Bromido-1κBr-tricarbonyl-2κ3C-(2η5-cyclo­penta­dien­yl)molybdenum(I)tungsten(I)(W—Mo)

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

doi:10.1107/S1600536808012828

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m780

doi:10.1107/S1600536808012828

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Bromido-1κBr-tricarbonyl-2κ³C-(2η⁵-cyclopentadienyl)molybdenum(I)tungsten(I)(W—Mo)

Martin O. Onani,^a Jan-André Gertenbach ^b and Muhammad D. Bala ^c ^*

^aUniversity of the Western Cape, Modderdam Road, Bellville, Cape Town 7535, South Africa, ^bDepartment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa, and ^cSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
^*Correspondence e-mail: bala@ukzn.ac.za

(Received 23 April 2008; accepted 30 April 2008; online 7 May 2008)

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)°.

Related literature

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

Experimental

Crystal data

[WMoBr(C₅H₅)(CO)₃]
M_r = 508.82
Tetragonal, $[P \overline 42_1 c ]$
a = 11.9375 (9) Å
c = 15.546 (2) Å
V = 2215.4 (4) Å³
Z = 8
Mo Kα radiation
μ = 15.09 mm⁻¹
T = 100 (2) K
0.11 × 0.10 × 0.07 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.251, T_max = 0.347
13298 measured reflections
2673 independent reflections
2497 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.069
S = 1.02
2673 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 1.31 e Å⁻³
Δρ_min = −0.72 e Å⁻³
Absolute structure: Flack (1983 ), 1118 Friedel pairs
Flack parameter: 0.00 (1)

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; 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 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012828/dn2343sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012828/dn2343Isup2.hkl

checkCIF report

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.

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

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]	D_x = 3.051 Mg m⁻³
M_r = 508.82	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42₁c	Cell parameters from 2238 reflections
Hall symbol: P -4 2n	θ = 2.2–25.5°
a = 11.9375 (9) Å	µ = 15.09 mm⁻¹
c = 15.546 (2) Å	T = 100 K
V = 2215.4 (4) Å³	Block, yellow
Z = 8	0.11 × 0.10 × 0.07 mm
F(000) = 1824

Data collection top

Bruker APEX CCD area-detector diffractometer	2673 independent reflections
Radiation source: fine-focus sealed tube	2497 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −15→14
T_min = 0.251, T_max = 0.347	k = −8→15
13298 measured reflections	l = −20→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0238P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2673 reflections	Δρ_max = 1.31 e Å⁻³
127 parameters	Δρ_min = −0.72 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1118 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (1)

Crystal data top

[WMoBr(C₅H₅)(CO)₃]	Z = 8
M_r = 508.82	Mo Kα radiation
Tetragonal, P42₁c	µ = 15.09 mm⁻¹
a = 11.9375 (9) Å	T = 100 K
c = 15.546 (2) Å	0.11 × 0.10 × 0.07 mm
V = 2215.4 (4) Å³

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)
T_min = 0.251, T_max = 0.347	R_int = 0.048
13298 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 1.31 e Å⁻³
S = 1.02	Δρ_min = −0.72 e Å⁻³
2673 reflections	Absolute structure: Flack (1983), 1118 Friedel pairs
127 parameters	Absolute structure parameter: 0.00 (1)
0 restraints

