Dicarbon­yl[4-(2,6-dimethyl­phenyl­amino)­pent-3-en-2-onato-κ2N,O]rhodium(I)

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

doi:10.1107/S1600536812017175

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m666-m667

doi:10.1107/S1600536812017175

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Dicarbonyl[4-(2,6-dimethylphenylamino)pent-3-en-2-onato-κ²N,O]rhodium(I)

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

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

(Received 11 April 2012; accepted 18 April 2012; online 25 April 2012)

In the title compound, [Rh(C₁₃H₁₆NO)(CO)₂], a square-planar coordination geometry is observed around the Rh^I atom, formed by the N and O atoms of the bidentate ligand and two C atoms from two carbonyl ligands. The Rh^I atom is displaced from the plane through these surrounding atoms by 0.0085 (2) Å. The dihedral angle between the benzene ring and the N—C—C—C—O plane is 89.82 (6)°, and the N—Rh—O bite angle for the bidentate ligand is 90.53 (6)°. An intermolecular C—H⋯O interaction is observed between a methyl group of the benzene ring and a carbonyl O atom.

Related literature

For background to the ligand preparation, see: Shaheen et al. (2006 ); Venter et al. (2010a ,b ). For applications of rhodium compounds containing bidentate ligand systems, see: Cornils & Herrmann (1996 ); Steyn et al. (1997 ); Trzeciak & Ziolkowski (1994 ); Van Rooy et al. (1995 ). For related rhodium enaminoketonato complexes, see: Brink et al. (2010 ); Damoense et al. (1994 ); Otto et al. (1998 ); Roodt et al. (2011 ); Steyn et al. (1992 ); Varshavsky et al. (2001 ); Venter et al. (2009a ,b ).

Experimental

Crystal data

[Rh(C₁₃H₁₆NO)(CO)₂]
M_r = 361.2
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.9191 (7) Å
b = 12.3873 (5) Å
c = 15.393 (6) Å
V = 1510.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 100 K
0.34 × 0.20 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.699, T_max = 0.885
20802 measured reflections
3767 independent reflections
3746 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.042
S = 1.07
3767 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.57 e Å⁻³
Absolute structure: Flack (1983 ), 1605 Friedel pairs
Flack parameter: −0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C118—H11D⋯O12ⁱ	0.98	2.51	3.441 (2)	159
Symmetry code: (i) x-1, y, z.

Table 2
Comparative geometrical parameters for the title complex with [Rh(N,O-bid)(CO)(PPh₃)]^a complexes (Å, °)

Parameters	I	II	III	IV	V
Rh1—N11	2.048 (2)	2.077 (2)	2.069 (2)	2.045 (4)	2.045 (3)
Rh1—O12	2.021 (1)	2.027 (2)	2.028 (2)	2.044 (3)	2.045 (2)
Rh1—C13^b	1.880 (2)	2.2704 (7)	2.2635 (6)	2.275 (1)	2.281 (2)
Rh1—C14	1.852 (2)	1.812 (3)	1.807 (2)	1.784 (5)	1.804 (3)
N11⋯O12	2.890 (2)	2.885 (3)	2.885 (3)	2.826 (6)	2.841 (3)
N11—Rh1—O12	90.53 (6)	89.31 (9)	89.54 (8)	87.4 (1)	87.95 (8)
O12—Rh1—C13^b	87.25 (8)	85.95 (6)	84.97 (5)	89.7 (1)	89.91 (5)
C13^b—Rh1—C14	89.8 (1)	91.57 (9)	91.87 (7)	90.3 (2)	89.48 (9)
N11—Rh1—C14	92.41 (8)	93.1 (1)	93.6 (1)	92.6 (2)	92.6 (1)
N11—C2—C4—O12	1.6 (2)	−2.6 (2)	4.1 (2)	1.2 (4)	1.5 (2)
(I) This work. (II) Carbonyl[4-(2,6-dimethylphenylamino)pent-3-en-2-onato- κ²N,O](triphenylphosphine-κP)rhodium(I) (Venter et al., 2009b). (III) Carbonyl[4-(2,3-dimethylphenylamino)pent-3-en-2-onato-κ²N,O](triphenylphosphine-κP)rhodium(I) (Venter et al., 2009a). (IV) Carbonyl(4-aminopent-3-en-2-onato-κ²N,O)(triphenylphosphine-κP)rhodium(I) (Damoense et al., 1994). (V) Carbonyl(4-amino-1,1,1-trifluoro-pent-3-en-2-onato-κ²N,O)(triphenylphosphine-κP)rhodium(I) (Varshavsky et al., 2001). (a) N,O-bid is a mono-anionic bidentate ligand coordinated to a metal via (N,O) donor atoms. (b) P13 atom is used in comparative complexes instead of C13 atom.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017175/hy2537sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017175/hy2537Isup2.hkl

