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Acta Cryst. (2008). E64, m780    [ doi:10.1107/S1600536808012828 ]

Bromido-1[kappa]Br-tricarbonyl-2[kappa]3C-(2[eta]5-cyclopentadienyl)molybdenum(I)tungsten(I)(W-Mo)

M. O. Onani, J.-A. Gertenbach and M. D. Bala

Abstract top

The title compound, [WMoBr(C5H5)(CO)3], is built up from a pseudo-square-pyramidal piano-stool coordination around the Mo atom, the important geometry being Mo-W = 2.6872 (7) Å, W-Br = 2.5591 (9) Å and Mo-W-Br = 158.35 (3)°.

Comment top

The compound I was a by-product of a study on the functionalization of paraffins using transition metals. The functionalized compounds have potential applications in catalysis and organic syntheses (Changamu et al., 2006). The compound I is similar to the reported structure of (η5-C5H5(CO)3MoHgCl (Bueno et al., 1981), Albright et al. (1978). The bond distances of W—Mo, 2.6872 (7) Å and W—Br, 2.5591 (9) Å are comparable to Hg—Mo, 2.693 (30) Å and Hg—Cl, 2.437 (8) Å respectively. The slight difference between the bond lenghts involving the halides could be attributed to the difference in electronegativity and hence basicity between bromine and chlorine.The coordination around Mo is a pseudo-square pyramidal piano stool arrangement.(Fig. 1)

Related literature top

For related literature, see Albright et al. (1978); Bueno & Churchill (1981); Changamu et al. (2006); Friedrich et al. (2004).

Experimental top

The compound I was prepared according to a reported procedure (Friedrich et al., 2004) and crystals were grown by slow evaporation of a mixture of dichloromethane and hexane at 263 K.

