PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): m252.
Published online 2010 February 3. doi:  10.1107/S1600536810003569
PMCID: PMC2983531

Di-μ-chlorido-bis­{[4-chloro-2-(dimethyl­amino­meth­yl)phenyl-κ2 C 1,N]palladium(II)}

Abstract

The title compound, [Pd2(C9H11ClN)2Cl2], consists of two Pd atoms which are bridged by two Cl atoms, forming a centrosymmetric binuclear complex with a square-planar coordination for each of the Pd atoms. The Pd atom is chelated by one N and one C atom from a 4-chloro-2-(dimethyl­amino­meth­yl)phenyl ligand, forming a five-membered ring (N—Pd—C—C—C). In the crystal structure, weak C—H (...)Cl hydrogen bonds link the mol­ecules in rows.

Related literature

For cyclo­palladated complexes (CPCs) of tertiary aryl­mines as efficient catalysts in coupling reactions, see: Morales-Morales (2007 [triangle]); Joshaghani et al. (2008 [triangle]); Xu et al. (2009 [triangle]); Yang et al. (2002 [triangle]); Zheng et al. (2003 [triangle]). For the crystal structures of related CPCs, see: Calmuschi-Cula et al. (2005 [triangle]); Yang et al. (2003 [triangle]); Zhou et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m252-scheme1.jpg

Experimental

Crystal data

  • [Pd2(C9H11ClN)2Cl2]
  • M r = 620.98
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m252-efi1.jpg
  • a = 28.450 (2) Å
  • b = 5.6325 (5) Å
  • c = 14.2844 (11) Å
  • β = 111.702 (1)°
  • V = 2126.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.20 mm−1
  • T = 296 K
  • 0.48 × 0.41 × 0.35 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.576, T max = 1.000
  • 5903 measured reflections
  • 2315 independent reflections
  • 2173 reflections with I > 2σ(I)
  • R int = 0.071

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.087
  • S = 1.10
  • 2315 reflections
  • 119 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.78 e Å−3
  • Δρmin = −0.59 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003569/bq2191sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003569/bq2191Isup2.hkl

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

Acknowledgments

We are grateful to the Laboratory of Organic Functional Mol­ecules, Sino-French Institute, ECNU for support.

supplementary crystallographic information

Comment

Since the discovery of cyclopalladated complexes (CPCs) a half a century ago, these organometallic compounds have found a plethora of applications (Morales-Morales, 2007; Joshaghani et al., 2008; Xu et al., 2009). We have reported the crystal structures of chiral acetate-bridged binuclear cyclopalladated complexes and the application of some cyclopalladated complexes of tertiary arylamines in coupling reactions (Yang et al., 2002; Zheng et al., 2003). In order to compare the catalytic activities of different substituted tertiary arylamine palladacycles at the aromatic ring, we synthesized a series of these compounds by the reaction of 3-substituted N,N-dimethylbenzylaime with Li2PdCl4. Herein we report the structure of chloro substituted cyclopalladated complex, Di-µ-chlorobis{4-chloro-2-[(dimethylamino- κN)methyl]phenyl-κC}dipalladium (I).

The two Pd atoms were bridged by two Cl atoms, forming a diamond-planar geometry center (Fig. 1). Each of the two Pd atoms was chelated by one N and one C atoms forming a five-member ring. In the crystal structure, weak C—H···Cl hydrogen bonds link the molecules in rows (Table 1, Fig. 2).

Experimental

3-Chloro-N,N-dimethylbenzylamine (3.0 mmol, 0.51 g) and the solution of Li2PdCl4 (0.26 g, 1.0 mmol) in anhydrous methanol (10 ml) were mixed, and the mixture was stirred for 24 h at room temperature. The reaction mixture was filtered. The yellowish solid was recrystallized with CH2Cl2 to afford light yellowish crystal.

Refinement

H atoms were positioned with idealized geometry using a riding model [C—H = 0.93—0.97 Å]. All H atoms were refined with isotropic displacement parameters [set to 1.2 (1.5 for methyl) times of the Ueq of the parent atom].

Figures

Fig. 1.
The molecular structure of the title compound, (I), with displacement ellipsoids drawn at 40% probability level. Symmetry code: (i) -x, -y, -z.
Fig. 2.
Molecular packing of (I). Dashed lines show H-bonds.

