Carbonyl[4-(2,6-dimethyl­phenyl­amino)pent-3-en-2-onato-κ2N,O](triphenyl­phosphine-κP)rhodium(I) acetone hemi­solvate

Venter, G.J.S.; Steyl, G.; Roodt, A.

doi:10.1107/S160053680904817X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1606-m1607

doi:10.1107/S160053680904817X

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Carbonyl[4-(2,6-dimethylphenylamino)pent-3-en-2-onato-κ²N,O](triphenylphosphine-κP)rhodium(I) acetone hemisolvate

Gertruida J. S. Venter,^a ^* Gideon Steyl ^a and Andreas Roodt ^a

^aDepartment of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein, 9300, South Africa
^*Correspondence e-mail: truidie@hotmail.com

(Received 23 October 2009; accepted 13 November 2009; online 18 November 2009)

In the title compound, [Rh(C₁₃H₁₆NO)(C₁₈H₁₅P)(CO)]·0.5C₃H₆O, the Rh atom exhibits a square-planar coordination geometry, being coordinated by the N and O atoms of the bidentate β-diketonato ligand, a P atom from the triphenylphosphine unit and a C atom from the carbonyl group. The asymmetric unit also contains a disordered half-molecule, lying about an inversion center, of the acetone solvate. Intermolecular C—H⋯O hydrogen bonds are observed between a C—H group of the triphenylphosphine unit and a carbonyl O atom and between the methyl group of the enaminoketonato backbone and the solvent O atom. In addition, an intramolecular interaction is observed between a C—H group of the triphenylphosphine unit and the O atom of the enaminoketonato ligand.

Related literature

For synthetic background, see: Shaheen et al. (2006 ); Cornils & Hermann (1996); Bonati & Wilkinson (1964 ). For appplications of rhodium(I) dicarbonyl complexes, see: Cornils & Herrmann (1996 ); Trzeciak & Ziolkowski (1994 ); Van Rooy et al. (1995 ). For related structures, see: Damoense et al. (1994 ); Varshavsky et al. (2001 ); Venter et al. (2009 ).

Experimental

Crystal data

[Rh(C₁₃H₁₆NO)(C₁₈H₁₅P)(CO)]·0.5C₃H₆O
M_r = 624.5
Monoclinic, P 2₁ /c
a = 16.8558 (8) Å
b = 11.4028 (5) Å
c = 16.4059 (8) Å
β = 108.733 (1)°
V = 2986.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 100 K
0.31 × 0.15 × 0.11 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.822, T_max = 0.931
23158 measured reflections
7425 independent reflections
6081 reflections with > 2σI)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.112
S = 1.09
7425 reflections
354 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.54 e Å⁻³
Δρ_min = −1.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C332—H332⋯O12	0.95	2.38	3.201 (3)	144
C334—H334⋯O14ⁱ	0.95	2.51	3.201 (4)	130
C1—H1B⋯O01ⁱⁱ	0.98	2.54	3.372 (9)	142
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Comparative geometrical parameters (Å, °) for similar [Rh(N,O-bid)(CO)(PPh₃)] complexes

Parameters	(I)^a	(II)^b	(III)^c	(IV)^d
Rh1—N11	2.077 (2)	2.069 (2)	2.045 (4)	2.045 (3)
Rh1—O12	2.027 (2)	2.028 (2)	2.044 (3)	2.045 (2)
Rh1—P13	2.2704 (7)	2.2635 (6)	2.275 (1)	2.281 (2)
Rh1—C14	1.812 (3)	1.807 (2)	1.784 (5)	1.804 (3)
C14—O14	1.147 (3)	1.152 (3)	1.142 (7)	1.148 (4)
N11⋯O12	2.885 (3)	2.885 (3)	2.826 (6)	2.841 (3)
N11—Rh1—O12	89.31 (9)	89.54 (8)	87.4 (1)	87.95 (8)
O12—Rh1—P13	85.95 (6)	84.97 (5)	89.7 (1)	89.91 (5)
P13—Rh1—C14	91.57 (9)	91.87 (7)	90.3 (2)	89.48 (9)
N11—Rh1—C14	93.1 (1)	93.6 (1)	92.6 (2)	92.6 (1)
N11—C2—C4—O12	−2.6 (2)	4.1 (2)	1.2 (4)	1.5 (2)
θ_E^e	155.77 (2)	156.39 (3)	156.0 (2)	156.23 (4)
Notes: (a) This work; (b) N,O-bid = 4-(2,3-dimethyl phenylamino)pent-3-en-2-onato (Venter et al., 2009); (c) N,O-bid = 4-amino-pent-3-en-2-onato (Damoense et al., 1994); (d) N,O-bid = 4-amino-1,1,1-trifluoro-pent-3-en-2-onato (Varshavsky et al., 2001); (e) cone angle (Tolman, 1977 ).

