C62—H62A0.9700
C64—C651.512 (6)C62—H62B0.9700
C65—C661.507 (6)C63—H63A0.9700
C11—H11A0.9800C63—H63B0.9700
C12—H12A0.9700C64—H64A0.9700
C12—H12B0.9700C64—H64B0.9700
C13—H13A0.9700C65—H65A0.9700
C13—H13B0.9700C65—H65B0.9700
C14—H14A0.9700C66—H66A0.9700
C14—H14B0.9700C66—H66B0.9700
C2—Mo—C384.2 (2)H35A—C35—H35B107.9
C2—Mo—C185.8 (2)C35—C36—H36A109.5
C3—Mo—C187.7 (2)C31—C36—H36A109.5
C2—Mo—C487.8 (2)C35—C36—H36B109.5
C3—Mo—C486.6 (2)C31—C36—H36B109.5
C1—Mo—C4171.8 (3)H36A—C36—H36B108.1
C2—Mo—P284.81 (17)C46—C41—H41A107.9
C3—Mo—P2167.64 (16)C42—C41—H41A107.9
C1—Mo—P297.26 (16)P2—C41—H41A107.9
C4—Mo—P287.27 (16)C43—C42—H42A109.5
C2—Mo—P1169.87 (16)C41—C42—H42A109.5
C3—Mo—P186.47 (17)C43—C42—H42B109.5
C1—Mo—P189.77 (16)C41—C42—H42B109.5
C4—Mo—P195.73 (16)H42A—C42—H42B108.1
P2—Mo—P1104.81 (5)C44—C43—H43A109.3
C11—P1—C31102.0 (2)C42—C43—H43A109.3
C11—P1—C2198.9 (2)C44—C43—H43B109.3
C31—P1—C21106.1 (2)C42—C43—H43B109.3
C11—P1—Mo114.67 (16)H43A—C43—H43B108.0
C31—P1—Mo118.71 (15)C45—C44—H44A109.1
C21—P1—Mo113.96 (17)C43—C44—H44A109.1
C61—P2—C41101.8 (2)C45—C44—H44B109.1
C61—P2—C51107.4 (2)C43—C44—H44B109.1
C41—P2—C51101.4 (2)H44A—C44—H44B107.8
C61—P2—Mo118.00 (17)C44—C45—H45A109.6
C41—P2—Mo113.60 (16)C46—C45—H45A109.6
C51—P2—Mo112.87 (17)C44—C45—H45B109.6
O1—C1—Mo173.5 (6)C46—C45—H45B109.6
O2—C2—Mo177.2 (5)H45A—C45—H45B108.1
O3—C3—Mo176.0 (5)C41—C46—H46A109.1
O4—C4—Mo174.0 (6)C45—C46—H46A109.1
C12—C11—C16109.5 (4)C41—C46—H46B109.1
C12—C11—P1113.7 (3)C45—C46—H46B109.1
C16—C11—P1113.2 (3)H46A—C46—H46B107.8
C11—C12—C13111.3 (4)C52—C51—H51A103.5
C14—C13—C12113.0 (4)C56—C51—H51A103.5
C13—C14—C15110.8 (5)P2—C51—H51A103.5
C16—C15—C14112.1 (5)C51—C52—H52A109.2
C15—C16—C11112.5 (4)C53—C52—H52A109.2
C26—C21—C22111.0 (4)C51—C52—H52B109.2
C26—C21—P1117.1 (4)C53—C52—H52B109.2
C22—C21—P1116.5 (3)H52A—C52—H52B107.9
C23—C22—C21110.8 (5)C54—C53—H53A109.6
C24—C23—C22111.0 (5)C52—C53—H53A109.6
C25—C24—C23110.5 (5)C54—C53—H53B109.6
C24—C25—C26111.4 (5)C52—C53—H53B109.6
C21—C26—C25110.6 (4)H53A—C53—H53B108.1
C36—C31—C32108.4 (4)C53—C54—H54A109.1
C36—C31—P1120.2 (3)C55—C54—H54A109.1
C32—C31—P1112.5 (3)C53—C54—H54B109.1
C33—C32—C31112.8 (4)C55—C54—H54B109.1
C32—C33—C34111.8 (4)H54A—C54—H54B107.8
C33—C34—C35110.3 (4)C54—C55—H55A109.2
C36—C35—C34112.0 (4)C56—C55—H55A109.2
C35—C36—C31110.9 (4)C54—C55—H55B109.2
C46—C41—C42112.1 (4)C56—C55—H55B109.2
C46—C41—P2109.6 (3)H55A—C55—H55B107.9
C42—C41—P2111.4 (3)C51—C56—H56A109.8
C43—C42—C41110.7 (4)C55—C56—H56A109.8
C44—C43—C42111.7 (4)C51—C56—H56B109.8
C45—C44—C43112.5 (5)C55—C56—H56B109.8
C44—C45—C46110.5 (5)H56A—C56—H56B108.2
C41—C46—C45112.4 (4)C62—C61—H61A105.1
C52—C51—C56110.3 (4)C66—C61—H61A105.1
C52—C51—P2117.8 (4)P2—C61—H61A105.1
C56—C51—P2116.1 (4)C61—C62—H62A109.3
C51—C52—C53112.0 (5)C63—C62—H62A109.3
C54—C53—C52110.5 (5)C61—C62—H62B109.3
C53—C54—C55112.6 (5)C63—C62—H62B109.3
C54—C55—C56112.1 (5)H62A—C62—H62B108.0
