Di-μ-carbonyl-bis­[bis­(triphenyl­phos­phane)rhodium(0)](Rh—Rh) acetone disolvate

Gueorguieva, P.G.; Laneman, S.A.; Stanley, G.G.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536812043528

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1408-m1409

doi:10.1107/S1600536812043528

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Di-μ-carbonyl-bis[bis(triphenylphosphane)rhodium(0)](Rh—Rh) acetone disolvate¹

Petia G. Gueorguieva,^a ‡ Scott A. Laneman,^a § George G. Stanley,^a Frank R. Fronczek ^a ^* and Steven F. Watkins ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 1 October 2012; accepted 19 October 2012; online 27 October 2012)

The dirhodium complex, [Rh₂(C₁₈H₁₅P)₄(CO)₂]·2(CH₃)₂CO, has crystallographic twofold symmetry and the Rh—Rh distance is 2.6266 (8) Å. The four atoms proximate to each Rh atom [Rh—P = 2.3222 (7) and 2.3283 (8) Å, and Rh—C = 1.961 (3) and 2.045 (3) Å] form a distorted tetrahedron with large deviations from the putative tetrahedral angles [r.m.s. deviation = 23 (1)°]. The six angles more closely approximate those of a trigonal bipyramid [r.m.s. deviation = 14 (1)°] with one missing equatorial ligand. The two bridging carbonyl ligands are much more linearly coordinated to one Rh [Rh—C≡O = 151.0 (2)°] than to the other [127.0 (2)°], and the two Rh₂CO planes form a dihedral angle of 45.43 (5)°. The two acetone solvent molecules are disordered, and their estimated scattering contribution was subtracted from the observed diffraction data using the SQUEEZE routine in PLATON [Spek (2009 ). Acta Cryst. D65, 148–155].

Related literature

For other dirhodium complex structures, see CCDC Refcode QAFHEM: Dzik et al. (2010 ), YOSMEZ: Okazaki et al. (2009 ), DEFJII: Douglas et al. (2005 ), TPCDRH10: Singh et al. (1973 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For the use of SQUEEZE, see: Spek (2009).

Experimental

Crystal data

[Rh₂(C₁₈H₁₅P)₄(CO)₂]·2C₃H₆O
M_r = 1427.16
Monoclinic, C 2/c
a = 23.535 (3) Å
b = 13.0758 (11) Å
c = 24.650 (2) Å
β = 115.67 (2)°
V = 6837.1 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 298 K
0.38 × 0.38 × 0.23 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.797, T_max = 0.869
6874 measured reflections
6718 independent reflections
5170 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 3 reflections intensity decay: 4.0%

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 1.03
6718 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ) and SQUEEZE in PLATON (Spek, 2009); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043528/lh5542sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043528/lh5542Isup2.hkl

checkCIF report

Comment top

The dirhodium complex (I), (Rh(CO)(PPh₃)₂)₂, is a precursor for HRh(CO)₂(PPh₃)₂, a hydroformylation catalyst. A less precise crystal structure of I, as the dichloromethane solvate, was reported by Singh et al. (1973). In both solvates, the complex lies on a crystallographic twofold axis, with Rh—Rh = 2.6266 (8) Å (Singh et al.: 2.630 (1) Å). The four atoms proximate to Rh (Rh—P1 = 2.3222 (7), Rh—P2 = 2.3283 (8), Rh—C40 = 1.961 (3), Rh—C40' = 2.045 (3) Å) form a distorted tetrahedron, but the six angles deviate markedly from the ideal tetrahedral angle (δ_r.m.s. = 23 (1)°). The angles approximate more closely those of a trigonal bipyramid (δ_r.m.s. = 14 (1)°), with P1 and C40 in axial and P2 and C40' in equatorial positions, wth one equatorial position vacant. The two bridging carbonyl ligands do not lie in the same plane, the two Rh₂CO planes forming a dihedral angle of 45.43 (5)°. Furthermore, each carbonyl is asymmetrically coordinated to the two Rh atoms, with a Rh—C distance of 1.961 (3) Å and Rh—C≡O angle 151.0 (2)° to one Rh, 2.045 (3) Å and 127.0 (2)° to the other. This asymmetric carbonyl bridging is also seen in the DCM solvate structure (Singh et al., 1973).

Related literature top

For other dirhodium complex structures, see CCDC Refcode QAFHEM: Dzik et al. (2010), YOSMEZ: Okazaki et al. (2009), DEFJII: Douglas et al. (2005), TPCDRH10: Singh et al. (1973). For a description of the Cambridge Structural Database, see: Allen (2002). For the use of SQUEEZE, see: Spek (2009).

Experimental top

Rh₂(CO)₂(PPh₃)₄ was synthesized from Rh(acac)(CO)₂ and excess triphenylphosphine under hydroformylation conditions, with acetone as solvent: A small autoclave was charged with a solution of Rh(acac)(CO)₂ (0.010 g), PPh₃ (9.750 g), and 1-hexene 7.883 g) in acetone (40 ml) while inside a glovebox. The autoclave was sealed, removed from the glovebox, and placed in a heating mantle. The headspace of the autoclave was purged with syn gas (1:1 H₂:CO, 3 x 60psig purges), and pressurized to 60psig with syn gas. The vessel was heated to 80°C and the syn gas pressure was adjusted to 80psig. After 18 h, the vessel was depressurized and purged with nitrogen (3x 60psig). The reaction mixture was analyzed with ¹H NMR: 91% aldehydes, 6.7% olefin isomerization, 2.2% 1-hexene. The n/i ratio of the aldehydes were 13.6. The reaction mixture slowly concentrated upon sitting in a glove box to afford a few red crystals of (I).

Structure description top

For other dirhodium complex structures, see CCDC Refcode QAFHEM: Dzik et al. (2010), YOSMEZ: Okazaki et al. (2009), DEFJII: Douglas et al. (2005), TPCDRH10: Singh et al. (1973). For a description of the Cambridge Structural Database, see: Allen (2002). For the use of SQUEEZE, see: Spek (2009).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and SQUEEZE in PLATON (Spek, 2009); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids). Unlabeled atoms are related by the symmetry operator (-x+2, y, -z+3/2).

Di-µ-carbonyl-bis[bis(triphenylphosphane)rhodium(0)](Rh—Rh) acetone disolvate top

Crystal data top

[Rh₂(C₁₈H₁₅P)₄(CO)₂]·2C₃H₆O	F(000) = 2936
M_r = 1427.16	D_x = 1.386 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 23.535 (3) Å	θ = 2.6–27.5°
b = 13.0758 (11) Å	µ = 0.63 mm⁻¹
c = 24.650 (2) Å	T = 298 K
β = 115.67 (2)°	Prism, red
V = 6837.1 (16) Å³	0.38 × 0.38 × 0.23 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	5170 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 26.0°, θ_min = 1.8°
θ/2θ scans	h = 0→28
Absorption correction: ψ scan (North et al., 1968)	k = 0→16
T_min = 0.797, T_max = 0.869	l = −30→27
6874 measured reflections	3 standard reflections every 3 reflections
6718 independent reflections	intensity decay: 4.0%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0423P)² + 0.3727P] where P = (F_o² + 2F_c²)/3
6718 reflections	(Δ/σ)_max = 0.003
370 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³
0 constraints

Crystal data top

[Rh₂(C₁₈H₁₅P)₄(CO)₂]·2C₃H₆O	V = 6837.1 (16) Å³
M_r = 1427.16	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 23.535 (3) Å	µ = 0.63 mm⁻¹
b = 13.0758 (11) Å	T = 298 K
c = 24.650 (2) Å	0.38 × 0.38 × 0.23 mm
β = 115.67 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	5170 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.026
T_min = 0.797, T_max = 0.869	3 standard reflections every 3 reflections
6874 measured reflections	intensity decay: 4.0%
6718 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.03	Δρ_max = 0.39 e Å⁻³
6718 reflections	Δρ_min = −0.27 e Å⁻³
370 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.88187 (3)	−0.11053 (5)	0.72824 (3)	0.03726 (16)
C1	0.81798 (13)	−0.0719 (2)	0.74770 (11)	0.0410 (6)
C2	0.80127 (16)	0.0298 (2)	0.74235 (14)	0.0549 (8)
H2	0.8229	0.0768	0.73	0.066*
C3	0.7526 (2)	0.0623 (3)	0.75522 (17)	0.0752 (11)
H3	0.7419	0.1313	0.7518	0.09*
C4	0.71999 (19)	−0.0065 (3)	0.77297 (17)	0.0768 (11)
H4	0.6865	0.0155	0.7804	0.092*
C5	0.73669 (16)	−0.1068 (3)	0.77967 (14)	0.0621 (9)
H5	0.7148	−0.1534	0.792	0.075*
C6	0.78618 (15)	−0.1396 (2)	0.76812 (13)	0.0524 (7)
H6	0.7983	−0.2079	0.7741	0.063*
C7	0.84532 (13)	−0.19569 (19)	0.66282 (12)	0.0411 (6)
C8	0.87874 (15)	−0.2110 (2)	0.62867 (14)	0.0547 (8)
H8	0.9177	−0.1797	0.6398	0.066*
C9	0.85363 (17)	−0.2730 (3)	0.57799 (15)	0.0671 (10)
H9	0.8756	−0.2824	0.5548	0.081*
C10	0.79721 (18)	−0.3200 (3)	0.56208 (15)	0.0706 (10)
H10	0.7811	−0.3625	0.5285	0.085*
C11	0.76397 (18)	−0.3051 (3)	0.59513 (16)	0.0694 (10)
H11	0.7249	−0.3363	0.5835	0.083*
C12	0.78835 (15)	−0.2437 (2)	0.64586 (13)	0.0560 (8)
H12	0.7659	−0.2349	0.6686	0.067*
C13	0.92309 (13)	−0.2033 (2)	0.78900 (12)	0.0436 (6)
C14	0.93637 (16)	−0.3018 (2)	0.77782 (15)	0.0613 (9)
H14	0.9245	−0.3234	0.7384	0.074*
C15	0.96749 (18)	−0.3687 (3)	0.82533 (18)	0.0770 (11)
H15	0.9769	−0.4345	0.8174	0.092*
C16	0.98448 (17)	−0.3396 (3)	0.88318 (17)	0.0736 (11)
H16	1.0041	−0.3856	0.9146	0.088*
C17	0.97239 (17)	−0.2422 (3)	0.89466 (15)	0.0717 (10)
H17	0.9847	−0.2213	0.9342	0.086*
C18	0.94185 (15)	−0.1738 (3)	0.84792 (14)	0.0585 (8)
H18	0.934	−0.1074	0.8564	0.07*
P2	0.86831 (3)	0.09673 (5)	0.62360 (3)	0.03564 (16)
C19	0.88124 (12)	0.2359 (2)	0.63031 (12)	0.0401 (6)
C20	0.90876 (14)	0.2779 (2)	0.68686 (13)	0.0521 (8)
