(Acetyl­acetonato-κ2O,O′)carbon­yl(cyclohexyl­diphenyl­phosphine-κP)rhodium(I)

Brink, A.; Roodt, A.; Visser, H.G.

doi:10.1107/S1600536807052427

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(Acetylacetonato-κ²O,O′)carbonyl(cyclohexyldiphenylphosphine-κP)rhodium(I)

A. Brink, A. Roodt and H. G. Visser

The title compound, [Rh(C₅H₇O₂)(C₁₈H₂₁P)(CO)], has the acetylacetonate-chelated Rh^I atom in a square-planar geometry. Intramolecular C—H

O hydrogen bonds exist between the acetylacetonate group and the cyclohexyl ring, resulting in a buckling of the acetylacetonate skeleton. Molecules are packed in positions of least steric hindrance, with the phosphine ligands positioned above and below the Rh–acetylacetonate backbone.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052427/ng2345sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052427/ng2345Isup2.hkl Contains datablock I

CCDC reference: 667229

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.005 Å
R factor = 0.024
wR factor = 0.061
Data-to-parameter ratio = 18.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.56 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C14    -   C15     ..       6.20 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C15    -   C16     ..       5.02 su

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.00
           From the CIF: _reflns_number_total               4825
           Count of symmetry unique reflns         2762
           Completeness (_total/calc)            174.69%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2063
           Fraction of Friedel pairs measured     0.747
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

This work is part of an ongoing investigation aimed at determing the steric and electronic effects induced by various phosphine ligands on a rhodium(I) metal centre. Previous work illustrating the catalytic importance of the rhodium(I) square-planar moieties has been conducted on rhodium mono- and di-phosphine complexes containing the symmetrical bidentate ligand, acac (acac = acetylacetonate) (Moloy et al., 1989). Symmetrical di-phosphine ligands result in the producton of acetaldehyde, whereas unsymmetrical di-phosphine ligands are more stable and efficient catalysts for the carbonylation of methanol to acetic acid (Carraz et al., 2000). The title compound, [Rh(acac)(CO)(PCyPh₂)] (Cy = cyclohexyl, Ph = phenyl), (Fig. 1), forms part of our study on complexes of the type [Rh(β-diketone)(CO)(PR₁R₂R₃)] (R₁, R₂ and R₃ = cyclohexyl or phenyl).

Slight distortion of the square-planar coordination sphere is observed as illustrated by a 5.04 (4)° deviation from the square plane. The Rh(I) atom deviates by 0.0596 (2) Å from the plane defined by the four coordinate atoms O2, O3, P1 and C1. The acetylacetonate ligand exhibits a bite angle of 88.72 (7)° and the C1—Rh—P1 bond angle is 88.51 (8)°. The carbonyl ligand is nearly linear (Rh1—C1—O1 = 179.2 (3)°). Intramolecular C—H···O interaction (Table 2) results in twisting of the the acetylacetonate backbone as indicated by the C2—O2—O3—C4 torsion angle (3.1 (2)°).

The steric demand of the cyclohexyldiphenyl phosphine ligand is quantified by the effective cone angle (θ_E), calculated using the actual Rh—P bond distance (Otto et al., 2000). The θ_E value of 151° agrees with the value determined by Meij et al. (2003) for the trans-[PdCl₂(PCyPh₂)₂] complex (151 and 155°). The value of the effective cone angle of the title compound fits the sequence of 163° for [Rh(acac)(CO)(PCy₂Ph)] (Brink et al., 2007) and of 145 and 170° for the corresponding Vaska-type rhodium complexes trans- [Rh(CO)(Cl)(PPh₃)₂] and trans-[Rh(CO)(Cl)(PCy₃)₂] (Roodt et al., 2003). In Table 3, the title compound is compared with other closely related Rh(I) phosphine complexes from literature containing the acetylacetonate bidentate ligand.

