Acta Cryst. (2009). E65, m673 [ doi:10.1107/S1600536809018509 ]
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N)palladium(II)In the title compound, [PdCl2(C7H9NO)2], the Pd atom is situated on a crystallographic centre of inversion. The coordination environment of the Pd atom shows a slightly distorted square-planar geometry. The crystal structure exhibits weak intermolecular Pd
Cl interactions, with PdCl distances of 3.6912 (6) Å. A chain-like arrangement of molecules realized by intermolecular N-HCl hydrogen bonds is observed along [010].
The yellow plate shaped crystals of the title compound were grown by slow evaporation of 10 ml of an ethanolic solution containing a mixture of 0.01 M H2[PdCl4] and 4-methoxyaniline in a 1:2 molar ratio 1:2.
H atoms bonded to N were located in a difference map and refined freely. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.98 Å for CH3 [Uiso(H) = 1.5Ueq(C)] and C—H = 0.95 Å for CH [Uiso(H) = 1.2Ueq(C)]
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).
![[Figure 1]](./im2115fig1thm.gif)
| Fig. 1. The title compound showing 50% probability displacement ellipsoids for the non-hydrogen atoms [Symmetry code: (i) -x, -y, -z]. |
![[Figure 2]](./im2115fig2thm.gif)
| Fig. 2. Crystal packing of title compound, projection down the a axis. Dashed lines indicate hydrogen bonds [Symmetry code: (i) x, y + 1, z]. |
| [PdCl2(C7H9NO)2] | F000 = 424 |
| Mr = 423.60 | Dx = 1.793 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2257 reflections |
| a = 4.7333 (1) Å | θ = 3.0–26.4º |
| b = 6.0071 (1) Å | µ = 1.53 mm−1 |
| c = 27.6918 (5) Å | T = 173 K |
| β = 94.806 (1)º | Plate, yellow |
| V = 784.60 (3) Å3 | 0.25 × 0.08 × 0.04 mm |
| Z = 2 |
| Bruker APEXII CCD diffractometer | 1577 independent reflections |
| Radiation source: fine-focus sealed tube | 1326 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.024 |
| Detector resolution: 8.26 pixels mm-1 | θmax = 26.4º |
| T = 173 K | θmin = 1.5º |
| φ and ω scans | h = −2→5 |
| Absorption correction: numerical (SADABS; Bruker, 2005) | k = −7→7 |
| Tmin = 0.701, Tmax = 0.941 | l = −34→34 |
| 4837 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0205P)2 + 0.3835P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 1577 reflections | Δρmax = 0.31 e Å−3 |
| 106 parameters | Δρmin = −0.39 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [PdCl2(C7H9NO)2] | V = 784.60 (3) Å3 |
| Mr = 423.60 | Z = 2 |
| Monoclinic, P21/c | Mo Kα |
| a = 4.7333 (1) Å | µ = 1.53 mm−1 |
| b = 6.0071 (1) Å | T = 173 K |
| c = 27.6918 (5) Å | 0.25 × 0.08 × 0.04 mm |
| β = 94.806 (1)º |
| Bruker APEXII CCD diffractometer | 1577 independent reflections |
| Absorption correction: numerical (SADABS; Bruker, 2005) | 1326 reflections with I > 2σ(I) |
| Tmin = 0.701, Tmax = 0.941 | Rint = 0.024 |
| 4837 measured reflections |
| R[F2 > 2σ(F2)] = 0.023 | 106 parameters |
| wR(F2) = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.31 e Å−3 |
| 1577 reflections | Δρmin = −0.39 e Å−3 |
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. |
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. |
| x | y | z | Uiso*/Ueq | ||
| Pd1 | 0.0000 | 0.0000 | 0.0000 | 0.01570 (9) | |
| Cl1 | −0.30064 (12) | −0.26378 (11) | 0.02745 (2) | 0.02254 (15) | |
| N1 | −0.1173 (4) | 0.2075 (4) | 0.05318 (8) | 0.0188 (5) | |
| H1A | −0.162 (5) | 0.332 (5) | 0.0398 (9) | 0.019 (7)* | |
| H1B | −0.282 (6) | 0.151 (5) | 0.0615 (10) | 0.029 (8)* | |
| O1 | 0.6985 (4) | 0.2939 (4) | 0.21008 (7) | 0.0347 (5) | |
| C1 | 0.0967 (5) | 0.2336 (4) | 0.09336 (9) | 0.0191 (5) | |
| C2 | 0.2570 (5) | 0.4248 (4) | 0.09767 (9) | 0.0202 (6) | |
| H2 | 0.2259 | 0.5402 | 0.0744 | 0.024* | |
| C3 | 0.4636 (5) | 0.4498 (4) | 0.13583 (9) | 0.0231 (6) | |
| H3 | 0.5742 | 0.5818 | 0.1387 | 0.028* | |
| C4 | 0.5079 (5) | 0.2813 (5) | 0.16982 (9) | 0.0251 (6) | |
| C5 | 0.3517 (6) | 0.0864 (5) | 0.16452 (10) | 0.0290 (6) | |
| H5 | 0.3861 | −0.0310 | 0.1872 | 0.035* | |
| C6 | 0.1466 (6) | 0.0617 (4) | 0.12644 (10) | 0.0256 (6) | |
| H6 | 0.0401 | −0.0722 | 0.1229 | 0.031* | |
| C7 | 0.8612 (6) | 0.4926 (6) | 0.21595 (11) | 0.0395 (7) | |
| H7A | 0.9714 | 0.5130 | 0.1879 | 0.059* | |
| H7B | 0.9903 | 0.4817 | 0.2454 | 0.059* | |
| H7C | 0.7340 | 0.6199 | 0.2186 | 0.059* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pd1 | 0.01623 (13) | 0.01298 (15) | 0.01751 (14) | −0.00122 (12) | −0.00092 (9) | −0.00012 (13) |
| Cl1 | 0.0220 (3) | 0.0164 (3) | 0.0292 (3) | −0.0035 (3) | 0.0023 (2) | 0.0032 (3) |
| N1 | 0.0196 (11) | 0.0148 (12) | 0.0217 (12) | 0.0004 (10) | −0.0008 (9) | 0.0007 (10) |
| O1 | 0.0334 (10) | 0.0448 (14) | 0.0237 (10) | 0.0059 (10) | −0.0100 (8) | −0.0007 (10) |
| C1 | 0.0191 (12) | 0.0210 (14) | 0.0173 (12) | 0.0030 (11) | 0.0029 (10) | −0.0047 (12) |
| C2 | 0.0245 (13) | 0.0187 (14) | 0.0177 (13) | 0.0003 (11) | 0.0040 (10) | 0.0011 (11) |
| C3 | 0.0221 (12) | 0.0239 (16) | 0.0230 (14) | −0.0030 (11) | 0.0009 (10) | −0.0037 (12) |
| C4 | 0.0222 (13) | 0.0359 (18) | 0.0171 (13) | 0.0067 (13) | 0.0000 (10) | −0.0053 (13) |
| C5 | 0.0380 (16) | 0.0260 (15) | 0.0226 (15) | 0.0066 (13) | −0.0005 (12) | 0.0049 (13) |
| C6 | 0.0329 (14) | 0.0191 (15) | 0.0245 (14) | 0.0004 (12) | 0.0013 (11) | −0.0004 (12) |
| C7 | 0.0320 (15) | 0.055 (2) | 0.0303 (15) | −0.0001 (17) | −0.0054 (12) | −0.0113 (17) |
| Pd1—N1 | 2.042 (2) | C2—C3 | 1.387 (3) |
| Pd1—N1i | 2.042 (2) | C2—H2 | 0.9500 |
| Pd1—Cl1 | 2.3010 (6) | C3—C4 | 1.387 (4) |
| Pd1—Cl1i | 2.3010 (6) | C3—H3 | 0.9500 |
| N1—C1 | 1.449 (3) | C4—C5 | 1.386 (4) |
| N1—H1A | 0.85 (3) | C5—C6 | 1.380 (4) |
| N1—H1B | 0.90 (3) | C5—H5 | 0.9500 |
| O1—C4 | 1.376 (3) | C6—H6 | 0.9500 |
| O1—C7 | 1.422 (4) | C7—H7A | 0.9800 |
| C1—C2 | 1.376 (4) | C7—H7B | 0.9800 |
| C1—C6 | 1.387 (4) | C7—H7C | 0.9800 |