Refinement top

Hydrogen atoms were treated as riding on their parent C atoms with C–H = 0.95 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2001).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title complex showing the atom numbering scheme. Ellipsoids are drawn at the 50% probability level.
Bromido-1κBr-tricarbonyl-2κ3C-(2η5- cyclopentadienyl)molybdenum(I)tungsten(I)(W—Mo) top
Crystal data top
[WMoBr(C5H5)(CO)3]Z = 8
Mr = 508.82F000 = 1824
Tetragonal, P421cDx = 3.051 Mg m−3
Hall symbol: P -4 2nMo Kα radiation
λ = 0.71073 Å
a = 11.9375 (9) ÅCell parameters from 2238 reflections
b = 11.9375 (9) Åθ = 2.2–25.5º
c = 15.546 (2) ŵ = 15.09 mm−1
α = 90ºT = 100 (2) K
β = 90ºBlock, yellow
γ = 90º0.11 × 0.10 × 0.07 mm
V = 2215.4 (4) Å3
Data collection top
Bruker APEX CCD area-detector
diffractometer		2673 independent reflections
Radiation source: fine-focus sealed tube2497 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
T = 100(2) Kθmax = 28.3º
ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −15→14
Tmin = 0.251, Tmax = 0.347k = −8→15
13298 measured reflectionsl = −20→18
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.030  w = 1/[σ2(Fo2) + (0.0238P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.069(Δ/σ)max = 0.001
S = 1.02Δρmax = 1.31 e Å−3
2673 reflectionsΔρmin = −0.72 e Å−3
127 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1118 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.00 (1)
Crystal data top
[WMoBr(C5H5)(CO)3]γ = 90º
Mr = 508.82V = 2215.4 (4) Å3
Tetragonal, P421cZ = 8
a = 11.9375 (9) ÅMo Kα
b = 11.9375 (9) ŵ = 15.09 mm−1
c = 15.546 (2) ÅT = 100 (2) K
α = 90º0.11 × 0.10 × 0.07 mm
β = 90º
Data collection top
Bruker APEX CCD area-detector
diffractometer		2673 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		2497 reflections with I > 2σ(I)
Tmin = 0.251, Tmax = 0.347Rint = 0.048
13298 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.069Δρmax = 1.31 e Å−3
S = 1.02Δρmin = −0.72 e Å−3
2673 reflectionsAbsolute structure: Flack (1983), 1118 Friedel pairs
127 parametersFlack parameter: 0.00 (1)
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
W10.64476 (3)0.39974 (3)0.89630 (2)0.01742 (9)
Mo10.73518 (6)0.20182 (6)0.85204 (5)0.01833 (16)
Br10.62054 (7)0.61253 (7)0.90359 (5)0.01974 (17)
O10.5124 (6)0.1402 (6)0.9503 (5)0.0480 (19)
O20.6348 (5)0.0161 (6)0.7340 (4)0.0402 (17)
O30.6948 (5)0.3305 (6)0.6794 (4)0.0330 (16)
C10.5937 (8)0.1680 (7)0.9122 (6)0.031 (2)
C20.6724 (7)0.0833 (7)0.7766 (6)0.026 (2)
C30.7057 (7)0.2868 (8)0.7450 (6)0.027 (2)
