metal-organic compounds Acta Crystallographica Section E
Experimental
Structure Reports Online
Crystal data
ISSN 1600-5368
Chlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-(2-thienyl)ethanaminej2N,P}methylpalladium(II) dichloromethane hemisolvate Martin O. Onani,a* William M. Motswainyana,a Emmanuel I. Iwuoha,a James Darkwab and Roger A. Lalancettec a
University of the Western Cape, Cape Town, Bellville 7535, South Africa, University of Johannesburg, Auckland Park Kingsway Campus, Johannesburg 2006, South Africa, and cDepartment of Chemistry, Rutgers State University, 73 Warren St, Newark, NJ 07102, USA Correspondence e-mail:
[email protected] b
[Pd(CH3)Cl(C25H22NPS)]0.5C2H2Cl2 Mr = 598.81 Monoclinic, P21 =n ˚ a = 9.9960 (6) A ˚ b = 18.6584 (11) A ˚ c = 13.8167 (8) A
= 94.517 (1) ˚3 V = 2568.9 (3) A Z=4 Mo K radiation = 1.09 mm 1 T = 173 K 0.16 0.15 0.14 mm
Data collection Bruker Kappa DUO APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2006) Tmin = 0.683, Tmax = 0.746
31867 measured reflections 6376 independent reflections 5600 reflections with I > 2(I) Rint = 0.028
Refinement R[F 2 > 2(F 2)] = 0.029 wR(F 2) = 0.074 S = 1.03 6376 reflections 321 parameters
2 restraints H-atom parameters constrained ˚ 3 max = 1.34 e A ˚ 3 min = 1.04 e A
Received 26 April 2010; accepted 14 May 2010
Table 1 ˚; Key indicators: single-crystal X-ray study; T = 173 K; mean (C–C) = 0.003 A disorder in main residue; R factor = 0.029; wR factor = 0.074; data-to-parameter ratio = 19.9.
˚ ). Selected bond lengths (A
In the title compound, [Pd(CH3)Cl(C25H22NPS)]0.5C2H2Cl2, the PdII atom is coordinated by the N,P-bidentate ligand, a methyl group and a chloride ion, generating a distorted square-planar PdCClNS coordination geometry, with the N and Cl atoms trans. The thiophene ring is equally disordered over two orientations and the dichloromethane solvent molecule is disordered about an inversion centre.
Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.
Pd1—C1 Pd1—N1
2.045 (2) 2.158 (2)
Pd1—P1 Pd1—Cl1
2.2039 (6) 2.3628 (6)
We acknowledge the University of the Western Cape and the Ministry of Health of Botswana (WMM) for funding.
Related literature For metal-organic compounds with ligands containing both pyridyl and phosphine donor groups and for typical Pd—C, Pd—Cl, Pd—P and Pd—N bond lengths, see: Shaffer & Schmidt (2009). For the properties of related compounds, see: Tongwa et al. (2009); Jun-Gill et al. (2009).
m688
Onani et al.
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5421).
References Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191 Bruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Jun-Gill, K., Sung-Il, O., Dong-Hee, C., Min-Kook, N., Changmoon, P., Young Ju, B., Woo, T. H., Young, J. P., Sang, W. L. & In, T. K. (2009). Bull. Korean Chem. Soc. 30, 1157–1163 Shaffer, A. R. & Schmidt, J. A. (2009). Organometallica, 28, 2494–2504. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Tongwa, P., Kinnibrugh, T. L., Kicchaiahgari, G. R., Khrustalev, V. N. & Timofeeva, T. V. (2009). Acta Cryst. C65, o155–o159.
doi:10.1107/S1600536810017824
Acta Cryst. (2010). E66, m688
supplementary materials
supplementary materials Acta Cryst. (2010). E66, m688
[ doi:10.1107/S1600536810017824 ]
Chlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-(2-thienyl)ethanamine2
N,P}methylpalladium(II) dichloromethane hemisolvate
M. O. Onani, W. M. Motswainyana, E. I. Iwuoha, J. Darkwa and R. A. Lalancette Comment The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF. The solvent molecule dichloromethane exhibits high thermal motions and were refined isotropically with temperature factors in the range of 0.101 – 0.122. It is situated close to a centre of inversion. The five-membered ring was disordered and shows two orientations each at 50% s.o.f.: the first ring C7, C8A, C9A, C10A and S1A (ring A) and the second ring C7, C8B, C9B, C10B and S1B (ring B). Ring A and ring B share two common atom sites at C7 and C10A (or C10B). C10A and C10B are on the same site and refined anisotropically with the same temperature factors. The maximum and minimum deviations from the least-squares planes of both rings are 0.086 (4) Å and -0.084 (3) Å for C7 and S1A in ring A, 0.095 (5) Å and -0.090 (3) Å for C7 and S1B in ring B. Angle from the least-square plane of ring A to that of ring B is 36.2 (3)°. Experimental The iminophosphine heterocyclic ligand was prepared via the condensation reaction of 2-(diphenylphosphino)benzaldehyde with 2-thien-2-ylethanamine. The ligand was further refluxed with an equimolar Pd(cod)Cl2 in dichloromethane and gave over 80% yield of a yellow complex. Light-yellow blocks of (I) were grown via slow diffusion of a dichloromethane solution of the complex in hexane a 4 Refinement The solvent molecule dichloromethane exhibits high thermal motions and were refined isotropically with temperature factors in the range of 0.101 – 0.122. It is situated on the centre of inversion. Therefore only half of the molecule is in the asymmetric unit and it is modelled as a whole molecule with 50% site occupancy factor (s.o.f.). The 5 member ring was disordered and shows two preferred orientations each at 50% s.o.f.: the first ring C7, C8A, C9A, C10A and S1A (ring A) and the second ring C7, C8B, C9B, C10B and S1B (ring B). Ring A and ring B share two common atom sites at C7 and C10A (or C10B). C10A and C10B are on the same site and refined anisotropically with the same temperature factors. The maximum and minimum deviations from the least-squares planes of both rings are 0.086 (4) Å and -0.084 (3) Å for C7 and S1A in ring A, 0.095 (5) Å and -0.090 (3) Å for C7 and S1B in ring B. Angle from the least-square plane of ring A to that of ring B is 36.2 (3)o. All hydrogen atoms were positioned geometrically with C—H = 0.95 – 0.99 Å and refined as riding on their parent atoms with Uiso (H) = 1.2 - 1.5 Ueq (C).
