[(1R,4S)-(+)-3-Benzoyl-1,7,7-trimethyl­bicyclo­[2.2.1]heptan-2-olato-κ2O2,O3](η4-norbornadiene)rhodium(I)

Harrad, M.A.; Boualy, B.; Ali, M.A.; Firdoussi, L.E.; Rizzoli, C.

doi:10.1107/S160053681002667X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages m915-m916

https://doi.org/10.1107/S160053681002667X

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[(1R,4S)-(+)-3-Benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olato-κ²O²,O³](η⁴-norbornadiene)rhodium(I)

Mohamed Anoir Harrad,^a Brahim Boualy,^a Mustapha Ait Ali,^a Larbi El Firdoussi ^a and Corrado Rizzoli ^b ^*

^aLaboratoire de Chimie de Coordination, Faculté des Sciences-Semlalia, BP 2390, 40001 Marrakech, Morocco, and ^bDipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universitá degli Studi di Parma, Viale G. P. Usberti 17/A, I-43100 Parma, Italy
^*Correspondence e-mail: corrado.rizzoli@unipr.it

(Received 2 July 2010; accepted 6 July 2010; online 10 July 2010)

In the title complex molecule, [Rh(C₁₇H₁₉O₂)(C₇H₈)], the rhodium(I) metal centre is coordinated by the O atoms of a benzoylcamphorate anion and the C=C bonds of the norbornadiene molecule into a slightly distorted square-planar coordination geometry. The six-membered chelate ring is essentially planar (r.m.s. deviation = 0.0378 Å) and forms a dihedral angle of 31.67 (11)° with the phenyl ring.

Related literature

For the synthesis and properties of rhodium complexes in enantioselective transformations, see: Noyori (1994 ); Breuzard et al. (2000 ); Bernard et al. (2001 ). For the chemistry and applications of camphor-derived compounds, see: Togni (1990 ); Togni et al. (1993 ); Guo & Sadler (1999 ). For the synthesis, structure and applications of transition metal complexes in catalytic asymmetric reactions, see: Naili et al. (2000 ); Ait Ali, Allaoud et al. (2000 ); Fdil et al. (2002 ). For related structures, see: Spannenberg et al. (2002 ); Ait Ali, El Firdoussi et al. (2000 ); Ait Ali et al. (2001 , 2006 ); El Firdoussi et al. (2007 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Rh(C₁₇H₁₉O₂)(C₇H₈)]
M_r = 450.37
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.4755 (11) Å
b = 8.2817 (13) Å
c = 38.320 (6) Å
V = 2055.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 295 K
0.33 × 0.16 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.855, T_max = 0.937
21718 measured reflections
3990 independent reflections
3953 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.074
S = 1.27
3990 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −1.11 e Å⁻³
Absolute structure: Flack (1983 ), 1643 Friedel pairs
Flack parameter: 0.03 (4)

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and SCHAKAL97 (Keller, 1997 ); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681002667X/gk2290sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681002667X/gk2290Isup2.hkl

checkCIF report

Comment top

Rhodium complexes are widely used in organic chemistry due to their ability to mediate numerous transformations of organic molecules, often in catalytic mode. In particular, rhodium complexes of chiral ligands have shown to perform highly enantioselective transformations (Noyori, 1994; Breuzard et al., 2000; Bernard et al., 2001). Camphor-derived 1,3-diketonato ligands are a potentially attractive class of ligands in organometallic development, because these compounds are readily synthesized and easily varied (Togni, 1990; Togni et al., 1993). Moreover, some of their transition metal complexes can be used as therapeutic drugs (Guo & Sadler, 1999). As a contribution to our research programs aimed at the preparation of transition metal complexes (Spannenberg et al., 2002; Ait Ali, El Firdoussi et al., 2000; Ait Ali et al., 2001, 2006; El Firdoussi et al., 2007) and their application in catalytic asymmetric reactions (Naili et al., 2000; Ait Ali, Allaoud et al., 2000; Fdil et al., 2002), we report here the synthesis and crystal structure of the title compound.

