trans-Dichloridobis(4-nitro­aniline-κN1)palladium(II)

Feng, T.-J.

doi:10.1107/S1600536812042134

metal-organic compounds

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Volume 68| Part 11| November 2012| Page m1351

doi:10.1107/S1600536812042134

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trans-Dichloridobis(4-nitroaniline-κN¹)palladium(II)

Tian-Jun Feng ^a ^*

^aCollege of Mathematics, Physics and Software Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: fengtj707@126.com

(Received 28 September 2012; accepted 8 October 2012; online 13 October 2012)

In the title compound, [PdCl₂(C₆H₆N₂O₂)₂], the Pd^II atom is coordinated in a distorted square-planar geometry by two N atoms from two 4-nitroaniline ligands and two Cl atoms in a trans arrangement. Intermolecular N—H⋯Cl hydrogen bonds involving the amino groups and chloride anions lead to a chain along [100]. These chains are further self-assembled into a three-dimensional network through N—H⋯O and N—H⋯Cl hydrogen bonds.

Related literature

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

Experimental

Crystal data

[PdCl₂(C₆H₆N₂O₂)₂]
M_r = 453.56
Monoclinic, C c
a = 5.6014 (8) Å
b = 26.246 (4) Å
c = 11.0763 (16) Å
β = 99.828 (2)°
V = 1604.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 296 K
0.33 × 0.30 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.626, T_max = 0.688
4453 measured reflections
2135 independent reflections
2075 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.077
S = 1.06
2135 reflections
208 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 696 Friedel pairs
Flack parameter: 0.46 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.90	2.40	3.293 (5)	175
N1—H1B⋯Cl2ⁱⁱ	0.90	2.71	3.474 (5)	143
N2—H2A⋯O3ⁱⁱⁱ	0.90	2.52	3.287 (7)	143
N2—H2B⋯Cl2^iv	0.90	2.46	3.310 (5)	157
Symmetry codes: (i) x-1, y, z; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x+1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812042134/hy2592sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042134/hy2592Isup2.hkl

checkCIF report

Comment top

Palladium compounds have attracted much attention due to their applications in homogeneous and heterogeneous catalyses (Padmanabhan et al., 1985). Some dramatic results in the homogeneous catalysis of the 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 the crystal structure of the title compound, a new palladium(II) complex obtained by the reaction of 4-nitroaniline with palladium chloride in ethanol solution.

As illustrated in Fig. 1, the Pd^II atom exhibits a distorted square-planar coordination geometry, defined by two N atoms from two 4-nitroaniline ligands and two chloride atoms. The molecule adopts the trans configuration. The bond distances of Pd—N [2.061 (2) Å] and Pd—Cl [2.302 (3) Å] are comparable with the values found in related complexes (Chen et al., 2002; Newkome et al., 1982). The dihedral angle between the aromatic ring plane and the square plane around Pd1 is 70.54 (2)°. Intermolecular N—H···Cl hydrogen bonds involving the amino groups and chlorine anions (Table 1) lead to a chain along [100] (Fig. 2). These chains are further self-assembled into a three-dimensional network through N—H···O and N—H···Cl hydrogen bonds (Fig. 3).

Related literature top

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

Experimental top

A mixture of palladium chloride (0.1 mmol, 0.018 g) and 4-nitroaniline (0.2 mmol, 0.027 g) in 10 ml of anhydrous ethanol was sealed in an autoclave equipped with a Teflon liner (23 ml) and then heated at 353 K for 2 days. Yellow crystals were obtained by slow evaporation of the solvent at room temperature (yield: 49% based on 4-nitroaniline).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. View of the chain structure in the title compound. Hydrogen bonds are shown as pink dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.
	Fig. 3. Crystal packing of the title compound. Hydrogen bonds are shown as pink dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.

trans-Dichloridobis(4-nitroaniline-κN¹)palladium(II) top

Crystal data top

[PdCl₂(C₆H₆N₂O₂)₂]	F(000) = 896
M_r = 453.56	D_x = 1.878 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5300 reflections
a = 5.6014 (8) Å	θ = 1.3–28.0°
b = 26.246 (4) Å	µ = 1.51 mm⁻¹
c = 11.0763 (16) Å	T = 296 K
β = 99.828 (2)°	Block, yellow
V = 1604.5 (4) Å³	0.33 × 0.30 × 0.26 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2135 independent reflections
Radiation source: fine-focus sealed tube	2075 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.626, T_max = 0.688	k = −28→31
4453 measured reflections	l = −13→10