Related literature top

For background literature on the catalytic activity of rhodium–phosphine adducts, see Carraz et al. (2000); Moloy & Wegman (1989). Corresponding [Rh(acac)(CO)(PR₁R₂R₃)] complexes, such as [Rh(acac)(CO)(PPh₃)] (Leipoldt et al., 1978), [Rh(acac)(CO)(PCy₂Ph)] (Brink et al., 2007) and [Rh(acac)(CO)(PCy₃)] (Trzeciak et al., 2004) have similar square-planar geometries. For related structures, see Marthinus Janse van Rensburg et al. (2006). For comparison of electronic parameters, see Otto & Roodt (2004).For a related palladium compound, see Meij et al. (2003). For the related Vaska-type compunds, see Otto et al. (2000); Roodt et al. (2003). For the synthesis of the starting dirhodium compound, see McCleverty & Wilkinson (1990).

Experimental top

[RhCl(CO)₂]₂ was prepared according to McCleverty and Wilkinson (1990). [Rh(acac)(CO)₂] was synthesized by mixing a solution of acetylacetonate (85.0 mg, 0.849 mmol) in dimethylformamide (DMF) and [RhCl(CO)₂]₂ (121.5 mg, 0.313 mmol) in DMF. Upon addition of ice-water, the complex precipitated and was filtered off. Ligand substitution on the complex [Rh(acac)(CO)₂] was performed by dissolving (80.0 mg, 0.310 mmol) in acetone followed by slow addition of PCyPh₂ (95.5 mg, 0.356 mmol). Crystals of (I) were obtained by slow evaporation of the reaction mixture. Spectroscopic analysis: ³¹P{H} NMR (CDCl₃, 121.495 MHz, p.p.m.): 53.3 [d, ¹J(Rh—P) = 171.3 Hz]; IR υ(CO): 1971.2 cm^-1; (CH₂Cl₂) υ(CO): 1959.3 cm^-1.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of (I), with atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. For the C atoms in rings; the first digit indicates ring number and the second digit indicates the position of the atom in the ring.
	Fig. 2. Unit cell view, showing the intermolecular H-bonding. The interaction is indicated with dashed lines. [Symmetry operators: (Rh1) x, y, z]

(Acetylacetonato-κ²O,O')carbonyl(cyclohexyldiphenylphosphine- κP)rhodium(I) top

Crystal data top

[Rh(C₅H₇O₂)(C₁₈H₂₁P)(CO)]	F(000) = 1024
M_r = 498.34	D_x = 1.485 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7313 reflections
a = 9.4682 (5) Å	θ = 2.4–28.3°
b = 12.7534 (6) Å	µ = 0.86 mm⁻¹
c = 18.4602 (9) Å	T = 100 K
V = 2229.10 (19) Å³	Plate, yellow
Z = 4	0.42 × 0.27 × 0.06 mm

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	4825 independent reflections
Radiation source: sealed tube	4672 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 512 pixels mm^-1	θ_max = 27°, θ_min = 2.2°
ω and φ scans	h = −11→12
Absorption correction: multi-scan SADABS (Bruker, 2004)	k = −16→16
T_min = 0.714, T_max = 0.950	l = −23→12
12624 measured reflections

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0301P)² + 1.123P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.024	(Δ/σ)_max = 0.001
wR(F²) = 0.061	Δρ_max = 0.56 e Å⁻³
S = 1.06	Δρ_min = −0.62 e Å⁻³
4825 reflections	Absolute structure: Flack (1983), 2064 Friedel pairs
258 parameters	Absolute structure parameter: −0.02 (2)
3 restraints

Crystal data top

[Rh(C₅H₇O₂)(C₁₈H₂₁P)(CO)]	V = 2229.10 (19) Å³
M_r = 498.34	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.4682 (5) Å	µ = 0.86 mm⁻¹
b = 12.7534 (6) Å	T = 100 K
c = 18.4602 (9) Å	0.42 × 0.27 × 0.06 mm

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	4825 independent reflections
Absorption correction: multi-scan SADABS (Bruker, 2004)	4672 reflections with I > 2σ(I)
T_min = 0.714, T_max = 0.950	R_int = 0.023
12624 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.061	Δρ_max = 0.56 e Å⁻³
S = 1.06	Δρ_min = −0.62 e Å⁻³
4825 reflections	Absolute structure: Flack (1983), 2064 Friedel pairs
258 parameters	Absolute structure parameter: −0.02 (2)
3 restraints

Special details top

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 10 s/frame. A total of 566 frames were collected with a frame width of 0.5° covering up to θ = 27.00° with 99.0% completeness accomplized.

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
C1	0.2396 (3)	0.5478 (2)	0.07028 (15)	0.0204 (6)
O1	0.3520 (2)	0.56474 (19)	0.04995 (13)	0.0321 (5)
P1	0.07950 (8)	0.66367 (5)	0.17222 (3)	0.01498 (14)
O2	0.0442 (2)	0.38392 (14)	0.04299 (9)	0.0194 (4)
O3	−0.1404 (2)	0.50184 (14)	0.13645 (10)	0.0200 (4)
C2	−0.0620 (4)	0.32317 (19)	0.04253 (13)	0.0192 (5)
C4	−0.2233 (3)	0.4269 (2)	0.11987 (14)	0.0184 (6)
C3	−0.1889 (3)	0.3388 (2)	0.07867 (14)	0.0212 (6)
H3	−0.258	0.2851	0.075	0.025*
C5	−0.0467 (4)	0.2258 (2)	−0.00365 (16)	0.0288 (7)
H5A	−0.0188	0.2459	−0.0529	0.043*
H5B	−0.1371	0.1884	−0.0053	0.043*
H5C	0.0257	0.1801	0.0173	0.043*
C6	−0.3723 (3)	0.4384 (3)	0.14649 (17)	0.0264 (7)
H6A	−0.3726	0.4778	0.1921	0.04*
H6B	−0.4133	0.3688	0.1545	0.04*
H6C	−0.4283	0.476	0.1102	0.04*
C31	0.1614 (4)	0.7821 (2)	0.13684 (15)	0.0265 (7)
C21	0.1791 (3)	0.6308 (2)	0.25351 (14)	0.0189 (6)
C11	−0.0933 (3)	0.7092 (3)	0.20456 (16)	0.0270 (7)
H11	−0.1385	0.6428	0.2215	0.032*
C16	−0.1869 (3)	0.7417 (2)	0.14486 (15)	0.0236 (6)
H16A	−0.146	0.8046	0.1214	0.028*
H16B	−0.1894	0.685	0.1082	0.028*
C12	−0.1011 (4)	0.7767 (3)	0.26998 (19)	0.0344 (6)
H12A	−0.0491	0.7422	0.3099	0.041*
H12B	−0.0538	0.8442	0.2596	0.041*
C14	−0.3460 (4)	0.8275 (3)	0.2347 (2)	0.0372 (8)
H14A	−0.444	0.8203	0.2528	0.045*
H14B	−0.3308	0.9024	0.2229	0.045*
C15	−0.3322 (4)	0.7656 (3)	0.1672 (2)	0.0430 (9)
H15A	−0.3837	0.6987	0.1736	0.052*
H15B	−0.379	0.8046	0.1275	0.052*
C13	−0.2474 (4)	0.7977 (3)	0.29391 (19)	0.0344 (6)
H13A	−0.2456	0.8549	0.3302	0.041*
H13B	−0.2845	0.7342	0.3182	0.041*
C22	0.1109 (4)	0.5767 (2)	0.30957 (15)	0.0260 (7)
H22	0.0128	0.5618	0.3061	0.031*
C23	0.1872 (5)	0.5446 (2)	0.37068 (16)	0.0373 (9)
H23	0.1403	0.509	0.4089	0.045*
C26	0.3233 (4)	0.6486 (2)	0.25875 (17)	0.0261 (7)
H26	0.3717	0.6823	0.2201	0.031*
C24	0.3293 (5)	0.5644 (3)	0.37565 (19)	0.0471 (11)
H24	0.3807	0.5419	0.417	0.056*
C25	0.3979 (4)	0.6174 (2)	0.3202 (2)	0.0393 (9)
H25	0.4959	0.6324	0.3241	0.047*
C32	0.1993 (3)	0.8649 (2)	0.18374 (15)	0.0223 (6)
H32	0.1853	0.858	0.2345	0.027*
C34	0.2447 (4)	0.9782 (3)	0.08060 (18)	0.0388 (8)
H34	0.261	1.0468	0.0623	0.047*
C36	0.1472 (4)	0.8045 (3)	0.06191 (16)	0.0278 (7)
H36	0.0974	0.7577	0.031	0.033*
C33	0.2576 (4)	0.9577 (2)	0.15549 (18)	0.0350 (8)
H33	0.305	1.0058	0.1863	0.042*
C35	0.2078 (5)	0.8969 (3)	0.03382 (18)	0.0434 (10)
