Dichlorido(2,3-di-2-pyridyl-pyrazine-κN,N)palladium(II).

The Pd(II) ion in the title complex, [PdCl(2)(C(14)H(10)N(4))], is four-coordinated in a distorted square-planar environment defined by two N atoms of a chelating 2,3-di-2-pyridyl-pyrazine (dpp) ligand and two chloride anions. The pyridine ring coordinated to the Pd atom is inclined slightly to its carrier pyrazine ring [dihedral angle = 14.4 (3)°], whereas the uncoordinated pyridine ring is inclined considerably to the pyrazine ring [dihedral angle = 52.2 (2)°]. The dihedral angle between the two pyridine rings is 58.8 (2)°. In the crystal, complex mol-ecules are connected by inter-molecular C-H⋯Cl and C-H⋯N hydrogen bonds, forming a three-dimensional network. Intra-molecular C-H⋯Cl hydrogen bonds are also present.

Related literature

For related crystal structures of [PtX 2(dpp)] (X = Br, Cl), see: Ha (2011a ▶,b ▶).

Experimental

Crystal data

[PdCl2(C14H10N4)]

M = 411.56

Triclinic,

a = 8.1681 (10) Å

b = 9.5480 (11) Å

c = 10.1137 (12) Å

α = 84.543 (2)°

β = 71.400 (2)°

γ = 71.475 (2)°

V = 708.81 (15) Å3

Z = 2

Mo Kα radiation

μ = 1.68 mm−1

T = 200 K

0.26 × 0.16 × 0.12 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.748, T max = 1.000

5225 measured reflections

3406 independent reflections

2608 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.115

S = 1.24

3406 reflections

190 parameters

H-atom parameters constrained

Δρmax = 1.18 e Å−3

Δρmin = −2.09 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 datablock(s) global, I. DOI: 10.1107/S1600536811044369/tk5006sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044369/tk5006Isup2.hkl

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

[PdCl2(C14H10N4)]	Z = 2
Mr = 411.56	F(000) = 404
Triclinic, P1	Dx = 1.928 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1681 (10) Å	Cell parameters from 2636 reflections
b = 9.5480 (11) Å	θ = 2.8–28.2°
c = 10.1137 (12) Å	µ = 1.68 mm−1
α = 84.543 (2)°	T = 200 K
β = 71.400 (2)°	Block, orange
γ = 71.475 (2)°	0.26 × 0.16 × 0.12 mm
V = 708.81 (15) Å3

Bruker SMART 1000 CCD diffractometer	3406 independent reflections
Radiation source: fine-focus sealed tube	2608 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.748, Tmax = 1.000	k = −12→11
5225 measured reflections	l = −12→13

