PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m205.
Published online 2010 January 27. doi:  10.1107/S1600536810000449
PMCID: PMC2979718

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

Abstract

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 RhI atom (m symmetry). A weak inter­molecular C—H(...)O contact is observed.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-66-0m205-scheme1.jpg

Experimental

Crystal data

  • [Rh(C17H15Cl2N2)(CO)2]
  • M r = 477.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m205-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.017
  • wR(F 2) = 0.050
  • S = 0.93
  • 2555 reflections
  • 149 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.85 e Å−3

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

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000449/gw2073Isup2.hkl

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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%).

Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(parent) of the parent atom with a C—H distance of 0.99 (methyl) and 0.95 (aromatic).

Figures

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

Crystal data

[Rh(C17H15Cl2N2)(CO)2]F(000) = 476
Mr = 477.14Dx = 1.656 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 7852 reflections
a = 9.6726 (3) Åθ = 2.7–28.3°
b = 7.5911 (2) ŵ = 1.19 mm1
c = 13.6484 (4) ÅT = 100 K
β = 107.247 (1)°Cuboid, colourless
V = 957.08 (5) Å30.36 × 0.31 × 0.3 mm
Z = 2

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer2555 independent reflections
Radiation source: sealed tube2491 reflections with I > 2σ(I)
graphiteRint = 0.026
Detector resolution: 512 pixels mm-1θmax = 28.3°, θmin = 2.2°
ω and [var phi] scansh = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2004)k = −10→10
Tmin = 0.675, Tmax = 0.717l = −18→15
27556 measured reflections

Refinement

Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.017w = 1/[σ2(Fo2) + (0.0354P)2 + 0.5478P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.050(Δ/σ)max = 0.001
S = 0.93Δρmax = 0.36 e Å3
2555 reflectionsΔρmin = −0.85 e Å3
149 parameters

Special details

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)

