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Acta Cryst. (2009). E65, m396    [ doi:10.1107/S1600536809008472 ]

trans-Dichloridobis(2-methylaniline-[kappa]N)palladium(II)

V. Bon, A. Dudko, S. Orysyk and V. Pekhnyo

Abstract top

In the title compound, [PdCl2(C7H9N)2], the Pd atom is situated on an inversion centre and displays a distorted square-planar coordination environment. The crystal structure displays weak intermolecular N-H...Cl hydrogen bonding.

Comment top

Palladium complex compounds with N–containing organic ligands attract constant scientific interest due to its cytostatic and antitumoral activity (Curic et al., 1996; Casas et al., 2008). Asymmetric unit of title compound contains half of a molecule, other one generates by the symmetry operator of inversion centre (Fig. 1). Pd atom shows a square–planar geometry of coordination environment, which contain two chlorine atoms in trans–position and a two amino groups of o–toluidine. Bond lengths and angles have normal values (Allen et al., 1987). The crystal structure displays week intermolecular N—H···Cl hydrogen bonding (Table 1) creating the layered structure (Fig. 2).

Related literature top

For the cytostatic and antitumoral activity of Pd complexes with N-containing organic ligands, see: Casas et al. (2008); Curic et al. (1996). For related structures, see: Baldovino-Pantaleon et al. (2007); Navarro–Ranninger et al. (1987); Vogels et al. (1999). For bond-length data, see: Allen et al. (1987).

Experimental top

The 5 ml of 0.02 M chloroform o–toluidine solution was poured into the test–tube. The other reactant, 5 ml 0.01 M water solution of K2PdCl4 was carefully added on the top of the organic part. The sealed test–tube with double–layer mixture was put in a dark place. Two weeks later, the yellow plate shape crystals were grown in the chloroform part of the solution.

Refinement top

H atoms bonded to N atoms were located in a difference map. Other H atoms which bonded to C were positioned geometrically and refined using a riding model with C—H = 0.98 Å for CH3 with Uiso(H) = 1.5Ueq(C) and C—H = 0.95 Å for CH with Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability lervel. H atoms are presented as a small spheres of arbitrary radius. Symmetry code: (i) -x, 1-y, -z.
[Figure 2] Fig. 2. Crystal packing of title compound, projection along b axis. Dashed lines indicate hydrogen bonds [Symmetry code: (i) -x, y-1/2, 1/2-z; (ii) x, 3/2-y, 1/2+z].
trans-Dichloridobis(2-methylaniline-κN)palladium(II) top
Crystal data top
[PdCl2(C7H9N)2]F(000) = 392
Mr = 391.60Dx = 1.770 Mg m−3
Monoclinic, P21/cMelting point: 560 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 12.1841 (3) ÅCell parameters from 1337 reflections
b = 8.0653 (2) Åθ = 3.0–22.5°
c = 7.5407 (2) ŵ = 1.61 mm−1
β = 97.346 (2)°T = 173 K
V = 734.93 (3) Å3Plate, yellow
Z = 20.17 × 0.16 × 0.04 mm
Data collection top
Bruker APEXII CCD
diffractometer		1502 independent reflections
Radiation source: Fine–focus sealed tube1118 reflections with I > 2σ(I)
GraphiteRint = 0.074
Detector resolution: 8.26 pixels mm-1θmax = 26.4°, θmin = 1.7°
φ and ω scansh = −15→15
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		k = −10→10
Tmin = 0.777, Tmax = 0.932l = −9→9
8179 measured reflections
Refinement top
Refinement on F2Primary atom site location: Direct
Least-squares matrix: FullSecondary atom site location: Difmap
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: Geom
wR(F2) = 0.060H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0118P)2 + 0.6868P]
where P = (Fo2 + 2Fc2)/3
1502 reflections(Δ/σ)max < 0.001
97 parametersΔρmax = 0.48 e Å−3
2 restraintsΔρmin = −0.66 e Å−3
Crystal data top
[PdCl2(C7H9N)2]V = 734.93 (3) Å3
Mr = 391.60Z = 2
Monoclinic, P21/cMo Kα radiation
a = 12.1841 (3) ŵ = 1.61 mm−1
b = 8.0653 (2) ÅT = 173 K
c = 7.5407 (2) Å0.17 × 0.16 × 0.04 mm
β = 97.346 (2)°
Data collection top
Bruker APEXII CCD
diffractometer		1502 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		1118 reflections with I > 2σ(I)
Tmin = 0.777, Tmax = 0.932Rint = 0.074
8179 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.060Δρmax = 0.48 e Å−3
S = 1.03Δρmin = −0.66 e Å−3
1502 reflectionsAbsolute structure: ?
97 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

