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ISSN: 2056-9890

trans-Di­chloridobis(2,4-di­methyl­aniline-κN)palladium(II)

aCollege of Chemistry and Chemical Engineering, Zhaoqing University, Zhaoqing 526061, People's Republic of China, and bCollege of Chemical Engineering, Inner Mongolia University of Technology, Inner Mongolia 010051, People's Republic of China
*Correspondence e-mail: guohaifu@zqu.edu.cn

(Received 2 April 2012; accepted 7 April 2012; online 13 April 2012)

In the title compound, [PdCl2(C8H11N)2], the PdII atom is located on a crystallographic inversion center and adopts a square-planar coordination geometry, with pairs of equivalent ligands in trans positions. In the crystal, adjacent mol­ecules are linked with each other through weak N—H⋯Cl hydrogen bonds and ππ stacking inter­actions between the phenyl rings [shortest centroid–centroid distance = 3.720 (2) Å], leading to the formation of layers parallel to the a-axis direction.

Related literature

For general background to the application of palladium compounds in homogeneous and heterogeneous catalysis, see: Padmanabhan et al. (1985[Padmanabhan, V. M., Patel, R. P. & Ranganathan, T. N. (1985). Acta Cryst. C41, 1305-1307.]); Hartley (1973[Hartley, F. R. (1973). In The Chemistry of Platinum and Palladium. New York: John Wiley and Sons.]). For related structures, see: Newkome et al. (1982[Newkome, G. R., Fronczek, F. R., Grupta, V. K., Puckett, W. E., Pantaleo, D. C. & Kiefer, G. E. (1982). J. Am. Chem. Soc. 104, 1782-1783.]); Chen et al. (2002[Chen, Y. B., Li, Z. J., Qin, Y. Y., Kang, Y., Wu, L. & Yao, Y. G. (2002). Chin. J. Struct. Chem. 21, 530-532.]).

[Scheme 1]

Experimental

Crystal data
  • [PdCl2(C8H11N)2]

  • Mr = 419.66

  • Monoclinic, P 21 /c

  • a = 14.315 (6) Å

  • b = 8.081 (3) Å

  • c = 7.420 (3) Å

  • β = 104.705 (7)°

  • V = 830.3 (6) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.43 mm−1

  • T = 246 K

  • 0.30 × 0.28 × 0.22 mm

Data collection
  • Bruker APEXII area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.669, Tmax = 0.740

  • 4058 measured reflections

  • 1485 independent reflections

  • 1226 reflections with I > 2σ(I)

  • Rint = 0.027

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.076

  • S = 1.06

  • 1485 reflections

  • 99 parameters

  • H-atom parameters constrained

  • Δρmax = 1.65 e Å−3

  • Δρmin = −0.66 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1B⋯Cl1i 0.91 2.68 3.376 (3) 134
N1—H1A⋯Cl1ii 0.91 2.39 3.287 (3) 168
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]; (ii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2004)[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]; cell refinement: SAINT (Bruker, 2004)[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Palladium compounds have attracted much attention due to their application in homogeneous and heterogeneous catalyses (Padmanabhan et al. 1985). Some dramatic results in homogeneous catalysis of reactions of organic compounds, particularly the successful commercial exploitation of the Wacker one stage process for the homogeneous catalytic oxidation of ethylene to acetaldehyde in the presence of palladium (II) chloride (Hartley 1973), have contributed to this interest. In this paper we report crystallization of the title compound, a new palladium(II) complex obtained by the reaction of 2,4-dimethylaniline with palladium chloride in ethanol. As illustrated in Fig.1, the PdII atom exhibits a square-planar coordination sphere, defined by two N atoms from two 2,4-dimethylaniline and two chloride atoms. The molecule adopts the trans configuration in the solid state. The bond distances of Pd—N (2.055 (2)) and Pd—Cl (2.293 (3) Å) are comparable with the values found in related complexes (Newkome et al. 1982; Chen et al. 2002). The dihedral angle between the plane of the phenyl ring and the square plane around Pd is 63.03 (1) °. In the crystal structure, intermolecular N—H···Cl hydrogen bonding interactions involving the amino groups and chlorine anions (Table 1) and ππ stacking interactions (centroid-centroid distance = 3.720 (2) Å) occurring between neighboring phenyl rings of centrosymmetrically related complexes form a layer network running parallel to the a axis (Fig. 2).

Related literature top

For general background to the application of palladium compounds in homogeneous and heterogeneous catalysis, see: Padmanabhan et al. (1985); Hartley (1973). For related structures, see: Newkome et al. (1982); Chen et al. (2002).

Experimental top

A mixture of palladium chloride (0.1 mmol, 0.018 g) and 2,4-dimethylaniline (0.2 mmol, 0.024 g) in 12 ml of anhydrous ethanol was sealed in an autoclave equipped with a Teflon liner (25 ml) and then heated at 353 K for 1 day. Yellow crystals were obtained by slow evaporation of the solvent at room temperature (0.093 g, 45%). IR (KBr pellet) (cm-1): 3452(s), 3023(m), 2928(m), 1619(s), 1582(s), 1556(m), 1488(s), 1452(m), 1383(s), 1283(w), 1231(w), 1184(w), 1143(m), 1106(s), 1053(m), 979(w), 954(w), 891(m), 817(s), 738(m), 607(w), 575(m), 466(m), 424(m).

Refinement top

All H atoms were positioned geometrically and refined using a riding model with the distances of 0.97 Å for methyl groups with Uiso(H) = 1.5Ueq(C) and 0.94 Å for phenyl groups with Uiso(H) = 1.2Ueq(C), respectively. H atoms bonded to N atoms were placed at calculated positions and refined with distance constraints of N—H = 0.91 Å, and with Uiso(H) = 1.2 Ueq(N). The hightest residual electron density peak is located 0.93 Å from Pd1 and the deepest hole is located 0.95 Å from Pd1.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. Symmetry code: (i) 1 - x, 1 - y, 2 - z.
[Figure 2] Fig. 2. View of one of the two-dimensional layers of the title compound. The intermolecular hydrogen bonds and ππ stacking interactions are shown as turquiose and red dashed lines, respectively. H atoms not involved in hydrogen bonds have been omitted for clarity.
trans-Dichloridobis(2,4-dimethylaniline-κN)palladium(II) top
Crystal data top
[PdCl2(C8H11N)2]F(000) = 424
Mr = 419.66Dx = 1.679 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5300 reflections
a = 14.315 (6) Åθ = 1.3–28.0°
b = 8.081 (3) ŵ = 1.43 mm1
c = 7.420 (3) ÅT = 246 K
β = 104.705 (7)°Block, yellow
V = 830.3 (6) Å30.30 × 0.28 × 0.22 mm
Z = 2
Data collection top
Bruker APEXII area-detector
diffractometer
1485 independent reflections
Radiation source: fine-focus sealed tube1226 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ϕ and ω scanθmax = 25.2°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 178
Tmin = 0.669, Tmax = 0.740k = 99
4058 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0402P)2 + 0.6953P]
where P = (Fo2 + 2Fc2)/3
1485 reflections(Δ/σ)max < 0.001
99 parametersΔρmax = 1.65 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
[PdCl2(C8H11N)2]V = 830.3 (6) Å3
Mr = 419.66Z = 2
Monoclinic, P21/cMo Kα radiation
a = 14.315 (6) ŵ = 1.43 mm1
b = 8.081 (3) ÅT = 246 K
c = 7.420 (3) Å0.30 × 0.28 × 0.22 mm
β = 104.705 (7)°
Data collection top
Bruker APEXII area-detector
diffractometer
1485 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1226 reflections with I > 2σ(I)
Tmin = 0.669, Tmax = 0.740Rint = 0.027
4058 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.06Δρmax = 1.65 e Å3
1485 reflectionsΔρmin = 0.66 e Å3
99 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3227 (3)0.3340 (4)1.0653 (5)0.0177 (7)
C20.2358 (3)0.4055 (4)0.9726 (5)0.0238 (8)
C30.1603 (3)0.3005 (4)0.8916 (6)0.0270 (9)
H30.10090.34710.82820.032*
C40.1686 (3)0.1303 (4)0.9001 (6)0.0257 (9)
C50.2558 (3)0.0642 (4)0.9939 (5)0.0242 (8)
H50.26330.05141.00160.029*
C60.3321 (3)0.1643 (4)1.0765 (5)0.0203 (8)
H60.39110.11701.14100.024*
C70.2219 (3)0.5877 (5)0.9583 (7)0.0365 (11)
H7A0.23820.63581.08220.055*
H7B0.15500.61210.89730.055*
H7C0.26330.63420.88620.055*
C80.0835 (3)0.0239 (5)0.8099 (7)0.0385 (11)
H8A0.08070.01040.67870.058*
H8B0.02460.07620.82280.058*
H8C0.09030.08370.86980.058*
Cl10.55490 (6)0.23246 (9)1.01658 (12)0.0208 (2)
N10.4044 (2)0.4353 (3)1.1530 (4)0.0181 (6)
H1A0.43820.38111.25670.022*
H1B0.38150.53021.19180.022*