H20	0.9236	0.2352	0.7203	0.063*
C21	0.91480 (16)	0.3830 (2)	0.69503 (15)	0.0636 (9)
H21	0.9334	0.4101	0.7337	0.076*
C22	0.89343 (16)	0.4465 (2)	0.64633 (17)	0.0654 (9)
H22	0.8971	0.517	0.6518	0.079*
C23	0.86680 (18)	0.4065 (3)	0.58989 (17)	0.0717 (10)
H23	0.8526	0.4499	0.5567	0.086*
C24	0.86062 (16)	0.3016 (2)	0.58135 (14)	0.0593 (8)
H24	0.8425	0.275	0.5425	0.071*
C25	0.78347 (12)	0.0915 (2)	0.60350 (11)	0.0398 (6)
C26	0.74864 (14)	0.1729 (2)	0.60884 (13)	0.0523 (7)
H26	0.7679	0.2362	0.6214	0.063*
C27	0.68550 (16)	0.1614 (3)	0.59578 (16)	0.0680 (9)
H27	0.6628	0.2171	0.5995	0.082*
C28	0.65644 (16)	0.0694 (3)	0.57752 (16)	0.0685 (10)
H28	0.6143	0.0619	0.5697	0.082*
C29	0.68964 (15)	−0.0129 (3)	0.57065 (15)	0.0597 (8)
H29	0.6696	−0.0755	0.5574	0.072*
C30	0.75280 (14)	−0.0021 (2)	0.58356 (13)	0.0470 (7)
H30	0.775	−0.0577	0.5789	0.056*
C31	0.86728 (13)	0.0638 (2)	0.55073 (12)	0.0414 (6)
C32	0.81587 (15)	0.0855 (2)	0.49619 (12)	0.0545 (8)
H32	0.7809	0.1187	0.4962	0.065*
C33	0.81608 (19)	0.0587 (3)	0.44229 (14)	0.0676 (10)
H33	0.7815	0.0745	0.4063	0.081*
C34	0.8669 (2)	0.0088 (3)	0.44120 (16)	0.0728 (11)
H34	0.8673	−0.0083	0.4047	0.087*
C35	0.9171 (2)	−0.0156 (3)	0.49460 (19)	0.0835 (12)
H35	0.9514	−0.0503	0.4942	0.1*
C36	0.91725 (16)	0.0110 (3)	0.54926 (15)	0.0639 (9)
H36	0.9513	−0.007	0.5851	0.077*
Rh1	0.941218 (9)	0.013747 (14)	0.708963 (9)	0.03409 (7)
C40	1.01769 (13)	0.0593 (2)	0.70298 (12)	0.0435 (7)
O40	1.04318 (10)	0.09216 (19)	0.67507 (10)	0.0660 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0398 (4)	0.0314 (3)	0.0343 (3)	−0.0018 (3)	0.0101 (3)	−0.0004 (3)
C1	0.0425 (15)	0.0420 (16)	0.0325 (13)	−0.0010 (12)	0.0106 (12)	−0.0010 (11)
C2	0.072 (2)	0.0469 (18)	0.0517 (18)	0.0104 (15)	0.0326 (16)	0.0081 (14)
C3	0.094 (3)	0.064 (2)	0.081 (3)	0.031 (2)	0.051 (2)	0.015 (2)
C4	0.075 (3)	0.101 (3)	0.071 (2)	0.027 (2)	0.048 (2)	0.016 (2)
C5	0.063 (2)	0.078 (2)	0.0519 (19)	−0.0085 (18)	0.0311 (17)	0.0064 (17)
C6	0.0587 (19)	0.0476 (17)	0.0506 (17)	−0.0074 (14)	0.0234 (15)	−0.0024 (14)
C7	0.0443 (15)	0.0309 (13)	0.0369 (14)	0.0001 (11)	0.0071 (12)	−0.0004 (11)
C8	0.0515 (18)	0.0554 (19)	0.0513 (18)	0.0051 (15)	0.0169 (15)	−0.0078 (14)
C9	0.074 (2)	0.068 (2)	0.0511 (19)	0.0114 (19)	0.0190 (17)	−0.0148 (17)