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H-atom parameters constrained
S = 1.24	w = 1/[σ2(Fo2) + (0.P)2 + 3.5422P] where P = (Fo2 + 2Fc2)/3
3406 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 1.18 e Å−3
0 restraints	Δρmin = −2.09 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	0.71773 (7)	0.48277 (5)	−0.10860 (5)	0.02952 (14)
Cl1	0.6858 (3)	0.43540 (19)	−0.31486 (17)	0.0416 (4)
Cl2	0.6748 (2)	0.72437 (18)	−0.17098 (19)	0.0416 (4)
N1	0.7538 (6)	0.2716 (5)	−0.0374 (5)	0.0241 (10)
N2	0.7697 (8)	0.0024 (6)	0.0868 (6)	0.0384 (13)
N3	0.7611 (6)	0.5057 (5)	0.0743 (5)	0.0249 (10)
N4	0.8648 (8)	−0.0406 (6)	0.3339 (6)	0.0398 (14)
C1	0.7696 (8)	0.2515 (7)	0.0931 (6)	0.0305 (14)
C2	0.7656 (9)	0.1158 (7)	0.1572 (7)	0.0313 (14)
C3	0.7645 (11)	0.0272 (8)	−0.0442 (7)	0.0450 (18)
H3	0.7708	−0.0524	−0.0972	0.054*
C4	0.7504 (9)	0.1629 (7)	−0.1050 (7)	0.0349 (15)
H4	0.7381	0.1782	−0.1960	0.042*
C5	0.7923 (7)	0.3781 (6)	0.1508 (6)	0.0228 (12)
C6	0.8494 (9)	0.3771 (7)	0.2643 (7)	0.0362 (15)
H6	0.8776	0.2883	0.3149	0.043*
C7	0.8667 (9)	0.5053 (8)	0.3064 (7)	0.0368 (15)
H7	0.9028	0.5056	0.3868	0.044*
C8	0.8305 (9)	0.6301 (8)	0.2296 (7)	0.0381 (16)
H8	0.8414	0.7189	0.2558	0.046*
C9	0.7787 (8)	0.6264 (6)	0.1150 (7)	0.0288 (13)
H9	0.7541	0.7140	0.0621	0.035*
C10	0.7479 (8)	0.0837 (7)	0.3079 (6)	0.0290 (13)
C11	0.6105 (9)	0.1744 (7)	0.4115 (7)	0.0362 (15)
H11	0.5300	0.2628	0.3891	0.043*
C12	0.5941 (10)	0.1325 (8)	0.5488 (7)	0.0434 (17)
H12	0.5014	0.1921	0.6228	0.052*
C13	0.7126 (11)	0.0043 (8)	0.5770 (7)	0.0461 (19)
H13	0.7026	−0.0273	0.6704	0.055*
C14	0.8465 (11)	−0.0774 (8)	0.4673 (8)	0.049 (2)
H14	0.9305	−0.1649	0.4874	0.059*

	U11	U22	U33	U12	U13	U23
Pd1	0.0345 (3)	0.0262 (3)	0.0292 (3)	−0.0109 (2)	−0.0108 (2)	0.00380 (18)
Cl1	0.0574 (11)	0.0411 (9)	0.0321 (9)	−0.0175 (8)	−0.0211 (8)	0.0073 (7)
Cl2	0.0506 (10)	0.0293 (8)	0.0514 (11)	−0.0165 (7)	−0.0235 (9)	0.0126 (7)
N1	0.024 (2)	0.022 (2)	0.024 (3)	−0.008 (2)	−0.006 (2)	0.0076 (19)
N2	0.057 (4)	0.025 (3)	0.036 (3)	−0.013 (3)	−0.019 (3)	0.005 (2)
N3	0.027 (3)	0.022 (2)	0.030 (3)	−0.010 (2)	−0.014 (2)	0.009 (2)
N4	0.055 (4)	0.030 (3)	0.036 (3)	−0.006 (3)	−0.022 (3)	0.001 (2)
C1	0.032 (3)	0.036 (4)	0.022 (3)	−0.008 (3)	−0.009 (3)	0.000 (3)
C2	0.037 (3)	0.024 (3)	0.030 (3)	−0.007 (3)	−0.008 (3)	−0.004 (2)
C3	0.076 (5)	0.032 (4)	0.036 (4)	−0.020 (4)	−0.024 (4)	−0.006 (3)
C4	0.059 (4)	0.024 (3)	0.028 (3)	−0.016 (3)	−0.016 (3)	−0.006 (2)
C5	0.023 (3)	0.023 (3)	0.022 (3)	−0.005 (2)	−0.007 (2)	−0.004 (2)
C6	0.040 (4)	0.032 (3)	0.039 (4)	−0.010 (3)	−0.017 (3)	0.001 (3)
C7	0.034 (3)	0.053 (4)	0.028 (3)	−0.019 (3)	−0.011 (3)	0.000 (3)
C8	0.042 (4)	0.040 (4)	0.032 (4)	−0.018 (3)	−0.004 (3)	−0.007 (3)
C9	0.030 (3)	0.020 (3)	0.037 (4)	−0.009 (2)	−0.008 (3)	−0.002 (2)
C10	0.037 (3)	0.026 (3)	0.029 (3)	−0.013 (3)	−0.013 (3)	0.001 (2)
C11	0.046 (4)	0.032 (4)	0.033 (4)	−0.014 (3)	−0.013 (3)	−0.002 (3)
C12	0.058 (5)	0.050 (4)	0.027 (4)	−0.027 (4)	−0.008 (3)	0.000 (3)
C13	0.081 (6)	0.044 (4)	0.029 (4)	−0.035 (4)	−0.024 (4)	0.009 (3)
C14	0.075 (6)	0.040 (4)	0.055 (5)	−0.025 (4)	−0.046 (5)	0.015 (4)