In the mononuclear title complex molecule (Fig. 1), the rhodium(I) metal atom assumes a slightly tetrahedrally distorted square-planar coordination geometry provided by the O atoms of the chelating benzoylcamphorato anion and the centroids of the C═C double bonds of the norbornadiene molecule (maximum displacement 0.078 (5) Å for the centroid of the C18═C19 bonds). The RhO₂C₃ six-membered chelate ring is essentially planar (r.m.s. deviation = 0.0378 Å) and forms a dihedral angle of 31.67 (11)° with the C12–C17 phenyl ring. The C–O (O1–C2 = 1.265 (5) Å; O2–C11 = 1.298 (5) Å) and C–C (C2–C3 = 1.427 (6) Å; C3–C11 = 1.402 (5) Å) bond lengths pattern within the metallacycle indicates a high degree of π-delocalization. The Rh–O bond lengths (2.047 (3) and 2.059 (2) Å) are not significantly different from those observed in the closely related compound (cycloocta-1,5-diene)[(1R)-(+)-3-benzoyl-camphoryl]rhodium(I) (2.047 (3) and 2.059 (2) Å; Spannenberg et al., 2002). The Rh–C (mean value 2.113 (4) Å) and the donor C═C double bonds distances (mean value 1.388 (7) Å) involving the norbornadiene molecule are in agreement with the range of values observed in 286 related structures (mean values: Rh–C, 2.164 Å; C═C, 1.384 Å; Cambridge Structural Database; Version 5.31, November 2009; Allen, 2002). The crystal packing (Fig. 2) is stabilized only by van der Waals interactions.

Related literature top

For the synthesis and properties of rhodium complexes in enantioselective transformations, see: Noyori (1994); Breuzard et al. (2000); Bernard et al. (2001). For the chemistry and applications of camphor-derived compounds, see: Togni (1990); Togni et al. (1993); Guo & Sadler (1999). For the synthesis, structure and applications of transition metal complexes in catalytic asymmetric reactions, see: Naili et al. (2000); Ait Ali, Allaoud et al. (2000); Fdil et al. (2002). For related structures, see: Spannenberg et al. (2002); Ait Ali, El Firdoussi et al. (2000); Ait Ali et al. (2001, 2006); El Firdoussi et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

A solution of [Rh(norbornadiene)Cl]₂ (0.18 mmol, 100 mg) in THF (10 ml) was added to a suspension of (1R)-(+)-3-benzoylcamphor (0.32 mmol, 83.4 mg) and Na₂CO₃ (0.94 mmol, 100 mg) in THF (10 ml). The mixture was stirred for 3 h at room temperature, then it was evaporated to dryness under reduced pressure. The residue was extracted with CH₂Cl₂ (3 × 10 ml), and the recovered filtrate was evaporated to dryness to give an orange solid (yield 86%). Crystals suitable for X-ray analysis were obtained by slow evaporation of a diethyl ether solution.

Structure description top

For the synthesis and properties of rhodium complexes in enantioselective transformations, see: Noyori (1994); Breuzard et al. (2000); Bernard et al. (2001). For the chemistry and applications of camphor-derived compounds, see: Togni (1990); Togni et al. (1993); Guo & Sadler (1999). For the synthesis, structure and applications of transition metal complexes in catalytic asymmetric reactions, see: Naili et al. (2000); Ait Ali, Allaoud et al. (2000); Fdil et al. (2002). For related structures, see: Spannenberg et al. (2002); Ait Ali, El Firdoussi et al. (2000); Ait Ali et al. (2001, 2006); El Firdoussi et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL97 (Keller, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Crystal packing of the title compound viewed approximately along the a axis.

[(1R,4S)-(+)-3-Benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan- 2-olato-κ²O²,O³](η⁴-norbornadiene)rhodium(I) top

Crystal data top

[Rh(C₁₇H₁₉O₂)(C₇H₈)]	F(000) = 928
M_r = 450.37	D_x = 1.456 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 772 reflections
a = 6.4755 (11) Å	θ = 5.2–24.8°
b = 8.2817 (13) Å	µ = 0.85 mm⁻¹
c = 38.320 (6) Å	T = 295 K
V = 2055.0 (6) Å³	Block, orange
Z = 4	0.33 × 0.16 × 0.10 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3990 independent reflections
Radiation source: fine-focus sealed tube	3953 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 26.0°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −7→7
T_min = 0.855, T_max = 0.937	k = −10→10
21718 measured reflections	l = −47→47