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004); 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: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904817X/pv2227sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680904817X/pv2227Isup2.hkl

checkCIF report

Comment top

Rhodium(I) dicarbonyl complexes of the type [Rh(L,L')(CO)₂] containing chelating mono-anionic bidentate (L,L') ligands coordinated to rhodium via (O,O) donor atoms have been studied as catalyst precursors (Cornils & Herrmann, 1996; Trzeciak et al., 1994; Van Rooy et al., 1995). The investigation of these complexes is followed by complexes containing bidentate β-enaminoketonato ligands such as 4-(phenylamino)pent-3-en-2-onato (Phony) (Shaheen et al., 2006) coordinated to rhodium via (N,O) donor atoms. It was suggested that only one CO-group in a [Rh(N,O-bid)(CO)₂]-type complex will be substituted by triphenyl phosphine, with the product being one of two possible isomers (Bonati & Wilkinson, 1964). Since the N-donor atom has a larger trans-influence than the O-atom, the CO-group trans to the N-atom will be substituted. This is evident in the title compound, (I), where [Rh(2,6-diMe-Phony)(CO)(PPh₃)] is formed by the substitution of the carbonyl ligand in the dicarbonyl rhodium(I) complex [Rh(2,6-diMe-Phony)(CO)₂] by PPh₃.

In the title complex (Fig. 1), the bond distances involving rhodium differ significantly from the distances in related complexes, with the exception of [Rh(2,3-diMe-Phony)(CO)(PPh₃)] (Venter et al., 2009), wherein all angles and distances are comparable to (I) (Table 2). The distance, Rh—N, in (I) is longer than in similar complexes while the Rh—O bond distance is shorter. This is due to the steric influence of the phenyl group connected to nitrogen in the title compound, as opposed to the hydrogen in the related complexes. The Rh—C and the carbonyl C—O distances are comparable with those distances in the related complexes (Table 2). The N—Rh—O bite angle is slightly larger than that observed in similar complexes found in the literature. The effective cone angle, θ_E, (Tolman, 1977) of 155.77 (2)° is similar to the angles in the related compounds. The acetone solvate was disordered and was located about an inversion center. Intermolecular and intramolecular hydrogen bonds of the type C—H···O are observed in the structure.

Related literature top

For synthetic background, see: Shaheen et al. (2006); Cornils & Herrmann (1996); Bonati & Wilkinson (1964). For appplications of rhodium(I) dicarbonyl complexes, see: Cornils & Herrmann (1996); Trzeciak & Ziolkowski (1994); Van Rooy et al. (1995). For related structures, see: Damoense et al. (1994); Varshavsky et al. (2001); Venter et al. (2009).

Experimental top

To a 5 ml acetone solution of [Rh(2,6-diMe-Phony)(CO)₂] (0.0302 g, 83.61 µmol) was added PPh₃ (0.0219 g, 83.50 µmol) resulting in an immediate evolution of gas with the formation of the title compound. Crystallization from acetone produced yellow crystals of (I) in quantitative (0.0516 g, 100%) yield. IR (KBr): ν_CO 1971.1 s cm^-1.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability displacement level. H atoms and disordered solvate molecule have been omitted for clarity.
	Fig. 2. A view of the unit cell of (I) illustrating the C—H···O interactions; hydrogen atoms have been omitted for clarity.

Carbonyl[4-(2,6-dimethylphenylamino)pent-3-en-2-onato- κ²N,O](triphenylphosphine-κP)rhodium(I) acetone hemisolvate top

Crystal data top

[Rh(C₁₃H₁₆NO)(C₁₈H₁₅P)(CO)]·0.5C₃H₆O	F(000) = 1288
M_r = 624.5	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6670 reflections
a = 16.8558 (8) Å	θ = 2.5–28.2°
b = 11.4028 (5) Å	µ = 0.66 mm⁻¹
c = 16.4059 (8) Å	T = 100 K
β = 108.733 (1)°	Cuboid, yellow
V = 2986.2 (2) Å³	0.31 × 0.15 × 0.11 mm
Z = 4

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	7425 independent reflections
Radiation source: fine-focus sealed tube	6081 reflections with > 2σI)
Graphite monochromator	R_int = 0.042
ω and ϕ scans	θ_max = 28.3°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −21→22
T_min = 0.822, T_max = 0.931	k = −15→11
23158 measured reflections	l = −21→21