C10	0.080 (3)	0.056 (2)	0.0483 (19)	0.0008 (19)	0.0029 (18)	−0.0171 (16)
C11	0.072 (2)	0.059 (2)	0.063 (2)	−0.0199 (18)	0.0158 (19)	−0.0109 (17)
C12	0.061 (2)	0.0533 (19)	0.0499 (17)	−0.0183 (15)	0.0205 (15)	−0.0082 (14)
C13	0.0429 (15)	0.0394 (15)	0.0425 (15)	0.0003 (12)	0.0129 (13)	0.0071 (12)
C14	0.067 (2)	0.0473 (18)	0.0561 (19)	0.0123 (16)	0.0140 (16)	0.0040 (15)
C15	0.081 (3)	0.049 (2)	0.079 (3)	0.0132 (19)	0.014 (2)	0.0149 (19)
C16	0.063 (2)	0.067 (2)	0.073 (3)	0.0084 (18)	0.0131 (19)	0.035 (2)
C17	0.071 (2)	0.084 (3)	0.0462 (19)	0.000 (2)	0.0128 (17)	0.0166 (18)
C18	0.067 (2)	0.0502 (18)	0.0500 (18)	−0.0006 (16)	0.0172 (16)	0.0045 (14)
P2	0.0333 (3)	0.0350 (4)	0.0313 (3)	0.0018 (3)	0.0071 (3)	0.0008 (3)
C19	0.0349 (14)	0.0352 (14)	0.0426 (15)	0.0018 (11)	0.0097 (11)	0.0019 (11)
C20	0.0530 (18)	0.0422 (16)	0.0472 (17)	0.0042 (14)	0.0087 (14)	−0.0011 (13)
C21	0.067 (2)	0.0438 (18)	0.062 (2)	−0.0012 (16)	0.0106 (16)	−0.0124 (15)
C22	0.066 (2)	0.0346 (16)	0.087 (3)	−0.0006 (15)	0.025 (2)	−0.0032 (17)
C23	0.088 (3)	0.0410 (18)	0.075 (2)	0.0024 (17)	0.025 (2)	0.0164 (17)
C24	0.072 (2)	0.0459 (18)	0.0479 (18)	−0.0008 (16)	0.0146 (16)	0.0047 (14)
C25	0.0343 (14)	0.0432 (15)	0.0334 (13)	0.0033 (11)	0.0067 (11)	0.0032 (11)
C26	0.0454 (17)	0.0526 (18)	0.0557 (18)	0.0042 (14)	0.0188 (15)	−0.0013 (14)
C27	0.051 (2)	0.075 (2)	0.082 (2)	0.0142 (18)	0.0320 (19)	0.0062 (19)
C28	0.0387 (17)	0.086 (3)	0.076 (2)	−0.0043 (18)	0.0207 (17)	0.012 (2)
C29	0.0460 (17)	0.060 (2)	0.064 (2)	−0.0115 (15)	0.0156 (15)	0.0076 (16)
C30	0.0418 (15)	0.0487 (17)	0.0435 (15)	−0.0005 (13)	0.0118 (12)	0.0039 (12)
C31	0.0430 (15)	0.0404 (15)	0.0372 (14)	−0.0042 (12)	0.0141 (12)	−0.0014 (11)
C32	0.062 (2)	0.0548 (18)	0.0376 (15)	0.0089 (15)	0.0132 (14)	0.0042 (13)
C33	0.092 (3)	0.063 (2)	0.0361 (16)	−0.003 (2)	0.0164 (17)	0.0008 (15)
C34	0.096 (3)	0.081 (3)	0.051 (2)	−0.026 (2)	0.040 (2)	−0.0163 (18)
C35	0.071 (3)	0.111 (3)	0.080 (3)	−0.006 (2)	0.044 (2)	−0.027 (2)
C36	0.0499 (18)	0.085 (3)	0.0538 (19)	0.0008 (17)	0.0195 (15)	−0.0136 (17)
Rh1	0.03109 (11)	0.03049 (11)	0.03132 (11)	−0.00057 (8)	0.00472 (8)	0.00033 (8)
C40	0.0425 (16)	0.0366 (14)	0.0378 (14)	−0.0003 (12)	0.0047 (12)	0.0054 (12)
O40	0.0493 (13)	0.0884 (17)	0.0531 (13)	−0.0058 (12)	0.0154 (11)	0.0280 (12)