H35	0.2235	0.9038	−0.0168	0.052*
Rh1	0.06207 (2)	0.522795 (15)	0.100971 (10)	0.01435 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0230 (16)	0.0182 (14)	0.0201 (13)	0.0012 (10)	−0.0019 (12)	−0.0027 (10)
O1	0.0224 (13)	0.0363 (13)	0.0375 (12)	−0.0007 (9)	0.0068 (10)	−0.0054 (10)
P1	0.0197 (4)	0.0144 (3)	0.0109 (3)	−0.0002 (3)	−0.0014 (3)	−0.0011 (2)
O2	0.0264 (12)	0.0162 (9)	0.0155 (8)	−0.0010 (9)	0.0038 (9)	−0.0021 (7)
O3	0.0222 (11)	0.0178 (11)	0.0199 (9)	−0.0002 (7)	0.0036 (8)	−0.0021 (7)
C2	0.0292 (15)	0.0164 (12)	0.0120 (11)	−0.0011 (13)	−0.0025 (13)	0.0023 (9)
C4	0.0209 (15)	0.0191 (12)	0.0152 (13)	0.0002 (11)	−0.0003 (10)	0.0050 (10)
C3	0.0267 (16)	0.0167 (12)	0.0202 (13)	−0.0051 (12)	−0.0016 (12)	0.0002 (10)
C5	0.043 (2)	0.0180 (14)	0.0250 (13)	−0.0045 (14)	0.0063 (15)	−0.0072 (11)
C6	0.0235 (16)	0.0287 (16)	0.0268 (15)	−0.0007 (13)	0.0037 (12)	0.0043 (12)
C31	0.046 (2)	0.0160 (13)	0.0173 (13)	−0.0047 (13)	−0.0026 (14)	0.0035 (11)
C21	0.0291 (16)	0.0155 (13)	0.0120 (11)	−0.0003 (11)	−0.0047 (12)	−0.0002 (10)
C11	0.0209 (18)	0.0337 (16)	0.0264 (14)	0.0049 (12)	−0.0039 (12)	−0.0160 (13)
C16	0.0217 (16)	0.0277 (15)	0.0215 (13)	0.0030 (12)	−0.0002 (12)	−0.0003 (11)
C12	0.0340 (15)	0.0293 (12)	0.0400 (13)	0.0005 (10)	0.0058 (11)	−0.0135 (10)
C14	0.0270 (19)	0.0256 (17)	0.059 (2)	−0.0020 (13)	0.0096 (17)	0.0005 (16)
C15	0.032 (2)	0.041 (2)	0.055 (2)	0.0136 (16)	−0.0134 (18)	−0.0221 (18)
C13	0.0340 (15)	0.0293 (12)	0.0400 (13)	0.0005 (10)	0.0058 (11)	−0.0135 (10)
C22	0.042 (2)	0.0177 (14)	0.0183 (13)	−0.0026 (12)	−0.0014 (13)	0.0004 (11)
C23	0.078 (3)	0.0185 (15)	0.0153 (12)	0.0046 (16)	−0.0058 (17)	0.0013 (11)
C26	0.0294 (18)	0.0163 (14)	0.0325 (16)	−0.0016 (12)	−0.0064 (14)	−0.0008 (12)
C24	0.084 (3)	0.0221 (16)	0.0351 (18)	0.0128 (19)	−0.038 (2)	−0.0035 (14)
C25	0.042 (2)	0.0219 (15)	0.054 (2)	0.0050 (14)	−0.0323 (18)	−0.0090 (15)
C32	0.0242 (16)	0.0227 (14)	0.0200 (13)	−0.0049 (12)	−0.0014 (12)	0.0034 (11)
C34	0.046 (2)	0.0363 (17)	0.0337 (17)	−0.0129 (18)	0.0090 (15)	0.0143 (16)
C36	0.038 (2)	0.0290 (16)	0.0167 (14)	−0.0021 (14)	0.0033 (13)	−0.0016 (12)
C33	0.053 (2)	0.0193 (15)	0.0332 (17)	−0.0011 (14)	0.0033 (16)	0.0041 (13)
C35	0.080 (3)	0.0309 (18)	0.0194 (15)	0.0161 (19)	0.0104 (18)	0.0101 (13)
Rh1	0.01800 (10)	0.01415 (9)	0.01091 (8)	0.00045 (8)	0.00012 (9)	−0.00112 (8)