Refinement top

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.059P)² + 0.1195P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
2135 reflections	Δρ_max = 0.50 e Å⁻³
208 parameters	Δρ_min = −0.37 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 696 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.46 (4)

Crystal data top

[PdCl₂(C₆H₆N₂O₂)₂]	V = 1604.5 (4) Å³
M_r = 453.56	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 5.6014 (8) Å	µ = 1.51 mm⁻¹
b = 26.246 (4) Å	T = 296 K
c = 11.0763 (16) Å	0.33 × 0.30 × 0.26 mm
β = 99.828 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2135 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2075 reflections with I > 2σ(I)
T_min = 0.626, T_max = 0.688	R_int = 0.018
4453 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.077	Δρ_max = 0.50 e Å⁻³
S = 1.06	Δρ_min = −0.37 e Å⁻³
2135 reflections	Absolute structure: Flack (1983), 696 Friedel pairs
208 parameters	Absolute structure parameter: 0.46 (4)
2 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.7813 (8)	0.46008 (19)	0.2257 (5)	0.0324 (10)
C2	0.6105 (10)	0.4507 (2)	0.2984 (6)	0.0405 (13)
H2	0.4896	0.4745	0.3037	0.049*
C3	0.6200 (9)	0.4053 (2)	0.3641 (5)	0.0406 (12)
H3	0.5098	0.3985	0.4161	0.049*
C4	0.7981 (9)	0.37081 (19)	0.3496 (5)	0.0358 (11)
C5	0.9644 (10)	0.3795 (2)	0.2764 (5)	0.0403 (12)
H5	1.0798	0.3547	0.2692	0.048*
C6	0.9651 (10)	0.4245 (2)	0.2123 (5)	0.0380 (12)
H6	1.0801	0.4311	0.1629	0.046*
C7	1.1775 (9)	0.66743 (19)	0.2754 (5)	0.0313 (10)
C8	0.9834 (10)	0.6949 (2)	0.3044 (5)	0.0371 (11)
H8	0.8961	0.6828	0.3628	0.045*
C9	0.9216 (10)	0.7412 (2)	0.2439 (5)	0.0380 (12)
H9	0.7917	0.7605	0.2606	0.046*
C10	1.0586 (8)	0.75750 (18)	0.1588 (4)	0.0307 (10)
C11	1.2582 (9)	0.73067 (19)	0.1320 (5)	0.0358 (11)
H11	1.3503	0.7432	0.0762	0.043*
C12	1.3145 (9)	0.6845 (2)	0.1918 (5)	0.0366 (11)
H12	1.4445	0.6653	0.1753	0.044*
Cl1	1.2293 (4)	0.55635 (8)	0.0903 (2)	0.0436 (6)
Cl2	0.7793 (4)	0.56838 (7)	0.4000 (2)	0.0408 (5)
N1	0.7776 (8)	0.50756 (15)	0.1568 (4)	0.0356 (9)
H1A	0.6253	0.5198	0.1427	0.043*