xyzUiso*/UeqOcc. (<1)
Rh10.637102 (13)0.250.465229 (9)0.01730 (6)
N10.70723 (16)0.250.33783 (11)0.0184 (3)
N20.84799 (16)0.250.55685 (11)0.0174 (3)
O010.51242 (16)0.250.64255 (11)0.0306 (3)
O020.32539 (17)0.250.34080 (13)0.0470 (5)
Cl110.25234 (6)0.25−0.06636 (4)0.04074 (14)
Cl210.87899 (6)0.250.99767 (3)0.03319 (12)
C010.5641 (2)0.250.57800 (15)0.0233 (4)
C10.84413 (19)0.250.33584 (13)0.0183 (3)
C020.4448 (2)0.250.38608 (15)0.0298 (4)
C20.96380 (18)0.250.42351 (13)0.0185 (3)
H21.05570.250.41160.022*
C30.96652 (19)0.250.52655 (13)0.0178 (3)
C40.8736 (2)0.250.23319 (13)0.0231 (4)
H4A0.820 (4)0.152 (3)0.1908 (14)0.035*0.5
H4B0.9787 (16)0.235 (5)0.2437 (2)0.035*0.5
H4C0.841 (4)0.363 (3)0.1977 (13)0.035*0.5
C51.11412 (19)0.250.60505 (14)0.0221 (3)
H5A1.1388 (9)0.364 (2)0.6276 (10)0.033*0.5
H5B1.1816 (12)0.206 (2)0.5756 (6)0.033*0.5
H5C1.1122 (5)0.180 (2)0.6599 (12)0.033*0.5
C110.59706 (19)0.250.23963 (13)0.0206 (3)
C120.54311 (14)0.09167 (18)0.19293 (10)0.0243 (3)
H120.5792−0.01650.22550.029*
C130.43608 (14)0.0908 (2)0.09835 (10)0.0278 (3)
H130.3988−0.01720.0660.033*
C140.3853 (2)0.250.05267 (15)0.0281 (4)
C210.86559 (18)0.250.66523 (12)0.0185 (3)
C220.86893 (17)0.40678 (19)0.71687 (10)0.0303 (3)
H220.86830.51510.68190.036*
C230.87317 (17)0.4078 (2)0.81978 (10)0.0322 (3)
H230.87490.5160.85520.039*
C240.8748 (2)0.250.86918 (13)0.0232 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Rh10.01599 (8)0.02468 (8)0.01164 (8)00.00473 (5)0
N10.0194 (7)0.0248 (7)0.0112 (6)00.0046 (5)0
N20.0191 (7)0.0228 (7)0.0102 (6)00.0044 (5)0
O010.0300 (7)0.0437 (8)0.0230 (7)00.0154 (6)0
O020.0194 (7)0.0851 (14)0.0326 (9)00.0018 (6)0
Cl110.0270 (2)0.0652 (4)0.0215 (2)0−0.00592 (18)0
Cl210.0342 (2)0.0550 (3)0.01086 (19)00.00754 (17)0
C010.0192 (8)0.0295 (9)0.0207 (8)00.0052 (7)0
C10.0230 (8)0.0206 (7)0.0123 (7)00.0068 (6)0
C020.0240 (9)0.0461 (12)0.0206 (9)00.0087 (7)0
C20.0175 (7)0.0238 (8)0.0151 (7)00.0063 (6)0
C30.0194 (8)0.0187 (7)0.0150 (7)00.0047 (6)0
C40.0241 (9)0.0332 (9)0.0138 (8)00.0081 (7)0
C50.0184 (8)0.0298 (9)0.0170 (8)00.0038 (6)0
C110.0201 (8)0.0305 (9)0.0116 (7)00.0055 (6)0
C120.0253 (6)0.0302 (6)0.0170 (5)−0.0013 (5)0.0056 (5)−0.0004 (5)
C130.0255 (6)0.0376 (7)0.0196 (6)−0.0056 (6)0.0055 (5)−0.0053 (5)
C140.0186 (8)0.0500 (13)0.0136 (7)00.0013 (6)0
C210.0171 (7)0.0268 (8)0.0116 (7)00.0044 (6)0
C220.0500 (8)0.0255 (6)0.0179 (6)−0.0132 (6)0.0140 (6)−0.0030 (5)
C230.0489 (8)0.0319 (7)0.0182 (6)−0.0150 (6)0.0135 (6)−0.0094 (5)
C240.0203 (8)0.0391 (10)0.0098 (7)00.0041 (6)0

Geometric parameters (Å, °)

