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Acta Cryst. (2007). E63, m2542    [ doi:10.1107/S1600536807044261 ]

Tris(tert-butylisonitrile)hexacarbonyl-[mu]3-ethylidyne-triangulo-tricobalt(I)(3 Co-Co)

J. M. Brown and B. K. Nicholson

Abstract top

The title molecule, [Co3(C2H3)(C5H9N)3(CO)6] or [Co3([mu]3-CCH3)(CNtBu)3(CO)6], lies on a threefold rotation axis. The three isonitrile ligands each occupy an equatorial site on each of the three Co atoms. The average Co-Co bond length is 2.4769 (6) Å. The tert-butyl groups are disordered over two orientations, with site occupancies of ca 0.6:0.4.

Comment top

The title compound is the first structurally characterized isonitrile derivative of a [Co3(µ3-CR)(CO)9] cluster. The three CNBut ligands have displaced three equatorial CO ligands in the parent molecule, to give a molecule with C3 symmetry. The substitution has had little effect on the parameters of the cluster core with average Co—Co and Co—C distances (2.4769 (6) and 1.908 (3) Å respectively) that do not differ significantly from those of parent (2.467 (7) and 1.90 (2) Å, (Sutton & Dahl, 1967) though the low precision of the earlier study would mask any small changes.

Related literature top

For details of the synthesis, see Newman & Manning (1974). For the structure of the parent nonacarbonyl cluster, see Sutton & Dahl (1967). Other examples of equatorially trisubstituted derivatives of [Co3(µ3-CR)(CO)9] include the (MeO)3P derivative (Dawson et al., 1979). Axial substitution appears to be favoured only by very bulky or chelating ligands (D'Agostino et al., 1991; Renouard et al., 1996).

Experimental top

The compound was prepared by thermal reaction between [Co3(µ3-CR)(CO)9] and CNBut (Newman & Manning, 1974). X-ray crystals were grown from pentane.

Refinement top

The tert-butyl groups are disordered over two orientations which refined to a 0.64:0.36 occupancy ratio; this accounts for the large differences between the displacement parameters of the C4 carbon atom and the attached CH3 carbon atoms. All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.96 Å, Uiso = 1.5Ueq (C).