Pd10.50000.50001.00000.01533 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0191 (18)0.0188 (16)0.0165 (18)0.0024 (14)0.0070 (15)0.0018 (14)
C20.022 (2)0.0193 (18)0.029 (2)0.0006 (16)0.0055 (17)0.0025 (15)
C30.0184 (19)0.0231 (19)0.037 (2)0.0011 (16)0.0018 (17)0.0026 (17)
C40.025 (2)0.0218 (18)0.031 (2)0.0067 (17)0.0068 (18)0.0052 (15)
C50.029 (2)0.0158 (16)0.030 (2)0.0039 (16)0.0114 (18)0.0018 (15)
C60.022 (2)0.0186 (16)0.0195 (19)0.0013 (15)0.0047 (16)0.0025 (14)
C70.026 (2)0.0183 (19)0.061 (3)0.0018 (17)0.003 (2)0.0023 (19)
C80.026 (2)0.031 (2)0.055 (3)0.0114 (19)0.006 (2)0.008 (2)
Cl10.0274 (5)0.0131 (4)0.0224 (4)0.0013 (4)0.0071 (4)0.0008 (3)
N10.0223 (16)0.0142 (13)0.0168 (15)0.0007 (12)0.0033 (13)0.0007 (12)
Pd10.0192 (2)0.0107 (2)0.0155 (2)0.00095 (15)0.00342 (15)0.00031 (14)
Geometric parameters (Å, º) top
C1—C61.378 (5)C7—H7A0.9700
C1—C21.385 (5)C7—H7B0.9700
C1—N11.441 (4)C7—H7C0.9700
C2—C31.385 (5)C8—H8A0.9700
C2—C71.486 (5)C8—H8B0.9700
C3—C41.381 (5)C8—H8C0.9700
C3—H30.9400Cl1—Pd12.2930 (11)
C4—C51.373 (5)N1—Pd12.055 (3)
C4—C81.503 (5)N1—H1A0.9100
C5—C61.372 (5)N1—H1B0.9100
C5—H50.9400Pd1—N1i2.055 (3)
C6—H60.9400Pd1—Cl1i2.2930 (11)
C6—C1—C2120.4 (3)C2—C7—H7C109.5
C6—C1—N1118.8 (3)H7A—C7—H7C109.5
C2—C1—N1120.8 (3)H7B—C7—H7C109.5
C1—C2—C3117.6 (3)C4—C8—H8A109.5
C1—C2—C7122.4 (3)C4—C8—H8B109.5
C3—C2—C7120.0 (3)H8A—C8—H8B109.5
C4—C3—C2122.8 (4)C4—C8—H8C109.5
C4—C3—H3118.6H8A—C8—H8C109.5
C2—C3—H3118.6H8B—C8—H8C109.5
C5—C4—C3117.9 (3)C1—N1—Pd1118.3 (2)
C5—C4—C8122.2 (3)C1—N1—H1A107.7
C3—C4—C8120.0 (4)Pd1—N1—H1A107.7
C4—C5—C6121.0 (3)C1—N1—H1B107.7
C4—C5—H5119.5Pd1—N1—H1B107.7
C6—C5—H5119.5H1A—N1—H1B107.1
C5—C6—C1120.4 (3)N1—Pd1—N1i180.0
C5—C6—H6119.8N1—Pd1—Cl189.86 (8)
C1—C6—H6119.8N1i—Pd1—Cl190.14 (8)
C2—C7—H7A109.5N1—Pd1—Cl1i90.14 (8)
C2—C7—H7B109.5N1i—Pd1—Cl1i89.86 (8)
H7A—C7—H7B109.5Cl1—Pd1—Cl1i180.0
Symmetry code: (i) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl1ii0.912.683.376 (3)134
N1—H1A···Cl1iii0.912.393.287 (3)168
Symmetry codes: (ii) x+1, y+1/2, z+5/2; (iii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[PdCl2(C8H11N)2]
Mr419.66
Crystal system, space groupMonoclinic, P21/c
Temperature (K)246
a, b, c (Å)14.315 (6), 8.081 (3), 7.420 (3)
β (°) 104.705 (7)
V3)830.3 (6)
Z2
Radiation typeMo Kα
µ (mm1)1.43
Crystal size (mm)0.30 × 0.28 × 0.22
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.669, 0.740
No. of measured, independent and
observed [I > 2σ(I)] reflections
4058, 1485, 1226
Rint0.027
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.076, 1.06
No. of reflections1485
No. of parameters99
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.65, 0.66

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl1i0.912.683.376 (3)134.0
N1—H1A···Cl1ii0.912.393.287 (3)168.2
Symmetry codes: (i) x+1, y+1/2, z+5/2; (ii) x, y+1/2, z+1/2.
 

Acknowledgements

The authors acknowledge Zhaoqing University for supporting this work.

References

First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChen, Y. B., Li, Z. J., Qin, Y. Y., Kang, Y., Wu, L. & Yao, Y. G. (2002). Chin. J. Struct. Chem. 21, 530–532.  CAS Google Scholar
First citationHartley, F. R. (1973). In The Chemistry of Platinum and Palladium. New York: John Wiley and Sons.  Google Scholar
First citationNewkome, G. R., Fronczek, F. R., Grupta, V. K., Puckett, W. E., Pantaleo, D. C. & Kiefer, G. E. (1982). J. Am. Chem. Soc. 104, 1782–1783.  CSD CrossRef CAS Web of Science Google Scholar
First citationPadmanabhan, V. M., Patel, R. P. & Ranganathan, T. N. (1985). Acta Cryst. C41, 1305–1307.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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