checkCIF report

Comment top

Rhodium(I) dicarbonyl complexes of the type [Rh(L,L')(CO)₂], where L,L' is a chelating mono-anionic bidentate ligand coordinated to rhodium via (O, O') donor atoms, have been studied as catalyst precursors (Cornils & Herrmann, 1996; Trzeciak & Ziolkowski, 1994; Van Rooy et al., 1995). In this study 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; Venter et al., 2010a,b) coordinated to rhodium via (N, O) donor atoms. Studies have also been conducted involving complexes of the type [Rh(L,L')(CO)(PPh₃)], where one of the CO-ligands in the [Rh(L,L')(CO)₂] complex is substituted by a PPh₃ ligand (Brink et al., 2010; Otto et al., 1998; Roodt et al., 2011; Steyn et al., 1992), as well as the mechanism of oxidative addition of methyl iodide to complexes of this type (Steyn et al., 1997).

Bond distances involving the Rh^I atom in the title complex differ from complexes in literature involving triphenylphosphine as ligand, with especially the Rh1—C14 distance that is significantly longer (Table 2). The title complex displays similar Rh—N distances to complexes containing a hydrogen atom instead of an aryl moiety, but is more closely related to complexes containing similar aryl moieties when comparing the Rh—O distance. Complexes containing a bulky substituent on the nitrogen atom also display larger N—Rh—O bite angles than complexes containing a hydrogen atom. Due to the trans influence of the nitrogen atom, the Rh1—C13 distance is significantly longer than the Rh1—C14 distance [1.880 (2) and 1.852 (2) Å].

Intermolecular C—H···O interaction is observed between a methyl group on the aryl moiety and oxygen of the bidentate ligand. The dihedral angle between the plane formed by the N, O and C atoms of the pentenone backbone and the aryl ring moiety is 89.82 (6) °. This angle is distorted from the ideal value of 0° for delocalized electron due to the steric interference of the aryl ring, and is exacerbated by the presence of the methyl groups on the ring.

Related literature top

For background to the ligand preparation, see: Shaheen et al. (2006); Venter et al. (2010a,b). For applications of rhodium compounds containing bidentate ligand systems, see: Cornils & Herrmann (1996); Steyn et al. (1997); Trzeciak & Ziolkowski (1994); Van Rooy et al. (1995). For related rhodium enaminoketonato complexes, see: Brink et al. (2010); Damoense et al. (1994); Otto et al. (1998); Roodt et al. (2011); Steyn et al. (1992); Varshavsky et al. (2001); Venter et al. (2009a,b).

Experimental top

[RhCl(CO)₂]₂ was prepared in situ by heating RhCl₃.3H₂O (0.1014 g, 0.385 mmol) in 2 ml DMF under reflux for 30 min. 2,6-diMe-PhonyH (0.0892 g, 0.439 mmol) was added to the cooled DMF solution of [RhCl(CO)₂]₂. The product was precipitated by ice-water and centrifuge, and recrystallized from acetone. Yellow crystals suitable for X-Ray diffraction were collected in 80.09% yield (0.1114 g). IR (KBr, cm^-1): ν_CO,_sym 2064.5 s, ν_CO,_asym 1985.8 s.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); 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 level.