| N1—Pd1—N1i | 180.00 (8) | C2—C3—C4 | 119.7 (2) |
| N1—Pd1—Cl1 | 88.23 (7) | C2—C3—H3 | 120.2 |
| N1i—Pd1—Cl1 | 91.77 (7) | C4—C3—H3 | 120.2 |
| N1—Pd1—Cl1i | 91.77 (7) | O1—C4—C5 | 116.1 (3) |
| N1i—Pd1—Cl1i | 88.23 (7) | O1—C4—C3 | 124.1 (3) |
| Cl1—Pd1—Cl1i | 180.0 | C5—C4—C3 | 119.7 (2) |
| C1—N1—Pd1 | 113.89 (15) | C6—C5—C4 | 120.4 (3) |
| C1—N1—H1A | 111.6 (18) | C6—C5—H5 | 119.8 |
| Pd1—N1—H1A | 107.2 (17) | C4—C5—H5 | 119.8 |
| C1—N1—H1B | 114.1 (17) | C5—C6—C1 | 119.6 (3) |
| Pd1—N1—H1B | 104.4 (18) | C5—C6—H6 | 120.2 |
| H1A—N1—H1B | 105 (2) | C1—C6—H6 | 120.2 |
| C4—O1—C7 | 116.8 (2) | O1—C7—H7A | 109.5 |
| C2—C1—C6 | 120.1 (2) | O1—C7—H7B | 109.5 |
| C2—C1—N1 | 120.1 (2) | H7A—C7—H7B | 109.5 |
| C6—C1—N1 | 119.7 (2) | O1—C7—H7C | 109.5 |
| C1—C2—C3 | 120.3 (2) | H7A—C7—H7C | 109.5 |
| C1—C2—H2 | 119.8 | H7B—C7—H7C | 109.5 |
| C3—C2—H2 | 119.8 | ||
| Cl1—Pd1—N1—C1 | 105.56 (18) | C7—O1—C4—C3 | −1.1 (4) |
| Cl1i—Pd1—N1—C1 | −74.44 (18) | C2—C3—C4—O1 | −177.0 (2) |
| Pd1—N1—C1—C2 | 103.7 (2) | C2—C3—C4—C5 | 2.0 (4) |
| Pd1—N1—C1—C6 | −73.9 (2) | O1—C4—C5—C6 | 177.2 (2) |
| C6—C1—C2—C3 | −1.9 (4) | C3—C4—C5—C6 | −1.9 (4) |
| N1—C1—C2—C3 | −179.5 (2) | C4—C5—C6—C1 | −0.1 (4) |
| C1—C2—C3—C4 | −0.2 (4) | C2—C1—C6—C5 | 2.0 (4) |
| C7—O1—C4—C5 | 179.8 (2) | N1—C1—C6—C5 | 179.6 (2) |
| Symmetry codes: (i) −x, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Cl1ii | 0.85 (3) | 2.53 (3) | 3.353 (2) | 162 (2) |
| Symmetry codes: (ii) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Cl1i | 0.85 (3) | 2.53 (3) | 3.353 (2) | 162 (2) |
| Symmetry codes: (i) x, y+1, z. |
Bon, V., Dudko, A., Orysyk, S. & Pekhnyo, V. (2009). Acta Cryst. E65, m396.
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.
Ojwach, S. O., Westman, G. & Darkwa, J. (2007). Polyhedron, 26, 5544–5552.
Pan, Y.-L., Zhao, F. & Yang, S. (2006). Acta Cryst. E62, m239–m240.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2009). publCIF. In preparation.
Coordination compounds of Pd with N-containing organic ligands attract considerable interest due to their antitumoral and catalytic activity (Casas et al., 2008; Ojwach et al., 2007). Similar structures with respect to the title compound differing in terms of the position of substituents at the aromatic ring were published earlier (Pan et al., 2006; Bon et al., 2009). The asymmetric unit of the title compound contains one-half of the molecule because Pd occupies a special position on the crystallographic centre of inversion. Pd shows a slightly distorted square-planar geometry of the coordination environment containing two chlorine atoms and two amino groups in trans position (Fig. 1). The crystal structure shows weak intermolecular Pd···Cl interactions with Pd—Cl distances of 3.6912 (6) Å. A chain-like arrangement of molecules realized by weak N—H···Cl hydrogen bonds is observed along 010 direction (Fig. 2; Table 1).