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SAINT (Bruker 2001); data reduction: SAINT (Bruker 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Version 1.70.01; Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Structure of [Co3(µ3-CCH3)(CO)6(CNBut)3] with diplacement parameters drawn at the 30% probability level. Only the major disorder component of the t-butyl group is shown.
[Figure 2] Fig. 2. A view down the threefold axis. Only the major disorder component of the t-butyl group is shown.
tris(tert-butylisonitrile)hexacarbonyl-µ3-ethylidyne- triangulo-tricobalt(I)(3 Co—Co) top
Crystal data top
[Co3(C2H3)(C5H9N)3(CO)6]Z = 6
Mr = 621.29F000 = 1908
Trigonal, R3cDx = 1.420 Mg m−3
Hall symbol: R 3 -2"cMo Kα radiation
λ = 0.71073 Å
a = 16.9804 (6) ÅCell parameters from 5750 reflections
b = 16.9804 (6) Åθ = 2.4–26.4º
c = 17.4605 (11) ŵ = 1.73 mm−1
α = 90ºT = 293 (2) K
β = 90ºHexagonal rod, black
γ = 120º0.54 × 0.13 × 0.11 mm
V = 4360.0 (4) Å3
Data collection top
Siemens SMART CCD
diffractometer		1991 independent reflections
Radiation source: fine-focus sealed tube1757 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
T = 293(2) Kθmax = 26.4º
multi–scanθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −21→20
Tmin = 0.672, Tmax = 0.830k = −21→21
10767 measured reflectionsl = −21→21
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025  w = 1/[σ2(Fo2) + (0.0388P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.059(Δ/σ)max = 0.002
S = 1.00Δρmax = 0.21 e Å−3
1991 reflectionsΔρmin = −0.16 e Å−3
134 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), with 989 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (2)
Secondary atom site location: difference Fourier map
Crystal data top
[Co3(C2H3)(C5H9N)3(CO)6]γ = 120º
Mr = 621.29V = 4360.0 (4) Å3
Trigonal, R3cZ = 6
a = 16.9804 (6) ÅMo Kα
b = 16.9804 (6) ŵ = 1.73 mm−1
c = 17.4605 (11) ÅT = 293 (2) K
α = 90º0.54 × 0.13 × 0.11 mm
β = 90º
Data collection top
Siemens SMART CCD
diffractometer		1991 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1757 reflections with I > 2σ(I)
Tmin = 0.672, Tmax = 0.830Rint = 0.036
10767 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.059Δρmax = 0.21 e Å−3
S = 1.00Δρmin = −0.16 e Å−3
1991 reflectionsAbsolute structure: Flack (1983), with 989 Friedel pairs
134 parametersFlack parameter: 0.01 (2)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.92643 (2)0.01828 (2)0.164850 (14)0.04289 (10)
N10.91952 (19)0.17320 (19)0.24181 (17)0.0676 (7)
C11.00000.00000.2372 (3)0.0441 (9)
C21.00000.00000.3218 (3)0.0698 (14)
H2A1.01160.05810.34010.105*0.333
H2B1.0466−0.01160.34010.105*0.333
H2C0.9419−0.04660.34010.105*0.333
C30.92327 (19)0.1150 (2)0.21234 (18)0.0557 (7)
C40.9179 (2)0.2509 (2)0.27631 (19)0.0684 (9)
C110.9168 (2)0.0388 (2)0.06419 (19)0.0593 (7)
O110.9109 (2)0.0514 (2)0.00155 (15)0.0992 (9)
C120.8144 (2)−0.0659 (2)0.18837 (19)0.0618 (8)
O120.74179 (17)−0.1194 (2)0.2037 (2)0.1022 (10)
C50.9649 (10)0.3290 (5)0.2265 (6)0.120 (5)0.640 (16)
H510.93280.31710.17880.180*0.640 (16)
H521.02550.34050.21720.180*0.640 (16)
H530.96760.38120.25060.180*0.640 (16)
C60.9631 (13)0.2680 (9)0.3533 (7)0.166 (8)0.640 (16)
H610.92980.21550.38530.249*0.640 (16)
H620.96430.31970.37680.249*0.640 (16)
H631.02430.27970.34700.249*0.640 (16)
C70.8180 (6)0.2243 (6)0.2791 (9)0.135 (6)0.640 (16)
H710.78580.17290.31240.202*0.640 (16)
H720.79260.20860.22850.202*0.640 (16)
H730.81260.27450.29800.202*0.640 (16)
C5A1.0165 (10)0.3310 (10)0.2776 (15)0.126 (10)0.360 (16)
H51A1.04000.34410.22630.188*0.360 (16)
H52A1.05330.31500.30830.188*0.360 (16)
H53A1.01760.38360.29890.188*0.360 (16)