Crystal data

[Pd2(C9H11ClN)2Cl2]F(000) = 1216
Mr = 620.98Dx = 1.939 Mg m3
Monoclinic, C2/cMelting point: 473 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 28.450 (2) ÅCell parameters from 4334 reflections
b = 5.6325 (5) Åθ = 5.1–56.7°
c = 14.2844 (11) ŵ = 2.20 mm1
β = 111.702 (1)°T = 296 K
V = 2126.7 (3) Å3Prismatic, colourless
Z = 40.48 × 0.41 × 0.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer2315 independent reflections
Radiation source: fine-focus sealed tube2173 reflections with I > 2σ(I)
graphiteRint = 0.071
phi and ω scansθmax = 27.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −36→32
Tmin = 0.576, Tmax = 1.000k = −7→5
5903 measured reflectionsl = −16→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.087w = 1/[σ2(Fo2) + (0.0385P)2 + 2.2145P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.003
2315 reflectionsΔρmax = 0.78 e Å3
119 parametersΔρmin = −0.59 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00136 (18)

Special details

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. 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
C10.61584 (12)0.7531 (6)0.6472 (2)0.0377 (6)
C20.63683 (13)0.6229 (7)0.7349 (3)0.0451 (7)
H20.62170.48150.74220.054*
C30.68036 (14)0.7007 (7)0.8124 (3)0.0504 (9)
H30.69430.61310.87150.061*
C40.70230 (13)0.9093 (7)0.8000 (3)0.0475 (8)
C50.68411 (13)1.0366 (6)0.7124 (3)0.0476 (8)
H50.70051.17370.70460.057*
C60.64054 (12)0.9577 (6)0.6348 (2)0.0402 (7)
C70.61785 (14)1.0829 (6)0.5364 (3)0.0482 (8)
H7A0.59631.21140.54180.058*
H7B0.64431.14940.51680.058*
C80.62160 (16)0.7642 (8)0.4257 (3)0.0571 (10)
H8A0.64510.67970.48190.086*
H8B0.63980.86660.39730.086*
H8C0.60190.65300.37560.086*
C90.55179 (15)1.0332 (8)0.3720 (3)0.0621 (10)
H9A0.52941.12840.39280.093*
H9B0.53250.91940.32280.093*
H9C0.57011.13350.34310.093*
N10.58771 (10)0.9079 (5)0.4600 (2)0.0394 (6)
Cl10.75511 (4)1.0154 (2)0.89840 (8)0.0736 (3)
Cl20.47788 (3)0.5844 (2)0.38205 (6)0.0541 (3)
Pd0.554347 (8)0.67878 (4)0.530312 (17)0.03578 (13)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0328 (15)0.0447 (15)0.0372 (16)−0.0005 (14)0.0147 (13)−0.0023 (14)
C20.0404 (17)0.0540 (18)0.0401 (18)−0.0104 (16)0.0141 (15)0.0013 (16)
C30.0437 (19)0.066 (2)0.0407 (19)−0.0012 (17)0.0142 (16)0.0021 (16)
C40.0343 (15)0.062 (2)0.0442 (19)−0.0047 (16)0.0128 (14)−0.0132 (17)
C50.0427 (17)0.0464 (17)0.055 (2)−0.0107 (15)0.0196 (15)−0.0109 (16)
C60.0388 (15)0.0407 (16)0.0419 (17)−0.0043 (14)0.0160 (13)−0.0042 (13)
C70.0504 (19)0.0382 (16)0.054 (2)−0.0067 (16)0.0172 (16)0.0016 (15)
C80.057 (2)0.067 (2)0.062 (2)−0.006 (2)0.040 (2)−0.006 (2)
C90.054 (2)0.065 (2)0.055 (2)−0.005 (2)0.0054 (18)0.0188 (19)
N10.0345 (13)0.0446 (14)0.0395 (14)−0.0032 (12)0.0143 (11)0.0020 (12)
Cl10.0546 (5)0.0955 (8)0.0562 (6)−0.0190 (6)0.0036 (5)−0.0209 (6)
Cl20.0381 (4)0.0759 (6)0.0446 (4)−0.0177 (4)0.0109 (3)0.0122 (4)
Pd0.02757 (16)0.04355 (18)0.03759 (18)−0.00378 (9)0.01365 (12)0.00214 (9)

Geometric parameters (Å, °)

