[N,N′-Bis(4-chloro­phen­yl)pentane-2,4-diiminato]dicarbonyl­rhodium(I)

Hill, T.N.; Steyl, G.

doi:10.1107/S1600536810000449

metal-organic compounds

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Volume 66| Part 2| February 2010| Page m205

https://doi.org/10.1107/S1600536810000449

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[N,N′-Bis(4-chlorophenyl)pentane-2,4-diiminato]dicarbonylrhodium(I)

T. N. Hill ^a ^* and G. Steyl ^a

^aDepartment of Chemistry, University of the Free State, Bloemfontein 9300, South Africa
^*Correspondence e-mail: tania.hill@gmail.com

(Received 30 October 2009; accepted 5 January 2010; online 27 January 2010)

The title compound, [Rh(C₁₇H₁₅Cl₂N₂)(CO)₂], is a rhodium(I) derivative of a β-diketiminato moiety. It is an example of a new type of β-diketiminate derivative that has not yet been characterized via solid-state methods. The complex crystallizes with a distorted square-planar geometry about the Rh^I atom (m symmetry). A weak intermolecular C—H⋯O contact is observed.

Related literature

For related diketiminato complexes, see: Smith et al. (2002 , 2006 ).

Experimental

Crystal data

[Rh(C₁₇H₁₅Cl₂N₂)(CO)₂]
M_r = 477.14
Monoclinic, P 2₁ /m
a = 9.6726 (3) Å
b = 7.5911 (2) Å
c = 13.6484 (4) Å
β = 107.247 (1)°
V = 957.08 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 100 K
0.36 × 0.31 × 0.30 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.675, T_max = 0.717
27556 measured reflections
2555 independent reflections
2491 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.050
S = 0.93
2555 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Rh1—C02	1.854 (2)
Rh1—C01	1.8741 (19)
Rh1—N1	2.0453 (14)
Rh1—N2	2.0523 (14)
O01—C01	1.134 (2)
O02—C02	1.137 (3)

C02—Rh1—C01	85.48 (8)
C02—Rh1—N1	91.89 (7)
C01—Rh1—N2	92.76 (7)
N1—Rh1—N2	89.87 (6)
O01—C01—Rh1	176.21 (17)
O02—C02—Rh1	177.45 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯O02ⁱ	0.95	2.54	3.1723 (18)	124
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000449/gw2073sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000449/gw2073Isup2.hkl

checkCIF report

Comment top

In literature similar iron complexes have been reported containing tertiary butyl, isopropyl and methyl derivatives (Smith et al., 2002; Smith et al., 2006). Using a comparable ligand system, with electron withdrawing substituents on the phenyl ring, a series of rhodium(I) dicarbonyl complexes were prepared. The title compound (I) is a novel example of a 4-Chlorophenyl derivative. (Figure 1)

Due to the highly symmetrical nature of the complex both the Rh—C and Rh—N bond distances are similar. The carbonyl oxygen bond distances are the same, with the carbonyl's themselves being close to linearity. The mirror plane bisects the complex passing through the metal centre, the ketimine backbone and carbonyl moeities. (Table 1)

A staggared head-to-tail stacking is observed with no Rh—Rh interaction. The closest contact is a weak hydrogen bond between the phenyl ring (C22) of the diketiminato ligand and the adjacent carbonyl oxygen O02 (Table 2).

Related literature top

For related diketiminato complexes, see: Smith et al. (2002, 2006)

Experimental top

The title complex was synthesized by the addition of N,N'-bis-(4-chlorophenyl)pentane-2,4-di-imine (167 mg, 0.514 mmol) to an acetone solution of the [Rh(µ-Cl)(CO)₂]₂ (100 mg, 0.257 mmol). On slow evaporation of the solvent; crystals suitable for X-Ray crystallography were obtained. Yield: 147 mg (60%).

Structure description top

For related diketiminato complexes, see: Smith et al. (2002, 2006)

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids)

[N,N'-Bis(4-chlorophenyl)pentane-2,4- diiminato]dicarbonylrhodium(I) top

Crystal data top

[Rh(C₁₇H₁₅Cl₂N₂)(CO)₂]	F(000) = 476
M_r = 477.14	D_x = 1.656 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 7852 reflections
a = 9.6726 (3) Å	θ = 2.7–28.3°
b = 7.5911 (2) Å	µ = 1.19 mm⁻¹
c = 13.6484 (4) Å	T = 100 K
β = 107.247 (1)°	Cuboid, colourless
V = 957.08 (5) Å³	0.36 × 0.31 × 0.3 mm
Z = 2