C40.8467 (10)0.1507 (11)0.9698 (7)0.047 (3)
H40.81510.12451.02220.057*
C50.8729 (8)0.0831 (8)0.9024 (7)0.038 (2)
H50.86220.00430.89960.046*
C60.9203 (7)0.1535 (11)0.8354 (6)0.044 (3)
H60.94680.13080.78050.052*
C70.9181 (9)0.2684 (10)0.8715 (9)0.059 (4)
H70.94310.33590.84550.071*
C80.8694 (10)0.2533 (11)0.9549 (7)0.052 (3)
H80.85570.31260.99430.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
W10.01888 (17)0.01447 (16)0.01889 (15)0.00532 (12)0.00265 (14)−0.00152 (14)
Mo10.0158 (3)0.0170 (3)0.0222 (3)0.0033 (3)0.0015 (3)−0.0020 (3)
Br10.0214 (4)0.0168 (4)0.0209 (4)0.0015 (3)0.0032 (3)0.0010 (3)
O10.036 (4)0.032 (4)0.076 (5)0.006 (3)0.029 (4)0.011 (4)
O20.034 (4)0.033 (4)0.054 (4)0.006 (3)−0.008 (3)−0.016 (3)
O30.035 (4)0.045 (4)0.019 (3)0.007 (3)−0.005 (3)0.002 (3)
C10.032 (5)0.015 (4)0.045 (6)0.009 (4)0.004 (5)0.003 (4)
C20.020 (5)0.020 (5)0.037 (5)0.003 (4)0.006 (4)−0.012 (4)
C30.020 (5)0.033 (5)0.029 (5)0.002 (4)−0.004 (4)−0.008 (4)
C40.042 (6)0.069 (8)0.030 (5)−0.002 (7)0.000 (5)0.002 (6)
C50.033 (5)0.030 (5)0.053 (6)0.015 (4)−0.025 (5)0.004 (5)
C60.016 (5)0.091 (9)0.024 (5)0.028 (5)−0.007 (4)−0.007 (5)
C70.025 (6)0.043 (7)0.110 (11)−0.014 (5)−0.036 (6)0.048 (7)
C80.037 (7)0.058 (8)0.061 (7)0.015 (6)−0.016 (5)−0.035 (7)
Geometric parameters (Å, °) top
W1—Br12.5591 (9)O3—C31.152 (12)
W1—Mo12.6872 (7)C4—C81.276 (17)
Mo1—C11.972 (10)C4—C51.359 (15)
Mo1—C31.980 (10)C4—H40.9500
Mo1—C21.985 (8)C5—C61.453 (15)
Mo1—C62.298 (8)C5—H50.9500
Mo1—C52.307 (8)C6—C71.482 (17)
Mo1—C72.344 (10)C6—H60.9500
Mo1—C42.345 (12)C7—C81.433 (16)
Mo1—C82.346 (10)C7—H70.9500
O1—C11.184 (11)C8—H80.9500
O2—C21.132 (10)
Br1—W1—Mo1158.35 (3)C4—Mo1—W1104.9 (3)
C1—Mo1—C3110.5 (4)C8—Mo1—W182.5 (3)
C1—Mo1—C279.1 (4)O1—C1—Mo1175.0 (8)
C3—Mo1—C278.5 (4)O2—C2—Mo1178.9 (8)
C1—Mo1—C6145.6 (4)O3—C3—Mo1174.3 (8)
C3—Mo1—C6101.8 (4)C8—C4—C5112.4 (11)
C2—Mo1—C696.8 (4)C8—C4—Mo174.3 (7)
C1—Mo1—C5108.9 (4)C5—C4—Mo171.5 (6)
C3—Mo1—C5136.6 (4)C8—C4—H4123.8
C2—Mo1—C591.8 (4)C5—C4—H4123.8
C6—Mo1—C536.8 (4)Mo1—C4—H4121.9
C1—Mo1—C7143.7 (4)C4—C5—C6107.4 (10)
C3—Mo1—C795.8 (4)C4—C5—Mo174.5 (6)
C2—Mo1—C7132.1 (4)C6—C5—Mo171.3 (5)
C6—Mo1—C737.2 (4)C4—C5—H5126.3
C5—Mo1—C760.0 (4)C6—C5—H5126.3
C1—Mo1—C493.6 (4)Mo1—C5—H5119.8
C3—Mo1—C4152.9 (4)C5—C6—C7104.9 (9)
C2—Mo1—C4119.4 (4)C5—C6—Mo171.9 (5)
C6—Mo1—C458.5 (4)C7—C6—Mo173.0 (5)
C5—Mo1—C434.0 (4)C5—C6—H6127.6
C7—Mo1—C457.2 (4)C7—C6—H6127.6
C1—Mo1—C8108.4 (4)Mo1—C6—H6119.6
C3—Mo1—C8124.1 (4)C8—C7—C6103.5 (9)
C2—Mo1—C8148.0 (4)C8—C7—Mo172.3 (6)
C6—Mo1—C859.1 (4)C6—C7—Mo169.7 (5)