C51—C56—C55109.5 (4)C64—C63—H63A109.3
C62—C61—C66107.7 (4)C62—C63—H63A109.3
C62—C61—P2119.6 (4)C64—C63—H63B109.3
C66—C61—P2112.9 (3)C62—C63—H63B109.3
C61—C62—C63111.4 (5)H63A—C63—H63B108.0
C64—C63—C62111.5 (4)C63—C64—H64A109.3
C63—C64—C65111.4 (5)C65—C64—H64A109.3
C66—C65—C64111.7 (5)C63—C64—H64B109.3
C65—C66—C61112.9 (4)C65—C64—H64B109.3
C12—C11—H11A106.7H64A—C64—H64B108.0
C16—C11—H11A106.7C66—C65—H65A109.3
P1—C11—H11A106.7C64—C65—H65A109.3
C33—C34—H34A109.6C66—C65—H65B109.3
C35—C34—H34A109.6C64—C65—H65B109.3
C33—C34—H34B109.6H65A—C65—H65B107.9
C35—C34—H34B109.6C65—C66—H66A109.0
H34A—C34—H34B108.1C61—C66—H66A109.0
C36—C35—H35A109.2C65—C66—H66B109.0
C34—C35—H35A109.2C61—C66—H66B109.0
C36—C35—H35B109.2H66A—C66—H66B107.8
C34—C35—H35B109.2
C2—Mo—P1—C11107.6 (9)C11—P1—C21—C2252.2 (4)
C3—Mo—P1—C1183.9 (2)C31—P1—C21—C2253.2 (4)
C1—Mo—P1—C11171.6 (2)Mo—P1—C21—C22174.4 (3)
C4—Mo—P1—C112.3 (2)C26—C21—C22—C2356.2 (6)
P2—Mo—P1—C1190.95 (17)P1—C21—C22—C23166.3 (4)
C2—Mo—P1—C31131.5 (10)C21—C22—C23—C2457.6 (7)
C3—Mo—P1—C31155.2 (2)C22—C23—C24—C2558.2 (7)
C1—Mo—P1—C3167.5 (2)C23—C24—C25—C2656.5 (7)
C4—Mo—P1—C31118.6 (2)C22—C21—C26—C2554.3 (6)
P2—Mo—P1—C3129.92 (16)P1—C21—C26—C25168.5 (4)
C2—Mo—P1—C215.4 (10)C24—C25—C26—C2155.2 (7)
C3—Mo—P1—C2129.1 (2)C11—P1—C31—C3625.7 (4)
C1—Mo—P1—C2158.6 (2)C21—P1—C31—C3677.4 (4)
C4—Mo—P1—C21115.3 (2)Mo—P1—C31—C36152.8 (3)
P2—Mo—P1—C21156.03 (17)C11—P1—C31—C32155.3 (3)
C2—Mo—P2—C61150.0 (2)C21—P1—C31—C3252.1 (4)
C3—Mo—P2—C61122.2 (8)Mo—P1—C31—C3277.6 (3)
C1—Mo—P2—C61124.9 (2)C36—C31—C32—C3356.3 (5)
C4—Mo—P2—C6162.0 (2)P1—C31—C32—C33168.3 (3)
P1—Mo—P2—C6133.22 (18)C31—C32—C33—C3456.0 (5)
C2—Mo—P2—C4191.0 (2)C32—C33—C34—C3553.7 (6)
C3—Mo—P2—C41118.7 (8)C33—C34—C35—C3655.3 (6)
C1—Mo—P2—C415.9 (2)C34—C35—C36—C3157.8 (5)
C4—Mo—P2—C41179.0 (2)C32—C31—C36—C3556.6 (5)
P1—Mo—P2—C4185.80 (18)P1—C31—C36—C35172.1 (3)
C2—Mo—P2—C5123.8 (2)C61—P2—C41—C4666.6 (4)
C3—Mo—P2—C514.0 (8)C51—P2—C41—C46177.3 (4)
C1—Mo—P2—C51108.9 (2)Mo—P2—C41—C4661.3 (4)
C4—Mo—P2—C5164.2 (2)C61—P2—C41—C42168.8 (3)
P1—Mo—P2—C51159.45 (18)C51—P2—C41—C4258.1 (4)
C2—Mo—C1—O138 (4)Mo—P2—C41—C4263.3 (4)
C3—Mo—C1—O147 (5)C46—C41—C42—C4352.0 (6)
C4—Mo—C1—O11 (6)P2—C41—C42—C43175.2 (3)
P2—Mo—C1—O1122 (4)C41—C42—C43—C4452.7 (6)
P1—Mo—C1—O1133 (5)C42—C43—C44—C4556.1 (7)
C3—Mo—C2—O26 (10)C43—C44—C45—C4656.1 (6)
C1—Mo—C2—O282 (10)C42—C41—C46—C4553.6 (6)
C4—Mo—C2—O293 (10)P2—C41—C46—C45177.9 (4)
P2—Mo—C2—O2180 (100)C44—C45—C46—C4155.2 (6)
P1—Mo—C2—O218 (11)C61—P2—C51—C5282.1 (5)
C2—Mo—C3—O345 (8)C41—P2—C51—C52171.5 (4)
C1—Mo—C3—O3131 (8)Mo—P2—C51—C5249.6 (5)
C4—Mo—C3—O343 (8)C61—P2—C51—C5652.0 (4)
P2—Mo—C3—O318 (8)C41—P2—C51—C5654.4 (4)
P1—Mo—C3—O3139 (8)Mo—P2—C51—C56176.3 (3)
C2—Mo—C4—O442 (4)C56—C51—C52—C5356.9 (6)
C3—Mo—C4—O442 (4)P2—C51—C52—C53166.6 (4)
C1—Mo—C4—O43 (6)C51—C52—C53—C5455.6 (7)
P2—Mo—C4—O4127 (4)C52—C53—C54—C5554.5 (8)