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.017P)² + 2.5414P] where P = (F_o² + 2F_c²)/3
S = 1.27	(Δ/σ)_max = 0.001
3990 reflections	Δρ_max = 0.59 e Å⁻³
244 parameters	Δρ_min = −1.11 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1643 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (4)

Crystal data top

[Rh(C₁₇H₁₉O₂)(C₇H₈)]	V = 2055.0 (6) Å³
M_r = 450.37	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.4755 (11) Å	µ = 0.85 mm⁻¹
b = 8.2817 (13) Å	T = 295 K
c = 38.320 (6) Å	0.33 × 0.16 × 0.10 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3990 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3953 reflections with I > 2σ(I)
T_min = 0.855, T_max = 0.937	R_int = 0.040
21718 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.074	Δρ_max = 0.59 e Å⁻³
S = 1.27	Δρ_min = −1.11 e Å⁻³
3990 reflections	Absolute structure: Flack (1983), 1643 Friedel pairs
244 parameters	Absolute structure parameter: 0.03 (4)
0 restraints

Special details top

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
Rh1	0.56683 (5)	0.36256 (3)	0.081995 (8)	0.03291 (9)
O1	0.3616 (4)	0.1728 (3)	0.08213 (8)	0.0400 (6)
O2	0.5107 (4)	0.4086 (3)	0.13360 (7)	0.0398 (7)
C1	0.1414 (6)	−0.0255 (5)	0.11061 (11)	0.0368 (9)
C2	0.2775 (6)	0.1238 (5)	0.11000 (10)	0.0344 (8)
C3	0.2779 (6)	0.1910 (5)	0.14431 (10)	0.0318 (8)
C4	0.1389 (6)	0.0796 (5)	0.16545 (11)	0.0355 (9)
H4	0.1590	0.0847	0.1908	0.043*
C5	−0.0856 (7)	0.1121 (6)	0.15294 (11)	0.0471 (10)
H5A	−0.1853	0.0554	0.1673	0.056*
H5B	−0.1171	0.2266	0.1532	0.056*
C6	−0.0825 (8)	0.0446 (6)	0.11516 (12)	0.0460 (10)
H6A	−0.1088	0.1296	0.0983	0.055*
H6B	−0.1855	−0.0394	0.1123	0.055*
C7	0.1856 (7)	−0.0886 (5)	0.14854 (12)	0.0380 (9)
C8	0.0410 (9)	−0.2252 (5)	0.16093 (13)	0.0531 (12)
H8A	−0.1000	−0.1941	0.1571	0.080*
H8B	0.0628	−0.2445	0.1854	0.080*
H8C	0.0703	−0.3219	0.1480	0.080*
C9	0.4082 (7)	−0.1450 (6)	0.15381 (13)	0.0512 (10)
H9A	0.5013	−0.0621	0.1461	0.077*
H9B	0.4317	−0.2415	0.1405	0.077*
H9C	0.4315	−0.1667	0.1781	0.077*
C10	0.1716 (7)	−0.1380 (6)	0.07994 (14)	0.0571 (12)
H10A	0.0806	−0.2289	0.0822	0.086*
H10B	0.3121	−0.1749	0.0795	0.086*
H10C	0.1413	−0.0815	0.0587	0.086*
C11	0.3863 (6)	0.3304 (4)	0.15408 (10)	0.0327 (9)
C12	0.3729 (7)	0.4015 (5)	0.19004 (11)	0.0394 (10)
C13	0.5477 (10)	0.4824 (5)	0.20309 (12)	0.0527 (12)
H13	0.6684	0.4859	0.1900	0.063*
C14	0.5404 (13)	0.5571 (7)	0.23555 (14)	0.0759 (19)
H14	0.6574	0.6083	0.2442	0.091*
C15	0.3625 (13)	0.5558 (8)	0.25484 (16)	0.086 (2)
H15	0.3576	0.6085	0.2763	0.103*
C16	0.1911 (12)	0.4765 (7)	0.24245 (15)	0.0758 (19)
H16	0.0718	0.4738	0.2559	0.091*