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0577P)² + 1.4787P] where P = (F_o² + 2F_c²)/3
7425 reflections	(Δ/σ)_max = 0.002
354 parameters	Δρ_max = 1.54 e Å⁻³
1 restraint	Δρ_min = −1.32 e Å⁻³

Crystal data top

[Rh(C₁₃H₁₆NO)(C₁₈H₁₅P)(CO)]·0.5C₃H₆O	V = 2986.2 (2) Å³
M_r = 624.5	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.8558 (8) Å	µ = 0.66 mm⁻¹
b = 11.4028 (5) Å	T = 100 K
c = 16.4059 (8) Å	0.31 × 0.15 × 0.11 mm
β = 108.733 (1)°

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	7425 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	6081 reflections with > 2σI)
T_min = 0.822, T_max = 0.931	R_int = 0.042
23158 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.112	H-atom parameters constrained
S = 1.09	Δρ_max = 1.54 e Å⁻³
7425 reflections	Δρ_min = −1.32 e Å⁻³
354 parameters

Special details top

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 60 s/frame. A total of 688 frames were collected with a frame width of 0.5° covering up to θ = 28.24° with 99.8% completeness accomplished.

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	Occ. (<1)
C1	0.7144 (2)	0.7625 (3)	0.4744 (2)	0.0257 (7)
H1A	0.7697	0.7807	0.5152	0.039*
H1B	0.6712	0.7804	0.5007	0.039*
H1C	0.7048	0.8097	0.4222	0.039*
C2	0.71032 (17)	0.6337 (2)	0.45128 (18)	0.0168 (5)
C3	0.65757 (17)	0.5637 (2)	0.48382 (18)	0.0183 (6)
H3	0.6324	0.6017	0.5209	0.022*
C4	0.63880 (17)	0.4461 (2)	0.46740 (19)	0.0180 (6)
C5	0.57863 (19)	0.3856 (3)	0.5045 (2)	0.0265 (7)
H5A	0.5288	0.3609	0.4577	0.04*
H5B	0.5621	0.4399	0.5425	0.04*
H5C	0.6058	0.3167	0.5375	0.04*
C14	0.84522 (17)	0.4446 (2)	0.32802 (17)	0.0166 (5)
C111	0.80357 (17)	0.6734 (2)	0.37352 (18)	0.0164 (5)
C112	0.76869 (19)	0.7250 (2)	0.2919 (2)	0.0223 (6)
C113	0.8183 (2)	0.8000 (3)	0.2624 (2)	0.0271 (7)
H113	0.7952	0.8365	0.2078	0.033*
C114	0.9008 (2)	0.8226 (2)	0.3109 (2)	0.0292 (7)
H114	0.9338	0.8746	0.2897	0.035*
C115	0.93503 (19)	0.7690 (2)	0.3902 (2)	0.0242 (6)
H115	0.9919	0.7836	0.4228	0.029*
C116	0.88743 (18)	0.6938 (2)	0.42310 (19)	0.0194 (6)
C117	0.6798 (2)	0.6980 (3)	0.2380 (2)	0.0318 (7)
H11A	0.6667	0.7385	0.1826	0.048*
H11B	0.6414	0.7247	0.2682	0.048*
H11C	0.6734	0.6132	0.2283	0.048*
C118	0.92484 (19)	0.6332 (3)	0.5082 (2)	0.0257 (7)
H11D	0.9859	0.6413	0.5269	0.039*
H11E	0.9099	0.5499	0.5021	0.039*
H11F	0.9031	0.6689	0.551	0.039*
C311	0.82259 (17)	0.1691 (2)	0.27715 (17)	0.0149 (5)
C312	0.90839 (17)	0.1910 (2)	0.30147 (18)	0.0168 (5)
H312	0.9352	0.2308	0.354	0.02*