Dicarbonyl[4-(2,6-dimethylphenylamino)pent-3-en-2-onato- κ²N,O]rhodium(I) top

Crystal data top

[Rh(C₁₃H₁₆NO)(CO)₂]	F(000) = 728
M_r = 361.2	D_x = 1.589 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9513 reflections
a = 7.9191 (7) Å	θ = 2.9–28.3°
b = 12.3873 (5) Å	µ = 1.14 mm⁻¹
c = 15.393 (6) Å	T = 100 K
V = 1510.0 (6) Å³	Cuboid, yellow
Z = 4	0.34 × 0.20 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	3767 independent reflections
Radiation source: fine-focus sealed tube	3746 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→10
T_min = 0.699, T_max = 0.885	k = −16→16
20802 measured reflections	l = −17→20

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.017	w = 1/[σ²(F_o²) + (0.0159P)² + 0.9823P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.042	(Δ/σ)_max = 0.002
S = 1.07	Δρ_max = 0.79 e Å⁻³
3767 reflections	Δρ_min = −0.57 e Å⁻³
174 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0163 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1605 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (2)

Crystal data top

[Rh(C₁₃H₁₆NO)(CO)₂]	V = 1510.0 (6) Å³
M_r = 361.2	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.9191 (7) Å	µ = 1.14 mm⁻¹
b = 12.3873 (5) Å	T = 100 K
c = 15.393 (6) Å	0.34 × 0.20 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	3767 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3746 reflections with I > 2σ(I)
T_min = 0.699, T_max = 0.885	R_int = 0.029
20802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.042	Δρ_max = 0.79 e Å⁻³
S = 1.07	Δρ_min = −0.57 e Å⁻³
3767 reflections	Absolute structure: Flack (1983), 1605 Friedel pairs
174 parameters	Absolute structure parameter: −0.01 (2)
0 restraints

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 1033 frames were collected with a frame width of 0.5° covering up to θ = 28.31° with 99.8% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