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	2555 independent reflections
Radiation source: sealed tube	2491 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 512 pixels mm^-1	θ_max = 28.3°, θ_min = 2.2°
ω and φ scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −10→10
T_min = 0.675, T_max = 0.717	l = −18→15
27556 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.017	w = 1/[σ²(F_o²) + (0.0354P)² + 0.5478P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.050	(Δ/σ)_max = 0.001
S = 0.93	Δρ_max = 0.36 e Å⁻³
2555 reflections	Δρ_min = −0.85 e Å⁻³
149 parameters

Crystal data top

[Rh(C₁₇H₁₅Cl₂N₂)(CO)₂]	V = 957.08 (5) Å³
M_r = 477.14	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 9.6726 (3) Å	µ = 1.19 mm⁻¹
b = 7.5911 (2) Å	T = 100 K
c = 13.6484 (4) Å	0.36 × 0.31 × 0.3 mm
β = 107.247 (1)°

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	2555 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2491 reflections with I > 2σ(I)
T_min = 0.675, T_max = 0.717	R_int = 0.026
27556 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.36 e Å⁻³
2555 reflections	Δρ_min = −0.85 e Å⁻³
149 parameters

Special details top

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)
Rh1	0.637102 (13)	0.25	0.465229 (9)	0.01730 (6)
N1	0.70723 (16)	0.25	0.33783 (11)	0.0184 (3)
N2	0.84799 (16)	0.25	0.55685 (11)	0.0174 (3)
O01	0.51242 (16)	0.25	0.64255 (11)	0.0306 (3)
O02	0.32539 (17)	0.25	0.34080 (13)	0.0470 (5)
Cl11	0.25234 (6)	0.25	−0.06636 (4)	0.04074 (14)
Cl21	0.87899 (6)	0.25	0.99767 (3)	0.03319 (12)
C01	0.5641 (2)	0.25	0.57800 (15)	0.0233 (4)
C1	0.84413 (19)	0.25	0.33584 (13)	0.0183 (3)
C02	0.4448 (2)	0.25	0.38608 (15)	0.0298 (4)
C2	0.96380 (18)	0.25	0.42351 (13)	0.0185 (3)
H2	1.0557	0.25	0.4116	0.022*
C3	0.96652 (19)	0.25	0.52655 (13)	0.0178 (3)
C4	0.8736 (2)	0.25	0.23319 (13)	0.0231 (4)
H4A	0.820 (4)	0.152 (3)	0.1908 (14)	0.035*	0.5
H4B	0.9787 (16)	0.235 (5)	0.2437 (2)	0.035*	0.5
H4C	0.841 (4)	0.363 (3)	0.1977 (13)	0.035*	0.5
C5	1.11412 (19)	0.25	0.60505 (14)	0.0221 (3)
H5A	1.1388 (9)	0.364 (2)	0.6276 (10)	0.033*	0.5
H5B	1.1816 (12)	0.206 (2)	0.5756 (6)	0.033*	0.5
H5C	1.1122 (5)	0.180 (2)	0.6599 (12)	0.033*	0.5
C11	0.59706 (19)	0.25	0.23963 (13)	0.0206 (3)
C12	0.54311 (14)	0.09167 (18)	0.19293 (10)	0.0243 (3)
H12	0.5792	−0.0165	0.2255	0.029*
C13	0.43608 (14)	0.0908 (2)	0.09835 (10)	0.0278 (3)
H13	0.3988	−0.0172	0.066	0.033*
C14	0.3853 (2)	0.25	0.05267 (15)	0.0281 (4)
C21	0.86559 (18)	0.25	0.66523 (12)	0.0185 (3)
C22	0.86893 (17)	0.40678 (19)	0.71687 (10)	0.0303 (3)
H22	0.8683	0.5151	0.6819	0.036*
C23	0.87317 (17)	0.4078 (2)	0.81978 (10)	0.0322 (3)
H23	0.8749	0.516	0.8552	0.039*
C24	0.8748 (2)	0.25	0.86918 (13)	0.0232 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.01599 (8)	0.02468 (8)	0.01164 (8)	0	0.00473 (5)	0
N1	0.0194 (7)	0.0248 (7)	0.0112 (6)	0	0.0046 (5)	0
N2	0.0191 (7)	0.0228 (7)	0.0102 (6)	0	0.0044 (5)	0
O01	0.0300 (7)	0.0437 (8)	0.0230 (7)	0	0.0154 (6)	0
O02	0.0194 (7)	0.0851 (14)	0.0326 (9)	0	0.0018 (6)	0
Cl11	0.0270 (2)	0.0652 (4)	0.0215 (2)	0	−0.00592 (18)	0
Cl21	0.0342 (2)	0.0550 (3)	0.01086 (19)	0	0.00754 (17)	0
C01	0.0192 (8)	0.0295 (9)	0.0207 (8)	0	0.0052 (7)	0
C1	0.0230 (8)	0.0206 (7)	0.0123 (7)	0	0.0068 (6)	0
C02	0.0240 (9)	0.0461 (12)	0.0206 (9)	0	0.0087 (7)	0
C2	0.0175 (7)	0.0238 (8)	0.0151 (7)	0	0.0063 (6)	0
C3	0.0194 (8)	0.0187 (7)	0.0150 (7)	0	0.0047 (6)	0
C4	0.0241 (9)	0.0332 (9)	0.0138 (8)	0	0.0081 (7)	0
C5	0.0184 (8)	0.0298 (9)	0.0170 (8)	0	0.0038 (6)	0
C11	0.0201 (8)	0.0305 (9)	0.0116 (7)	0	0.0055 (6)	0
C12	0.0253 (6)	0.0302 (6)	0.0170 (5)	−0.0013 (5)	0.0056 (5)	−0.0004 (5)
C13	0.0255 (6)	0.0376 (7)	0.0196 (6)	−0.0056 (6)	0.0055 (5)	−0.0053 (5)
C14	0.0186 (8)	0.0500 (13)	0.0136 (7)	0	0.0013 (6)	0
C21	0.0171 (7)	0.0268 (8)	0.0116 (7)	0	0.0044 (6)	0
C22	0.0500 (8)	0.0255 (6)	0.0179 (6)	−0.0132 (6)	0.0140 (6)	−0.0030 (5)
C23	0.0489 (8)	0.0319 (7)	0.0182 (6)	−0.0150 (6)	0.0135 (6)	−0.0094 (5)
C24	0.0203 (8)	0.0391 (10)	0.0098 (7)	0	0.0041 (6)	0