C17	0.1928 (9)	0.3994 (6)	0.20983 (12)	0.0535 (12)
H17	0.0751	0.3476	0.2016	0.064*
C18	0.5765 (9)	0.4075 (6)	0.02782 (11)	0.0517 (11)
H18	0.4397	0.3876	0.0218	0.062*
C19	0.7252 (7)	0.2940 (5)	0.03643 (11)	0.0413 (10)
H19	0.7076	0.1827	0.0375	0.050*
C20	0.9252 (8)	0.3882 (5)	0.04392 (11)	0.0466 (10)
H20	1.0552	0.3276	0.0436	0.056*
C21	0.8629 (7)	0.4696 (5)	0.07839 (13)	0.0441 (10)
H21	0.9148	0.4467	0.1005	0.053*
C22	0.7137 (8)	0.5842 (5)	0.07018 (13)	0.0526 (13)
H22	0.6459	0.6529	0.0856	0.063*
C23	0.6835 (9)	0.5738 (6)	0.03026 (13)	0.0570 (13)
H23	0.6157	0.6652	0.0187	0.068*
C24	0.9039 (10)	0.5307 (6)	0.01829 (13)	0.0604 (14)
H24A	1.0027	0.6163	0.0227	0.072*
H24B	0.9101	0.4974	−0.0060	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.03562 (15)	0.03097 (13)	0.03214 (14)	−0.00890 (14)	0.00359 (13)	−0.00053 (14)
O1	0.0433 (15)	0.0385 (15)	0.0383 (14)	−0.0161 (11)	0.0057 (13)	−0.0017 (14)
O2	0.0494 (18)	0.0328 (15)	0.0372 (15)	−0.0137 (12)	0.0057 (12)	−0.0036 (11)
C1	0.031 (2)	0.036 (2)	0.043 (2)	−0.0109 (17)	0.0029 (17)	−0.0011 (18)
C2	0.0289 (18)	0.031 (2)	0.043 (2)	−0.0044 (18)	0.0009 (15)	0.0034 (19)
C3	0.031 (2)	0.0294 (19)	0.035 (2)	−0.0016 (15)	0.0032 (16)	0.0002 (16)
C4	0.035 (2)	0.037 (2)	0.035 (2)	−0.0034 (16)	0.0016 (16)	0.0032 (17)
C5	0.034 (2)	0.050 (3)	0.057 (3)	−0.002 (2)	0.007 (2)	0.002 (2)
C6	0.033 (2)	0.052 (3)	0.053 (3)	−0.008 (2)	−0.002 (2)	0.008 (2)
C7	0.035 (2)	0.029 (2)	0.050 (2)	−0.0058 (17)	0.0006 (18)	0.0041 (17)
C8	0.055 (3)	0.041 (2)	0.064 (3)	−0.014 (2)	0.005 (3)	0.013 (2)
C9	0.044 (3)	0.040 (2)	0.069 (3)	0.004 (3)	−0.003 (2)	0.000 (2)
C10	0.059 (3)	0.052 (2)	0.060 (3)	−0.026 (2)	0.010 (2)	−0.019 (3)
C11	0.039 (2)	0.0233 (19)	0.036 (2)	0.0011 (15)	0.0036 (16)	0.0002 (15)
C12	0.057 (3)	0.027 (2)	0.035 (2)	0.0042 (17)	0.0007 (18)	0.0028 (16)
C13	0.076 (4)	0.041 (2)	0.041 (2)	−0.006 (3)	−0.006 (3)	−0.0033 (18)
C14	0.117 (6)	0.061 (3)	0.049 (3)	−0.015 (4)	−0.019 (4)	−0.013 (3)
C15	0.149 (7)	0.062 (4)	0.047 (3)	−0.001 (4)	0.009 (4)	−0.025 (3)
C16	0.122 (6)	0.060 (3)	0.046 (3)	0.019 (4)	0.031 (3)	−0.001 (3)
C17	0.075 (3)	0.044 (3)	0.042 (2)	0.006 (2)	0.014 (2)	−0.002 (2)
C18	0.047 (2)	0.072 (3)	0.037 (2)	−0.014 (3)	−0.003 (2)	0.007 (2)
C19	0.053 (3)	0.039 (2)	0.031 (2)	−0.011 (2)	0.0085 (19)	−0.0046 (18)
C20	0.040 (2)	0.048 (2)	0.052 (2)	−0.006 (2)	0.008 (2)	0.0018 (19)
C21	0.046 (2)	0.045 (2)	0.040 (2)	−0.0219 (18)	0.000 (2)	0.000 (2)
C22	0.064 (3)	0.033 (2)	0.061 (3)	−0.013 (2)	0.021 (2)	0.002 (2)
C23	0.068 (3)	0.049 (3)	0.054 (3)	0.001 (3)	0.005 (3)	0.025 (2)
C24	0.070 (4)	0.061 (3)	0.050 (3)	−0.020 (3)	0.015 (3)	0.009 (2)