C313	0.95533 (17)	0.1553 (2)	0.24967 (19)	0.0193 (6)
H313	1.0138	0.1707	0.267	0.023*
C314	0.91660 (18)	0.0976 (2)	0.17315 (19)	0.0212 (6)
H314	0.9483	0.0736	0.1375	0.025*
C315	0.83113 (18)	0.0749 (2)	0.14845 (19)	0.0190 (6)
H315	0.8045	0.035	0.0959	0.023*
C316	0.78449 (17)	0.1103 (2)	0.20019 (18)	0.0168 (5)
H316	0.7261	0.0943	0.1829	0.02*
C321	0.66208 (17)	0.1553 (2)	0.30122 (17)	0.0153 (5)
C322	0.59944 (17)	0.2176 (2)	0.24164 (19)	0.0202 (6)
H322	0.6093	0.296	0.2279	0.024*
C323	0.52197 (18)	0.1657 (3)	0.2017 (2)	0.0243 (6)
H323	0.4799	0.208	0.1594	0.029*
C324	0.50573 (19)	0.0534 (3)	0.2231 (2)	0.0260 (7)
H324	0.4523	0.019	0.1966	0.031*
C325	0.5676 (2)	−0.0085 (3)	0.2829 (2)	0.0386 (9)
H325	0.557	−0.086	0.2979	0.046*
C326	0.6459 (2)	0.0424 (3)	0.3217 (2)	0.0335 (8)
H326	0.6884	−0.001	0.3627	0.04*
C331	0.81170 (17)	0.1399 (2)	0.44688 (17)	0.0156 (5)
C332	0.7927 (2)	0.1752 (3)	0.51929 (19)	0.0266 (7)
H332	0.7579	0.2416	0.5163	0.032*
C333	0.8240 (2)	0.1144 (3)	0.5959 (2)	0.0334 (8)
H333	0.8091	0.1378	0.6447	0.04*
C334	0.8770 (2)	0.0196 (3)	0.60188 (19)	0.0263 (7)
H334	0.8999	−0.0205	0.655	0.032*
C335	0.89635 (18)	−0.0163 (2)	0.53013 (19)	0.0222 (6)
H335	0.932	−0.082	0.5339	0.027*
C336	0.86407 (18)	0.0429 (2)	0.45242 (19)	0.0196 (6)
H336	0.8775	0.0176	0.4032	0.024*
N11	0.75420 (14)	0.59212 (18)	0.40401 (15)	0.0148 (5)
O12	0.66821 (11)	0.37910 (16)	0.42069 (13)	0.0174 (4)
O14	0.90058 (13)	0.46375 (18)	0.30306 (13)	0.0225 (4)
P13	0.76530 (4)	0.22182 (6)	0.34722 (4)	0.01315 (15)
Rh1	0.761010 (12)	0.417429 (17)	0.371227 (13)	0.01263 (8)
O01	0.4759 (6)	0.3631 (7)	0.0331 (6)	0.0963 (16)	0.5
C01	0.4182 (4)	0.5252 (5)	−0.0389 (4)	0.0963 (16)
H01A	0.366	0.4813	−0.0482	0.144*
H01B	0.4236	0.5472	−0.0946	0.144*
H01C	0.4173	0.5961	−0.0055	0.144*
C02	0.4899 (9)	0.4513 (10)	0.0086 (9)	0.0963 (16)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0290 (16)	0.0158 (14)	0.0378 (18)	0.0010 (12)	0.0183 (14)	−0.0024 (13)
C2	0.0145 (13)	0.0149 (13)	0.0204 (14)	0.0019 (10)	0.0049 (11)	0.0014 (10)
C3	0.0165 (13)	0.0185 (13)	0.0215 (14)	0.0041 (11)	0.0082 (11)	0.0009 (11)
C4	0.0127 (13)	0.0192 (13)	0.0220 (14)	0.0039 (10)	0.0056 (11)	0.0037 (11)
C5	0.0233 (15)	0.0239 (15)	0.0378 (18)	−0.0002 (12)	0.0176 (14)	0.0045 (13)
C14	0.0190 (14)	0.0134 (12)	0.0157 (13)	−0.0017 (10)	0.0032 (11)	−0.0036 (10)
C111	0.0206 (14)	0.0097 (12)	0.0224 (14)	−0.0009 (10)	0.0118 (12)	−0.0016 (10)
C112	0.0273 (15)	0.0152 (13)	0.0279 (16)	0.0027 (11)	0.0137 (13)	0.0022 (11)