Geometric parameters (Å, º) top

Rh1—C02	1.854 (2)	C4—H4C	0.9902
Rh1—C01	1.8741 (19)	C5—H5A	0.9234
Rh1—N1	2.0453 (14)	C5—H5B	0.9234
Rh1—N2	2.0523 (14)	C5—H5C	0.9234
N1—C1	1.332 (2)	C11—C12	1.3877 (16)
N1—C11	1.444 (2)	C11—C12ⁱ	1.3877 (16)
N2—C3	1.329 (2)	C12—C13	1.3949 (17)
N2—C21	1.438 (2)	C12—H12	0.95
O01—C01	1.134 (2)	C13—C14	1.3816 (18)
O02—C02	1.137 (3)	C13—H13	0.95
Cl11—C14	1.748 (2)	C14—C13ⁱ	1.3816 (18)
Cl21—C24	1.7420 (18)	C21—C22	1.3787 (16)
C1—C2	1.397 (2)	C21—C22ⁱ	1.3787 (16)
C1—C4	1.510 (2)	C22—C23	1.3929 (17)
C2—C3	1.399 (2)	C22—H22	0.95
C2—H2	0.95	C23—C24	1.3727 (17)
C3—C5	1.510 (2)	C23—H23	0.95
C4—H4A	0.9902	C24—C23ⁱ	1.3727 (17)
C4—H4B	0.9902

C02—Rh1—C01	85.48 (8)	C3—C5—H5B	109.5
C02—Rh1—N1	91.89 (7)	H5A—C5—H5B	109.5
C01—Rh1—N1	177.37 (6)	C3—C5—H5C	109.5
C02—Rh1—N2	178.24 (7)	H5A—C5—H5C	109.5
C01—Rh1—N2	92.76 (7)	H5B—C5—H5C	109.5
N1—Rh1—N2	89.87 (6)	C12—C11—C12ⁱ	120.01 (16)
C1—N1—C11	116.46 (14)	C12—C11—N1	119.99 (8)
C1—N1—Rh1	126.83 (12)	C12ⁱ—C11—N1	119.99 (8)
C11—N1—Rh1	116.72 (11)	C11—C12—C13	120.27 (13)
C3—N2—C21	118.04 (14)	C11—C12—H12	119.9
C3—N2—Rh1	127.13 (12)	C13—C12—H12	119.9
C21—N2—Rh1	114.83 (11)	C14—C13—C12	118.70 (14)
O01—C01—Rh1	176.21 (17)	C14—C13—H13	120.7
N1—C1—C2	123.98 (15)	C12—C13—H13	120.7
N1—C1—C4	118.73 (15)	C13ⁱ—C14—C13	122.04 (18)
C2—C1—C4	117.29 (16)	C13ⁱ—C14—Cl11	118.98 (9)
O02—C02—Rh1	177.45 (18)	C13—C14—Cl11	118.98 (9)
C1—C2—C3	128.69 (16)	C22—C21—C22ⁱ	119.37 (16)
C1—C2—H2	115.7	C22—C21—N2	120.24 (8)
C3—C2—H2	115.7	C22ⁱ—C21—N2	120.24 (8)
N2—C3—C2	123.51 (15)	C21—C22—C23	120.65 (13)
N2—C3—C5	120.04 (15)	C21—C22—H22	119.7
C2—C3—C5	116.45 (15)	C23—C22—H22	119.7
C1—C4—H4A	109.5	C24—C23—C22	118.87 (14)
C1—C4—H4B	109.5	C24—C23—H23	120.6
H4A—C4—H4B	109.5	C22—C23—H23	120.6
C1—C4—H4C	109.5	C23ⁱ—C24—C23	121.59 (17)
H4A—C4—H4C	109.5	C23ⁱ—C24—Cl21	119.20 (8)
H4B—C4—H4C	109.5	C23—C24—Cl21	119.20 (8)
C3—C5—H5A	109.5