Geometric parameters (Å, º) top

Rh1—O2	2.047 (3)	C10—H10A	0.9600
Rh1—O1	2.059 (2)	C10—H10B	0.9600
Rh1—C19	2.103 (4)	C10—H10C	0.9600
Rh1—C18	2.110 (4)	C11—C12	1.501 (5)
Rh1—C22	2.116 (4)	C12—C17	1.391 (7)
Rh1—C21	2.116 (4)	C12—C13	1.407 (7)
O1—C2	1.265 (5)	C13—C14	1.390 (7)
O2—C11	1.298 (5)	C13—H13	0.9300
C1—C10	1.512 (6)	C14—C15	1.369 (10)
C1—C2	1.519 (5)	C14—H14	0.9300
C1—C7	1.571 (6)	C15—C16	1.374 (10)
C1—C6	1.572 (6)	C15—H15	0.9300
C2—C3	1.427 (6)	C16—C17	1.403 (7)
C3—C11	1.402 (5)	C16—H16	0.9300
C3—C4	1.522 (5)	C17—H17	0.9300
C4—C5	1.554 (6)	C18—C19	1.386 (7)
C4—C7	1.566 (6)	C18—C23	1.545 (7)
C4—H4	0.9800	C18—H18	0.9300
C5—C6	1.552 (6)	C19—C20	1.539 (6)
C5—H5A	0.9700	C19—H19	0.9300
C5—H5B	0.9700	C20—C21	1.537 (6)
C6—H6A	0.9700	C20—C24	1.541 (6)
C6—H6B	0.9700	C20—H20	0.9800
C7—C9	1.529 (6)	C21—C22	1.390 (7)
C7—C8	1.543 (6)	C21—H21	0.9300
C8—H8A	0.9600	C22—C23	1.544 (7)
C8—H8B	0.9600	C22—H22	0.9300
C8—H8C	0.9600	C23—C24	1.541 (8)
C9—H9A	0.9600	C23—H23	0.9800
C9—H9B	0.9600	C24—H24A	0.9700
C9—H9C	0.9600	C24—H24B	0.9700