Geometric parameters (Å, º) top

C1—O1	1.149 (4)	C16—H16A	0.99
C1—Rh1	1.802 (3)	C16—H16B	0.99
P1—C31	1.819 (3)	C12—C13	1.479 (5)
P1—C21	1.821 (3)	C12—H12A	0.99
P1—C11	1.836 (3)	C12—H12B	0.99
P1—Rh1	2.2328 (6)	C14—C15	1.480 (5)
O2—C2	1.269 (4)	C14—C13	1.487 (5)
O2—Rh1	2.0764 (18)	C14—H14A	0.99
O3—C4	1.274 (3)	C14—H14B	0.99
O3—Rh1	2.044 (2)	C15—H15A	0.99
C2—C3	1.388 (4)	C15—H15B	0.99
C2—C5	1.513 (4)	C13—H13A	0.99
C4—O3	1.274 (3)	C13—H13B	0.99
C4—O3	1.274 (3)	C22—C23	1.401 (4)
C4—C3	1.395 (4)	C22—H22	0.95
C4—C6	1.501 (4)	C23—C24	1.372 (6)
C3—H3	0.95	C23—H23	0.95
C5—H5A	0.98	C26—C25	1.394 (4)
C5—H5B	0.98	C26—H26	0.95
C5—H5C	0.98	C24—C25	1.387 (6)
C6—H6A	0.98	C24—H24	0.95
C6—H6B	0.98	C25—H25	0.95
C6—H6C	0.98	C32—C33	1.406 (4)
C31—C32	1.412 (4)	C32—H32	0.95
C31—C36	1.419 (4)	C34—C35	1.393 (5)
C21—C26	1.388 (5)	C34—C33	1.412 (5)
C21—C22	1.402 (4)	C34—H34	0.95
C11—C16	1.473 (4)	C36—C35	1.410 (5)
C11—C12	1.485 (4)	C36—H36	0.95
C11—H11	1	C33—H33	0.95
C16—C15	1.469 (5)	C35—H35	0.95