Geometric parameters (Å, º) top

P1—C1	1.836 (3)	P2—Rh1	2.3283 (8)
P1—C7	1.838 (3)	C19—C20	1.372 (4)
P1—C13	1.843 (3)	C19—C24	1.386 (4)
P1—Rh1	2.3222 (7)	C20—C21	1.387 (4)
C1—C2	1.376 (4)	C20—H20	0.93
C1—C6	1.387 (4)	C21—C22	1.364 (5)
C2—C3	1.382 (5)	C21—H21	0.93
C2—H2	0.93	C22—C23	1.359 (5)
C3—C4	1.372 (5)	C22—H22	0.93
C3—H3	0.93	C23—C24	1.386 (4)
C4—C5	1.359 (5)	C23—H23	0.93
C4—H4	0.93	C24—H24	0.93
C5—C6	1.382 (4)	C25—C26	1.384 (4)
C5—H5	0.93	C25—C30	1.397 (4)
C6—H6	0.93	C26—C27	1.386 (4)
C7—C12	1.372 (4)	C26—H26	0.93
C7—C8	1.393 (4)	C27—C28	1.361 (5)
C8—C9	1.389 (4)	C27—H27	0.93
C8—H8	0.93	C28—C29	1.383 (5)
C9—C10	1.358 (5)	C28—H28	0.93
C9—H9	0.93	C29—C30	1.386 (4)
C10—C11	1.366 (5)	C29—H29	0.93
C10—H10	0.93	C30—H30	0.93
C11—C12	1.384 (4)	C31—C36	1.377 (4)
C11—H11	0.93	C31—C32	1.394 (4)
C12—H12	0.93	C32—C33	1.376 (4)
C13—C18	1.378 (4)	C32—H32	0.93
C13—C14	1.381 (4)	C33—C34	1.373 (5)
C14—C15	1.389 (4)	C33—H33	0.93
C14—H14	0.93	C34—C35	1.372 (6)
C15—C16	1.358 (5)	C34—H34	0.93
C15—H15	0.93	C35—C36	1.390 (5)
C16—C17	1.361 (5)	C35—H35	0.93
C16—H16	0.93	C36—H36	0.93
C17—C18	1.388 (4)	Rh1—C40	1.961 (3)
C17—H17	0.93	Rh1—C40ⁱ	2.045 (3)
C18—H18	0.93	Rh1—Rh1ⁱ	2.6266 (8)
P2—C31	1.837 (3)	C40—O40	1.173 (3)
P2—C25	1.838 (3)	C40—Rh1ⁱ	2.045 (3)
P2—C19	1.841 (3)