C113	0.0408 (19)	0.0149 (13)	0.0312 (17)	0.0020 (13)	0.0193 (15)	0.0041 (12)
C114	0.0410 (19)	0.0138 (14)	0.043 (2)	−0.0063 (13)	0.0286 (16)	−0.0043 (13)
C115	0.0243 (15)	0.0173 (14)	0.0375 (18)	−0.0055 (11)	0.0189 (14)	−0.0117 (12)
C116	0.0220 (14)	0.0136 (12)	0.0242 (15)	−0.0014 (11)	0.0099 (12)	−0.0038 (11)
C117	0.0293 (17)	0.0335 (17)	0.0289 (17)	0.0046 (14)	0.0043 (14)	0.0104 (14)
C118	0.0217 (15)	0.0267 (16)	0.0243 (16)	−0.0035 (12)	0.0013 (13)	−0.0047 (12)
C311	0.0186 (13)	0.0098 (12)	0.0171 (13)	0.0012 (10)	0.0066 (11)	0.0014 (10)
C312	0.0165 (13)	0.0147 (12)	0.0180 (13)	−0.0017 (10)	0.0037 (11)	−0.0003 (10)
C313	0.0138 (13)	0.0189 (13)	0.0249 (15)	0.0030 (11)	0.0059 (11)	0.0037 (11)
C314	0.0225 (15)	0.0196 (14)	0.0242 (15)	0.0043 (11)	0.0112 (13)	0.0025 (11)
C315	0.0211 (14)	0.0176 (13)	0.0180 (14)	−0.0002 (11)	0.0060 (12)	−0.0023 (10)
C316	0.0165 (13)	0.0143 (12)	0.0187 (14)	−0.0012 (10)	0.0041 (11)	−0.0001 (10)
C321	0.0159 (13)	0.0149 (12)	0.0163 (13)	−0.0011 (10)	0.0067 (11)	−0.0025 (10)
C322	0.0173 (14)	0.0168 (13)	0.0251 (15)	−0.0012 (11)	0.0049 (12)	−0.0008 (11)
C323	0.0155 (14)	0.0265 (16)	0.0261 (16)	0.0030 (12)	0.0001 (12)	0.0001 (12)
C324	0.0166 (14)	0.0312 (16)	0.0283 (16)	−0.0067 (12)	0.0045 (13)	−0.0052 (13)
C325	0.0317 (18)	0.0261 (17)	0.048 (2)	−0.0167 (14)	−0.0006 (16)	0.0098 (15)
C326	0.0249 (16)	0.0237 (16)	0.041 (2)	−0.0047 (13)	−0.0047 (15)	0.0129 (14)
C331	0.0162 (13)	0.0134 (12)	0.0147 (13)	−0.0016 (10)	0.0014 (11)	−0.0017 (10)
C332	0.0368 (18)	0.0224 (15)	0.0195 (15)	0.0132 (13)	0.0077 (13)	0.0011 (12)
C333	0.054 (2)	0.0313 (17)	0.0153 (15)	0.0234 (16)	0.0113 (15)	0.0034 (13)
C334	0.0340 (17)	0.0214 (15)	0.0188 (15)	0.0074 (13)	0.0022 (13)	0.0031 (12)
C335	0.0246 (15)	0.0168 (14)	0.0233 (15)	0.0049 (11)	0.0052 (12)	0.0005 (11)
C336	0.0220 (14)	0.0160 (13)	0.0213 (14)	0.0013 (11)	0.0075 (12)	−0.0017 (11)
N11	0.0142 (11)	0.0107 (10)	0.0191 (12)	−0.0009 (8)	0.0049 (9)	0.0012 (8)
O12	0.0152 (9)	0.0148 (9)	0.0242 (10)	−0.0008 (8)	0.0091 (8)	0.0014 (8)
O14	0.0261 (11)	0.0180 (10)	0.0280 (11)	−0.0059 (8)	0.0152 (9)	−0.0034 (8)
P13	0.0123 (3)	0.0117 (3)	0.0142 (3)	−0.0008 (2)	0.0027 (3)	−0.0002 (2)
Rh1	0.01250 (12)	0.01060 (11)	0.01490 (12)	−0.00047 (7)	0.00457 (8)	0.00021 (7)
O01	0.139 (5)	0.057 (3)	0.104 (4)	−0.010 (3)	0.054 (4)	0.007 (2)
C01	0.139 (5)	0.057 (3)	0.104 (4)	−0.010 (3)	0.054 (4)	0.007 (2)
C02	0.139 (5)	0.057 (3)	0.104 (4)	−0.010 (3)	0.054 (4)	0.007 (2)