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 > 2σ(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
C1	−0.1665 (3)	0.74776 (15)	0.96601 (14)	0.0256 (4)
H1A	−0.2853	0.7323	0.9532	0.038*
H1B	−0.1389	0.821	0.9465	0.038*
H1C	−0.1472	0.7421	1.0287	0.038*
C2	−0.0554 (2)	0.66732 (14)	0.91901 (11)	0.0172 (3)
C3	0.0594 (3)	0.71073 (13)	0.85745 (11)	0.0192 (3)
H3	0.0598	0.787	0.8512	0.023*
C4	0.1704 (2)	0.65405 (15)	0.80574 (12)	0.0182 (3)
C5	0.2854 (3)	0.71425 (17)	0.74432 (13)	0.0261 (4)
H5A	0.4033	0.7006	0.7602	0.039*
H5B	0.2621	0.7918	0.7481	0.039*
H5C	0.2654	0.6894	0.6848	0.039*
C13	0.1968 (3)	0.33435 (18)	0.82539 (16)	0.0315 (3)
C14	−0.0362 (4)	0.33708 (18)	0.94754 (18)	0.0431 (4)
C111	−0.2003 (2)	0.53224 (12)	0.99790 (11)	0.0155 (3)
C112	−0.1618 (3)	0.52091 (15)	1.08635 (12)	0.0202 (4)
C113	−0.2906 (3)	0.48830 (15)	1.14235 (12)	0.0247 (4)
H113	−0.2669	0.4799	1.2025	0.03*
C114	−0.4521 (3)	0.46795 (14)	1.11235 (13)	0.0251 (4)
H114	−0.5385	0.4473	1.1518	0.03*
C115	−0.4876 (2)	0.47775 (14)	1.02404 (13)	0.0214 (4)
H115	−0.598	0.4624	1.0033	0.026*
C116	−0.3627 (2)	0.50984 (14)	0.96590 (12)	0.0169 (3)
C117	0.0141 (3)	0.54302 (18)	1.11936 (14)	0.0295 (4)
H11A	0.023	0.5194	1.18	0.044*
H11B	0.0375	0.6206	1.1157	0.044*
H11C	0.096	0.5034	1.0839	0.044*
C118	−0.3997 (2)	0.51770 (16)	0.87001 (12)	0.0229 (4)
H11D	−0.5215	0.5101	0.8604	0.034*
H11E	−0.3397	0.4601	0.8391	0.034*
H11F	−0.362	0.588	0.8482	0.034*
N11	−0.0694 (2)	0.56317 (11)	0.93686 (9)	0.0153 (2)
O12	0.18814 (16)	0.55013 (11)	0.80425 (8)	0.0188 (2)
O13	0.2774 (2)	0.27212 (12)	0.79070 (11)	0.0315 (3)
O14	−0.0990 (3)	0.27211 (12)	0.98856 (13)	0.0431 (4)
Rh1	0.066650 (17)	0.441740 (10)	0.879887 (8)	0.01597 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0296 (10)	0.0145 (8)	0.0327 (10)	0.0009 (8)	0.0099 (8)	0.0002 (7)
C2	0.0171 (8)	0.0171 (7)	0.0172 (7)	0.0007 (7)	−0.0010 (7)	−0.0001 (6)
C3	0.0205 (8)	0.0153 (7)	0.0219 (8)	−0.0015 (7)	−0.0008 (8)	0.0029 (6)
C4	0.0163 (8)	0.0216 (8)	0.0168 (8)	−0.0042 (7)	−0.0036 (6)	0.0030 (6)
C5	0.0250 (10)	0.0264 (9)	0.0268 (10)	−0.0043 (8)	0.0051 (8)	0.0059 (8)
C13	0.0282 (6)	0.0244 (6)	0.0419 (7)	0.0026 (5)	0.0101 (5)	−0.0036 (5)
C14	0.0567 (10)	0.0183 (5)	0.0543 (8)	0.0045 (6)	0.0297 (8)	0.0040 (5)
C111	0.0197 (8)	0.0119 (7)	0.0150 (7)	0.0013 (6)	0.0022 (6)	0.0002 (5)
C112	0.0263 (10)	0.0169 (8)	0.0175 (8)	−0.0014 (7)	−0.0018 (7)	0.0000 (6)
C113	0.0384 (12)	0.0210 (8)	0.0147 (8)	−0.0045 (8)	0.0017 (8)	0.0010 (6)
C114	0.0343 (10)	0.0196 (8)	0.0215 (8)	−0.0060 (7)	0.0098 (9)	0.0005 (6)
C115	0.0211 (9)	0.0168 (8)	0.0263 (9)	−0.0024 (7)	0.0038 (7)	−0.0015 (7)
C116	0.0193 (8)	0.0138 (7)	0.0177 (8)	0.0006 (6)	0.0010 (7)	0.0006 (6)
C117	0.0315 (9)	0.0357 (10)	0.0213 (8)	−0.0033 (8)	−0.0078 (8)	0.0027 (9)
C118	0.0196 (8)	0.0301 (9)	0.0191 (9)	−0.0017 (7)	−0.0023 (7)	0.0030 (7)
N11	0.0160 (6)	0.0149 (6)	0.0150 (6)	−0.0030 (7)	0.0004 (6)	0.0005 (5)
O12	0.0171 (6)	0.0194 (6)	0.0198 (6)	−0.0009 (6)	0.0010 (5)	0.0001 (5)
O13	0.0282 (6)	0.0244 (6)	0.0419 (7)	0.0026 (5)	0.0101 (5)	−0.0036 (5)
O14	0.0567 (10)	0.0183 (5)	0.0543 (8)	0.0045 (6)	0.0297 (8)	0.0040 (5)
Rh1	0.01566 (6)	0.01375 (6)	0.01848 (7)	0.00045 (5)	0.00126 (5)	−0.00015 (5)

Geometric parameters (Å, º) top

C1—C2	1.514 (3)	C111—N11	1.451 (2)
C1—H1A	0.98	C112—C113	1.395 (3)
C1—H1B	0.98	C112—C117	1.508 (3)
C1—H1C	0.98	C113—C114	1.383 (3)
C2—N11	1.324 (2)	C113—H113	0.95
C2—C3	1.419 (3)	C114—C115	1.393 (3)
C3—C4	1.378 (3)	C114—H114	0.95
C3—H3	0.95	C115—C116	1.392 (3)
C4—O12	1.295 (2)	C115—H115	0.95
C4—C5	1.510 (3)	C116—C118	1.508 (3)
C5—H5A	0.98	C117—H11A	0.98
C5—H5B	0.98	C117—H11B	0.98
C5—H5C	0.98	C117—H11C	0.98
C13—O13	1.134 (3)	C118—H11D	0.98
C13—Rh1	1.880 (2)	C118—H11E	0.98
C14—O14	1.138 (3)	C118—H11F	0.98
C14—Rh1	1.852 (2)	N11—Rh1	2.0476 (15)
C111—C112	1.402 (3)	O12—Rh1	2.0209 (13)
C111—C116	1.405 (3)