O2—Rh1—O1	91.44 (11)	H10A—C10—H10B	109.5
O2—Rh1—C19	159.91 (16)	C1—C10—H10C	109.5
O1—Rh1—C19	96.36 (14)	H10A—C10—H10C	109.5
O2—Rh1—C18	157.38 (16)	H10B—C10—H10C	109.5
O1—Rh1—C18	98.99 (17)	O2—C11—C3	124.1 (4)
C19—Rh1—C18	38.40 (19)	O2—C11—C12	113.3 (3)
O2—Rh1—C22	97.18 (16)	C3—C11—C12	122.6 (3)
O1—Rh1—C22	162.36 (18)	C17—C12—C13	119.1 (4)
C19—Rh1—C22	80.64 (18)	C17—C12—C11	123.0 (4)
C18—Rh1—C22	67.9 (2)	C13—C12—C11	117.8 (4)
O2—Rh1—C21	98.38 (15)	C14—C13—C12	120.2 (6)
O1—Rh1—C21	154.79 (15)	C14—C13—H13	119.9
C19—Rh1—C21	67.50 (18)	C12—C13—H13	119.9
C18—Rh1—C21	80.5 (2)	C15—C14—C13	120.5 (6)
C22—Rh1—C21	38.35 (19)	C15—C14—H14	119.7
C2—O1—Rh1	121.6 (3)	C13—C14—H14	119.7
C11—O2—Rh1	127.0 (2)	C14—C15—C16	119.8 (5)
C10—C1—C2	114.5 (3)	C14—C15—H15	120.1
C10—C1—C7	119.4 (4)	C16—C15—H15	120.1
C2—C1—C7	100.3 (3)	C15—C16—C17	121.3 (6)
C10—C1—C6	115.7 (4)	C15—C16—H16	119.4
C2—C1—C6	103.7 (3)	C17—C16—H16	119.4
C7—C1—C6	100.9 (3)	C12—C17—C16	119.1 (6)
O1—C2—C3	130.7 (4)	C12—C17—H17	120.5
O1—C2—C1	121.6 (4)	C16—C17—H17	120.5
C3—C2—C1	107.7 (3)	C19—C18—C23	106.2 (4)
C11—C3—C2	124.6 (4)	C19—C18—Rh1	70.5 (2)
C11—C3—C4	130.8 (4)	C23—C18—Rh1	96.4 (3)
C2—C3—C4	104.6 (3)	C19—C18—H18	126.9
C3—C4—C5	106.5 (3)	C23—C18—H18	126.9
C3—C4—C7	101.8 (3)	Rh1—C18—H18	100.7
C5—C4—C7	102.0 (3)	C18—C19—C20	106.6 (4)
C3—C4—H4	115.0	C18—C19—Rh1	71.1 (3)
C5—C4—H4	115.0	C20—C19—Rh1	96.8 (3)
C7—C4—H4	115.0	C18—C19—H19	126.7
C6—C5—C4	102.3 (4)	C20—C19—H19	126.7
C6—C5—H5A	111.3	Rh1—C19—H19	99.9
C4—C5—H5A	111.3	C21—C20—C19	99.3 (3)
C6—C5—H5B	111.3	C21—C20—C24	100.9 (4)
C4—C5—H5B	111.3	C19—C20—C24	101.2 (4)
H5A—C5—H5B	109.2	C21—C20—H20	117.5
C5—C6—C1	104.4 (4)	C19—C20—H20	117.5
C5—C6—H6A	110.9	C24—C20—H20	117.5
C1—C6—H6A	110.9	C22—C21—C20	106.7 (4)
C5—C6—H6B	110.9	C22—C21—Rh1	70.8 (2)
C1—C6—H6B	110.9	C20—C21—Rh1	96.3 (3)
H6A—C6—H6B	108.9	C22—C21—H21	126.7
C9—C7—C8	107.9 (4)	C20—C21—H21	126.7
C9—C7—C4	113.5 (4)	Rh1—C21—H21	100.5
C8—C7—C4	114.1 (4)	C21—C22—C23	105.9 (4)
C9—C7—C1	113.3 (4)	C21—C22—Rh1	70.8 (2)
C8—C7—C1	114.7 (4)	C23—C22—Rh1	96.1 (3)
C4—C7—C1	93.0 (3)	C21—C22—H22	127.0
C7—C8—H8A	109.5	C23—C22—H22	127.0
C7—C8—H8B	109.5	Rh1—C22—H22	100.6
H8A—C8—H8B	109.5	C24—C23—C22	101.0 (4)
C7—C8—H8C	109.5	C24—C23—C18	101.0 (4)
H8A—C8—H8C	109.5	C22—C23—C18	99.6 (3)
H8B—C8—H8C	109.5	C24—C23—H23	117.4
C7—C9—H9A	109.5	C22—C23—H23	117.4
C7—C9—H9B	109.5	C18—C23—H23	117.4
H9A—C9—H9B	109.5	C23—C24—C20	94.1 (4)
C7—C9—H9C	109.5	C23—C24—H24A	112.9
H9A—C9—H9C	109.5	C20—C24—H24A	112.9
H9B—C9—H9C	109.5	C23—C24—H24B	112.9
C1—C10—H10A	109.5	C20—C24—H24B	112.9
C1—C10—H10B	109.5	H24A—C24—H24B	110.3

Experimental details

Crystal data
Chemical formula	[Rh(C₁₇H₁₉O₂)(C₇H₈)]
M_r	450.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	6.4755 (11), 8.2817 (13), 38.320 (6)
V (Å³)	2055.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.33 × 0.16 × 0.10

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.855, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	21718, 3990, 3953
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.074, 1.27
No. of reflections	3990
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −1.11
Absolute structure	Flack (1983), 1643 Friedel pairs
Absolute structure parameter	0.03 (4)

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SIR97 (Altomare et al., 1999), ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL97 (Keller, 1997), SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Acknowledgements

Financial support from the Universitá degli Studi di Parma is gratefully acknowledged.

References

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