sup-1
supplementary materials Figures Fig. 1. : The molecular structure of (I) showing 30% displacement ellipsoids (all hydrogen atoms omitted for clarity). The solvent dichloromethane molecule is excluded.
Chlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-(2-thienyl)ethanamine- κ2N,P}methylpalladium(II) dichloromethane hemisolvate Crystal data [Pd(CH3)Cl(C25H22NPS)]·0.5C2H2Cl2
F(000) = 1212
Mr = 598.81
Dx = 1.548 Mg m−3
Monoclinic, P21/n
Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn a = 9.9960 (6) Å
Cell parameters from 31867 reflections θ = 2.2–28.3°
b = 18.6584 (11) Å
µ = 1.09 mm−1 T = 173 K Needle, light-yellow
c = 13.8167 (8) Å β = 94.517 (1)° V = 2568.9 (3) Å3 Z=4
0.16 × 0.15 × 0.14 mm
Data collection Bruker Kappa DUO APEXII CCD diffractometer Radiation source: fine-focus sealed tube
6376 independent reflections
graphite
5600 reflections with I > 2σ(I) Rint = 0.028
0.5° φ scans and ω scans
θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2006) Tmin = 0.683, Tmax = 0.746 31867 measured reflections
h = −13→13 k = −24→24 l = −18→18
Refinement
R[F2 > 2σ(F2)] = 0.029
Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074
H-atom parameters constrained
Refinement on F2 Least-squares matrix: full
S = 1.03 6376 reflections
sup-2
w = 1/[σ2(Fo2) + (0.0301P)2 + 3.2924P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.002
supplementary materials 321 parameters
Δρmax = 1.34 e Å−3
2 restraints
Δρmin = −1.04 e Å−3
Special details Experimental. Half sphere of data collected using SAINT strategy (Bruker, 2006). Crystal to detector distance = 50 mm; combination of φ and ω scans of 0.5°, 50 s per °, 2 iterations. Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. The solvent molecule dichloromethane exhibits high thermal motions and were refined isotropically with temperature factors in the range of 0.101 C 0.122. It is modelled as a whole molecule with 50% s.o.f. The 5 member ring was disordered and shows two preferred orientations each at 50% s.o.f. All hydrogen atoms were positioned geometrically with C—H = 0.95 C 0.99 A and refined as riding on their parent atoms with Uiso (H) = 1.2 - 1.5 Ueq (C). 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 > σ(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) Pd1 Cl1 Cl2A Cl2B S1A S1B P1 N1 C1 H1A H1B H1C C2 C3 C4 H4 C5 H5A H5B C6 H6A H6B C7 C8A
x
y
z
Uiso*/Ueq
0.636610 (16) 0.51346 (6) 1.0260 (4) 0.9080 (4) 0.3721 (8) 0.3499 (8) 0.76594 (5) 0.7551 (2) 0.5273 (2) 0.5795 0.5062 0.4438 0.9364 (2) 0.9725 (2) 0.8828 (3) 0.9235 0.6819 (3) 0.7465 0.6275 0.5910 (3) 0.6467 0.5284 0.5115 (3) 0.5216 (8)
0.296906 (8) 0.20048 (3) 0.55967 (18) 0.4537 (2) 0.3256 (4) 0.3404 (4) 0.38331 (3) 0.30566 (11) 0.28695 (14) 0.2602 0.3347 0.2612 0.34988 (11) 0.31802 (13) 0.31090 (14) 0.3101 0.30364 (16) 0.3037 0.2594 0.36912 (17) 0.4130 0.3689 0.37153 (19) 0.4289 (5)
0.583217 (12) 0.64253 (6) 1.0814 (2) 0.9486 (3) 0.9098 (5) 0.8969 (6) 0.53464 (4) 0.72019 (14) 0.45247 (18) 0.4074 0.4259 0.4615 0.56117 (16) 0.65212 (17) 0.73071 (18) 0.7952 0.80910 (18) 0.8672 0.8100 0.81044 (19) 0.8089 0.7513 0.8982 (2) 0.9701 (5)
0.02079 (5) 0.03899 (15) 0.1066 (9)* 0.1223 (11)* 0.0464 (12) 0.0443 (12) 0.01817 (11) 0.0289 (4) 0.0316 (5) 0.047* 0.047* 0.047* 0.0214 (4) 0.0268 (5) 0.0315 (5) 0.038* 0.0374 (6) 0.045* 0.045* 0.0402 (6) 0.048* 0.048* 0.0455 (7) 0.0549 (18)
Occ. (
