(2,2'-Bi-pyridine-κ(2) N,N')di-chloridopalladium(II) 1,4-dioxane hemisolvate.

The asymmetric unit of the title compound, [PdCl2(C10H8N2)]·0.5C4H8O2, consists of one Pd(II) complex mol-ecule and a half-mol-ecule of 1,4-dioxane, the complete mol-ecule being generated by inversion symmetry. The Pd(II) atom has an almost square-planar coordination formed by the 2,2'-bi-pyridine ligand and two chloride ligands. Two intra-molecular C-H⋯Cl hydrogen bonds occur. In the crystal, the Pd(II) complex and 1,4-dioxane mol-ecules are connected by C-H⋯O hydrogen bonds, forming a layer parallel to (10-1). Within the layer, weak π-π inter-actions [centroid-centroid distance = 3.817 (4) Å] are observed between the pyridine rings.

Related literature

For related structures, see: Maekawa et al. (1991 ▶); Vicente et al. (1997 ▶); Kim et al. (2009 ▶). For palladium complexes with chelate ligands, see: Pointillart et al. (2007 ▶); Pazderski et al. (2006 ▶); Ferbinteanu et al. (1998 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

[PdCl(C10H8N2)2]·0.5C4H8O2

M = 377.54

Monoclinic,

a = 7.2416 (5) Å

b = 14.6215 (10) Å

c = 12.9562 (9) Å

β = 105.423 (2)°

V = 1322.44 (16) Å3

Z = 4

Mo Kα radiation

μ = 1.80 mm−1

T = 298 K

0.40 × 0.07 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.365, T max = 0.906

7244 measured reflections

2414 independent reflections

1813 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.153

S = 1.03

2414 reflections

163 parameters

H-atom parameters constrained

Δρmax = 1.49 e Å−3

Δρmin = −1.13 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, New_Global_publ_block. DOI: 10.1107/S1600536814009507/is5358sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009507/is5358Isup2.hkl

CCDC reference: 999627

Additional supporting information: crystallographic information; 3D view; checkCIF report

[PdCl(C10H8N2)2]·0.5C4H8O2	F(000) = 744
Mr = 377.54	Dx = 1.896 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2416 (5) Å	Cell parameters from 4271 reflections
b = 14.6215 (10) Å	θ = 2.8–25.4°
c = 12.9562 (9) Å	µ = 1.80 mm−1
β = 105.423 (2)°	T = 298 K
V = 1322.44 (16) Å3	Prism, yellow
Z = 4	0.40 × 0.07 × 0.06 mm

Bruker APEXII CCD area-detector diffractometer	1813 reflections with I > 2σ(I)
Detector resolution: 0.83 pixels mm-1	Rint = 0.055
ω scans	θmax = 25.4°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→8
Tmin = 0.365, Tmax = 0.906	k = −17→16
7244 measured reflections	l = −14→15
2414 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.153	w = 1/[σ2(Fo2) + (0.0933P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2414 reflections	Δρmax = 1.49 e Å−3
163 parameters	Δρmin = −1.13 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.