Pd1—N3	2.035 (5)	C4—H4	0.9500
Pd1—N1	2.038 (5)	C5—C6	1.368 (8)
Pd1—Cl2	2.2787 (17)	C6—C7	1.395 (9)
Pd1—Cl1	2.2860 (17)	C6—H6	0.9500
N1—C4	1.308 (7)	C7—C8	1.363 (9)
N1—C1	1.357 (7)	C7—H7	0.9500
N2—C3	1.336 (8)	C8—C9	1.362 (9)
N2—C2	1.338 (8)	C8—H8	0.9500
N3—C9	1.323 (7)	C9—H9	0.9500
N3—C5	1.377 (7)	C10—C11	1.383 (9)
N4—C10	1.331 (8)	C11—C12	1.385 (9)
N4—C14	1.334 (9)	C11—H11	0.9500
C1—C2	1.398 (8)	C12—C13	1.368 (10)
C1—C5	1.477 (8)	C12—H12	0.9500
C2—C10	1.495 (8)	C13—C14	1.373 (11)
C3—C4	1.367 (9)	C13—H13	0.9500
C3—H3	0.9500	C14—H14	0.9500
N3—Pd1—N1	80.24 (19)	N3—C5—C1	114.2 (5)
N3—Pd1—Cl2	95.40 (14)	C5—C6—C7	120.6 (6)
N1—Pd1—Cl2	175.50 (15)	C5—C6—H6	119.7
N3—Pd1—Cl1	174.80 (14)	C7—C6—H6	119.7
N1—Pd1—Cl1	95.27 (14)	C8—C7—C6	118.5 (6)
Cl2—Pd1—Cl1	89.14 (6)	C8—C7—H7	120.8
C4—N1—C1	120.7 (5)	C6—C7—H7	120.8
C4—N1—Pd1	124.3 (4)	C9—C8—C7	119.4 (6)
C1—N1—Pd1	114.8 (4)	C9—C8—H8	120.3
C3—N2—C2	117.3 (6)	C7—C8—H8	120.3
C9—N3—C5	119.8 (5)	N3—C9—C8	122.6 (6)
C9—N3—Pd1	125.0 (4)	N3—C9—H9	118.7
C5—N3—Pd1	114.8 (4)	C8—C9—H9	118.7
C10—N4—C14	117.3 (6)	N4—C10—C11	123.3 (6)
N1—C1—C2	117.9 (6)	N4—C10—C2	115.6 (5)
N1—C1—C5	114.9 (5)	C11—C10—C2	121.0 (6)
C2—C1—C5	127.2 (5)	C10—C11—C12	117.9 (7)
N2—C2—C1	121.4 (6)	C10—C11—H11	121.0
N2—C2—C10	113.5 (5)	C12—C11—H11	121.0
C1—C2—C10	125.1 (5)	C13—C12—C11	119.4 (7)
N2—C3—C4	122.5 (6)	C13—C12—H12	120.3
N2—C3—H3	118.8	C11—C12—H12	120.3
C4—C3—H3	118.8	C12—C13—C14	118.5 (7)
N1—C4—C3	119.8 (6)	C12—C13—H13	120.7
N1—C4—H4	120.1	C14—C13—H13	120.7
C3—C4—H4	120.1	N4—C14—C13	123.5 (7)
C6—C5—N3	118.9 (5)	N4—C14—H14	118.2
C6—C5—C1	126.8 (6)	C13—C14—H14	118.2
N3—Pd1—N1—C4	−178.6 (5)	Pd1—N3—C5—C1	−6.1 (6)
Cl1—Pd1—N1—C4	−1.2 (5)	N1—C1—C5—C6	−164.9 (6)