C5—Mo1—C856.1 (4)C8—C7—H7128.2
C7—Mo1—C835.6 (4)C6—C7—H7128.2
C4—Mo1—C831.6 (4)Mo1—C7—H7121.7
C1—Mo1—W173.4 (2)C4—C8—C7111.8 (10)
C3—Mo1—W172.1 (3)C4—C8—Mo174.2 (7)
C2—Mo1—W1128.8 (3)C7—C8—Mo172.1 (6)
C6—Mo1—W1129.5 (3)C4—C8—H8124.1
C5—Mo1—W1137.7 (3)C7—C8—H8124.1
C7—Mo1—W192.5 (3)Mo1—C8—H8121.1
Br1—W1—Mo1—C1−172.7 (3)C8—Mo1—C6—C573.6 (7)
Br1—W1—Mo1—C3−54.0 (3)W1—Mo1—C6—C5119.9 (6)
Br1—W1—Mo1—C2−112.2 (3)C1—Mo1—C6—C7−115.9 (9)
Br1—W1—Mo1—C636.8 (3)C3—Mo1—C6—C783.9 (7)
Br1—W1—Mo1—C587.2 (4)C2—Mo1—C6—C7163.6 (6)
Br1—W1—Mo1—C741.3 (3)C5—Mo1—C6—C7−112.4 (8)
Br1—W1—Mo1—C497.9 (3)C4—Mo1—C6—C7−76.0 (7)
Br1—W1—Mo1—C875.5 (3)C8—Mo1—C6—C7−38.9 (6)
C1—Mo1—C4—C8−120.1 (8)W1—Mo1—C6—C77.4 (7)
C3—Mo1—C4—C833.5 (13)C5—C6—C7—C8−0.4 (9)
C2—Mo1—C4—C8160.4 (7)Mo1—C6—C7—C865.0 (7)
C6—Mo1—C4—C881.2 (8)C5—C6—C7—Mo1−65.4 (6)
C5—Mo1—C4—C8120.8 (11)C1—Mo1—C7—C88.5 (10)
C7—Mo1—C4—C836.9 (7)C3—Mo1—C7—C8145.7 (7)
W1—Mo1—C4—C8−46.3 (8)C2—Mo1—C7—C8−134.5 (8)
C1—Mo1—C4—C5119.1 (7)C6—Mo1—C7—C8−112.3 (8)
C3—Mo1—C4—C5−87.3 (11)C5—Mo1—C7—C8−72.6 (7)
C2—Mo1—C4—C539.6 (8)C4—Mo1—C7—C8−32.7 (6)
C6—Mo1—C4—C5−39.6 (7)W1—Mo1—C7—C873.4 (7)
C7—Mo1—C4—C5−83.8 (8)C1—Mo1—C7—C6120.8 (8)
C8—Mo1—C4—C5−120.8 (11)C3—Mo1—C7—C6−102.0 (6)
W1—Mo1—C4—C5−167.1 (6)C2—Mo1—C7—C6−22.2 (8)
C8—C4—C5—C60.7 (13)C5—Mo1—C7—C639.7 (6)
Mo1—C4—C5—C664.2 (6)C4—Mo1—C7—C679.6 (7)
C8—C4—C5—Mo1−63.4 (10)C8—Mo1—C7—C6112.3 (8)
C1—Mo1—C5—C4−67.1 (8)W1—Mo1—C7—C6−174.3 (6)
C3—Mo1—C5—C4138.6 (7)C5—C4—C8—C7−1.0 (14)
C2—Mo1—C5—C4−146.2 (7)Mo1—C4—C8—C7−62.8 (8)
C6—Mo1—C5—C4115.0 (10)C5—C4—C8—Mo161.8 (9)
C7—Mo1—C5—C474.7 (8)C6—C7—C8—C40.9 (12)
C8—Mo1—C5—C432.8 (7)Mo1—C7—C8—C464.1 (9)
W1—Mo1—C5—C418.7 (9)C6—C7—C8—Mo1−63.2 (6)
C1—Mo1—C5—C6177.9 (6)C1—Mo1—C8—C465.5 (8)
C3—Mo1—C5—C623.6 (8)C3—Mo1—C8—C4−162.4 (7)
C2—Mo1—C5—C698.8 (6)C2—Mo1—C8—C4−33.5 (12)
C7—Mo1—C5—C6−40.2 (6)C6—Mo1—C8—C4−79.1 (8)
C4—Mo1—C5—C6−115.0 (10)C5—Mo1—C8—C4−35.3 (7)
C8—Mo1—C5—C6−82.2 (7)C7—Mo1—C8—C4−119.8 (10)
W1—Mo1—C5—C6−96.2 (7)W1—Mo1—C8—C4135.2 (7)
C4—C5—C6—C7−0.1 (10)C1—Mo1—C8—C7−174.7 (7)
Mo1—C5—C6—C766.2 (6)C3—Mo1—C8—C7−42.6 (8)
C4—C5—C6—Mo1−66.3 (7)C2—Mo1—C8—C786.3 (11)
C1—Mo1—C6—C5−3.5 (10)C6—Mo1—C8—C740.7 (6)
C3—Mo1—C6—C5−163.7 (6)C5—Mo1—C8—C784.5 (7)
C2—Mo1—C6—C5−84.0 (6)C4—Mo1—C8—C7119.8 (10)
C7—Mo1—C6—C5112.4 (8)W1—Mo1—C8—C7−105.0 (7)
C4—Mo1—C6—C536.5 (6)
Acknowledgements top

The authors are grateful to the NRF, WSU and UWC for funding, and to Miss Lungelwa Dyantyi for assistance with the experimental work.

references
References top

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