H1B	0.8208	0.5010	0.0837	0.043*
N2	1.2299 (8)	0.61827 (16)	0.3332 (4)	0.0365 (9)
H2A	1.2109	0.6202	0.4122	0.044*
H2B	1.3851	0.6099	0.3316	0.044*
N3	0.8016 (11)	0.3224 (2)	0.4165 (6)	0.0463 (15)
N4	0.9877 (9)	0.80407 (15)	0.0883 (5)	0.0404 (10)
O1	0.6631 (11)	0.3158 (2)	0.4860 (6)	0.0769 (16)
O2	0.9473 (9)	0.28974 (16)	0.3938 (5)	0.0609 (12)
O3	0.7966 (11)	0.8248 (2)	0.1012 (5)	0.0674 (18)
O4	1.1159 (9)	0.82003 (16)	0.0195 (5)	0.0601 (12)
Pd1	1.00552 (7)	0.562350 (12)	0.24606 (5)	0.02914 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.027 (2)	0.035 (3)	0.035 (3)	−0.0012 (19)	0.005 (2)	0.000 (2)
C2	0.029 (3)	0.037 (3)	0.056 (4)	0.001 (2)	0.010 (3)	−0.008 (3)
C3	0.034 (3)	0.045 (3)	0.047 (3)	−0.006 (2)	0.020 (2)	−0.003 (3)
C4	0.038 (3)	0.032 (3)	0.036 (3)	−0.006 (2)	0.004 (2)	−0.002 (2)
C5	0.039 (3)	0.041 (3)	0.042 (3)	0.006 (2)	0.010 (2)	−0.003 (2)
C6	0.038 (3)	0.044 (3)	0.033 (3)	−0.003 (2)	0.011 (2)	0.002 (2)
C7	0.029 (2)	0.029 (2)	0.036 (2)	−0.0016 (19)	0.005 (2)	−0.005 (2)
C8	0.040 (3)	0.039 (3)	0.036 (3)	−0.005 (2)	0.016 (2)	0.004 (2)
C9	0.035 (2)	0.033 (3)	0.046 (3)	0.0080 (19)	0.007 (3)	−0.005 (2)
C10	0.028 (2)	0.031 (2)	0.033 (3)	−0.0011 (18)	0.006 (2)	0.000 (2)
C11	0.033 (2)	0.038 (3)	0.039 (3)	0.000 (2)	0.013 (2)	−0.001 (2)
C12	0.029 (2)	0.040 (3)	0.041 (3)	0.004 (2)	0.007 (2)	−0.002 (2)
Cl1	0.0384 (10)	0.0581 (11)	0.0374 (11)	0.0009 (7)	0.0154 (8)	0.0016 (7)
Cl2	0.0420 (10)	0.0447 (9)	0.0380 (11)	0.0022 (6)	0.0133 (8)	−0.0019 (7)
N1	0.033 (2)	0.035 (2)	0.038 (2)	−0.0002 (17)	0.0059 (18)	−0.0011 (18)
N2	0.036 (2)	0.036 (2)	0.036 (2)	0.0006 (17)	0.0009 (18)	0.0037 (18)
N3	0.059 (3)	0.043 (3)	0.037 (3)	−0.003 (3)	0.008 (3)	0.004 (2)
N4	0.045 (2)	0.031 (2)	0.045 (3)	0.0020 (19)	0.007 (2)	0.001 (2)
O1	0.084 (4)	0.069 (3)	0.087 (4)	−0.002 (3)	0.040 (3)	0.028 (3)
O2	0.076 (3)	0.044 (2)	0.056 (3)	0.008 (2)	−0.005 (2)	0.006 (2)
O3	0.086 (4)	0.068 (4)	0.057 (3)	0.042 (3)	0.036 (3)	0.024 (3)
O4	0.064 (3)	0.053 (3)	0.071 (3)	0.004 (2)	0.031 (2)	0.023 (2)
Pd1	0.02850 (17)	0.02877 (19)	0.03039 (19)	0.00214 (16)	0.00572 (12)	0.00207 (17)

Geometric parameters (Å, º) top

C1—C2	1.374 (8)	C9—H9	0.9300
C1—C6	1.416 (8)	C10—C11	1.395 (7)
C1—N1	1.459 (7)	C10—N4	1.468 (6)
C2—C3	1.394 (9)	C11—C12	1.390 (7)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.376 (8)	C12—H12	0.9300
C3—H3	0.9300	Cl1—Pd1	2.305 (2)
C4—C5	1.354 (8)	Cl2—Pd1	2.297 (2)
C4—N3	1.470 (8)	N1—Pd1	2.060 (4)
C5—C6	1.379 (8)	N1—H1A	0.9000
C5—H5	0.9300	N1—H1B	0.9000
C6—H6	0.9300	N2—Pd1	2.062 (4)
C7—C12	1.375 (8)	N2—H2A	0.9000
C7—C8	1.387 (7)	N2—H2B	0.9000
C7—N2	1.448 (7)	N3—O1	1.196 (9)
C8—C9	1.403 (8)	N3—O2	1.238 (8)
C8—H8	0.9300	N4—O4	1.207 (7)
C9—C10	1.381 (8)	N4—O3	1.231 (7)

C2—C1—C6	122.3 (5)	C12—C11—C10	117.6 (5)
C2—C1—N1	120.6 (5)	C12—C11—H11	121.2
C6—C1—N1	117.0 (5)	C10—C11—H11	121.2
C1—C2—C3	119.4 (5)	C7—C12—C11	119.9 (5)
C1—C2—H2	120.3	C7—C12—H12	120.1
C3—C2—H2	120.3	C11—C12—H12	120.1
C4—C3—C2	117.7 (5)	C1—N1—Pd1	113.1 (3)
C4—C3—H3	121.1	C1—N1—H1A	109.0
C2—C3—H3	121.1	Pd1—N1—H1A	109.0
C5—C4—C3	123.1 (5)	C1—N1—H1B	109.0
C5—C4—N3	119.7 (5)	Pd1—N1—H1B	109.0
C3—C4—N3	117.2 (5)	H1A—N1—H1B	107.8
C4—C5—C6	120.9 (5)	C7—N2—Pd1	111.5 (3)
C4—C5—H5	119.5	C7—N2—H2A	109.3
C6—C5—H5	119.5	Pd1—N2—H2A	109.3
C5—C6—C1	116.5 (5)	C7—N2—H2B	109.3
C5—C6—H6	121.8	Pd1—N2—H2B	109.3
C1—C6—H6	121.8	H2A—N2—H2B	108.0
C12—C7—C8	122.4 (5)	O1—N3—O2	123.6 (6)
C12—C7—N2	119.7 (5)	O1—N3—C4	119.7 (6)
C8—C7—N2	117.9 (5)	O2—N3—C4	116.6 (6)
C7—C8—C9	118.6 (5)	O4—N4—O3	122.9 (5)
C7—C8—H8	120.7	O4—N4—C10	119.2 (5)
C9—C8—H8	120.7	O3—N4—C10	117.9 (5)
C10—C9—C8	118.3 (5)	N1—Pd1—N2	178.86 (17)
C10—C9—H9	120.8	N1—Pd1—Cl2	91.68 (14)
C8—C9—H9	120.8	N2—Pd1—Cl2	88.43 (15)
C9—C10—C11	123.2 (5)	N1—Pd1—Cl1	87.97 (15)
C9—C10—N4	119.3 (4)	N2—Pd1—Cl1	91.91 (15)
C11—C10—N4	117.5 (4)	Cl2—Pd1—Cl1	179.48 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.40	3.293 (5)	175
N1—H1B···Cl2ⁱⁱ	0.90	2.71	3.474 (5)	143
N2—H2A···O3ⁱⁱⁱ	0.90	2.52	3.287 (7)	143
N2—H2B···Cl2^iv	0.90	2.46	3.310 (5)	157

Symmetry codes: (i) x−1, y, z; (ii) x, −y+1, z−1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[PdCl₂(C₆H₆N₂O₂)₂]
M_r	453.56
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	5.6014 (8), 26.246 (4), 11.0763 (16)
β (°)	99.828 (2)
V (Å³)	1604.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.51
Crystal size (mm)	0.33 × 0.30 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.626, 0.688
No. of measured, independent and observed [I > 2σ(I)] reflections	4453, 2135, 2075
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.077, 1.06
No. of reflections	2135
No. of parameters	208
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.37
Absolute structure	Flack (1983), 696 Friedel pairs
Absolute structure parameter	0.46 (4)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.40	3.293 (5)	175
N1—H1B···Cl2ⁱⁱ	0.90	2.71	3.474 (5)	143
N2—H2A···O3ⁱⁱⁱ	0.90	2.52	3.287 (7)	143
N2—H2B···Cl2^iv	0.90	2.46	3.310 (5)	157

Symmetry codes: (i) x−1, y, z; (ii) x, −y+1, z−1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) x+1, y, z.

Acknowledgements

The author acknowledges Lanzhou Jiaotong University for supporting this work.

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