Geometric parameters (Å, º) top

C1—C2	1.513 (4)	C313—H313	0.95
C1—H1A	0.98	C314—C315	1.390 (4)
C1—H1B	0.98	C314—H314	0.95
C1—H1C	0.98	C315—C316	1.389 (4)
C2—N11	1.320 (4)	C315—H315	0.95
C2—C3	1.420 (4)	C316—H316	0.95
C3—C4	1.384 (4)	C321—C326	1.380 (4)
C3—H3	0.95	C321—C322	1.383 (4)
C4—O12	1.289 (3)	C321—P13	1.824 (3)
C4—C5	1.507 (4)	C322—C323	1.391 (4)
C5—H5A	0.98	C322—H322	0.95
C5—H5B	0.98	C323—C324	1.378 (4)
C5—H5C	0.98	C323—H323	0.95
C14—O14	1.154 (3)	C324—C325	1.375 (4)
C14—Rh1	1.805 (3)	C324—H324	0.95
C111—C116	1.405 (4)	C325—C326	1.394 (4)
C111—C112	1.406 (4)	C325—H325	0.95
C111—N11	1.439 (3)	C326—H326	0.95
C112—C113	1.387 (4)	C331—C332	1.385 (4)
C112—C117	1.507 (4)	C331—C336	1.400 (4)
C113—C114	1.388 (5)	C331—P13	1.827 (3)
C113—H113	0.95	C332—C333	1.383 (4)
C114—C115	1.385 (5)	C332—H332	0.95
C114—H114	0.95	C333—C334	1.386 (4)
C115—C116	1.396 (4)	C333—H333	0.95
C115—H115	0.95	C334—C335	1.380 (4)
C116—C118	1.503 (4)	C334—H334	0.95
C117—H11A	0.98	C335—C336	1.390 (4)
C117—H11B	0.98	C335—H335	0.95
C117—H11C	0.98	C336—H336	0.95
C118—H11D	0.98	N11—Rh1	2.076 (2)
C118—H11E	0.98	O12—Rh1	2.0277 (19)
C118—H11F	0.98	P13—Rh1	2.2701 (7)
C311—C316	1.391 (4)	O01—C02	1.135 (12)
C311—C312	1.394 (4)	C01—C02	1.474 (13)
C311—P13	1.825 (3)	C01—H01A	0.98
C312—C313	1.395 (4)	C01—H01B	0.98
C312—H312	0.95	C01—H01C	0.98
C313—C314	1.382 (4)	C02—C01ⁱ	1.492 (16)

C2—C1—H1A	109.5	C314—C315—H315	119.8
C2—C1—H1B	109.5	C315—C316—C311	120.5 (3)
H1A—C1—H1B	109.5	C315—C316—H316	119.7
C2—C1—H1C	109.5	C311—C316—H316	119.7
H1A—C1—H1C	109.5	C326—C321—C322	119.0 (3)
H1B—C1—H1C	109.5	C326—C321—P13	121.6 (2)
N11—C2—C3	123.8 (2)	C322—C321—P13	119.3 (2)
N11—C2—C1	120.5 (2)	C321—C322—C323	120.2 (3)
C3—C2—C1	115.8 (2)	C321—C322—H322	119.9
C4—C3—C2	127.1 (3)	C323—C322—H322	119.9
C4—C3—H3	116.5	C324—C323—C322	120.6 (3)
C2—C3—H3	116.5	C324—C323—H323	119.7
O12—C4—C3	125.6 (3)	C322—C323—H323	119.7
O12—C4—C5	113.9 (2)	C325—C324—C323	119.4 (3)
C3—C4—C5	120.4 (3)	C325—C324—H324	120.3
C4—C5—H5A	109.5	C323—C324—H324	120.3
C4—C5—H5B	109.5	C324—C325—C326	120.1 (3)
H5A—C5—H5B	109.5	C324—C325—H325	119.9
C4—C5—H5C	109.5	C326—C325—H325	119.9
H5A—C5—H5C	109.5	C321—C326—C325	120.6 (3)
H5B—C5—H5C	109.5	C321—C326—H326	119.7
O14—C14—Rh1	177.7 (2)	C325—C326—H326	119.7
C116—C111—C112	121.1 (3)	C332—C331—C336	119.2 (3)
C116—C111—N11	119.5 (2)	C332—C331—P13	117.9 (2)
C112—C111—N11	119.3 (2)	C336—C331—P13	122.8 (2)
C113—C112—C111	118.4 (3)	C333—C332—C331	120.5 (3)
C113—C112—C117	121.2 (3)	C333—C332—H332	119.7
C111—C112—C117	120.4 (3)	C331—C332—H332	119.7
C112—C113—C114	121.3 (3)	C332—C333—C334	120.3 (3)
C112—C113—H113	119.3	C332—C333—H333	119.9
C114—C113—H113	119.3	C334—C333—H333	119.9
C115—C114—C113	119.6 (3)	C335—C334—C333	119.6 (3)
C115—C114—H114	120.2	C335—C334—H334	120.2
C113—C114—H114	120.2	C333—C334—H334	120.2
C114—C115—C116	121.2 (3)	C334—C335—C336	120.5 (3)
C114—C115—H115	119.4	C334—C335—H335	119.7
C116—C115—H115	119.4	C336—C335—H335	119.7
C115—C116—C111	118.3 (3)	C335—C336—C331	119.8 (3)
C115—C116—C118	121.3 (3)	C335—C336—H336	120.1
C111—C116—C118	120.4 (3)	C331—C336—H336	120.1
C112—C117—H11A	109.5	C2—N11—C111	118.0 (2)
C112—C117—H11B	109.5	C2—N11—Rh1	125.79 (18)
H11A—C117—H11B	109.5	C111—N11—Rh1	116.24 (17)
C112—C117—H11C	109.5	C4—O12—Rh1	127.13 (18)
H11A—C117—H11C	109.5	C311—P13—C321	103.27 (12)
H11B—C117—H11C	109.5	C311—P13—C331	103.55 (12)
C116—C118—H11D	109.5	C321—P13—C331	103.59 (12)
C116—C118—H11E	109.5	C311—P13—Rh1	119.08 (9)
H11D—C118—H11E	109.5	C321—P13—Rh1	113.64 (9)
C116—C118—H11F	109.5	C331—P13—Rh1	112.06 (9)
H11D—C118—H11F	109.5	C14—Rh1—O12	177.36 (10)
H11E—C118—H11F	109.5	C14—Rh1—N11	93.02 (11)
C316—C311—C312	118.7 (3)	O12—Rh1—N11	89.38 (8)
C316—C311—P13	123.2 (2)	C14—Rh1—P13	91.59 (9)
C312—C311—P13	118.1 (2)	O12—Rh1—P13	85.95 (6)
C311—C312—C313	120.8 (3)	N11—Rh1—P13	174.36 (7)
C311—C312—H312	119.6	C02—C01—H01A	109.5
C313—C312—H312	119.6	C02—C01—H01B	109.5
C314—C313—C312	119.8 (3)	H01A—C01—H01B	109.5
C314—C313—H313	120.1	C02—C01—H01C	109.5
C312—C313—H313	120.1	H01A—C01—H01C	109.5
C313—C314—C315	119.8 (3)	H01B—C01—H01C	109.5
C313—C314—H314	120.1	O01—C02—C01	117.7 (13)
C315—C314—H314	120.1	O01—C02—C01ⁱ	110.6 (12)
C316—C315—C314	120.3 (3)	C01—C02—C01ⁱ	131.4 (9)
C316—C315—H315	119.8