P1—Mo—C4—O4128 (4)C53—C54—C55—C5655.5 (8)
C31—P1—C11—C12165.5 (3)C52—C51—C56—C5555.6 (6)
C21—P1—C11—C1256.8 (4)P2—C51—C56—C55167.1 (4)
Mo—P1—C11—C1264.8 (4)C54—C55—C56—C5155.2 (7)
C31—P1—C11—C1668.7 (4)C41—P2—C61—C6231.0 (4)
C21—P1—C11—C16177.4 (4)C51—P2—C61—C6275.1 (4)
Mo—P1—C11—C1661.0 (4)Mo—P2—C61—C62156.1 (3)
C16—C11—C12—C1353.7 (5)C41—P2—C61—C66159.3 (3)
P1—C11—C12—C13178.6 (3)C51—P2—C61—C6653.2 (4)
C11—C12—C13—C1454.8 (6)Mo—P2—C61—C6675.7 (4)
C12—C13—C14—C1553.9 (7)C66—C61—C62—C6356.3 (5)
C13—C14—C15—C1654.0 (7)P2—C61—C62—C63173.1 (3)
C14—C15—C16—C1155.8 (6)C61—C62—C63—C6457.4 (6)
C12—C11—C16—C1555.0 (6)C62—C63—C64—C6554.2 (6)
P1—C11—C16—C15177.0 (3)C63—C64—C65—C6653.9 (6)
C11—P1—C21—C26172.9 (4)C64—C65—C66—C6155.9 (6)
C31—P1—C21—C2681.7 (4)C62—C61—C66—C6556.7 (6)
Mo—P1—C21—C2650.8 (4)P2—C61—C66—C65169.1 (4)
(II) pentacarbonyl(tricyclohexylphosphine)molybdenum(0) top
Crystal data top
[Mo(C18H33P)(CO)5]F(000) = 1072
Mr = 516.40Dx = 1.360 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.785 (3) ÅCell parameters from 42 reflections
b = 16.760 (7) Åθ = 12–16°
c = 12.779 (4) ŵ = 0.61 mm1
β = 92.15 (2)°T = 293 K
V = 2522.3 (14) Å3Rod, colorless
Z = 40.40 × 0.20 × 0.18 mm
Data collection top
Siemens P3
diffractometer
2498 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.089
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
Detector resolution: not applicable pixels mm-1h = 014
ω scansk = 019
4655 measured reflectionsl = 1515
4435 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 0.90Calculated w = 1/[σ2(Fo2) + (0.0499P)2]
where P = (Fo2 + 2Fc2)/3
4435 reflections(Δ/σ)max < 0.001
308 parametersΔρmax = 0.77 e Å3
78 restraintsΔρmin = 0.52 e Å3
Crystal data top
[Mo(C18H33P)(CO)5]V = 2522.3 (14) Å3
Mr = 516.40Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.785 (3) ŵ = 0.61 mm1
b = 16.760 (7) ÅT = 293 K
c = 12.779 (4) Å0.40 × 0.20 × 0.18 mm
β = 92.15 (2)°
Data collection top
Siemens P3
diffractometer
2498 reflections with I > 2σ(I)
4655 measured reflectionsRint = 0.089
4435 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04578 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 0.90Δρmax = 0.77 e Å3
4435 reflectionsΔρmin = 0.52 e Å3
308 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Mo0.12595 (4)0.80324 (3)0.93431 (3)0.04578 (15)
P0.13190 (10)0.84953 (7)0.74092 (9)0.0380 (3)
O10.3066 (4)0.9354 (3)1.0056 (3)0.0901 (14)
O20.0694 (4)0.6776 (3)0.8803 (4)0.1133 (18)
O30.0706 (4)0.9186 (3)1.0032 (3)0.0866 (14)
O40.3236 (3)0.6769 (2)0.9129 (3)0.0861 (14)
O50.1302 (5)0.7478 (3)1.1679 (3)0.1119 (17)
C10.2418 (5)0.8890 (3)0.9781 (4)0.0627 (16)
C20.0032 (5)0.7212 (3)0.8975 (5)0.0730 (18)
C30.0018 (5)0.8786 (4)0.9732 (4)0.0642 (17)
C40.2511 (5)0.7228 (3)0.9147 (4)0.0572 (16)
C50.1272 (5)0.7669 (3)1.0811 (5)0.0700 (17)
C110.1080 (12)0.7660 (8)0.6442 (10)0.041 (4)0.638 (13)