C2—C1—H1A	109.5	C113—C114—C115	119.77 (18)
C2—C1—H1B	109.5	C113—C114—H114	120.1
H1A—C1—H1B	109.5	C115—C114—H114	120.1
C2—C1—H1C	109.5	C116—C115—C114	120.58 (19)
H1A—C1—H1C	109.5	C116—C115—H115	119.7
H1B—C1—H1C	109.5	C114—C115—H115	119.7
N11—C2—C3	124.18 (16)	C115—C116—C111	118.78 (17)
N11—C2—C1	119.57 (16)	C115—C116—C118	120.65 (17)
C3—C2—C1	116.24 (15)	C111—C116—C118	120.55 (16)
C4—C3—C2	126.95 (16)	C112—C117—H11A	109.5
C4—C3—H3	116.5	C112—C117—H11B	109.5
C2—C3—H3	116.5	H11A—C117—H11B	109.5
O12—C4—C3	125.86 (17)	C112—C117—H11C	109.5
O12—C4—C5	114.49 (17)	H11A—C117—H11C	109.5
C3—C4—C5	119.65 (17)	H11B—C117—H11C	109.5
C4—C5—H5A	109.5	C116—C118—H11D	109.5
C4—C5—H5B	109.5	C116—C118—H11E	109.5
H5A—C5—H5B	109.5	H11D—C118—H11E	109.5
C4—C5—H5C	109.5	C116—C118—H11F	109.5
H5A—C5—H5C	109.5	H11D—C118—H11F	109.5
H5B—C5—H5C	109.5	H11E—C118—H11F	109.5
O13—C13—Rh1	177.7 (2)	C2—N11—C111	116.87 (15)
O14—C14—Rh1	179.4 (2)	C2—N11—Rh1	125.65 (12)
C112—C111—C116	121.30 (17)	C111—N11—Rh1	117.35 (10)
C112—C111—N11	120.00 (17)	C4—O12—Rh1	126.77 (12)
C116—C111—N11	118.64 (15)	C14—Rh1—C13	89.80 (11)
C113—C112—C111	118.04 (18)	C14—Rh1—O12	176.97 (9)
C113—C112—C117	121.31 (17)	C13—Rh1—O12	87.25 (8)
C111—C112—C117	120.65 (18)	C14—Rh1—N11	92.41 (8)
C114—C113—C112	121.50 (18)	C13—Rh1—N11	177.76 (9)
C114—C113—H113	119.2	O12—Rh1—N11	90.53 (6)
C112—C113—H113	119.2

N11—C2—C3—C4	1.4 (3)	N11—C111—C116—C118	0.1 (2)
C1—C2—C3—C4	−178.66 (18)	C3—C2—N11—C111	−176.47 (16)
C2—C3—C4—O12	0.4 (3)	C1—C2—N11—C111	3.6 (2)
C2—C3—C4—C5	−179.26 (18)	C3—C2—N11—Rh1	−0.8 (3)
C116—C111—C112—C113	−1.1 (3)	C1—C2—N11—Rh1	179.31 (13)
N11—C111—C112—C113	−178.36 (15)	C112—C111—N11—C2	−94.1 (2)
C116—C111—C112—C117	178.70 (17)	C116—C111—N11—C2	88.55 (19)
N11—C111—C112—C117	1.4 (3)	C112—C111—N11—Rh1	89.86 (16)
C111—C112—C113—C114	−0.3 (3)	C116—C111—N11—Rh1	−87.51 (17)
C117—C112—C113—C114	180.00 (18)	C3—C4—O12—Rh1	−2.7 (3)
C112—C113—C114—C115	1.4 (3)	C5—C4—O12—Rh1	177.03 (12)
C113—C114—C115—C116	−1.2 (3)	C4—O12—Rh1—C13	−177.21 (16)
C114—C115—C116—C111	−0.1 (3)	C4—O12—Rh1—N11	2.46 (14)
C114—C115—C116—C118	178.41 (17)	C2—N11—Rh1—C14	178.50 (18)
C112—C111—C116—C115	1.2 (3)	C111—N11—Rh1—C14	−5.83 (15)
N11—C111—C116—C115	178.54 (15)	C2—N11—Rh1—O12	−0.78 (15)
C112—C111—C116—C118	−177.26 (17)	C111—N11—Rh1—O12	174.89 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C118—H11D···O12ⁱ	0.98	2.51	3.441 (2)	159