N11—C2—C3—C4	−4.8 (5)	P13—C331—C336—C335	−179.2 (2)
C1—C2—C3—C4	175.4 (3)	C3—C2—N11—C111	178.5 (3)
C2—C3—C4—O12	1.8 (5)	C1—C2—N11—C111	−1.7 (4)
C2—C3—C4—C5	−177.6 (3)	C3—C2—N11—Rh1	−3.0 (4)
C116—C111—C112—C113	−2.1 (4)	C1—C2—N11—Rh1	176.8 (2)
N11—C111—C112—C113	−177.7 (3)	C116—C111—N11—C2	91.5 (3)
C116—C111—C112—C117	177.3 (3)	C112—C111—N11—C2	−92.9 (3)
N11—C111—C112—C117	1.7 (4)	C116—C111—N11—Rh1	−87.2 (3)
C111—C112—C113—C114	1.2 (4)	C112—C111—N11—Rh1	88.5 (3)
C117—C112—C113—C114	−178.3 (3)	C3—C4—O12—Rh1	9.0 (4)
C112—C113—C114—C115	0.4 (5)	C5—C4—O12—Rh1	−171.64 (18)
C113—C114—C115—C116	−1.1 (4)	C316—C311—P13—C321	9.9 (3)
C114—C115—C116—C111	0.1 (4)	C312—C311—P13—C321	−171.4 (2)
C114—C115—C116—C118	178.5 (3)	C316—C311—P13—C331	117.7 (2)
C112—C111—C116—C115	1.5 (4)	C312—C311—P13—C331	−63.6 (2)
N11—C111—C116—C115	177.1 (2)	C316—C311—P13—Rh1	−117.1 (2)
C112—C111—C116—C118	−176.9 (3)	C312—C311—P13—Rh1	61.6 (2)
N11—C111—C116—C118	−1.3 (4)	C326—C321—P13—C311	83.9 (3)
C316—C311—C312—C313	0.3 (4)	C322—C321—P13—C311	−93.4 (2)
P13—C311—C312—C313	−178.5 (2)	C326—C321—P13—C331	−23.8 (3)
C311—C312—C313—C314	0.1 (4)	C322—C321—P13—C331	158.9 (2)
C312—C313—C314—C315	−0.3 (4)	C326—C321—P13—Rh1	−145.7 (2)
C313—C314—C315—C316	0.2 (4)	C322—C321—P13—Rh1	37.0 (2)
C314—C315—C316—C311	0.1 (4)	C332—C331—P13—C311	168.3 (2)
C312—C311—C316—C315	−0.4 (4)	C336—C331—P13—C311	−12.7 (3)
P13—C311—C316—C315	178.3 (2)	C332—C331—P13—C321	−84.2 (2)
C326—C321—C322—C323	−1.5 (4)	C336—C331—P13—C321	94.8 (3)
P13—C321—C322—C323	175.9 (2)	C332—C331—P13—Rh1	38.7 (3)
C321—C322—C323—C324	2.2 (5)	C336—C331—P13—Rh1	−142.3 (2)
C322—C323—C324—C325	−1.5 (5)	C4—O12—Rh1—N11	−11.8 (2)
C323—C324—C325—C326	0.2 (6)	C4—O12—Rh1—P13	165.0 (2)
C322—C321—C326—C325	0.2 (5)	C2—N11—Rh1—C14	−170.1 (2)
P13—C321—C326—C325	−177.2 (3)	C111—N11—Rh1—C14	8.5 (2)
C324—C325—C326—C321	0.5 (6)	C2—N11—Rh1—O12	8.8 (2)
C336—C331—C332—C333	−0.9 (5)	C111—N11—Rh1—O12	−172.62 (19)
P13—C331—C332—C333	178.1 (3)	C311—P13—Rh1—C14	−14.40 (13)
C331—C332—C333—C334	2.0 (5)	C321—P13—Rh1—C14	−136.42 (13)
C332—C333—C334—C335	−2.0 (5)	C331—P13—Rh1—C14	106.57 (13)
C333—C334—C335—C336	0.9 (5)	C311—P13—Rh1—O12	166.55 (12)
C334—C335—C336—C331	0.2 (4)	C321—P13—Rh1—O12	44.53 (11)
C332—C331—C336—C335	−0.2 (4)	C331—P13—Rh1—O12	−72.48 (11)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C332—H332···O12	0.95	2.38	3.201 (3)	144
C334—H334···O14ⁱⁱ	0.95	2.51	3.201 (4)	130
C1—H1B···O01ⁱⁱⁱ	0.98	2.54	3.372 (9)	142

Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Rh(C₁₃H₁₆NO)(C₁₈H₁₅P)(CO)]·0.5C₃H₆O
M_r	624.5
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	16.8558 (8), 11.4028 (5), 16.4059 (8)
β (°)	108.733 (1)
V (Å³)	2986.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.31 × 0.15 × 0.11

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.822, 0.931
No. of measured, independent and observed ( > 2σI)) reflections	23158, 7425, 6081
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.112, 1.09
No. of reflections	7425
No. of parameters	354
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.54, −1.32

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C332—H332···O12	0.95	2.38	3.201 (3)	144
C334—H334···O14ⁱ	0.95	2.51	3.201 (4)	130
C1—H1B···O01ⁱⁱ	0.98	2.54	3.372 (9)	142

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2.

Comparative geometrical parameters (Å, °) for similar [Rh(N,O-bid)(CO)(PPh₃)] complexes top

Parameters	(I)^a	(II)^b	(III)^c	(IV)^d
Rh1—N11	2.077 (2)	2.069 (2)	2.045 (4)	2.045 (3)
Rh1—O12	2.027 (2)	2.028 (2)	2.044 (3)	2.045 (2)
Rh1—P13	2.2704 (7)	2.2635 (6)	2.275 (1)	2.281 (2)
Rh1—C14	1.812 (3)	1.807 (2)	1.784 (5)	1.804 (3)
C14—O14	1.147 (3)	1.152 (3)	1.142 (7)	1.148 (4)
N11···O12	2.885 (3)	2.885 (3)	2.826 (6)	2.841 (3)
N11—Rh1—O12	89.31 (9)	89.54 (8)	87.4 (1)	87.95 (8)
O12—Rh1—P13	85.95 (6)	84.97 (5)	89.7 (1)	89.91 (5)
P13—Rh1—C14	91.57 (9)	91.87 (7)	90.3 (2)	89.48 (9)
N11—Rh1—C14	93.1 (1)	93.6 (1)	92.6 (2)	92.6 (1)
N11—C2—C4—O12	-2.6 (2)	4.1 (2)	1.2 (4)	1.5 (2)
θ_E^e	155.77 (2)	156.39 (3)	156.0 (2)	156.23 (4)

Notes: (a) This work; (b) N,O-bid = 4-(2,3-dimethyl phenylamino)pent-3-en-2-onato (Venter et al., 2009); (c) N,O-bid = 4-amino-pent-3-en-2-onato (Damoense et al., 1994); (d) N,O-bid = 4-amino-1,1,1-trifluoro-pent-3-en-2-onato (Varshavsky et al., 2001); (e) Tolman (1977).

Acknowledgements

Financial assistance from the University of the Free State is gratefully acknowledged, while Mr Leo Kirsten is thanked for the data collection. We also express our gratitude to SASOL and the South African National Research Foundation (SA-NRF/THRIP) for financial support of this project. Part of this material is based on work supported by the SA-NRF/THRIP under grant No. GUN 2068915. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the SA-NRF.

References

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