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

	x	y	z	U_iso*/U_eq
W1	0.64476 (3)	0.39974 (3)	0.89630 (2)	0.01742 (9)
Mo1	0.73518 (6)	0.20182 (6)	0.85204 (5)	0.01833 (16)
Br1	0.62054 (7)	0.61253 (7)	0.90359 (5)	0.01974 (17)
O1	0.5124 (6)	0.1402 (6)	0.9503 (5)	0.0480 (19)
O2	0.6348 (5)	0.0161 (6)	0.7340 (4)	0.0402 (17)
O3	0.6948 (5)	0.3305 (6)	0.6794 (4)	0.0330 (16)
C1	0.5937 (8)	0.1680 (7)	0.9122 (6)	0.031 (2)
C2	0.6724 (7)	0.0833 (7)	0.7766 (6)	0.026 (2)
C3	0.7057 (7)	0.2868 (8)	0.7450 (6)	0.027 (2)
C4	0.8467 (10)	0.1507 (11)	0.9698 (7)	0.047 (3)
H4	0.8151	0.1245	1.0222	0.057*
C5	0.8729 (8)	0.0831 (8)	0.9024 (7)	0.038 (2)
H5	0.8622	0.0043	0.8996	0.046*
C6	0.9203 (7)	0.1535 (11)	0.8354 (6)	0.044 (3)
H6	0.9468	0.1308	0.7805	0.052*
C7	0.9181 (9)	0.2684 (10)	0.8715 (9)	0.059 (4)
H7	0.9431	0.3359	0.8455	0.071*
C8	0.8694 (10)	0.2533 (11)	0.9549 (7)	0.052 (3)
H8	0.8557	0.3126	0.9943	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01888 (17)	0.01447 (16)	0.01889 (15)	0.00532 (12)	0.00265 (14)	−0.00152 (14)
Mo1	0.0158 (3)	0.0170 (3)	0.0222 (3)	0.0033 (3)	0.0015 (3)	−0.0020 (3)
Br1	0.0214 (4)	0.0168 (4)	0.0209 (4)	0.0015 (3)	0.0032 (3)	0.0010 (3)
O1	0.036 (4)	0.032 (4)	0.076 (5)	0.006 (3)	0.029 (4)	0.011 (4)
O2	0.034 (4)	0.033 (4)	0.054 (4)	0.006 (3)	−0.008 (3)	−0.016 (3)
O3	0.035 (4)	0.045 (4)	0.019 (3)	0.007 (3)	−0.005 (3)	0.002 (3)
C1	0.032 (5)	0.015 (4)	0.045 (6)	0.009 (4)	0.004 (5)	0.003 (4)
C2	0.020 (5)	0.020 (5)	0.037 (5)	0.003 (4)	0.006 (4)	−0.012 (4)
C3	0.020 (5)	0.033 (5)	0.029 (5)	0.002 (4)	−0.004 (4)	−0.008 (4)
C4	0.042 (6)	0.069 (8)	0.030 (5)	−0.002 (7)	0.000 (5)	0.002 (6)
C5	0.033 (5)	0.030 (5)	0.053 (6)	0.015 (4)	−0.025 (5)	0.004 (5)
C6	0.016 (5)	0.091 (9)	0.024 (5)	0.028 (5)	−0.007 (4)	−0.007 (5)
C7	0.025 (6)	0.043 (7)	0.110 (11)	−0.014 (5)	−0.036 (6)	0.048 (7)
C8	0.037 (7)	0.058 (8)	0.061 (7)	0.015 (6)	−0.016 (5)	−0.035 (7)

Geometric parameters (Å, º) top

W1—Br1	2.5591 (9)	O3—C3	1.152 (12)
W1—Mo1	2.6872 (7)	C4—C8	1.276 (17)
Mo1—C1	1.972 (10)	C4—C5	1.359 (15)
Mo1—C3	1.980 (10)	C4—H4	0.9500
Mo1—C2	1.985 (8)	C5—C6	1.453 (15)
Mo1—C6	2.298 (8)	C5—H5	0.9500
Mo1—C5	2.307 (8)	C6—C7	1.482 (17)
Mo1—C7	2.344 (10)	C6—H6	0.9500
Mo1—C4	2.345 (12)	C7—C8	1.433 (16)
Mo1—C8	2.346 (10)	C7—H7	0.9500
O1—C1	1.184 (11)	C8—H8	0.9500
O2—C2	1.132 (10)

