Redetermination of (2,2'-bipyridine-κN,N')dichlorido-palladium(II) dichloro-methane solvate.

In the title compound, [PdCl(2)(C(10)H(8)N(2))]·CH(2)Cl(2), the Pd(2+) ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the 2,2'-bipyridine (bipy) ligand and two chloride ions. The compound displays intra-molecular C-H⋯Cl hydrogen bonds and pairs of complex mol-ecules are connected by inter-molecular C-H⋯Cl hydrogen bonds. Inter-molecular π-π inter-actions are present between the pyridine rings of the ligand, the shortest centroid-centroid distance being 4.096 (3) Å. As a result of the electronic nature of the chelate ring, it is possible to create π-π inter-actions to its symmetry-related counterpart [3.720 (2) Å] and also with a pyridine ring [3.570 (3) Å] of the bipy unit. The present structure is a redetermination of a previous structure [Vicente et al. (1997 ▶). Private communication (refcode PYCXMN02). CCDC, Cambridge, England]. In the new structure refinement all H atoms were located in a difference Fourier synthesis. Their coordinates were refined freely, together with isotropic displacement parameters.

Related literature

For crystal structures of [PdX 2(bipy)] (X = Cl or Br), see: Maekawa et al. (1991 ▶); Vicente et al. (1997 ▶); Smeets et al. (1997 ▶). For related Pt(II, IV)–bipyridine complexes, see: Osborn & Rogers (1974 ▶); Hambley (1986 ▶); Sartori et al. (2005 ▶); Momeni et al. (2007 ▶); Kim et al. (2009 ▶).

Experimental

Crystal data

[PdCl2(C10H8N2)]·CH2Cl2

M = 418.41

Triclinic,

a = 8.7913 (10) Å

b = 9.1115 (11) Å

c = 10.1846 (12) Å

α = 72.481 (2)°

β = 66.983 (2)°

γ = 81.429 (2)°

V = 715.58 (15) Å3

Z = 2

Mo Kα radiation

μ = 2.03 mm−1

T = 293 K

0.20 × 0.08 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.623, T max = 0.850

4221 measured reflections

2862 independent reflections

2298 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.097

S = 1.05

2862 reflections

203 parameters

All H-atom parameters refined

Δρmax = 0.56 e Å−3

Δρmin = −0.69 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016262/kp2220sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016262/kp2220Isup2.hkl

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

[PdCl2(C10H8N2)]·CH2Cl2	Z = 2
Mr = 418.41	F(000) = 408
Triclinic, P1	Dx = 1.942 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7913 (10) Å	Cell parameters from 983 reflections
b = 9.1115 (11) Å	θ = 2.3–21.7°
c = 10.1846 (12) Å	µ = 2.03 mm−1
α = 72.481 (2)°	T = 293 K
β = 66.983 (2)°	Stick, yellow
γ = 81.429 (2)°	0.20 × 0.08 × 0.08 mm
V = 715.58 (15) Å3

Bruker SMART 1000 CCD diffractometer	2862 independent reflections
Radiation source: fine-focus sealed tube	2298 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.623, Tmax = 0.850	k = −7→11
4221 measured reflections	l = −12→12

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	All H-atom parameters refined
S = 1.05	w = 1/[σ2(Fo2) + (0.0352P)2 + 0.5604P] where P = (Fo2 + 2Fc2)/3
2862 reflections	(Δ/σ)max < 0.001
203 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.69 e Å−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 > 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
Pd1	0.32112 (5)	0.28572 (4)	0.21130 (4)	0.04479 (15)
Cl1	0.36850 (18)	0.02764 (15)	0.30403 (16)	0.0612 (4)
Cl2	0.1458 (2)	0.22805 (17)	0.11857 (19)	0.0720 (5)
N1	0.2916 (5)	0.5169 (5)	0.1348 (4)	0.0454 (10)
N2	0.4786 (5)	0.3551 (5)	0.2803 (4)	0.0446 (10)
C1	0.1884 (7)	0.5895 (7)	0.0665 (6)	0.0545 (14)
H1	0.126 (6)	0.526 (6)	0.052 (5)	0.058 (16)*
C2	0.1803 (8)	0.7475 (7)	0.0175 (7)	0.0610 (15)
H2	0.101 (7)	0.800 (6)	−0.020 (6)	0.063 (17)*
C3	0.2768 (8)	0.8325 (7)	0.0413 (7)	0.0620 (16)
H3	0.273 (6)	0.930 (6)	0.018 (5)	0.043 (14)*
C4	0.3831 (7)	0.7585 (6)	0.1120 (6)	0.0515 (13)
H4	0.451 (6)	0.809 (6)	0.128 (5)	0.046 (14)*
C5	0.3887 (6)	0.6010 (6)	0.1590 (5)	0.0417 (11)
C6	0.4959 (6)	0.5099 (6)	0.2384 (5)	0.0466 (12)
C7	0.6069 (8)	0.5739 (7)	0.2675 (7)	0.0644 (16)
H7	0.623 (7)	0.683 (7)	0.236 (6)	0.081 (19)*
C8	0.7003 (9)	0.4784 (8)	0.3427 (8)	0.077 (2)
H8	0.775 (8)	0.512 (8)	0.355 (7)	0.09 (2)*
C9	0.6833 (8)	0.3223 (8)	0.3858 (8)	0.0717 (18)
H9	0.734 (6)	0.255 (6)	0.442 (5)	0.049 (15)*
C10	0.5692 (7)	0.2645 (7)	0.3546 (7)	0.0579 (15)
H10	0.562 (6)	0.166 (6)	0.376 (5)	0.043 (14)*
C11	0.0507 (9)	0.1175 (7)	0.6220 (8)	0.0614 (16)
H11A	−0.043 (7)	0.071 (6)	0.685 (6)	0.062 (17)*
H11B	0.115 (7)	0.087 (7)	0.529 (7)	0.09 (2)*
Cl3	−0.0049 (2)	0.31218 (19)	0.55636 (18)	0.0740 (5)
Cl4	0.1895 (2)	0.1016 (2)	0.7099 (2)	0.0887 (6)

	U11	U22	U33	U12	U13	U23
Pd1	0.0465 (2)	0.0387 (2)	0.0512 (3)	−0.00670 (17)	−0.01825 (18)	−0.01196 (18)
Cl1	0.0744 (9)	0.0386 (7)	0.0735 (9)	−0.0059 (7)	−0.0309 (8)	−0.0121 (7)
Cl2	0.0836 (11)	0.0561 (9)	0.0965 (12)	−0.0203 (8)	−0.0543 (9)	−0.0117 (8)
N1	0.045 (2)	0.044 (2)	0.048 (2)	−0.005 (2)	−0.017 (2)	−0.0118 (19)
N2	0.049 (2)	0.039 (2)	0.050 (2)	−0.0036 (19)	−0.021 (2)	−0.0121 (19)
C1	0.052 (3)	0.054 (3)	0.062 (3)	−0.002 (3)	−0.028 (3)	−0.012 (3)
C2	0.063 (4)	0.050 (4)	0.068 (4)	0.008 (3)	−0.029 (3)	−0.009 (3)
C3	0.072 (4)	0.039 (3)	0.074 (4)	−0.002 (3)	−0.025 (3)	−0.016 (3)
C4	0.057 (3)	0.039 (3)	0.063 (3)	−0.005 (3)	−0.025 (3)	−0.016 (3)
C5	0.041 (3)	0.039 (3)	0.044 (3)	−0.004 (2)	−0.010 (2)	−0.016 (2)
C6	0.046 (3)	0.044 (3)	0.045 (3)	−0.004 (2)	−0.012 (2)	−0.011 (2)
C7	0.080 (4)	0.052 (4)	0.078 (4)	−0.015 (3)	−0.045 (4)	−0.013 (3)
C8	0.084 (5)	0.070 (5)	0.097 (5)	−0.016 (4)	−0.058 (4)	−0.009 (4)
C9	0.074 (4)	0.063 (4)	0.092 (5)	−0.004 (3)	−0.054 (4)	−0.009 (4)
C10	0.065 (4)	0.045 (3)	0.067 (4)	−0.002 (3)	−0.032 (3)	−0.008 (3)
C11	0.065 (4)	0.052 (4)	0.072 (4)	−0.009 (3)	−0.026 (3)	−0.019 (3)
Cl3	0.0761 (10)	0.0652 (10)	0.0759 (10)	0.0022 (8)	−0.0354 (9)	−0.0044 (8)
Cl4	0.0906 (12)	0.0701 (11)	0.1211 (15)	0.0040 (9)	−0.0663 (12)	−0.0139 (10)

Pd1—N2	2.025 (4)	C4—H4	0.90 (5)
Pd1—N1	2.029 (4)	C5—C6	1.480 (7)
Pd1—Cl2	2.2853 (14)	C6—C7	1.371 (7)
Pd1—Cl1	2.2964 (14)	C7—C8	1.377 (9)
N1—C1	1.335 (6)	C7—H7	0.96 (6)
N1—C5	1.360 (6)	C8—C9	1.369 (9)
N2—C10	1.338 (7)	C8—H8	0.83 (6)
N2—C6	1.359 (6)	C9—C10	1.375 (8)
C1—C2	1.375 (8)	C9—H9	0.90 (5)
C1—H1	0.93 (5)	C10—H10	0.86 (5)
C2—C3	1.360 (8)	C11—Cl4	1.743 (6)
C2—H2	0.93 (5)	C11—Cl3	1.765 (6)
C3—C4	1.376 (8)	C11—H11A	0.90 (5)
C3—H3	0.85 (5)	C11—H11B	0.99 (6)
C4—C5	1.369 (7)
N2—Pd1—N1	81.04 (16)	N1—C5—C4	120.6 (5)
N2—Pd1—Cl2	174.97 (12)	N1—C5—C6	115.2 (4)
N1—Pd1—Cl2	94.27 (12)	C4—C5—C6	124.2 (5)
N2—Pd1—Cl1	94.74 (12)	N2—C6—C7	121.4 (5)
N1—Pd1—Cl1	175.78 (12)	N2—C6—C5	115.0 (4)
Cl2—Pd1—Cl1	89.94 (5)	C7—C6—C5	123.6 (5)
C1—N1—C5	119.3 (5)	C6—C7—C8	118.8 (6)
C1—N1—Pd1	126.5 (4)	C6—C7—H7	122 (4)
C5—N1—Pd1	114.2 (3)	C8—C7—H7	119 (4)
C10—N2—C6	118.9 (4)	C9—C8—C7	120.2 (6)
C10—N2—Pd1	126.6 (4)	C9—C8—H8	118 (5)
C6—N2—Pd1	114.4 (3)	C7—C8—H8	121 (5)
N1—C1—C2	121.4 (6)	C8—C9—C10	118.5 (6)
N1—C1—H1	116 (3)	C8—C9—H9	124 (3)
C2—C1—H1	123 (3)	C10—C9—H9	117 (3)
C3—C2—C1	119.7 (6)	N2—C10—C9	122.2 (6)
C3—C2—H2	118 (4)	N2—C10—H10	118 (3)
C1—C2—H2	122 (4)	C9—C10—H10	119 (3)
C2—C3—C4	119.2 (6)	Cl4—C11—Cl3	111.0 (3)
C2—C3—H3	124 (3)	Cl4—C11—H11A	111 (4)
C4—C3—H3	117 (3)	Cl3—C11—H11A	106 (4)
C5—C4—C3	119.8 (5)	Cl4—C11—H11B	106 (3)
C5—C4—H4	118 (3)	Cl3—C11—H11B	103 (4)
C3—C4—H4	123 (3)	H11A—C11—H11B	120 (5)
N2—Pd1—N1—C1	−177.3 (4)	C3—C4—C5—N1	0.8 (8)
Cl2—Pd1—N1—C1	4.6 (4)	C3—C4—C5—C6	−178.8 (5)
N2—Pd1—N1—C5	2.4 (3)	C10—N2—C6—C7	1.7 (8)
Cl2—Pd1—N1—C5	−175.7 (3)	Pd1—N2—C6—C7	−175.3 (4)
N1—Pd1—N2—C10	179.8 (5)	C10—N2—C6—C5	−179.1 (4)
Cl1—Pd1—N2—C10	−0.3 (5)	Pd1—N2—C6—C5	4.0 (5)
N1—Pd1—N2—C6	−3.5 (3)	N1—C5—C6—N2	−2.0 (6)
Cl1—Pd1—N2—C6	176.4 (3)	C4—C5—C6—N2	177.6 (5)
C5—N1—C1—C2	1.2 (8)	N1—C5—C6—C7	177.3 (5)
Pd1—N1—C1—C2	−179.2 (4)	C4—C5—C6—C7	−3.1 (8)
N1—C1—C2—C3	−1.3 (9)	N2—C6—C7—C8	−1.0 (9)
C1—C2—C3—C4	1.1 (9)	C5—C6—C7—C8	179.8 (6)
C2—C3—C4—C5	−0.8 (9)	C6—C7—C8—C9	0.7 (11)
C1—N1—C5—C4	−0.9 (7)	C7—C8—C9—C10	−1.2 (11)
Pd1—N1—C5—C4	179.4 (4)	C6—N2—C10—C9	−2.2 (9)
C1—N1—C5—C6	178.7 (4)	Pd1—N2—C10—C9	174.4 (5)
Pd1—N1—C5—C6	−1.0 (5)	C8—C9—C10—N2	1.9 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl2	0.93 (5)	2.59 (5)	3.230 (6)	126 (4)
C2—H2···Cl2i	0.93 (5)	2.79 (5)	3.595 (7)	145 (4)
C10—H10···Cl1	0.86 (5)	2.68 (5)	3.248 (6)	125 (4)
C11—H11B···Cl1	0.99 (6)	2.63 (6)	3.578 (8)	161 (5)

Table 1

Selected bond lengths (Å)

Pd1—N2	2.025 (4)
Pd1—N1	2.029 (4)
Pd1—Cl2	2.2853 (14)
Pd1—Cl1	2.2964 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl2	0.93 (5)	2.59 (5)	3.230 (6)	126 (4)
C2—H2⋯Cl2i	0.93 (5)	2.79 (5)	3.595 (7)	145 (4)
C10—H10⋯Cl1	0.86 (5)	2.68 (5)	3.248 (6)	125 (4)
C11—H11B⋯Cl1	0.99 (6)	2.63 (6)	3.578 (8)	161 (5)

Symmetry code: (i) .