H11A0.03290.74320.65570.049*0.638 (13)
C120.1970 (10)0.6981 (5)0.6598 (6)0.053 (3)0.638 (13)
H12A0.20550.68370.73320.063*0.638 (13)
H12B0.27030.71490.63550.063*0.638 (13)
C130.1499 (6)0.6254 (3)0.5931 (4)0.087 (2)
H13A0.19410.57770.60840.105*0.638 (13)
H13B0.07120.61500.60800.105*0.638 (13)
H13A'0.23220.62860.59710.105*0.362 (13)
H13B'0.12750.57190.61230.105*0.362 (13)
C140.1613 (14)0.6509 (10)0.4757 (9)0.075 (5)0.638 (13)
H14A0.23710.67040.46320.090*0.638 (13)
H14B0.14420.60660.42870.090*0.638 (13)
C150.0737 (12)0.7169 (6)0.4619 (8)0.060 (3)0.638 (13)
H15A0.00060.69830.48430.072*0.638 (13)
H15B0.06570.73160.38850.072*0.638 (13)
C160.1116 (5)0.7903 (3)0.5275 (3)0.0593 (15)
H16A0.06090.83490.51310.071*0.638 (13)
H16B0.18800.80610.51050.071*0.638 (13)
H16A'0.02950.79380.52230.071*0.362 (13)
H16B'0.14220.84200.50910.071*0.362 (13)
C11A0.1493 (19)0.7700 (15)0.6414 (15)0.032 (6)0.362 (13)
H11A'0.23120.76040.63990.038*0.362 (13)
C12A0.097 (2)0.6890 (9)0.6689 (11)0.082 (8)0.362 (13)
H12A'0.01460.69080.65820.099*0.362 (13)
H12B'0.11440.67550.74150.099*0.362 (13)
C14A0.104 (2)0.6457 (15)0.4812 (17)0.072 (9)0.362 (13)
H14A'0.12760.60510.43230.087*0.362 (13)
H14B'0.02180.64750.47940.087*0.362 (13)
C15A0.152 (2)0.7275 (9)0.4500 (13)0.073 (7)0.362 (13)
H15A'0.23430.72560.45170.088*0.362 (13)
H15B'0.12550.74110.37950.088*0.362 (13)
C210.0165 (4)0.9174 (3)0.6952 (4)0.0418 (12)
H21A0.02770.92720.62070.050*
C220.1015 (4)0.8805 (3)0.7029 (4)0.0578 (15)
H22A0.10500.83110.66350.069*
H22B0.11510.86810.77560.069*
C230.1931 (5)0.9370 (4)0.6609 (5)0.0768 (18)
H23A0.26700.91320.67040.092*
H23B0.18430.94470.58640.092*
C240.1876 (5)1.0174 (4)0.7156 (5)0.096 (2)
H24A0.24421.05290.68400.115*
H24B0.20421.01080.78890.115*
C250.0715 (5)1.0534 (3)0.7068 (5)0.0788 (19)
H25A0.06821.10340.74500.095*
H25B0.05861.06490.63380.095*
C260.0218 (4)0.9984 (3)0.7494 (4)0.0546 (14)
H26A0.01380.99120.82410.066*
H26B0.09521.02280.73880.066*
C310.2607 (4)0.9091 (3)0.7170 (3)0.0392 (12)
H31A0.26100.95110.77040.047*
C320.3713 (4)0.8638 (3)0.7377 (4)0.0506 (14)
H32A0.38080.82450.68300.061*
H32B0.36840.83590.80400.061*
C330.4732 (4)0.9214 (3)0.7409 (4)0.0588 (15)
H33A0.46760.95740.79990.071*
H33B0.54310.89120.75030.071*
C340.4764 (4)0.9698 (3)0.6396 (4)0.0629 (16)
H34A0.53821.00800.64510.075*
H34B0.49090.93430.58170.075*
C350.3670 (4)1.0132 (3)0.6176 (4)0.0594 (15)
H35A0.37071.04170.55180.071*
H35B0.35531.05200.67260.071*
C360.2672 (4)0.9541 (3)0.6120 (4)0.0562 (15)
H36A0.27760.91630.55570.067*
H36B0.19680.98270.59750.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo0.0568 (3)0.0436 (3)0.0369 (2)0.0042 (3)0.00034 (18)0.0040 (3)
P0.0389 (8)0.0402 (7)0.0345 (7)0.0026 (6)0.0035 (6)0.0023 (6)
O10.101 (4)0.078 (3)0.090 (3)0.029 (3)0.016 (3)0.009 (3)
O20.081 (3)0.074 (4)0.184 (5)0.029 (3)0.008 (3)0.007 (3)
O30.079 (3)0.093 (3)0.088 (3)0.012 (3)0.017 (3)0.017 (3)