Br1—W1—Mo1	158.35 (3)	C4—Mo1—W1	104.9 (3)
C1—Mo1—C3	110.5 (4)	C8—Mo1—W1	82.5 (3)
C1—Mo1—C2	79.1 (4)	O1—C1—Mo1	175.0 (8)
C3—Mo1—C2	78.5 (4)	O2—C2—Mo1	178.9 (8)
C1—Mo1—C6	145.6 (4)	O3—C3—Mo1	174.3 (8)
C3—Mo1—C6	101.8 (4)	C8—C4—C5	112.4 (11)
C2—Mo1—C6	96.8 (4)	C8—C4—Mo1	74.3 (7)
C1—Mo1—C5	108.9 (4)	C5—C4—Mo1	71.5 (6)
C3—Mo1—C5	136.6 (4)	C8—C4—H4	123.8
C2—Mo1—C5	91.8 (4)	C5—C4—H4	123.8
C6—Mo1—C5	36.8 (4)	Mo1—C4—H4	121.9
C1—Mo1—C7	143.7 (4)	C4—C5—C6	107.4 (10)
C3—Mo1—C7	95.8 (4)	C4—C5—Mo1	74.5 (6)
C2—Mo1—C7	132.1 (4)	C6—C5—Mo1	71.3 (5)
C6—Mo1—C7	37.2 (4)	C4—C5—H5	126.3
C5—Mo1—C7	60.0 (4)	C6—C5—H5	126.3
C1—Mo1—C4	93.6 (4)	Mo1—C5—H5	119.8
C3—Mo1—C4	152.9 (4)	C5—C6—C7	104.9 (9)
C2—Mo1—C4	119.4 (4)	C5—C6—Mo1	71.9 (5)
C6—Mo1—C4	58.5 (4)	C7—C6—Mo1	73.0 (5)
C5—Mo1—C4	34.0 (4)	C5—C6—H6	127.6
C7—Mo1—C4	57.2 (4)	C7—C6—H6	127.6
C1—Mo1—C8	108.4 (4)	Mo1—C6—H6	119.6
C3—Mo1—C8	124.1 (4)	C8—C7—C6	103.5 (9)
C2—Mo1—C8	148.0 (4)	C8—C7—Mo1	72.3 (6)
C6—Mo1—C8	59.1 (4)	C6—C7—Mo1	69.7 (5)
C5—Mo1—C8	56.1 (4)	C8—C7—H7	128.2
C7—Mo1—C8	35.6 (4)	C6—C7—H7	128.2
C4—Mo1—C8	31.6 (4)	Mo1—C7—H7	121.7
C1—Mo1—W1	73.4 (2)	C4—C8—C7	111.8 (10)
C3—Mo1—W1	72.1 (3)	C4—C8—Mo1	74.2 (7)
C2—Mo1—W1	128.8 (3)	C7—C8—Mo1	72.1 (6)
C6—Mo1—W1	129.5 (3)	C4—C8—H8	124.1
C5—Mo1—W1	137.7 (3)	C7—C8—H8	124.1
C7—Mo1—W1	92.5 (3)	Mo1—C8—H8	121.1