O1—C1—Rh1	179.0 (3)	C15—C14—C13	115.3 (3)
C31—P1—C21	105.44 (14)	C15—C14—H14A	108.5
C31—P1—C11	103.52 (16)	C13—C14—H14A	108.5
C21—P1—C11	105.45 (14)	C15—C14—H14B	108.5
C31—P1—Rh1	119.22 (10)	C13—C14—H14B	108.5
C21—P1—Rh1	109.80 (9)	H14A—C14—H14B	107.5
C11—P1—Rh1	112.35 (10)	C16—C15—C14	115.5 (3)
C2—O2—Rh1	126.06 (18)	C16—C15—H15A	108.4
C4—O3—Rh1	126.78 (18)	C14—C15—H15A	108.4
O2—C2—C3	126.5 (2)	C16—C15—H15B	108.4
O2—C2—C5	115.4 (3)	C14—C15—H15B	108.4
C3—C2—C5	118.2 (3)	H15A—C15—H15B	107.5
O3—C4—C3	126.3 (3)	C12—C13—C14	114.5 (3)
O3—C4—C6	115.3 (3)	C12—C13—H13A	108.6
C3—C4—C6	118.5 (3)	C14—C13—H13A	108.6
C2—C3—C4	125.4 (3)	C12—C13—H13B	108.6
C2—C3—H3	117.3	C14—C13—H13B	108.6
C4—C3—H3	117.3	H13A—C13—H13B	107.6
C2—C5—H5A	109.5	C23—C22—C21	120.0 (3)
C2—C5—H5B	109.5	C23—C22—H22	120
H5A—C5—H5B	109.5	C21—C22—H22	120
C2—C5—H5C	109.5	C24—C23—C22	120.4 (3)
H5A—C5—H5C	109.5	C24—C23—H23	119.8
H5B—C5—H5C	109.5	C22—C23—H23	119.8
C4—C6—H6A	109.5	C21—C26—C25	120.6 (3)
C4—C6—H6B	109.5	C21—C26—H26	119.7
H6A—C6—H6B	109.5	C25—C26—H26	119.7
C4—C6—H6C	109.5	C23—C24—C25	119.9 (3)
H6A—C6—H6C	109.5	C23—C24—H24	120
H6B—C6—H6C	109.5	C25—C24—H24	120
C32—C31—C36	118.1 (3)	C24—C25—C26	120.1 (3)
C32—C31—P1	120.6 (2)	C24—C25—H25	119.9
C36—C31—P1	118.5 (2)	C26—C25—H25	119.9
C26—C21—C22	118.9 (3)	C33—C32—C31	120.1 (3)
C26—C21—P1	122.0 (2)	C33—C32—H32	119.9
C22—C21—P1	118.9 (2)	C31—C32—H32	119.9
C16—C11—C12	114.6 (3)	C35—C34—C33	119.4 (3)
C16—C11—P1	112.4 (2)	C35—C34—H34	120.3
C12—C11—P1	119.5 (2)	C33—C34—H34	120.3
C16—C11—H11	102.4	C35—C36—C31	119.2 (3)
C12—C11—H11	102.4	C35—C36—H36	120.4
P1—C11—H11	102.4	C31—C36—H36	120.4
C15—C16—C11	114.3 (3)	C32—C33—C34	119.0 (3)
C15—C16—H16A	108.7	C32—C33—H33	120.5
C11—C16—H16A	108.7	C34—C33—H33	120.5
C15—C16—H16B	108.7	C34—C35—C36	119.7 (3)
C11—C16—H16B	108.7	C34—C35—H35	120.1
H16A—C16—H16B	107.6	C36—C35—H35	120.1
C13—C12—C11	113.3 (3)	C1—Rh1—O3	177.31 (10)
C13—C12—H12A	108.9	C1—Rh1—O2	93.72 (10)
C11—C12—H12A	108.9	O3—Rh1—O2	88.69 (8)
C13—C12—H12B	108.9	C1—Rh1—P1	88.50 (9)
C11—C12—H12B	108.9	O3—Rh1—P1	89.18 (5)
H12A—C12—H12B	107.7	O2—Rh1—P1	174.94 (5)