O40.074 (3)0.072 (3)0.111 (4)0.012 (2)0.008 (3)0.004 (3)
O50.195 (5)0.091 (3)0.049 (3)0.002 (3)0.007 (3)0.024 (3)
C10.083 (5)0.056 (4)0.049 (3)0.001 (4)0.007 (3)0.012 (3)
C20.074 (5)0.048 (4)0.098 (5)0.001 (3)0.010 (4)0.009 (3)
C30.072 (4)0.075 (5)0.047 (3)0.018 (4)0.016 (3)0.004 (3)
C40.059 (4)0.063 (4)0.049 (3)0.010 (3)0.006 (3)0.004 (3)
C50.097 (5)0.055 (4)0.058 (4)0.006 (3)0.009 (3)0.007 (3)
C110.043 (8)0.034 (6)0.044 (6)0.006 (6)0.011 (5)0.002 (4)
C120.069 (7)0.046 (5)0.042 (4)0.012 (6)0.018 (4)0.003 (5)
C130.164 (7)0.044 (4)0.050 (4)0.011 (4)0.023 (4)0.008 (3)
C140.085 (12)0.086 (11)0.052 (7)0.008 (9)0.027 (7)0.029 (7)
C150.081 (7)0.056 (7)0.041 (5)0.006 (5)0.019 (5)0.010 (4)
C160.089 (4)0.052 (3)0.035 (3)0.009 (3)0.020 (3)0.001 (3)
C11A0.016 (11)0.052 (13)0.027 (9)0.003 (9)0.001 (7)0.012 (7)
C12A0.12 (2)0.081 (15)0.044 (9)0.048 (14)0.011 (10)0.018 (10)
C14A0.069 (18)0.068 (17)0.077 (15)0.021 (16)0.028 (13)0.010 (11)
C15A0.083 (17)0.094 (17)0.044 (10)0.009 (13)0.016 (11)0.040 (10)
C210.040 (3)0.041 (3)0.044 (3)0.011 (3)0.004 (2)0.001 (2)
C220.034 (3)0.066 (4)0.073 (4)0.006 (3)0.007 (3)0.003 (3)
C230.044 (4)0.081 (5)0.104 (5)0.009 (3)0.008 (3)0.003 (4)
C240.063 (5)0.112 (6)0.111 (6)0.036 (5)0.001 (4)0.006 (5)
C250.082 (5)0.051 (4)0.103 (5)0.026 (4)0.004 (4)0.001 (3)
C260.056 (4)0.051 (3)0.056 (3)0.006 (3)0.006 (3)0.003 (3)
C310.037 (3)0.044 (3)0.036 (3)0.001 (2)0.001 (2)0.006 (2)
C320.039 (3)0.057 (3)0.056 (3)0.006 (3)0.006 (2)0.021 (3)
C330.038 (3)0.069 (4)0.070 (4)0.008 (3)0.004 (3)0.015 (3)
C340.047 (4)0.076 (4)0.066 (4)0.004 (3)0.008 (3)0.019 (3)
C350.047 (3)0.064 (4)0.067 (4)0.006 (3)0.003 (3)0.026 (3)
C360.053 (4)0.069 (4)0.047 (3)0.001 (3)0.002 (3)0.016 (3)
Geometric parameters (Å, º) top
Mo—C51.972 (6)C12—H12A0.97
Mo—C32.009 (7)C12—H12B0.97
Mo—C42.020 (6)C13—H13A0.97
Mo—C22.038 (7)C13—H13B0.97
Mo—C12.046 (7)C14—H14A0.97
Mo—P2.5938 (14)C14—H14B0.97
P—C211.851 (4)C15—H15A0.97
P—C311.851 (4)C15—H15B0.97
P—C11A1.86 (3)C16—H16A0.97
P—C111.882 (16)C16—H16B0.97
O1—C11.136 (6)C11A—H11A'0.98
O2—C21.140 (6)C12A—H12A'0.97
O3—C31.163 (6)C12A—H12B'0.97
O4—C41.151 (6)C14A—H14A'0.97
O5—C51.154 (6)C14A—H14B'0.97
C11—C161.548 (12)C15A—H15A'0.97
C11—C121.555 (13)C15A—H15B'0.97
C12—C131.576 (9)C21—H21A0.98
C13—C14A1.548 (17)C22—H22A0.97
C13—C141.570 (12)C22—H22B0.97
C13—C12A1.587 (16)C23—H23A0.97
C14—C151.520 (13)C23—H23B0.97
C15—C161.546 (9)C24—H24A0.97
C16—C15A1.534 (15)C24—H24B0.97
C16—C11A1.544 (16)C25—H25A0.97
C11A—C12A1.539 (17)C25—H25B0.97
C14A—C15A1.539 (17)C26—H26A0.97
C21—C261.525 (6)C26—H26B0.97
C21—C221.528 (6)C31—H31A0.98
C22—C231.518 (7)C32—H32A0.97
C23—C241.520 (8)C32—H32B0.97
C24—C251.503 (8)C33—H33A0.97
C25—C261.520 (7)C33—H33B0.97
C31—C321.524 (6)C34—H34A0.97
C31—C361.543 (6)C34—H34B0.97
C32—C331.540 (6)C35—H35A0.97
C33—C341.529 (6)C35—H35B0.97
C34—C351.498 (6)C36—H36A0.97
C35—C361.538 (6)C36—H36B0.97
C11—H11A0.98