	x	y	z	Uiso*/Ueq
Pd1	0.16709 (6)	0.48172 (3)	−0.14236 (4)	0.0377 (2)
Cl1	0.1430 (3)	0.56553 (14)	−0.29371 (14)	0.0636 (5)
Cl2	0.0446 (3)	0.35687 (14)	−0.24462 (15)	0.0657 (5)
N1	0.1942 (6)	0.4175 (3)	−0.0003 (4)	0.0376 (12)
C2	0.2757 (9)	0.4690 (4)	0.0871 (5)	0.0387 (15)
C3	0.3108 (10)	0.4325 (5)	0.1885 (5)	0.0487 (16)
H3	0.3678	0.4679	0.2481	0.058*
C4	0.2607 (10)	0.3433 (5)	0.2008 (6)	0.0542 (18)
H4	0.2840	0.3179	0.2688	0.065*
C5	0.1779 (9)	0.2927 (5)	0.1140 (5)	0.0512 (17)
H5	0.1436	0.2324	0.1221	0.061*
C6	0.1439 (9)	0.3305 (5)	0.0125 (6)	0.0496 (16)
H6	0.0858	0.2955	−0.0472	0.060*
N7	0.2849 (7)	0.5840 (3)	−0.0419 (4)	0.0401 (12)
C8	0.3249 (8)	0.5628 (4)	0.0654 (5)	0.0382 (14)
C9	0.4075 (9)	0.6253 (5)	0.1418 (5)	0.0493 (16)
H9	0.4329	0.6098	0.2138	0.059*
C10	0.4534 (10)	0.7111 (5)	0.1131 (6)	0.0587 (19)
H10	0.5092	0.7541	0.1650	0.070*
C11	0.4154 (10)	0.7319 (5)	0.0072 (7)	0.059 (2)
H11	0.4461	0.7894	−0.0139	0.071*
C12	0.3315 (9)	0.6679 (4)	−0.0688 (6)	0.0468 (16)
H12	0.3064	0.6833	−0.1408	0.056*
O1	0.4638 (7)	0.5658 (4)	0.4170 (4)	0.0603 (13)
C13	0.6526 (11)	0.5477 (6)	0.4826 (6)	0.0583 (19)
H13A	0.6822	0.5899	0.5426	0.070*
H13B	0.7444	0.5577	0.4413	0.070*
C14	0.6707 (11)	0.4527 (6)	0.5235 (6)	0.062 (2)
H14A	0.6504	0.4105	0.4637	0.075*
H14B	0.7994	0.4432	0.5688	0.075*

	U11	U22	U33	U12	U13	U23
Pd1	0.0384 (3)	0.0347 (4)	0.0405 (4)	0.00612 (19)	0.0114 (2)	−0.0008 (2)
Cl1	0.0829 (13)	0.0635 (13)	0.0483 (10)	0.0124 (10)	0.0241 (9)	0.0100 (9)
Cl2	0.0785 (12)	0.0538 (12)	0.0561 (11)	−0.0033 (9)	0.0025 (9)	−0.0138 (9)
N1	0.034 (2)	0.035 (3)	0.047 (3)	0.004 (2)	0.016 (2)	0.000 (2)
C2	0.038 (3)	0.036 (4)	0.048 (4)	0.006 (3)	0.023 (3)	−0.003 (3)
C3	0.053 (4)	0.054 (5)	0.041 (4)	0.000 (3)	0.017 (3)	0.002 (3)
C4	0.062 (4)	0.056 (5)	0.050 (4)	0.006 (3)	0.024 (3)	0.008 (4)
C5	0.058 (4)	0.034 (4)	0.069 (5)	0.000 (3)	0.029 (4)	0.009 (4)
C6	0.048 (4)	0.041 (4)	0.061 (4)	0.001 (3)	0.018 (3)	0.000 (3)
N7	0.036 (3)	0.037 (3)	0.051 (3)	0.004 (2)	0.016 (2)	−0.002 (3)
C8	0.034 (3)	0.033 (3)	0.051 (4)	0.000 (3)	0.019 (3)	−0.009 (3)
C9	0.054 (4)	0.046 (4)	0.051 (4)	−0.002 (3)	0.020 (3)	−0.010 (3)
C10	0.065 (4)	0.044 (4)	0.070 (5)	−0.008 (3)	0.023 (4)	−0.025 (4)
C11	0.055 (4)	0.025 (3)	0.108 (6)	0.002 (3)	0.043 (4)	0.000 (4)
C12	0.051 (4)	0.034 (4)	0.060 (4)	0.003 (3)	0.022 (3)	0.005 (3)
O1	0.078 (3)	0.055 (3)	0.052 (3)	0.013 (3)	0.023 (3)	0.013 (3)
C13	0.066 (5)	0.058 (5)	0.055 (4)	−0.007 (4)	0.022 (4)	−0.006 (4)
C14	0.062 (5)	0.062 (5)	0.064 (5)	0.008 (4)	0.018 (4)	0.014 (4)