Rh1—C021.854 (2)C4—H4C0.9902
Rh1—C011.8741 (19)C5—H5A0.9234
Rh1—N12.0453 (14)C5—H5B0.9234
Rh1—N22.0523 (14)C5—H5C0.9234
N1—C11.332 (2)C11—C121.3877 (16)
N1—C111.444 (2)C11—C12i1.3877 (16)
N2—C31.329 (2)C12—C131.3949 (17)
N2—C211.438 (2)C12—H120.95
O01—C011.134 (2)C13—C141.3816 (18)
O02—C021.137 (3)C13—H130.95
Cl11—C141.748 (2)C14—C13i1.3816 (18)
Cl21—C241.7420 (18)C21—C221.3787 (16)
C1—C21.397 (2)C21—C22i1.3787 (16)
C1—C41.510 (2)C22—C231.3929 (17)
C2—C31.399 (2)C22—H220.95
C2—H20.95C23—C241.3727 (17)
C3—C51.510 (2)C23—H230.95
C4—H4A0.9902C24—C23i1.3727 (17)
C4—H4B0.9902
C02—Rh1—C0185.48 (8)C3—C5—H5B109.5
C02—Rh1—N191.89 (7)H5A—C5—H5B109.5
C01—Rh1—N1177.37 (6)C3—C5—H5C109.5
C02—Rh1—N2178.24 (7)H5A—C5—H5C109.5
C01—Rh1—N292.76 (7)H5B—C5—H5C109.5
N1—Rh1—N289.87 (6)C12—C11—C12i120.01 (16)
C1—N1—C11116.46 (14)C12—C11—N1119.99 (8)
C1—N1—Rh1126.83 (12)C12i—C11—N1119.99 (8)
C11—N1—Rh1116.72 (11)C11—C12—C13120.27 (13)
C3—N2—C21118.04 (14)C11—C12—H12119.9
C3—N2—Rh1127.13 (12)C13—C12—H12119.9
C21—N2—Rh1114.83 (11)C14—C13—C12118.70 (14)
O01—C01—Rh1176.21 (17)C14—C13—H13120.7
N1—C1—C2123.98 (15)C12—C13—H13120.7
N1—C1—C4118.73 (15)C13i—C14—C13122.04 (18)
C2—C1—C4117.29 (16)C13i—C14—Cl11118.98 (9)
O02—C02—Rh1177.45 (18)C13—C14—Cl11118.98 (9)
C1—C2—C3128.69 (16)C22—C21—C22i119.37 (16)
C1—C2—H2115.7C22—C21—N2120.24 (8)
C3—C2—H2115.7C22i—C21—N2120.24 (8)
N2—C3—C2123.51 (15)C21—C22—C23120.65 (13)
N2—C3—C5120.04 (15)C21—C22—H22119.7
C2—C3—C5116.45 (15)C23—C22—H22119.7
C1—C4—H4A109.5C24—C23—C22118.87 (14)
C1—C4—H4B109.5C24—C23—H23120.6
H4A—C4—H4B109.5C22—C23—H23120.6
C1—C4—H4C109.5C23i—C24—C23121.59 (17)
H4A—C4—H4C109.5C23i—C24—Cl21119.20 (8)
H4B—C4—H4C109.5C23—C24—Cl21119.20 (8)
C3—C5—H5A109.5
C02—Rh1—N1—C1180C1—C2—C3—C5180
N2—Rh1—N1—C10C1—N1—C11—C1290.64 (14)
C02—Rh1—N1—C110Rh1—N1—C11—C12−89.36 (14)
N2—Rh1—N1—C11180C1—N1—C11—C12i−90.64 (14)
C01—Rh1—N2—C3180Rh1—N1—C11—C12i89.36 (14)
N1—Rh1—N2—C30C12i—C11—C12—C130.9 (3)
C01—Rh1—N2—C210N1—C11—C12—C13179.63 (13)
N1—Rh1—N2—C21180C11—C12—C13—C14−0.1 (2)
C11—N1—C1—C2180C12—C13—C14—C13i−0.8 (3)
Rh1—N1—C1—C20C12—C13—C14—Cl11179.46 (11)
C11—N1—C1—C40C3—N2—C21—C2292.31 (15)
Rh1—N1—C1—C4180Rh1—N2—C21—C22−87.69 (15)
N1—C1—C2—C30C3—N2—C21—C22i−92.31 (15)
C4—C1—C2—C3180Rh1—N2—C21—C22i87.69 (15)
C21—N2—C3—C2180C22i—C21—C22—C23−1.1 (3)
Rh1—N2—C3—C20N2—C21—C22—C23174.34 (15)
C21—N2—C3—C50C21—C22—C23—C240.4 (3)
Rh1—N2—C3—C5180C22—C23—C24—C23i0.4 (3)
C1—C2—C3—N20C22—C23—C24—Cl21−179.62 (13)

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C22—H22···O02ii0.952.543.1723 (18)124

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GW2073).

References

  • Brandenburg, K. & Putz, H. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2004). SAINT-Plus (including XPREP) and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smith, J. M., Lachicotte, R. J. & Holland, P. L. (2002). Organometallics, 21, 4808–4814.
  • Smith, J. M., Sadique, A. R., Cundari, T. R., Rodgers, K. R., Lukat-Rodgers, G., Lachicotte, R. J., Flaschenriem, C. J., Vela, J. & Holland, P. L. (2006). J. Am. Chem. Soc.128, 756–769. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography