Chlorido{2-[(dimethyl-amino)-methyl]phenyl-κC,N}(1-methyl-1H-imidazole-κN)palladium(II).

In the title compound, [Pd(C(9)H(12)N)Cl(C(4)H(6)N(2))], which was synthesized from the reaction of 1-methyl-imidazole with dimeric dichloridobis[2-(dimethyl-amino)-benz-yl]palla-dium(II), the ring-deprotonated N,N-dimethyl-benzyl-amine ligand acts in a C,N-bidentate fashion. The dihedral angle between the ring of the 1-methyl-imidazole ligand and the palladacycle plane is 57.88 (16)°. The two N atoms from the N,N-dimethyl-benzyl-amine and 1-methyl-imidazole ligands are trans coordinated to the Pd(II) atom.

Related literature

For an overview of the application of palladacycles in organic synthesis, see: DuPont & Flores (2009 ▶); Bedford et al. (2003 ▶); Fors & Buchwald (2010 ▶). For detoxification of phospho­rothio­nate pesticides, see: Lu et al. (2010 ▶). For studies converting the dimeric precursor (Cope & Friedrich, 1968 ▶) of the title compound into monomeric square-planar palladacycles, see: Mentes & Büyükgüngör (2004 ▶); Mentes et al. (2004 ▶); Deeming et al. (1978 ▶); Bose & Saha (1987 ▶). For crystal structures of neutral pyridine-palladacycles, see: Lu et al. (2005 ▶); Fun et al. (2006 ▶). For an approach to the study of the relative binding affinities of unidentate ligands for organopalladium(II) species, see: Hoffman et al. (2009 ▶).

Experimental

Crystal data

[Pd(C9H12N)Cl(C4H6N2)]

M = 358.15

Orthorhombic,

a = 25.5485 (15) Å

b = 10.0057 (6) Å

c = 5.6733 (4) Å

V = 1450.27 (16) Å3

Z = 4

Mo Kα radiation

μ = 1.45 mm−1

T = 290 K

0.43 × 0.15 × 0.09 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.788, T max = 1.00

6592 measured reflections

2373 independent reflections

2057 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.044

S = 0.96

2373 reflections

167 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.38 e Å−3

Absolute structure: Flack (1983 ▶), 852 Friedel pairs

Flack parameter: −0.04 (3)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810047367/ng5067sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047367/ng5067Isup2.hkl

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

[Pd(C9H12N)Cl(C4H6N2)]	F(000) = 720
Mr = 358.15	Dx = 1.640 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3299 reflections
a = 25.5485 (15) Å	θ = 3.1–25.6°
b = 10.0057 (6) Å	µ = 1.45 mm−1
c = 5.6733 (4) Å	T = 290 K
V = 1450.27 (16) Å3	Prism, colorless
Z = 4	0.43 × 0.15 × 0.09 mm

Oxford Diffraction Xcalibur E diffractometer	2373 independent reflections
Radiation source: fine-focus sealed tube	2057 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 16.0514 pixels mm-1	θmax = 25.7°, θmin = 3.1°
ω scans	h = −31→31
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −12→10
Tmin = 0.788, Tmax = 1.00	l = −6→6
6592 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.022	w = 1/[σ2(Fo2) + (0.0205P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.044	(Δ/σ)max = 0.003
S = 0.96	Δρmax = 0.31 e Å−3
2373 reflections	Δρmin = −0.38 e Å−3
167 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0038 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 852 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.04 (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 > 2σ(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	0.644535 (8)	0.91814 (2)	0.75150 (8)	0.02903 (8)
Cl1	0.67437 (4)	0.69431 (8)	0.66642 (19)	0.0466 (3)
C1	0.65047 (13)	1.1994 (4)	0.6894 (7)	0.0385 (12)
C2	0.62563 (13)	1.1054 (3)	0.8301 (6)	0.0331 (9)
C3	0.59495 (14)	1.1503 (4)	1.0170 (7)	0.0378 (9)
H3	0.5781	1.0885	1.1131	0.045*
C4	0.58921 (15)	1.2846 (4)	1.0615 (8)	0.0494 (11)
H4	0.5694	1.3131	1.1894	0.059*
C5	0.61300 (17)	1.3768 (4)	0.9156 (9)	0.0560 (13)
H5	0.6084	1.4677	0.9432	0.067*
C6	0.64348 (13)	1.3354 (3)	0.7301 (14)	0.0507 (11)
H6	0.6594	1.3979	0.6322	0.061*
C7	0.68436 (15)	1.1482 (4)	0.4924 (7)	0.0424 (10)
H7A	0.7140	1.2075	0.4690	0.051*
H7B	0.6644	1.1446	0.3470	0.051*
C8	0.71890 (16)	0.9419 (4)	0.3383 (7)	0.0460 (10)
H8A	0.7460	0.9922	0.2615	0.069*
H8B	0.6892	0.9346	0.2354	0.069*
H8C	0.7317	0.8541	0.3754	0.069*
C9	0.74967 (12)	1.0235 (3)	0.7096 (7)	0.0422 (11)
H9A	0.7773	1.0667	0.6236	0.063*
H9B	0.7610	0.9364	0.7585	0.063*
H9C	0.7410	1.0760	0.8458	0.063*
C10	0.53338 (14)	0.8549 (4)	0.9384 (8)	0.0464 (10)
H10	0.5162	0.9102	0.8317	0.056*
C11	0.51014 (15)	0.7778 (4)	1.1018 (7)	0.0475 (11)
H11	0.4744	0.7707	1.1295	0.057*
C12	0.59415 (13)	0.7524 (3)	1.1267 (7)	0.0397 (9)
H12	0.6268	0.7233	1.1774	0.048*
C13	0.54318 (17)	0.6178 (4)	1.4131 (8)	0.0577 (12)
H13A	0.5750	0.5678	1.4306	0.087*
H13B	0.5148	0.5577	1.3805	0.087*
H13C	0.5361	0.6658	1.5561	0.087*
N1	0.58669 (10)	0.8386 (3)	0.9548 (6)	0.0344 (7)
N2	0.70326 (11)	1.0106 (3)	0.5575 (5)	0.0312 (7)
N3	0.54872 (11)	0.7121 (3)	1.2190 (7)	0.0388 (8)

	U11	U22	U33	U12	U13	U23
Pd1	0.02726 (11)	0.02814 (13)	0.03167 (13)	−0.00098 (10)	0.0002 (2)	0.0043 (2)
Cl1	0.0495 (5)	0.0321 (5)	0.0582 (7)	0.0077 (4)	0.0119 (5)	0.0049 (4)
C1	0.0352 (19)	0.034 (2)	0.047 (4)	0.0014 (15)	−0.0090 (17)	0.0041 (17)
C2	0.0269 (16)	0.032 (2)	0.041 (3)	0.0007 (15)	−0.0080 (15)	0.0031 (16)
C3	0.034 (2)	0.037 (2)	0.043 (3)	0.0004 (17)	−0.0025 (18)	0.0003 (19)
C4	0.046 (2)	0.044 (3)	0.058 (3)	0.009 (2)	−0.004 (2)	−0.011 (2)
C5	0.048 (2)	0.033 (2)	0.087 (4)	0.0030 (19)	−0.018 (3)	−0.009 (2)
C6	0.0475 (19)	0.033 (2)	0.071 (3)	0.0001 (16)	−0.008 (3)	0.006 (3)
C7	0.044 (2)	0.042 (2)	0.041 (3)	−0.0068 (18)	−0.006 (2)	0.020 (2)
C8	0.051 (2)	0.053 (2)	0.034 (2)	−0.0084 (18)	0.0101 (18)	0.0017 (18)
C9	0.0295 (16)	0.060 (2)	0.037 (3)	−0.0068 (15)	−0.002 (2)	0.006 (2)
C10	0.034 (2)	0.053 (3)	0.052 (3)	0.0031 (18)	0.000 (2)	0.006 (2)
C11	0.031 (2)	0.056 (3)	0.055 (3)	−0.0065 (19)	0.006 (2)	0.002 (2)
C12	0.036 (2)	0.032 (2)	0.051 (2)	−0.0019 (17)	0.0034 (18)	0.000 (2)
C13	0.062 (3)	0.054 (3)	0.057 (3)	−0.007 (2)	0.018 (2)	0.013 (2)
N1	0.0316 (16)	0.0307 (17)	0.0410 (19)	−0.0003 (13)	0.0020 (14)	0.0018 (15)
N2	0.0309 (15)	0.0324 (17)	0.0302 (18)	−0.0020 (13)	−0.0020 (13)	0.0029 (14)
N3	0.0405 (15)	0.0363 (15)	0.039 (2)	−0.0060 (11)	0.0153 (18)	0.0031 (18)

Pd1—C2	1.985 (3)	C8—H8A	0.9600
Pd1—N1	2.037 (3)	C8—H8B	0.9600
Pd1—N2	2.078 (3)	C8—H8C	0.9600
Pd1—Cl1	2.4145 (9)	C9—N2	1.472 (4)
C1—C2	1.388 (5)	C9—H9A	0.9600
C1—C6	1.391 (5)	C9—H9B	0.9600
C1—C7	1.504 (5)	C9—H9C	0.9600
C2—C3	1.393 (5)	C10—C11	1.345 (5)
C3—C4	1.375 (5)	C10—N1	1.375 (4)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.381 (6)	C11—N3	1.358 (5)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.373 (8)	C12—N1	1.316 (4)
C5—H5	0.9300	C12—N3	1.335 (4)
C6—H6	0.9300	C12—H12	0.9300
C7—N2	1.505 (4)	C13—N3	1.457 (5)
C7—H7A	0.9700	C13—H13A	0.9600
C7—H7B	0.9700	C13—H13B	0.9600
C8—N2	1.476 (4)	C13—H13C	0.9600
C2—Pd1—N1	93.72 (13)	H8B—C8—H8C	109.5
C2—Pd1—N2	82.79 (13)	N2—C9—H9A	109.5
N1—Pd1—N2	176.23 (11)	N2—C9—H9B	109.5
C2—Pd1—Cl1	175.52 (10)	H9A—C9—H9B	109.5
N1—Pd1—Cl1	88.84 (8)	N2—C9—H9C	109.5
N2—Pd1—Cl1	94.54 (8)	H9A—C9—H9C	109.5
C2—C1—C6	120.6 (4)	H9B—C9—H9C	109.5
C2—C1—C7	117.4 (3)	C11—C10—N1	108.8 (4)
C6—C1—C7	122.0 (4)	C11—C10—H10	125.6
C1—C2—C3	118.4 (3)	N1—C10—H10	125.6
C1—C2—Pd1	113.5 (3)	C10—C11—N3	107.1 (3)
C3—C2—Pd1	127.8 (3)	C10—C11—H11	126.4
C4—C3—C2	121.0 (4)	N3—C11—H11	126.4
C4—C3—H3	119.5	N1—C12—N3	111.2 (3)
C2—C3—H3	119.5	N1—C12—H12	124.4
C3—C4—C5	119.7 (4)	N3—C12—H12	124.4
C3—C4—H4	120.1	N3—C13—H13A	109.5
C5—C4—H4	120.1	N3—C13—H13B	109.5
C6—C5—C4	120.5 (4)	H13A—C13—H13B	109.5
C6—C5—H5	119.8	N3—C13—H13C	109.5
C4—C5—H5	119.8	H13A—C13—H13C	109.5
C5—C6—C1	119.7 (5)	H13B—C13—H13C	109.5
C5—C6—H6	120.1	C12—N1—C10	105.8 (3)
C1—C6—H6	120.1	C12—N1—Pd1	124.8 (2)
C1—C7—N2	108.3 (3)	C10—N1—Pd1	129.3 (3)
C1—C7—H7A	110.0	C9—N2—C8	108.5 (3)
N2—C7—H7A	110.0	C9—N2—C7	108.8 (3)
C1—C7—H7B	110.0	C8—N2—C7	107.8 (3)
N2—C7—H7B	110.0	C9—N2—Pd1	108.1 (2)
H7A—C7—H7B	108.4	C8—N2—Pd1	115.7 (2)
N2—C8—H8A	109.5	C7—N2—Pd1	107.8 (2)
N2—C8—H8B	109.5	C12—N3—C11	107.0 (3)
H8A—C8—H8B	109.5	C12—N3—C13	125.2 (3)
N2—C8—H8C	109.5	C11—N3—C13	127.8 (3)
H8A—C8—H8C	109.5