trans-Di­chloridobis(4-meth­oxy­aniline-κN)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 Pd⋯Cl distances of 3.6912 (6) Å. A chain-like arrangement of mol­ecules realized by inter­molecular N—H⋯Cl hydrogen bonds is observed along [010].

Related literature

For catalytic activity of Pd complex compounds, see: Ojwach et al. (2007). For anti­tumoral properties of Pd compounds, see: Casas et al. (2008). For related structures, see: Bon et al. (2009); Pan et al. (2006).

Experimental

Crystal data

• [PdCl₂(C₇H₉NO)₂]

• M_r = 423.60

• Monoclinic, P 2₁ /c

• a = 4.7333 (1) Å

• b = 6.0071 (1) Å

• c = 27.6918 (5) Å

• β = 94.806 (1)°

• V = 784.60 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.53 mm⁻¹

• T = 173 K

• 0.25 × 0.08 × 0.04 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: numerical (SADABS; Bruker, 2005) T_min = 0.701, T_max = 0.941

• 4837 measured reflections

• 1577 independent reflections

• 1326 reflections with I > 2σ(I)

• R_int = 0.024

Refinement

• R[F² > 2σ(F²)] = 0.023

• wR(F²) = 0.049

• S = 1.04

• 1577 reflections

• 106 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1^i	0.85 (3)	2.53 (3)	3.353 (2)	162 (2)
Symmetry code: (i) x, y+1, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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).

Supporting information

S1. Comment

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).

Related literature

For catalytic activity of Pd complex compounds, see: Ojwach et al. (2007). For antitumoral properties of Pd compounds, see: Casas et al. (2008). For related structures, see: Bon et al. (2009); Pan et al. (2006).

S2. Experimental

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.

S3. Refinement

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 [U_iso(H) = 1.5Ueq(C)] and C—H = 0.95 Å for CH [U_iso(H) = 1.2Ueq(C)]

Computing details

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).

Figures

	Fig. 1. The title compound showing 50% probability displacement ellipsoids for the non-hydrogen atoms [Symmetry code: (i) -x, -y, -z].
	Fig. 2. Crystal packing of title compound, projection down the a axis. Dashed lines indicate hydrogen bonds [Symmetry code: (i) x, y + 1, z].

trans-Dichloridobis(4-methoxyaniline-κN)palladium(II)

Crystal data

[PdCl2(C7H9NO)2]	F(000) = 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 = 3.0–26.4°
b = 6.0071 (1) Å	µ = 1.53 mm^−1
c = 27.6918 (5) Å	T = 173 K
β = 94.806 (1)°	Plate, yellow
V = 784.60 (3) Å^3	0.25 × 0.08 × 0.04 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	1577 independent reflections
Radiation source: fine-focus sealed tube	1326 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 8.26 pixels mm^-1	θmax = 26.4°, θmin = 1.5°
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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0205P)^2 + 0.3835P] where P = (Fo^2 + 2Fc^2)/3
1577 reflections	(Δ/σ)max < 0.001
106 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Pd1—N1	2.042 (2)	C2—C3	1.387 (3)
Pd1—N1^i	2.042 (2)	C2—H2	0.9500
Pd1—Cl1	2.3010 (6)	C3—C4	1.387 (4)
Pd1—Cl1^i	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—N1^i	180.00 (8)	C2—C3—C4	119.7 (2)
N1—Pd1—Cl1	88.23 (7)	C2—C3—H3	120.2
N1^i—Pd1—Cl1	91.77 (7)	C4—C3—H3	120.2
N1—Pd1—Cl1^i	91.77 (7)	O1—C4—C5	116.1 (3)
N1^i—Pd1—Cl1^i	88.23 (7)	O1—C4—C3	124.1 (3)
Cl1—Pd1—Cl1^i	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)
Cl1^i—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 code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^ii	0.85 (3)	2.53 (3)	3.353 (2)	162 (2)

Symmetry code: (ii) x, y+1, z.