C02—Rh1—N1—C1	180	C1—C2—C3—C5	180
N2—Rh1—N1—C1	0	C1—N1—C11—C12	90.64 (14)
C02—Rh1—N1—C11	0	Rh1—N1—C11—C12	−89.36 (14)
N2—Rh1—N1—C11	180	C1—N1—C11—C12ⁱ	−90.64 (14)
C01—Rh1—N2—C3	180	Rh1—N1—C11—C12ⁱ	89.36 (14)
N1—Rh1—N2—C3	0	C12ⁱ—C11—C12—C13	0.9 (3)
C01—Rh1—N2—C21	0	N1—C11—C12—C13	179.63 (13)
N1—Rh1—N2—C21	180	C11—C12—C13—C14	−0.1 (2)
C11—N1—C1—C2	180	C12—C13—C14—C13ⁱ	−0.8 (3)
Rh1—N1—C1—C2	0	C12—C13—C14—Cl11	179.46 (11)
C11—N1—C1—C4	0	C3—N2—C21—C22	92.31 (15)
Rh1—N1—C1—C4	180	Rh1—N2—C21—C22	−87.69 (15)
N1—C1—C2—C3	0	C3—N2—C21—C22ⁱ	−92.31 (15)
C4—C1—C2—C3	180	Rh1—N2—C21—C22ⁱ	87.69 (15)
C21—N2—C3—C2	180	C22ⁱ—C21—C22—C23	−1.1 (3)
Rh1—N2—C3—C2	0	N2—C21—C22—C23	174.34 (15)
C21—N2—C3—C5	0	C21—C22—C23—C24	0.4 (3)
Rh1—N2—C3—C5	180	C22—C23—C24—C23ⁱ	0.4 (3)
C1—C2—C3—N2	0	C22—C23—C24—Cl21	−179.62 (13)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O02ⁱⁱ	0.95	2.54	3.1723 (18)	124

Symmetry code: (ii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Rh(C₁₇H₁₅Cl₂N₂)(CO)₂]
M_r	477.14
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	100
a, b, c (Å)	9.6726 (3), 7.5911 (2), 13.6484 (4)
β (°)	107.247 (1)
V (Å³)	957.08 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.36 × 0.31 × 0.3

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.675, 0.717
No. of measured, independent and observed [I > 2σ(I)] reflections	27556, 2555, 2491
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.050, 0.93
No. of reflections	2555
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.85

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Rh1—C02	1.854 (2)	Rh1—N2	2.0523 (14)
Rh1—C01	1.8741 (19)	O01—C01	1.134 (2)
Rh1—N1	2.0453 (14)	O02—C02	1.137 (3)

C02—Rh1—C01	85.48 (8)	N1—Rh1—N2	89.87 (6)
C02—Rh1—N1	91.89 (7)	O01—C01—Rh1	176.21 (17)
C01—Rh1—N2	92.76 (7)	O02—C02—Rh1	177.45 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O02ⁱ	0.95	2.54	3.1723 (18)	124.3

Symmetry code: (i) −x+1, y+1/2, −z+1.

Acknowledgements

Financial assistance from the University of the Free State and Professor A. Roodt is gratefully acknowledged. Mr. L. Kirsten is acknowledged for the data collection. Part of this material is based on work supported by the South African National Research Foundation (NRF) 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 NRF.

References

Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2004). SAINT-Plus (including XPREP) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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