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Rh(C₁₃H₁₆NO)(CO)₂]
M_r	361.2
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.9191 (7), 12.3873 (5), 15.393 (6)
V (Å³)	1510.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.34 × 0.20 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.699, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	20802, 3767, 3746
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.042, 1.07
No. of reflections	3767
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.57
Absolute structure	Flack (1983), 1605 Friedel pairs
Absolute structure parameter	−0.01 (2)

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 1999), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C118—H11D···O12ⁱ	0.98	2.51	3.441 (2)	159

Symmetry code: (i) x−1, y, z.

Comparative geometrical parameters for the title complex with [Rh(N,O-bid)(CO)(PPh₃)]^a complexes (Å, °). top

Parameters	I	II	III	IV	V
Rh1—N11	2.048 (2)	2.077 (2)	2.069 (2)	2.045 (4)	2.045 (3)
Rh1—O12	2.021 (1)	2.027 (2)	2.028 (2)	2.044 (3)	2.045 (2)
Rh1—C13^b	1.880 (2)	2.2704 (7)	2.2635 (6)	2.275 (1)	2.281 (2)
Rh1—C14	1.852 (2)	1.812 (3)	1.807 (2)	1.784 (5)	1.804 (3)
N11···O12	2.890 (2)	2.885 (3)	2.885 (3)	2.826 (6)	2.841 (3)
N11—Rh1—O12	90.53 (6)	89.31 (9)	89.54 (8)	87.4 (1)	87.95 (8)
O12—Rh1—C13^b	87.25 (8)	85.95 (6)	84.97 (5)	89.7 (1)	89.91 (5)
C13^b—Rh1—C14	89.8 (1)	91.57 (9)	91.87 (7)	90.3 (2)	89.48 (9)
N11—Rh1—C14	92.41 (8)	93.1 (1)	93.6 (1)	92.6 (2)	92.6 (1)
N11—C2—C4—O12	1.6 (2)	-2.6 (2)	4.1 (2)	1.2 (4)	1.5 (2)

(I) This work. (II) Carbonyl[4-(2,6-dimethylphenylamino)pent-3-en-2-onato- κ²N,O](triphenylphosphine-κP)rhodium(I) (Venter et al., 2009b). (III) Carbonyl[4-(2,3-dimethylphenylamino)pent -3-en-2-onato-κ²N,O](triphenylphosphine-κP)rhodium(I) (Venter et al., 2009a). (IV) Carbonyl(4-aminopent-3-en-2-onato-κ²N,O) (triphenylphosphine-κP)rhodium(I) (Damoense et al., 1994). (V) Carbonyl(4-amino-1,1,1-trifluoro-pent-3-en-2-onato-κ²N,O) (triphenylphosphine-κP)rhodium(I) (Varshavsky et al., 2001). (a) N,O-bid is a mono-anionic bidentate ligand coordinated to a metal via (N,O) donor atoms. (b) P13 atom is used in comparative complexes instead of C13 atom.

Acknowledgements

Ms Carla Pretorius is thanked for the data collection. Financial assistance from the University of the Free State Strategic Academic Cluster Initiative, SASOL, the South African National Research Foundation (SA-NRF/THRIP) and the Inkaba yeAfrika Research Initiative is gratefully acknowledged. 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.

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