Dicarbon-yl[4-(2,6-dimethyl-phenyl-amino)-pent-3-en-2-onato-κ(2)N,O]rhodium(I).

In the title compound, [Rh(C(13)H(16)NO)(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 inter-molecular C-H⋯O inter-action 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 n class="Gene">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 = 361.2

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.042

S = 1.07

3767 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.57 e Å−3

Absolute structure: Flack (1983 ▶), 1605 Friedel pairs

Flack parameter: −0.01 (2)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAIn class="Chemical">NT-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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017175/hy2537sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Rh(C13H16NO)(CO)2]	F(000) = 728
Mr = 361.2	Dx = 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

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

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(Fo2) + (0.0159P)2 + 0.9823P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.042	(Δ/σ)max = 0.002
S = 1.07	Δρmax = 0.79 e Å−3
3767 reflections	Δρmin = −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	Flack parameter: −0.01 (2)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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—C13b	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—C13b	87.25 (8)	85.95 (6)	84.97 (5)	89.7 (1)	89.91 (5)
C13b—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)

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) .

Table 2

Comparative geometrical parameters for the title complex with [Rh(N,O-bid)(CO)(PPh3)] 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—C13b	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—C13b	87.25 (8)	85.95 (6)	84.97 (5)	89.7 (1)	89.91 (5)
C13b—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- κ2 N,O](triphenyl­phosphine-κP)rhodium(I) (Venter et al., 2009b ▶). (III) Carbon­yl[4-(2,3-dimeth­yl­phenyl­amino)­pent-3-en-2-onato-κ2 N,O](triphenyl­phosphine-κP)rhodium(I) (Venter et al., 2009a ▶). (IV) Carbon­yl(4-amino­pent-3-en-2-onato-κ2 N,O)(triphenyl­phosphine-κP)rhodium(I) (Damoense et al., 1994 ▶). (V) Carbon­yl(4-amino-1,1,1-trifluoro-pent-3-en-2-onato-κ2 N,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.