PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): m396.
Published online 2009 March 14. doi:  10.1107/S1600536809008472
PMCID: PMC2968883

trans-Dichloridobis(2-methyl­aniline-κN)palladium(II)

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0m396-scheme1.jpg

Experimental

Crystal data

  • [PdCl2(C7H9N)2]
  • M r = 391.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m396-efi3.jpg
  • a = 12.1841 (3) Å
  • b = 8.0653 (2) Å
  • c = 7.5407 (2) Å
  • β = 97.346 (2)°
  • V = 734.93 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.61 mm−1
  • T = 173 K
  • 0.17 × 0.16 × 0.04 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.777, T max = 0.932
  • 8179 measured reflections
  • 1502 independent reflections
  • 1118 reflections with I > 2σ(I)
  • R int = 0.074

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.060
  • S = 1.03
  • 1502 reflections
  • 97 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.66 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008472/rk2132sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008472/rk2132Isup2.hkl

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

supplementary crystallographic information

Comment

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).

Experimental

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

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)].

Figures

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.
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].

Crystal data

[PdCl2(C7H9N)2]F(000) = 392
Mr = 391.60Dx = 1.770 Mg m3
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 mm1
β = 97.346 (2)°T = 173 K
V = 734.93 (3) Å3Plate, yellow
Z = 20.17 × 0.16 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer1502 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°
[var phi] 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

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 = 1.03w = 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 Å3
2 restraintsΔρmin = −0.66 e Å3

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2132).

References

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

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