C1—P1—C7	105.72 (13)	C20—C19—P2	118.3 (2)
C1—P1—C13	99.86 (13)	C24—C19—P2	123.5 (2)
C7—P1—C13	101.28 (12)	C19—C20—C21	121.2 (3)
C1—P1—Rh1	119.62 (9)	C19—C20—H20	119.4
C7—P1—Rh1	109.80 (9)	C21—C20—H20	119.4
C13—P1—Rh1	118.38 (9)	C22—C21—C20	120.0 (3)
C2—C1—C6	118.3 (3)	C22—C21—H21	120
C2—C1—P1	118.2 (2)	C20—C21—H21	120
C6—C1—P1	123.4 (2)	C23—C22—C21	119.8 (3)
C1—C2—C3	120.4 (3)	C23—C22—H22	120.1
C1—C2—H2	119.8	C21—C22—H22	120.1
C3—C2—H2	119.8	C22—C23—C24	120.5 (3)
C4—C3—C2	120.3 (3)	C22—C23—H23	119.7
C4—C3—H3	119.8	C24—C23—H23	119.7
C2—C3—H3	119.8	C19—C24—C23	120.4 (3)
C5—C4—C3	120.0 (3)	C19—C24—H24	119.8
C5—C4—H4	120	C23—C24—H24	119.8
C3—C4—H4	120	C26—C25—C30	118.0 (3)
C4—C5—C6	120.0 (3)	C26—C25—P2	124.4 (2)
C4—C5—H5	120	C30—C25—P2	117.6 (2)
C6—C5—H5	120	C25—C26—C27	121.0 (3)
C5—C6—C1	120.8 (3)	C25—C26—H26	119.5
C5—C6—H6	119.6	C27—C26—H26	119.5
C1—C6—H6	119.6	C28—C27—C26	120.5 (3)
C12—C7—C8	118.9 (3)	C28—C27—H27	119.8
C12—C7—P1	124.7 (2)	C26—C27—H27	119.8
C8—C7—P1	116.4 (2)	C27—C28—C29	119.9 (3)
C9—C8—C7	119.7 (3)	C27—C28—H28	120
C9—C8—H8	120.1	C29—C28—H28	120
C7—C8—H8	120.1	C28—C29—C30	119.9 (3)
C10—C9—C8	120.4 (3)	C28—C29—H29	120
C10—C9—H9	119.8	C30—C29—H29	120
C8—C9—H9	119.8	C29—C30—C25	120.6 (3)
C9—C10—C11	120.3 (3)	C29—C30—H30	119.7
C9—C10—H10	119.9	C25—C30—H30	119.7
C11—C10—H10	119.9	C36—C31—C32	118.1 (3)
C10—C11—C12	120.1 (3)	C36—C31—P2	119.6 (2)
C10—C11—H11	120	C32—C31—P2	122.2 (2)
C12—C11—H11	120	C33—C32—C31	121.0 (3)
C7—C12—C11	120.6 (3)	C33—C32—H32	119.5
C7—C12—H12	119.7	C31—C32—H32	119.5
C11—C12—H12	119.7	C34—C33—C32	120.5 (3)
C18—C13—C14	118.4 (3)	C34—C33—H33	119.7
C18—C13—P1	119.2 (2)	C32—C33—H33	119.7
C14—C13—P1	122.5 (2)	C35—C34—C33	119.1 (3)
C13—C14—C15	120.1 (3)	C35—C34—H34	120.4
C13—C14—H14	120	C33—C34—H34	120.4
C15—C14—H14	120	C34—C35—C36	120.8 (4)
C16—C15—C14	121.1 (3)	C34—C35—H35	119.6
C16—C15—H15	119.4	C36—C35—H35	119.6
C14—C15—H15	119.4	C31—C36—C35	120.4 (3)
C15—C16—C17	119.2 (3)	C31—C36—H36	119.8
C15—C16—H16	120.4	C35—C36—H36	119.8
C17—C16—H16	120.4	C40—Rh1—C40ⁱ	87.93 (14)
C16—C17—C18	120.7 (3)	C40—Rh1—P1	151.76 (8)
C16—C17—H17	119.7	C40ⁱ—Rh1—P1	92.09 (9)
C18—C17—H17	119.7	C40—Rh1—P2	97.56 (8)
C13—C18—C17	120.6 (3)	C40ⁱ—Rh1—P2	130.38 (8)
C13—C18—H18	119.7	P1—Rh1—P2	103.76 (3)
C17—C18—H18	119.7	C40—Rh1—Rh1ⁱ	50.44 (8)
C31—P2—C25	100.08 (12)	C40ⁱ—Rh1—Rh1ⁱ	47.66 (8)
C31—P2—C19	104.56 (13)	P1—Rh1—Rh1ⁱ	111.635 (19)
C25—P2—C19	100.32 (12)	P2—Rh1—Rh1ⁱ	144.50 (2)
C31—P2—Rh1	117.82 (9)	O40—C40—Rh1	151.0 (2)
C25—P2—Rh1	121.02 (9)	O40—C40—Rh1ⁱ	127.0 (2)
C19—P2—Rh1	110.55 (8)	Rh1—C40—Rh1ⁱ	81.90 (11)
C20—C19—C24	118.0 (3)

C7—P1—C1—C2	−115.7 (2)	Rh1—P2—C25—C26	107.8 (2)
C13—P1—C1—C2	139.5 (2)	C31—P2—C25—C30	61.5 (2)
Rh1—P1—C1—C2	8.7 (3)	C19—P2—C25—C30	168.5 (2)
C7—P1—C1—C6	65.1 (3)	Rh1—P2—C25—C30	−69.8 (2)
C13—P1—C1—C6	−39.7 (3)	C30—C25—C26—C27	1.1 (4)
Rh1—P1—C1—C6	−170.5 (2)	P2—C25—C26—C27	−176.5 (2)
C6—C1—C2—C3	−2.1 (5)	C25—C26—C27—C28	0.2 (5)
P1—C1—C2—C3	178.6 (3)	C26—C27—C28—C29	−1.4 (6)
C1—C2—C3—C4	−0.6 (6)	C27—C28—C29—C30	1.3 (5)
C2—C3—C4—C5	1.9 (6)	C28—C29—C30—C25	0.0 (5)
C3—C4—C5—C6	−0.5 (6)	C26—C25—C30—C29	−1.1 (4)
C4—C5—C6—C1	−2.2 (5)	P2—C25—C30—C29	176.6 (2)
C2—C1—C6—C5	3.5 (4)	C25—P2—C31—C36	−148.2 (3)
P1—C1—C6—C5	−177.3 (2)	C19—P2—C31—C36	108.3 (3)
C1—P1—C7—C12	−18.3 (3)	Rh1—P2—C31—C36	−14.9 (3)
C13—P1—C7—C12	85.5 (3)	C25—P2—C31—C32	28.3 (3)
Rh1—P1—C7—C12	−148.6 (2)	C19—P2—C31—C32	−75.2 (3)
C1—P1—C7—C8	161.5 (2)	Rh1—P2—C31—C32	161.6 (2)
C13—P1—C7—C8	−94.8 (2)	C36—C31—C32—C33	−2.6 (5)
Rh1—P1—C7—C8	31.2 (2)	P2—C31—C32—C33	−179.1 (3)
C12—C7—C8—C9	0.8 (4)	C31—C32—C33—C34	0.7 (5)
P1—C7—C8—C9	−179.0 (2)	C32—C33—C34—C35	1.1 (6)
C7—C8—C9—C10	−1.0 (5)	C33—C34—C35—C36	−1.0 (6)
C8—C9—C10—C11	1.3 (6)	C32—C31—C36—C35	2.7 (5)
C9—C10—C11—C12	−1.4 (6)	P2—C31—C36—C35	179.3 (3)
C8—C7—C12—C11	−1.0 (5)	C34—C35—C36—C31	−1.0 (6)
P1—C7—C12—C11	178.8 (2)	C1—P1—Rh1—C40	158.53 (19)
C10—C11—C12—C7	1.3 (5)	C7—P1—Rh1—C40	−79.1 (2)
C1—P1—C13—C18	−53.5 (3)	C13—P1—Rh1—C40	36.5 (2)
C7—P1—C13—C18	−161.9 (3)	C1—P1—Rh1—C40ⁱ	69.02 (13)
Rh1—P1—C13—C18	78.1 (3)	C7—P1—Rh1—C40ⁱ	−168.58 (12)
C1—P1—C13—C14	126.8 (3)	C13—P1—Rh1—C40ⁱ	−53.06 (13)
C7—P1—C13—C14	18.5 (3)	C1—P1—Rh1—P2	−63.55 (10)
Rh1—P1—C13—C14	−101.5 (3)	C7—P1—Rh1—P2	58.85 (9)
C18—C13—C14—C15	0.5 (5)	C13—P1—Rh1—P2	174.37 (11)
P1—C13—C14—C15	−179.9 (3)	C1—P1—Rh1—Rh1ⁱ	113.74 (9)
C13—C14—C15—C16	1.1 (6)	C7—P1—Rh1—Rh1ⁱ	−123.86 (9)
C14—C15—C16—C17	−2.0 (6)	C13—P1—Rh1—Rh1ⁱ	−8.34 (11)
C15—C16—C17—C18	1.4 (6)	C31—P2—Rh1—C40	59.88 (13)
C14—C13—C18—C17	−1.1 (5)	C25—P2—Rh1—C40	−176.87 (13)
P1—C13—C18—C17	179.3 (3)	C19—P2—Rh1—C40	−60.21 (13)
C16—C17—C18—C13	0.2 (5)	C31—P2—Rh1—C40ⁱ	153.61 (15)
C31—P2—C19—C20	−154.4 (2)	C25—P2—Rh1—C40ⁱ	−83.14 (15)
C25—P2—C19—C20	102.2 (2)	C19—P2—Rh1—C40ⁱ	33.52 (15)
Rh1—P2—C19—C20	−26.6 (3)	C31—P2—Rh1—P1	−101.46 (10)
C31—P2—C19—C24	30.4 (3)	C25—P2—Rh1—P1	21.78 (11)
C25—P2—C19—C24	−73.0 (3)	C19—P2—Rh1—P1	138.45 (10)
Rh1—P2—C19—C24	158.1 (2)	C31—P2—Rh1—Rh1ⁱ	82.89 (11)
C24—C19—C20—C21	1.2 (5)	C25—P2—Rh1—Rh1ⁱ	−153.87 (10)
P2—C19—C20—C21	−174.3 (3)	C19—P2—Rh1—Rh1ⁱ	−37.21 (11)
C19—C20—C21—C22	−0.3 (5)	C40ⁱ—Rh1—C40—O40	−150.3 (5)
C20—C21—C22—C23	−0.6 (6)	P1—Rh1—C40—O40	119.1 (5)
C21—C22—C23—C24	0.6 (6)	P2—Rh1—C40—O40	−19.8 (5)
C20—C19—C24—C23	−1.2 (5)	Rh1ⁱ—Rh1—C40—O40	177.3 (6)
P2—C19—C24—C23	174.0 (3)	C40ⁱ—Rh1—C40—Rh1ⁱ	32.40 (14)
C22—C23—C24—C19	0.3 (6)	P1—Rh1—C40—Rh1ⁱ	−58.2 (2)
C31—P2—C25—C26	−120.9 (3)	P2—Rh1—C40—Rh1ⁱ	162.88 (6)
C19—P2—C25—C26	−13.9 (3)

Symmetry code: (i) −x+2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Rh₂(C₁₈H₁₅P)₄(CO)₂]·2C₃H₆O
M_r	1427.16
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	23.535 (3), 13.0758 (11), 24.650 (2)
β (°)	115.67 (2)
V (Å³)	6837.1 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.38 × 0.38 × 0.23

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.797, 0.869
No. of measured, independent and observed [I > 2σ(I)] reflections	6874, 6718, 5170
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 1.03
No. of reflections	6718
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.27

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008) and SQUEEZE in PLATON (Spek, 2009), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Footnotes

¹CAS 47921–72–2, 48246–55–5.

‡Current address: School of Natural Sciences, University of California, Merced, 5200 North Lake Rd, Merced, CA 95343, USA.

§Current address: Digital Specialty Chemicals, Inc., 300 Apollo Ct., Vernon Hills, IL 60661, USA.

Acknowledgements

The purchase of the diffractometer was made possible by a National Science Foundation chemical instrumentation grant, which we gratefully acknowledge. Improvements to the LSU X-ray Crystallography Facility were supported by grant No. LEQSF(1196–97)-ENH-TR-10, administered by the Louisiana Board of Regents.

References

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