C1—C21.382 (5)C7—H7B0.9700
C1—C61.395 (5)C8—N11.474 (5)
C1—Pd1.966 (3)C8—H8A0.9600
C2—C31.392 (5)C8—H8B0.9600
C2—H20.9300C8—H8C0.9600
C3—C41.373 (5)C9—N11.475 (4)
C3—H30.9300C9—H9A0.9600
C4—C51.367 (5)C9—H9B0.9600
C4—Cl11.740 (3)C9—H9C0.9600
C5—C61.395 (5)N1—Pd2.068 (3)
C5—H50.9300Cl2—Pdi2.3356 (9)
C6—C71.490 (5)Cl2—Pd2.4683 (9)
C7—N11.485 (4)Pd—Cl2i2.3356 (9)
C7—H7A0.9700
C2—C1—C6119.0 (3)N1—C8—H8B109.5
C2—C1—Pd127.4 (3)H8A—C8—H8B109.5
C6—C1—Pd113.6 (2)N1—C8—H8C109.5
C1—C2—C3120.9 (3)H8A—C8—H8C109.5
C1—C2—H2119.6H8B—C8—H8C109.5
C3—C2—H2119.6N1—C9—H9A109.5
C4—C3—C2118.7 (3)N1—C9—H9B109.5
C4—C3—H3120.7H9A—C9—H9B109.5
C2—C3—H3120.7N1—C9—H9C109.5
C5—C4—C3122.1 (3)H9A—C9—H9C109.5
C5—C4—Cl1118.8 (3)H9B—C9—H9C109.5
C3—C4—Cl1119.2 (3)C8—N1—C9108.1 (3)
C4—C5—C6119.0 (3)C8—N1—C7109.7 (3)
C4—C5—H5120.5C9—N1—C7109.8 (3)
C6—C5—H5120.5C8—N1—Pd107.0 (2)
C1—C6—C5120.3 (3)C9—N1—Pd114.5 (2)
C1—C6—C7116.6 (3)C7—N1—Pd107.56 (19)
C5—C6—C7123.1 (3)Pdi—Cl2—Pd94.18 (3)
N1—C7—C6108.1 (3)C1—Pd—N181.70 (12)
N1—C7—H7A110.1C1—Pd—Cl2i94.72 (10)
C6—C7—H7A110.1N1—Pd—Cl2i176.12 (8)
N1—C7—H7B110.1C1—Pd—Cl2179.19 (9)
C6—C7—H7B110.1N1—Pd—Cl297.75 (8)
H7A—C7—H7B108.4Cl2i—Pd—Cl285.82 (3)
N1—C8—H8A109.5
C6—C1—C2—C33.6 (5)C2—C1—Pd—N1−159.6 (3)
Pd—C1—C2—C3−178.9 (3)C6—C1—Pd—N118.0 (2)
C1—C2—C3—C4−0.3 (6)C2—C1—Pd—Cl2i18.9 (3)
C2—C3—C4—C5−3.1 (6)C6—C1—Pd—Cl2i−163.5 (2)
C2—C3—C4—Cl1177.2 (3)C2—C1—Pd—Cl2−112 (7)
C3—C4—C5—C63.0 (5)C6—C1—Pd—Cl265 (8)
Cl1—C4—C5—C6−177.3 (3)C8—N1—Pd—C187.3 (3)
C2—C1—C6—C5−3.8 (5)C9—N1—Pd—C1−152.8 (3)
Pd—C1—C6—C5178.4 (2)C7—N1—Pd—C1−30.5 (2)
C2—C1—C6—C7176.5 (3)C8—N1—Pd—Cl2i64.6 (13)
Pd—C1—C6—C7−1.4 (4)C9—N1—Pd—Cl2i−175.6 (11)
C4—C5—C6—C10.5 (5)C7—N1—Pd—Cl2i−53.2 (13)
C4—C5—C6—C7−179.7 (3)C8—N1—Pd—Cl2−92.1 (2)
C1—C6—C7—N1−24.2 (4)C9—N1—Pd—Cl227.8 (3)
C5—C6—C7—N1156.0 (3)C7—N1—Pd—Cl2150.1 (2)
C6—C7—N1—C8−79.8 (3)Pdi—Cl2—Pd—C1131 (8)
C6—C7—N1—C9161.5 (3)Pdi—Cl2—Pd—N1178.46 (8)
C6—C7—N1—Pd36.3 (3)Pdi—Cl2—Pd—Cl2i0.0

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.763.283 (4)117
C9—H9B···Cl20.962.773.325 (5)118

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2191).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Calmuschi-Cula, B., Kalf, I., Wang, R. & Englert, U. (2005). Organometallics, 24, 5491–5493.
  • Joshaghani, M., Daryanavard, M., Rafiee, E. & Nadri, S. (2008). J. Organomet. Chem.693, 3135–3140.
  • Morales-Morales, D. (2007). The Chemistry of Pincer Compounds Amsterdam: Elsevier.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xu, C., Wang, Z. Q., Fu, W. J., Lou, X. H., Li, Y. F., Cen, F. F., Ma, H. J. & Ji, B. M. (2009). Organometallics, 28, 1916–1919.
  • Yang, F., Li, Y. P., Nie, J., Tang, J. & He, M. Y. (2003). Chin. J. Chem.21, 1039–1042.
  • Yang, F., Zhang, Y. M., Zheng, R., Tang, J. & He, M. Y. (2002). J. Organomet. Chem.651, 146–148.
  • Zheng, R., Yang, F., Zou, G., Tang, J. & He, M. Y. (2003). Chin. J. Chem.21, 1111–1113.
  • Zhou, J., Li, X. Y. & Sun, H. J. (2010). J. Organomet. Chem.695, 297–303.

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