N3—Pd1—N1—C1	6.0 (4)	C2—C1—C5—C6	14.1 (10)
Cl1—Pd1—N1—C1	−176.7 (4)	N1—C1—C5—N3	11.2 (7)
N1—Pd1—N3—C9	173.4 (5)	C2—C1—C5—N3	−169.8 (6)
Cl2—Pd1—N3—C9	−7.8 (5)	N3—C5—C6—C7	3.4 (9)
N1—Pd1—N3—C5	0.3 (4)	C1—C5—C6—C7	179.2 (6)
Cl2—Pd1—N3—C5	179.2 (4)	C5—C6—C7—C8	−1.9 (10)
C4—N1—C1—C2	−5.6 (9)	C6—C7—C8—C9	0.1 (10)
Pd1—N1—C1—C2	170.0 (4)	C5—N3—C9—C8	1.3 (9)
C4—N1—C1—C5	173.5 (5)	Pd1—N3—C9—C8	−171.3 (5)
Pd1—N1—C1—C5	−10.9 (6)	C7—C8—C9—N3	0.1 (10)
C3—N2—C2—C1	−4.7 (10)	C14—N4—C10—C11	−0.1 (10)
C3—N2—C2—C10	172.6 (6)	C14—N4—C10—C2	−176.2 (6)
N1—C1—C2—N2	8.5 (9)	N2—C2—C10—N4	50.6 (8)
C5—C1—C2—N2	−170.5 (6)	C1—C2—C10—N4	−132.3 (7)
N1—C1—C2—C10	−168.5 (6)	N2—C2—C10—C11	−125.6 (7)
C5—C1—C2—C10	12.5 (10)	C1—C2—C10—C11	51.5 (9)
C2—N2—C3—C4	−1.8 (11)	N4—C10—C11—C12	−0.5 (10)
C1—N1—C4—C3	−0.6 (10)	C2—C10—C11—C12	175.4 (6)
Pd1—N1—C4—C3	−175.8 (5)	C10—C11—C12—C13	0.0 (10)
N2—C3—C4—N1	4.6 (12)	C11—C12—C13—C14	1.0 (11)
C9—N3—C5—C6	−3.1 (8)	C10—N4—C14—C13	1.2 (11)
Pd1—N3—C5—C6	170.3 (4)	C12—C13—C14—N4	−1.7 (11)
C9—N3—C5—C1	−179.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl2i	0.95	2.73	3.632 (7)	159
C4—H4···Cl1	0.95	2.60	3.216 (7)	123
C8—H8···N4ii	0.95	2.58	3.529 (9)	178
C9—H9···Cl2	0.95	2.62	3.241 (7)	123
C13—H13···Cl2iii	0.95	2.76	3.530 (7)	139

Pd1—N3	2.035 (5)
Pd1—N1	2.038 (5)
Pd1—Cl2	2.2787 (17)
Pd1—Cl1	2.2860 (17)

N3—Pd1—N1	80.24 (19)
Cl2—Pd1—Cl1	89.14 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl2i	0.95	2.73	3.632 (7)	159
C4—H4⋯Cl1	0.95	2.60	3.216 (7)	123
C8—H8⋯N4ii	0.95	2.58	3.529 (9)	178
C9—H9⋯Cl2	0.95	2.62	3.241 (7)	123
C13—H13⋯Cl2iii	0.95	2.76	3.530 (7)	139

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