C5—Mo—C386.5 (2)C13—C12A—H12B'110.5
C5—Mo—C486.1 (2)H12A'—C12A—H12B'108.7
C3—Mo—C4172.6 (2)C15A—C14A—H14A'110.0
C5—Mo—C289.5 (2)C13—C14A—H14A'110.0
C3—Mo—C287.9 (2)C15A—C14A—H14B'110.0
C4—Mo—C292.1 (2)C13—C14A—H14B'110.0
C5—Mo—C188.6 (2)H14A'—C14A—H14B'108.4
C3—Mo—C188.6 (2)C16—C15A—H15A'110.0
C4—Mo—C191.1 (2)C14A—C15A—H15A'110.0
C2—Mo—C1176.2 (2)C16—C15A—H15B'110.0
C5—Mo—P177.94 (18)C14A—C15A—H15B'110.0
C3—Mo—P95.38 (16)H15A'—C15A—H15B'108.3
C4—Mo—P92.04 (15)C26—C21—H21A106.7
C2—Mo—P91.50 (18)C22—C21—H21A106.7
C1—Mo—P90.52 (15)P—C21—H21A106.7
C21—P—C31102.3 (2)C14A—C13—C12115.7 (11)
C21—P—C11A108.8 (6)C14—C13—C12105.4 (8)
C31—P—C11A99.3 (6)C14A—C13—C12A106.5 (15)
C21—P—C1199.2 (4)C14—C13—C12A116.8 (9)
C31—P—C11113.3 (5)C12—C13—C12A44.7 (7)
C11A—P—C1115.2 (8)C15—C14—C13103.1 (12)
C21—P—Mo116.05 (16)C14—C15—C16109.6 (10)
C31—P—Mo111.74 (14)C15A—C16—C11A111.9 (14)
C11A—P—Mo116.4 (4)C15A—C16—C1536.2 (7)
C11—P—Mo113.2 (3)C11A—C16—C15113.8 (11)
O1—C1—Mo177.7 (5)C15A—C16—C11117.5 (9)
O2—C2—Mo176.2 (5)C11A—C16—C1118.4 (10)
O3—C3—Mo174.4 (5)C15—C16—C11107.2 (8)
O4—C4—Mo174.0 (5)C12A—C11A—C16107.8 (16)
O5—C5—Mo177.8 (5)C12A—C11A—P114.9 (12)
C16—C11—C12105.9 (10)C16—C11A—P116.9 (14)
C16—C11—P115.3 (8)C11A—C12A—C13106.3 (15)
C12—C11—P112.1 (8)C15A—C14A—C13108.4 (17)
C11—C12—C13105.9 (9)C16—C15A—C14A108.6 (17)
C14A—C13—C1425.4 (10)C26—C21—C22110.6 (4)
C16—C11—H11A107.8C26—C21—P112.7 (3)
C12—C11—H11A107.8C22—C21—P113.0 (3)
P—C11—H11A107.8C23—C22—C21111.2 (4)
C11—C12—H12A110.6C23—C22—H22A109.4
C13—C12—H12A110.6C21—C22—H22A109.4
C11—C12—H12B110.6C23—C22—H22B109.4
C13—C12—H12B110.6C21—C22—H22B109.4
H12A—C12—H12B108.7H22A—C22—H22B108.0
C14A—C13—H13A122.3C22—C23—H23A109.2
C14—C13—H13A110.7C24—C23—H23A109.2
C12—C13—H13A110.7C22—C23—H23B109.2
C12A—C13—H13A130.7C24—C23—H23B109.2
C14A—C13—H13B85.3H23A—C23—H23B107.9
C14—C13—H13B110.7C25—C24—H24A109.6
C12—C13—H13B110.7C23—C24—H24A109.6
C12A—C13—H13B66.2C25—C24—H24B109.6
H13A—C13—H13B108.8C23—C24—H24B109.6
C14A—C13—H13A'110.4H24A—C24—H24B108.1
C14—C13—H13A'85.1C24—C25—H25A109.2
C12—C13—H13A'66.3C26—C25—H25A109.2
C12A—C13—H13A'110.4C24—C25—H25B109.2
H13A—C13—H13A'60.5C26—C25—H25B109.2
H13B—C13—H13A'163.9H25A—C25—H25B107.9
C14A—C13—H13B'110.4C25—C26—H26A109.4
C14—C13—H13B'121.8C21—C26—H26A109.4
C12—C13—H13B'132.2C25—C26—H26B109.4
C12A—C13—H13B'110.4C21—C26—H26B109.4
H13A—C13—H13B'48.3H26A—C26—H26B108.0
H13B—C13—H13B'60.8C32—C31—H31A104.8
H13A—C13—H13B'108.6C36—C31—H31A104.8
C15—C14—H14A111.1P—C31—H31A104.8
C13—C14—H14A111.1C31—C32—H32A109.5
C15—C14—H14B111.1C33—C32—H32A109.5
C13—C14—H14B111.1C31—C32—H32B109.5
H14A—C14—H14B109.1C33—C32—H32B109.5
C14—C15—H15A109.8H32A—C32—H32B108.1
C16—C15—H15A109.8C34—C33—H33A109.5
C14—C15—H15B109.8C32—C33—H33A109.5
C16—C15—H15B109.8C34—C33—H33B109.5
H15A—C15—H15B108.2C32—C33—H33B109.5
C15A—C16—H16A127.6H33A—C33—H33B108.1
C11A—C16—H16A120.1C35—C34—H34A109.3