C6A0.8664 (11)0.2787 (10)0.2206 (10)0.100 (7)0.360 (16)
H61A0.89680.29400.17190.150*0.360 (16)
H62A0.86460.33040.24070.150*0.360 (16)
H63A0.80540.22900.21420.150*0.360 (16)
C7A0.875 (2)0.2261 (16)0.3488 (9)0.154 (13)0.360 (16)
H71A0.90970.20940.38200.231*0.360 (16)
H72A0.81490.17540.34320.231*0.360 (16)
H73A0.87270.27660.37060.231*0.360 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.03864 (19)0.04002 (19)0.05232 (16)0.02140 (15)−0.00286 (15)−0.00329 (17)
N10.0639 (16)0.0525 (15)0.0928 (18)0.0338 (14)−0.0040 (15)−0.0173 (14)
C10.0416 (13)0.0416 (13)0.049 (2)0.0208 (7)0.0000.000
C20.077 (2)0.077 (2)0.055 (3)0.0386 (11)0.0000.000
C30.0456 (15)0.0494 (16)0.0751 (18)0.0259 (14)−0.0041 (13)−0.0059 (14)
C40.078 (2)0.0545 (18)0.081 (2)0.0398 (18)−0.0010 (18)−0.0181 (16)
C110.0538 (18)0.0548 (17)0.067 (2)0.0257 (14)−0.0064 (14)0.0037 (14)
O110.105 (2)0.111 (2)0.0676 (16)0.0438 (19)−0.0143 (14)0.0177 (15)
C120.0504 (19)0.0576 (18)0.083 (2)0.0312 (16)0.0002 (15)0.0059 (14)
O120.0457 (14)0.0793 (18)0.171 (3)0.0234 (13)0.0190 (16)0.0303 (18)
C50.169 (15)0.064 (5)0.121 (6)0.054 (7)0.021 (7)0.002 (4)
C60.29 (2)0.143 (12)0.095 (7)0.132 (15)−0.076 (12)−0.049 (8)
C70.096 (6)0.085 (6)0.237 (18)0.056 (5)0.031 (7)−0.024 (8)
C5A0.087 (9)0.075 (9)0.21 (3)0.038 (7)−0.026 (10)−0.075 (13)
C6A0.104 (14)0.079 (11)0.141 (12)0.063 (12)−0.024 (10)−0.024 (9)
C7A0.31 (4)0.132 (16)0.074 (13)0.15 (2)0.067 (19)0.015 (11)
Geometric parameters (Å, °) top
Co1—C121.764 (3)C5—H510.9600
Co1—C111.815 (3)C5—H520.9600
Co1—C31.865 (3)C5—H530.9600
Co1—C11.908 (3)C6—H610.9600
Co1—Co1i2.4769 (6)C6—H620.9600
N1—C31.143 (4)C6—H630.9600
N1—C41.464 (4)C7—H710.9600
C1—C21.477 (8)C7—H720.9600
C2—H2A0.9600C7—H730.9600
C2—H2B0.9600C5A—H51A0.9600
C2—H2C0.9600C5A—H52A0.9600
C4—C7A1.413 (16)C5A—H53A0.9600
C4—C51.446 (8)C6A—H61A0.9600
C4—C61.503 (10)C6A—H62A0.9600
C4—C71.522 (9)C6A—H63A0.9600
C4—C6A1.532 (14)C7A—H71A0.9600
C4—C5A1.541 (14)C7A—H72A0.9600
C11—O111.129 (4)C7A—H73A0.9600
C12—O121.139 (4)
C12—Co1—C11102.54 (15)O12—C12—Co1179.1 (3)
C12—Co1—C396.66 (13)C4—C5—H51109.5
C11—Co1—C3102.54 (14)C4—C5—H52109.5
C12—Co1—C1104.04 (11)H51—C5—H52109.5
C11—Co1—C1143.23 (15)C4—C5—H53109.5
C3—Co1—C199.12 (12)H51—C5—H53109.5
C12—Co1—Co1i150.03 (10)H52—C5—H53109.5
C11—Co1—Co1i96.93 (10)C4—C6—H61109.5
C3—Co1—Co1i101.12 (9)C4—C6—H62109.5
C1—Co1—Co1i49.53 (8)H61—C6—H62109.5
C12—Co1—Co1ii92.89 (10)C4—C6—H63109.5
C11—Co1—Co1ii104.41 (11)H61—C6—H63109.5
C3—Co1—Co1ii148.64 (9)H62—C6—H63109.5
Co1i—Co1—Co1ii60.0C4—C7—H71109.5
C3—N1—C4176.9 (4)C4—C7—H72109.5
C2—C1—Co1131.45 (10)H71—C7—H72109.5
Co1ii—C1—Co180.95 (16)C4—C7—H73109.5
C1—C2—H2A109.5H71—C7—H73109.5
C1—C2—H2B109.5H72—C7—H73109.5
H2A—C2—H2B109.5C4—C5A—H51A109.5
C1—C2—H2C109.5C4—C5A—H52A109.5
H2A—C2—H2C109.5H51A—C5A—H52A109.5
H2B—C2—H2C109.5C4—C5A—H53A109.5
N1—C3—Co1178.6 (3)H51A—C5A—H53A109.5
C7A—C4—N1109.7 (8)H52A—C5A—H53A109.5
C5—C4—N1109.2 (4)C4—C6A—H61A109.5
C5—C4—C6111.5 (7)C4—C6A—H62A109.5
N1—C4—C6107.7 (6)H61A—C6A—H62A109.5
C5—C4—C7108.3 (8)C4—C6A—H63A109.5
N1—C4—C7105.4 (4)H61A—C6A—H63A109.5
C6—C4—C7114.5 (9)H62A—C6A—H63A109.5
C7A—C4—C6A112.1 (14)C4—C7A—H71A109.5
N1—C4—C6A106.7 (5)C4—C7A—H72A109.5
C7A—C4—C5A114.7 (15)H71A—C7A—H72A109.5
N1—C4—C5A107.4 (5)C4—C7A—H73A109.5
C6A—C4—C5A105.9 (11)H71A—C7A—H73A109.5
O11—C11—Co1179.9 (4)H72A—C7A—H73A109.5
Symmetry codes: (i) −x+y+2, −x+1, z; (ii) −y+1, x−y−1, z.
Acknowledgements top

The authors thank Dr Jan Wikaira, University of Canterbury, New Zealand, for the collection of the X-ray intensity data.

references
References top

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