Rh1—O2—C2—C3	2.2 (4)	C11—C16—C15—C14	42.9 (4)
Rh1—O2—C2—C5	−179.09 (18)	C13—C14—C15—C16	−40.8 (5)
Rh1—O3—C4—C3	5.7 (4)	C11—C12—C13—C14	−45.8 (4)
Rh1—O3—C4—C6	−172.64 (18)	C15—C14—C13—C12	42.3 (4)
O2—C2—C3—C4	2.6 (5)	C26—C21—C22—C23	2.2 (4)
C5—C2—C3—C4	−176.1 (3)	P1—C21—C22—C23	176.0 (2)
O3—C4—C3—C2	−6.9 (5)	C21—C22—C23—C24	−1.0 (4)
C6—C4—C3—C2	171.3 (3)	C22—C21—C26—C25	−2.9 (4)
C21—P1—C31—C32	−43.6 (3)	P1—C21—C26—C25	−176.5 (2)
C11—P1—C31—C32	66.9 (3)	C22—C23—C24—C25	0.6 (5)
Rh1—P1—C31—C32	−167.5 (2)	C23—C24—C25—C26	−1.3 (5)
C21—P1—C31—C36	155.6 (3)	C21—C26—C25—C24	2.5 (5)
C11—P1—C31—C36	−93.9 (3)	C36—C31—C32—C33	−16.8 (5)
Rh1—P1—C31—C36	31.8 (3)	P1—C31—C32—C33	−177.6 (3)
C31—P1—C21—C26	−34.9 (3)	C32—C31—C36—C35	17.6 (5)
C11—P1—C21—C26	−144.0 (2)	P1—C31—C36—C35	178.9 (3)
Rh1—P1—C21—C26	94.7 (2)	C31—C32—C33—C34	16.1 (5)
C31—P1—C21—C22	151.5 (2)	C35—C34—C33—C32	−16.1 (6)
C11—P1—C21—C22	42.4 (3)	C33—C34—C35—C36	17.2 (6)
Rh1—P1—C21—C22	−78.9 (2)	C31—C36—C35—C34	−18.1 (6)
C31—P1—C11—C16	68.1 (2)	C4—O3—Rh1—O2	−1.2 (2)
C21—P1—C11—C16	178.6 (2)	C4—O3—Rh1—P1	−176.6 (2)
Rh1—P1—C11—C16	−61.8 (2)	C2—O2—Rh1—C1	178.6 (2)
C31—P1—C11—C12	−70.5 (3)	C2—O2—Rh1—O3	−2.6 (2)
C21—P1—C11—C12	40.0 (3)	C31—P1—Rh1—C1	42.38 (16)
Rh1—P1—C11—C12	159.6 (2)	C21—P1—Rh1—C1	−79.31 (14)
C12—C11—C16—C15	−46.9 (4)	C11—P1—Rh1—C1	163.68 (15)
P1—C11—C16—C15	172.4 (2)	C31—P1—Rh1—O3	−136.25 (14)
C16—C11—C12—C13	48.4 (4)	C21—P1—Rh1—O3	102.06 (12)
P1—C11—C12—C13	−173.9 (3)	C11—P1—Rh1—O3	−14.95 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O3	1	2.39	2.962 (3)	116
C16—H16B···O3	0.99	2.44	3.094 (3)	123

Experimental details

Crystal data
Chemical formula	[Rh(C₅H₇O₂)(C₁₈H₂₁P)(CO)]
M_r	498.34
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	9.4682 (5), 12.7534 (6), 18.4602 (9)
V (Å³)	2229.10 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.42 × 0.27 × 0.06

Data collection
Diffractometer	Bruker X8 APEXII 4K KappaCCD
Absorption correction	Multi-scan SADABS (Bruker, 2004)
T_min, T_max	0.714, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	12624, 4825, 4672
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.061, 1.06
No. of reflections	4825
No. of parameters	258
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.62
Absolute structure	Flack (1983), 2064 Friedel pairs
Absolute structure parameter	−0.02 (2)

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004) and XPREP (Bruker 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

C1—O1	1.149 (4)	O2—Rh1	2.0764 (18)
C1—Rh1	1.802 (3)	O3—Rh1	2.044 (2)
P1—Rh1	2.2328 (6)

O1—C1—Rh1	179.0 (3)	O3—Rh1—O2	88.69 (8)
C1—Rh1—O3	177.31 (10)	C1—Rh1—P1	88.50 (9)
C1—Rh1—O2	93.72 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O3	1	2.39	2.962 (3)	115.8
C16—H16B···O3	0.99	2.44	3.094 (3)	123.3

Comparative spectroscopic (cm^-1, ppm, Hz) and geometrical parameters (Å) for selected [Rh(acac)(CO)(P-Lig)] complexes. top

P-Lig	υ(CO)	δ³¹P	¹J(Rh-P)	Rh-P	C1-O1	notes
PPh₃	1983	46	177.4	2.244 (2)	1.153 (11)	(i,iv)
PCyPh₂	1959	53.3	171.3	2.2327 (6)	1.149 (4)	(ii)
PCy₂Ph	1949	58.8	168.3	2.2425 (9)	1.151 (3)	(iii)
PCy₃	1945	58	170.0	2.2613 (10)	1.169 (4)	(iv)

Notes: (i) Leipoldt et al. (1978); (ii) This work; (iii) Brink et al. (2007); (iv) Trzeciak et al. (2004).

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