Pd1—N7	2.017 (5)	C8—C9	1.363 (9)
Pd1—N1	2.029 (5)	C9—C10	1.374 (10)
Pd1—Cl1	2.2793 (18)	C9—H9	0.9300
Pd1—Cl2	2.2912 (19)	C10—C11	1.360 (11)
N1—C6	1.345 (8)	C10—H10	0.9300
N1—C2	1.357 (8)	C11—C12	1.376 (9)
C2—C3	1.377 (9)	C11—H11	0.9300
C2—C8	1.463 (9)	C12—H12	0.9300
C3—C4	1.375 (10)	O1—C14i	1.420 (8)
C3—H3	0.9300	O1—C13	1.430 (9)
C4—C5	1.346 (10)	C13—C14	1.479 (11)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.387 (9)	C13—H13B	0.9700
C5—H5	0.9300	C14—O1i	1.420 (8)
C6—H6	0.9300	C14—H14A	0.9700
N7—C12	1.344 (8)	C14—H14B	0.9700
N7—C8	1.377 (8)
N7—Pd1—N1	80.5 (2)	C9—C8—C2	124.8 (6)
N7—Pd1—Cl1	94.55 (16)	N7—C8—C2	114.1 (5)
N1—Pd1—Cl1	174.96 (15)	C8—C9—C10	120.4 (7)
N7—Pd1—Cl2	175.00 (15)	C8—C9—H9	119.8
N1—Pd1—Cl2	94.89 (15)	C10—C9—H9	119.8
Cl1—Pd1—Cl2	90.09 (7)	C11—C10—C9	118.5 (7)
C6—N1—C2	119.6 (5)	C11—C10—H10	120.7
C6—N1—Pd1	125.8 (5)	C9—C10—H10	120.7
C2—N1—Pd1	114.6 (4)	C10—C11—C12	120.2 (7)
N1—C2—C3	120.6 (6)	C10—C11—H11	119.9
N1—C2—C8	115.7 (5)	C12—C11—H11	119.9
C3—C2—C8	123.7 (6)	N7—C12—C11	121.9 (6)
C4—C3—C2	119.4 (6)	N7—C12—H12	119.0
C4—C3—H3	120.3	C11—C12—H12	119.0
C2—C3—H3	120.3	C14i—O1—C13	109.1 (6)
C5—C4—C3	119.8 (7)	O1—C13—C14	111.5 (6)
C5—C4—H4	120.1	O1—C13—H13A	109.3
C3—C4—H4	120.1	C14—C13—H13A	109.3
C4—C5—C6	120.0 (6)	O1—C13—H13B	109.3
C4—C5—H5	120.0	C14—C13—H13B	109.3
C6—C5—H5	120.0	H13A—C13—H13B	108.0
N1—C6—C5	120.6 (6)	O1i—C14—C13	111.4 (6)
N1—C6—H6	119.7	O1i—C14—H14A	109.3
C5—C6—H6	119.7	C13—C14—H14A	109.3
C12—N7—C8	117.8 (5)	O1i—C14—H14B	109.3
C12—N7—Pd1	127.0 (5)	C13—C14—H14B	109.3
C8—N7—Pd1	115.1 (4)	H14A—C14—H14B	108.0
C9—C8—N7	121.1 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1	0.93	2.55	3.471 (9)	170
C5—H5···O1ii	0.93	2.57	3.464 (8)	163
C9—H9···O1	0.93	2.66	3.587 (8)	174
C6—H6···Cl2	0.93	2.65	3.239 (7)	122
C12—H12···Cl1	0.93	2.65	3.238 (7)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1	0.93	2.55	3.471 (9)	170
C5—H5⋯O1i	0.93	2.57	3.464 (8)	163
C9—H9⋯O1	0.93	2.66	3.587 (8)	174
C6—H6⋯Cl2	0.93	2.65	3.239 (7)	122
C12—H12⋯Cl1	0.93	2.65	3.238 (7)	122

Symmetry code: (i) .