C15—C16—H16A110.3C33—C34—H34A109.3
C11—C16—H16A110.3C35—C34—H34B109.3
C15A—C16—H16B74.3C33—C34—H34B109.3
C11A—C16—H16B92.0H34A—C34—H34B108.0
C15—C16—H16B110.3C34—C35—H35A109.6
C11—C16—H16B110.3C36—C35—H35A109.6
H16A—C16—H16B108.5C34—C35—H35B109.6
C15A—C16—H16A'109.2C36—C35—H35B109.6
C11A—C16—H16A'109.2H35A—C35—H35B108.1
C15—C16—H16A'75.1C35—C36—H36A109.7
C11—C16—H16A'91.1C31—C36—H36A109.7
H16A—C16—H16A'48.3C35—C36—H36B109.7
H16B—C16—H16A'154.2C31—C36—H36B109.7
C15A—C16—H16B'109.2H36A—C36—H36B108.2
C11A—C16—H16B'109.2C22—C23—C24111.9 (5)
C15—C16—H16B'132.9C25—C24—C23110.1 (5)
C11—C16—H16B'119.6C24—C25—C26112.3 (5)
H16A—C16—H16B'59.9C25—C26—C21111.1 (4)
H16B—C16—H16B'49.3C32—C31—C36108.9 (4)
H16A—C16—H16B'107.9C32—C31—P113.9 (3)
C12A—C11A—H11A'105.4C36—C31—P118.4 (3)
C16—C11A—H11A'105.4C31—C32—C33110.7 (4)
P—C11A—H11A'105.4C34—C33—C32110.8 (4)
C11A—C12A—H12A'110.5C35—C34—C33111.6 (4)
C13—C12A—H12A'110.5C34—C35—C36110.3 (4)
C11A—C12A—H12B'110.5C35—C36—C31109.7 (4)
C5—Mo—P—C21162 (5)C12—C11—C16—C15A26 (2)
C3—Mo—P—C219.4 (2)P—C11—C16—C15A150.2 (12)
C4—Mo—P—C21170.8 (2)C12—C11—C16—C11A51 (4)
C2—Mo—P—C2178.7 (2)P—C11—C16—C11A74 (5)
C1—Mo—P—C2198.1 (2)C12—C11—C16—C1563.3 (13)
C5—Mo—P—C3145 (5)P—C11—C16—C15172.2 (7)
C3—Mo—P—C31107.4 (2)C15A—C16—C11A—C12A61 (2)
C4—Mo—P—C3172.4 (2)C15—C16—C11A—C12A21 (2)
C2—Mo—P—C31164.6 (2)C11—C16—C11A—C12A51 (4)
C1—Mo—P—C3118.7 (2)C15A—C16—C11A—P168.4 (12)
C5—Mo—P—C11A68 (5)C15—C16—C11A—P152.3 (10)
C3—Mo—P—C11A139.5 (8)C11—C16—C11A—P80 (5)
C4—Mo—P—C11A40.7 (8)C21—P—C11A—C12A102.1 (17)
C2—Mo—P—C11A51.4 (8)C31—P—C11A—C12A151.4 (17)
C1—Mo—P—C11A131.8 (8)C11—P—C11A—C12A50 (2)
C5—Mo—P—C1184 (5)Mo—P—C11A—C12A31 (2)
C3—Mo—P—C11123.2 (5)C21—P—C11A—C1625.6 (14)
C4—Mo—P—C1157.0 (5)C31—P—C11A—C1680.9 (13)
C2—Mo—P—C1135.1 (5)C11—P—C11A—C1678 (3)
C1—Mo—P—C11148.2 (5)Mo—P—C11A—C16159.1 (9)
C5—Mo—C1—O19 (14)C16—C11A—C12A—C1364 (2)
C3—Mo—C1—O196 (14)P—C11A—C12A—C13164.2 (10)
C4—Mo—C1—O177 (14)C14A—C13—C12A—C11A67 (2)
C2—Mo—C1—O170 (15)C14—C13—C12A—C11A42 (2)
P—Mo—C1—O1169 (14)C12—C13—C12A—C11A42.7 (12)
C5—Mo—C2—O266 (9)C14—C13—C14A—C15A52 (3)
C3—Mo—C2—O221 (9)C12—C13—C14A—C15A19 (3)
C4—Mo—C2—O2152 (9)C12A—C13—C14A—C15A66 (3)
C1—Mo—C2—O26 (11)C11A—C16—C15A—C14A58 (3)
P—Mo—C2—O2116 (9)C15—C16—C15A—C14A42.7 (13)
C5—Mo—C3—O313 (5)C11—C16—C15A—C14A39 (3)
C4—Mo—C3—O314 (7)C13—C14A—C15A—C1661 (3)
C2—Mo—C3—O377 (5)C31—P—C21—C2655.7 (4)
C1—Mo—C3—O3102 (5)C11A—P—C21—C26160.1 (6)
P—Mo—C3—O3168 (5)C11—P—C21—C26172.2 (5)
C5—Mo—C4—O418 (4)Mo—P—C21—C2666.2 (4)
C3—Mo—C4—O417 (6)C31—P—C21—C22177.9 (3)
C2—Mo—C4—O4107 (5)C11A—P—C21—C2273.5 (7)
C1—Mo—C4—O471 (5)C11—P—C21—C2261.4 (6)
P—Mo—C4—O4161 (4)Mo—P—C21—C2260.1 (4)
C3—Mo—C5—O582 (15)C26—C21—C22—C2354.7 (6)
C4—Mo—C5—O598 (15)P—C21—C22—C23177.9 (4)
C2—Mo—C5—O5170 (15)C21—C22—C23—C2455.8 (7)
C1—Mo—C5—O57 (15)C22—C23—C24—C2555.9 (7)
P—Mo—C5—O570 (17)C23—C24—C25—C2656.0 (7)
C21—P—C11—C1656.9 (9)C24—C25—C26—C2156.1 (6)
C31—P—C11—C1650.9 (9)C22—C21—C26—C2554.5 (6)
C11A—P—C11—C1674 (3)P—C21—C26—C25177.8 (4)
Mo—P—C11—C16179.5 (6)C21—P—C31—C32174.1 (3)
C21—P—C11—C12178.1 (10)C11A—P—C31—C3262.3 (6)
C31—P—C11—C1270.3 (10)C11—P—C31—C3268.3 (5)
C11A—P—C11—C1247 (2)Mo—P—C31—C3261.1 (3)
Mo—P—C11—C1258.3 (12)C21—P—C31—C3644.2 (4)
C16—C11—C12—C1366.4 (12)C11A—P—C31—C3667.6 (6)
P—C11—C12—C13167.1 (6)C11—P—C31—C3661.6 (5)
C11—C12—C13—C14A45.4 (18)Mo—P—C31—C36169.0 (3)
C11—C12—C13—C1470.3 (13)C36—C31—C32—C3358.5 (5)
C11—C12—C13—C12A42.4 (10)P—C31—C32—C33167.1 (3)
C14A—C13—C14—C1549 (3)C31—C32—C33—C3456.0 (5)
C12—C13—C14—C1569.0 (15)C32—C33—C34—C3555.3 (6)
C12A—C13—C14—C1522 (2)C33—C34—C35—C3657.1 (6)
C13—C14—C15—C1667.9 (17)C34—C35—C36—C3159.6 (6)
C14—C15—C16—C15A46.8 (13)C32—C31—C36—C3560.0 (5)
C14—C15—C16—C11A48.1 (19)P—C31—C36—C35167.9 (3)
C14—C15—C16—C1166.4 (17)

Experimental details

(I)(II)
Crystal data
Chemical formula[Mo(C18H33P)2(CO)4][Mo(C18H33P)(CO)5]
Mr768.81516.40
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)293293
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), 9090, 92.15 (2), 90
V3)4054 (3)2522.3 (14)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.440.61
Crystal size (mm)0.40 × 0.20 × 0.050.40 × 0.20 × 0.18
Data collection
DiffractometerSiemens P3
diffractometer
Siemens P3
diffractometer
Absorption correctionψ-scans
semi-empirical (using intensity measurements) (XEMP; Siemens, 1989)
Tmin, Tmax0.844, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
12628, 9302, 3635 4655, 4435, 2498
Rint0.0920.089
(sin θ/λ)max1)0.6500.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.080, 0.93 0.045, 0.091, 0.90
No. of reflections93024435
No. of parameters424308
No. of restraints078
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.59, 0.700.77, 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.

Selected geometric parameters (Å, º) for (I) top
Mo—C21.921 (6)Mo—P12.6569 (17)
Mo—C31.927 (6)O1—C11.123 (6)
Mo—C12.039 (5)O2—C21.211 (6)
Mo—C42.042 (6)O3—C31.159 (6)
Mo—P22.6529 (16)O4—C41.143 (6)
C2—Mo—C384.2 (2)C1—Mo—P297.26 (16)
C2—Mo—C185.8 (2)C4—Mo—P287.27 (16)
C3—Mo—C187.7 (2)C2—Mo—P1169.87 (16)
C2—Mo—C487.8 (2)C3—Mo—P186.47 (17)
C3—Mo—C486.6 (2)C1—Mo—P189.77 (16)
C1—Mo—C4171.8 (3)C4—Mo—P195.73 (16)
C2—Mo—P284.81 (17)P2—Mo—P1104.81 (5)
C3—Mo—P2167.64 (16)
Selected geometric parameters (Å, º) for (II) top
Mo—C51.972 (6)Mo—P2.5938 (14)
Mo—C32.009 (7)O1—C11.136 (6)
Mo—C42.020 (6)O2—C21.140 (6)
Mo—C22.038 (7)O3—C31.163 (6)
Mo—C12.046 (7)O4—C41.151 (6)
C5—Mo—C386.5 (2)C4—Mo—C191.1 (2)
C5—Mo—C486.1 (2)C2—Mo—C1176.2 (2)
C3—Mo—C4172.6 (2)C5—Mo—P177.94 (18)
C5—Mo—C289.5 (2)C3—Mo—P95.38 (16)
C3—Mo—C287.9 (2)C4—Mo—P92.04 (15)
C4—Mo—C292.1 (2)C2—Mo—P91.50 (18)
C5—Mo—C188.6 (2)C1—Mo—P90.52 (15)
C3—Mo—C188.6 (2)
 

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