Br1—W1—Mo1—C1	−172.7 (3)	C8—Mo1—C6—C5	73.6 (7)
Br1—W1—Mo1—C3	−54.0 (3)	W1—Mo1—C6—C5	119.9 (6)
Br1—W1—Mo1—C2	−112.2 (3)	C1—Mo1—C6—C7	−115.9 (9)
Br1—W1—Mo1—C6	36.8 (3)	C3—Mo1—C6—C7	83.9 (7)
Br1—W1—Mo1—C5	87.2 (4)	C2—Mo1—C6—C7	163.6 (6)
Br1—W1—Mo1—C7	41.3 (3)	C5—Mo1—C6—C7	−112.4 (8)
Br1—W1—Mo1—C4	97.9 (3)	C4—Mo1—C6—C7	−76.0 (7)
Br1—W1—Mo1—C8	75.5 (3)	C8—Mo1—C6—C7	−38.9 (6)
C1—Mo1—C4—C8	−120.1 (8)	W1—Mo1—C6—C7	7.4 (7)
C3—Mo1—C4—C8	33.5 (13)	C5—C6—C7—C8	−0.4 (9)
C2—Mo1—C4—C8	160.4 (7)	Mo1—C6—C7—C8	65.0 (7)
C6—Mo1—C4—C8	81.2 (8)	C5—C6—C7—Mo1	−65.4 (6)
C5—Mo1—C4—C8	120.8 (11)	C1—Mo1—C7—C8	8.5 (10)
C7—Mo1—C4—C8	36.9 (7)	C3—Mo1—C7—C8	145.7 (7)
W1—Mo1—C4—C8	−46.3 (8)	C2—Mo1—C7—C8	−134.5 (8)
C1—Mo1—C4—C5	119.1 (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—C5	39.6 (8)	C4—Mo1—C7—C8	−32.7 (6)
C6—Mo1—C4—C5	−39.6 (7)	W1—Mo1—C7—C8	73.4 (7)
C7—Mo1—C4—C5	−83.8 (8)	C1—Mo1—C7—C6	120.8 (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—C6	0.7 (13)	C5—Mo1—C7—C6	39.7 (6)
Mo1—C4—C5—C6	64.2 (6)	C4—Mo1—C7—C6	79.6 (7)
C8—C4—C5—Mo1	−63.4 (10)	C8—Mo1—C7—C6	112.3 (8)
C1—Mo1—C5—C4	−67.1 (8)	W1—Mo1—C7—C6	−174.3 (6)
C3—Mo1—C5—C4	138.6 (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—C4	115.0 (10)	C5—C4—C8—Mo1	61.8 (9)
C7—Mo1—C5—C4	74.7 (8)	C6—C7—C8—C4	0.9 (12)
C8—Mo1—C5—C4	32.8 (7)	Mo1—C7—C8—C4	64.1 (9)
W1—Mo1—C5—C4	18.7 (9)	C6—C7—C8—Mo1	−63.2 (6)
C1—Mo1—C5—C6	177.9 (6)	C1—Mo1—C8—C4	65.5 (8)
C3—Mo1—C5—C6	23.6 (8)	C3—Mo1—C8—C4	−162.4 (7)
C2—Mo1—C5—C6	98.8 (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—C4	135.2 (7)
C4—C5—C6—C7	−0.1 (10)	C1—Mo1—C8—C7	−174.7 (7)
Mo1—C5—C6—C7	66.2 (6)	C3—Mo1—C8—C7	−42.6 (8)
C4—C5—C6—Mo1	−66.3 (7)	C2—Mo1—C8—C7	86.3 (11)
C1—Mo1—C6—C5	−3.5 (10)	C6—Mo1—C8—C7	40.7 (6)
C3—Mo1—C6—C5	−163.7 (6)	C5—Mo1—C8—C7	84.5 (7)
C2—Mo1—C6—C5	−84.0 (6)	C4—Mo1—C8—C7	119.8 (10)
C7—Mo1—C6—C5	112.4 (8)	W1—Mo1—C8—C7	−105.0 (7)
C4—Mo1—C6—C5	36.5 (6)

Experimental details

Crystal data
Chemical formula	[WMoBr(C₅H₅)(CO)₃]
M_r	508.82
Crystal system, space group	Tetragonal, P42₁c
Temperature (K)	100
a, c (Å)	11.9375 (9), 15.546 (2)
V (Å³)	2215.4 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	15.09
Crystal size (mm)	0.11 × 0.10 × 0.07

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.251, 0.347
No. of measured, independent and observed [I > 2σ(I)] reflections	13298, 2673, 2497
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.069, 1.02
No. of reflections	2673
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.31, −0.72
Absolute structure	Flack (1983), 1118 Friedel pairs
Absolute structure parameter	0.00 (1)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour 2001), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2001).

Acknowledgements

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

References

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