Bromido-1κBr-tricarbonyl-2κ³ C-(2η⁵-cyclo­penta­dien­yl)molybdenum(I)tungsten(I)(W—Mo)

Abstract

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,

• a = 11.9375 (9) Å

• c = 15.546 (2) Å

• V = 2215.4 (4) ų

• 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[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1

supplementary crystallographic information

Comment

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)

Experimental

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

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

Figures

Fig. 1.

Molecular structure of the title complex showing the atom numbering scheme. Ellipsoids are drawn at the 50% probability level.

Crystal data

[WMoBr(C5H5)(CO)3]	Z = 8
Mr = 508.82	F000 = 1824
Tetragonal, P421c	Dx = 3.051 Mg m−3
Hall symbol: P -4 2n	Mo Kα radiation λ = 0.71073 Å
a = 11.9375 (9) Å	Cell parameters from 2238 reflections
b = 11.9375 (9) Å	θ = 2.2–25.5º
c = 15.546 (2) Å	µ = 15.09 mm−1
α = 90º	T = 100 (2) K
β = 90º	Block, yellow
γ = 90º	0.11 × 0.10 × 0.07 mm
V = 2215.4 (4) Å3

Data collection

Bruker APEX CCD area-detector diffractometer	2673 independent reflections
Radiation source: fine-focus sealed tube	2497 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.048
T = 100(2) K	θmax = 28.3º
ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2002)	h = −15→14
Tmin = 0.251, Tmax = 0.347	k = −8→15
13298 measured reflections	l = −20→18

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-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 = 1.02	Δρmax = 1.31 e Å−3
2673 reflections	Δρmin = −0.72 e Å−3
127 parameters	Extinction correction: none
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1118 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (1)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)