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 > 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) top
xyzUiso*/Ueq
Pd10.00000.50000.00000.01692 (12)
Cl10.06040 (8)0.77044 (11)0.02411 (13)0.0222 (2)
N10.1118 (3)0.4372 (4)0.2186 (5)0.0192 (8)
H1N0.130 (3)0.526 (4)0.276 (5)0.024 (12)*
H2N0.071 (3)0.386 (4)0.294 (5)0.025 (12)*
C10.2062 (3)0.3358 (5)0.1906 (5)0.0216 (9)
C20.3051 (4)0.4060 (6)0.1573 (6)0.0300 (11)
C30.3912 (3)0.2990 (6)0.1258 (6)0.0330 (11)
H30.45960.34460.10150.040*
C40.3790 (4)0.1308 (6)0.1291 (6)0.0390 (12)
H40.43870.06120.10730.047*
C50.2808 (4)0.0614 (6)0.1639 (6)0.0352 (12)
H50.2722−0.05560.16530.042*
C60.1949 (3)0.1643 (5)0.1967 (5)0.0271 (10)
H60.12750.11740.22380.032*
C70.3210 (4)0.5894 (6)0.1537 (7)0.0432 (14)
H7A0.27010.63730.05600.065*
H7B0.39740.61420.13500.065*
H7C0.30600.63700.26770.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0189 (2)0.0155 (2)0.0169 (2)0.0004 (2)0.00446 (15)−0.0002 (2)
Cl10.0272 (5)0.0174 (5)0.0222 (5)−0.0014 (4)0.0033 (4)0.0008 (4)
N10.0228 (18)0.0170 (17)0.019 (2)−0.0008 (14)0.0066 (16)−0.0040 (16)
C10.022 (2)0.025 (2)0.017 (2)0.0002 (17)0.0021 (18)0.0009 (17)
C20.029 (3)0.039 (3)0.022 (3)0.000 (2)0.004 (2)0.000 (2)
C30.022 (2)0.044 (3)0.033 (3)0.007 (2)0.004 (2)−0.004 (2)
C40.034 (3)0.047 (3)0.036 (3)0.014 (2)0.003 (2)−0.012 (2)
C50.041 (3)0.030 (2)0.033 (3)0.006 (2)0.000 (2)−0.005 (2)
C60.025 (2)0.034 (3)0.022 (3)0.0000 (19)0.0007 (19)0.0015 (19)
C70.031 (3)0.035 (3)0.063 (4)0.001 (2)0.002 (3)0.005 (3)
Geometric parameters (Å, °) top
Pd1—N12.063 (3)C3—C41.365 (6)
Pd1—N1i2.063 (3)C3—H30.9500
Pd1—Cl1i2.3017 (9)C4—C51.376 (6)
Pd1—Cl12.3017 (9)C4—H40.9500
N1—C11.449 (5)C5—C61.382 (5)
N1—H1N0.85 (2)C5—H50.9500
N1—H2N0.90 (2)C6—H60.9500
C1—C21.383 (5)C7—H7A0.9800
C1—C61.392 (5)C7—H7B0.9800
C2—C31.402 (6)C7—H7C0.9800
C2—C71.492 (5)
N1—Pd1—N1i180.0C4—C3—C2121.5 (4)
N1—Pd1—Cl1i90.13 (10)C4—C3—H3119.2
N1i—Pd1—Cl1i89.87 (10)C2—C3—H3119.2
N1—Pd1—Cl189.88 (10)C3—C4—C5120.5 (4)
N1i—Pd1—Cl190.13 (10)C3—C4—H4119.8
Cl1i—Pd1—Cl1180.0C5—C4—H4119.8
C1—N1—Pd1118.6 (3)C4—C5—C6119.1 (4)
C1—N1—H1N113 (3)C4—C5—H5120.4
Pd1—N1—H1N108 (3)C6—C5—H5120.4
C1—N1—H2N110 (2)C5—C6—C1120.7 (4)
Pd1—N1—H2N105 (3)C5—C6—H6119.7
H1N—N1—H2N101 (4)C1—C6—H6119.7
C2—C1—C6120.3 (4)C2—C7—H7A109.5
C2—C1—N1121.5 (4)C2—C7—H7B109.5
C6—C1—N1118.2 (4)H7A—C7—H7B109.5
C1—C2—C3117.8 (4)C2—C7—H7C109.5
C1—C2—C7121.8 (4)H7A—C7—H7C109.5
C3—C2—C7120.4 (4)H7B—C7—H7C109.5
Cl1i—Pd1—N1—C170.4 (3)C1—C2—C3—C4−0.5 (7)
Cl1—Pd1—N1—C1−109.6 (3)C7—C2—C3—C4179.7 (5)
Pd1—N1—C1—C290.5 (4)C2—C3—C4—C50.0 (7)
Pd1—N1—C1—C6−89.0 (4)C3—C4—C5—C6−0.5 (7)
C6—C1—C2—C31.6 (6)C4—C5—C6—C11.5 (7)
N1—C1—C2—C3−177.9 (4)C2—C1—C6—C5−2.1 (7)
C6—C1—C2—C7−178.7 (4)N1—C1—C6—C5177.4 (4)
N1—C1—C2—C71.9 (7)
Symmetry codes: (i) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl1ii0.85 (2)2.71 (3)3.410 (4)141 (3)
N1—H2N···Cl1iii0.90 (2)2.43 (3)3.319 (4)172 (3)
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl1i0.85 (2)2.71 (3)3.410 (4)141 (3)
N1—H2N···Cl1ii0.90 (2)2.43 (3)3.319 (4)172 (3)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Baldovino-Pantaleon, O., Morales-Morales, D., Hernandez-Ortega, S., Toscano, R. A. & Valdes–Martinez, J. (2007). Cryst. Growth Des. 7, 117–123.

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Casas, J. S., Castellano, E. E., Ellena, J., García–Tasende, M. S., Pérez–Parallé, M. L., Sánchez, A., Sánchez–González, A. & Touceda, A. (2008). J. Inorg. Biochem. 102, 33–45.

Curic, M., Tusek–Bozic, L., Vikic–Topic, D., Scarcia, V., Furlani, A., Balzarini, J. & De Clercq, E. (1996). J. Inorg. Biochem. 63, 125–142.

Navarro–Ranninger, M. C., Camazon, M. J., Alvarez–Valides, A., Masaguer, J. R., Martinez–Carrera, S. & Garcia–Blanco, S. (1987). Polyhedron, 6, 1059–1064.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Vogels, C. M., Wellwood, H. L., Biradha, K., Zaworotko, M. J. & Westcott, S. A. (1999). Can. J. Chem. 77, 1196–1207.

Westrip, S. P. (2009). publCIF. In preparation.