trans-Dichloridobis(4-nitro-aniline-κN(1))palladium(II).

In the title compound, [PdCl(2)(C(6)H(6)N(2)O(2))(2)], the Pd(II) atom is coordinated in a distorted square-planar geometry by two N atoms from two 4-nitro-aniline ligands and two Cl atoms in a trans arrangement. Inter-molecular 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 = 453.56

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.077

S = 1.06

2135 reflections

208 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.37 e Å−3

Absolute structure: Flack (1983 ▶), 696 Friedel pairs

Flack parameter: 0.46 (4)

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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812042134/hy2592sup1.cif

Click here for additional data file.

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

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

[PdCl2(C6H6N2O2)2]	F(000) = 896
Mr = 453.56	Dx = 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

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

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(Fo2) + (0.059P)2 + 0.1195P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.002
2135 reflections	Δρmax = 0.50 e Å−3
208 parameters	Δρmin = −0.37 e Å−3
2 restraints	Absolute structure: Flack (1983), 696 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.46 (4)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···Cl2iv	0.90	2.46	3.310 (5)	157

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⋯Cl2iv	0.90	2.46	3.310 (5)	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .