Dichloridobis[4-(1H-pyrazol-3-yl)pyridine-κN]zinc.

In the title compound, [ZnCl(2)(C(8)H(7)N(3))(2)], the Zn(II) cation is coordinated by two Cl(-) anions and two 4-(1H-pyrazol-3-yl)pyridine ligands in a distorted tetra-hedral geometry. In the two 4-(1H-pyrazol-3-yl)pyridine ligands, the dihedral angles between the pyrazole and pyridine rings are 3.3 (3) and 13.3 (3)°. Inter-molecular N-H⋯N and N-H⋯Cl hydrogen bonding is present in the crystal structure.

Related literature

For the synthesis of 4-(1H-pyrazol-3-yl)-pyridine, see: Davies et al. (2003 ▶). For a related complex, see: Davies et al. (2005 ▶).

Experimental

Crystal data

[ZnCl2(C8H7N3)2]

M = 426.60

Monoclinic,

a = 12.306 (3) Å

b = 7.8827 (16) Å

c = 18.883 (4) Å

β = 94.82 (3)°

V = 1825.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.65 mm−1

T = 293 K

0.24 × 0.21 × 0.02 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.693, T max = 0.971

14854 measured reflections

3283 independent reflections

2052 reflections with I > 2σ(I)

R int = 0.122

Refinement

R[F 2 > 2σ(F 2)] = 0.080

wR(F 2) = 0.138

S = 1.11

3283 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.30 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037585/xu5325sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037585/xu5325Isup2.hkl

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

[ZnCl2(C8H7N3)2]	F(000) = 864
Mr = 426.60	Dx = 1.552 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13142 reflections
a = 12.306 (3) Å	θ = 3.1–27.7°
b = 7.8827 (16) Å	µ = 1.65 mm−1
c = 18.883 (4) Å	T = 293 K
β = 94.82 (3)°	Platelet, colourless
V = 1825.3 (6) Å3	0.24 × 0.21 × 0.02 mm
Z = 4

Rigaku SCXmini diffractometer	3283 independent reflections
Radiation source: fine-focus sealed tube	2052 reflections with I > 2σ(I)
graphite	Rint = 0.122
ω scans	θmax = 25.2°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
Tmin = 0.693, Tmax = 0.971	k = −9→9
14854 measured reflections	l = −22→22

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3
3283 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.30 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
Zn1	0.46511 (6)	0.48942 (8)	0.20777 (3)	0.0476 (3)
Cl1	0.31124 (13)	0.34083 (19)	0.21462 (8)	0.0543 (5)
Cl2	0.61580 (14)	0.3545 (2)	0.18253 (9)	0.0761 (6)
N3	0.3040 (4)	1.2186 (7)	0.0109 (3)	0.0555 (14)
C5	0.4365 (5)	0.6564 (7)	0.0659 (3)	0.0502 (16)
H5	0.4609	0.5527	0.0499	0.060*
N1	0.4321 (4)	0.6807 (6)	0.1363 (2)	0.0435 (12)
C3	0.3709 (4)	0.9364 (7)	0.0374 (3)	0.0421 (15)
C6	0.3357 (4)	1.0691 (8)	−0.0137 (3)	0.0454 (15)
C4	0.4062 (4)	0.7799 (7)	0.0171 (3)	0.0448 (16)
H4	0.4096	0.7571	−0.0310	0.054*
C2	0.3689 (5)	0.9619 (8)	0.1100 (3)	0.0578 (18)
H2	0.3472	1.0663	0.1269	0.069*
C8	0.2886 (6)	1.2202 (10)	−0.1081 (4)	0.072 (2)
H8	0.2739	1.2588	−0.1544	0.087*
N4	0.2750 (4)	1.3070 (7)	−0.0484 (3)	0.0653 (16)
H4A	0.2502	1.4090	−0.0482	0.078*
C1	0.3987 (5)	0.8344 (8)	0.1565 (3)	0.0545 (17)
H1	0.3957	0.8548	0.2048	0.065*
C7	0.3281 (5)	1.0644 (8)	−0.0878 (3)	0.0590 (18)
H7	0.3459	0.9751	−0.1169	0.071*
C14	0.5765 (5)	0.8133 (7)	0.5098 (3)	0.0460 (16)
N6	0.6657 (5)	0.9532 (7)	0.5901 (3)	0.0718 (18)
H6	0.7140	1.0182	0.6115	0.086*
N5	0.6636 (4)	0.9156 (7)	0.5209 (3)	0.0592 (15)
C16	0.5854 (7)	0.8797 (9)	0.6228 (4)	0.071 (2)
H16	0.5727	0.8896	0.6705	0.086*
C15	0.5263 (6)	0.7882 (8)	0.5724 (3)	0.0578 (18)
H15	0.4650	0.7224	0.5784	0.069*
N2	0.4966 (4)	0.6034 (6)	0.3038 (2)	0.0433 (12)
C12	0.4504 (5)	0.6635 (7)	0.4214 (3)	0.0456 (15)
H12	0.3991	0.6554	0.4547	0.055*
C11	0.5491 (5)	0.7416 (7)	0.4388 (3)	0.0414 (15)
C13	0.4283 (5)	0.5978 (7)	0.3545 (3)	0.0463 (15)
H13	0.3610	0.5459	0.3440	0.056*
C9	0.5921 (5)	0.6814 (8)	0.3215 (3)	0.0617 (19)
H9	0.6419	0.6886	0.2873	0.074*
C10	0.6208 (5)	0.7512 (8)	0.3870 (3)	0.0574 (18)
H10	0.6880	0.8043	0.3963	0.069*

	U11	U22	U33	U12	U13	U23
Zn1	0.0574 (5)	0.0463 (5)	0.0385 (4)	0.0042 (4)	0.0010 (3)	−0.0037 (4)
Cl1	0.0668 (11)	0.0519 (10)	0.0422 (9)	−0.0083 (8)	−0.0073 (8)	0.0009 (8)
Cl2	0.0715 (14)	0.0823 (13)	0.0752 (13)	0.0279 (10)	0.0113 (10)	−0.0140 (11)
N3	0.055 (4)	0.059 (4)	0.053 (3)	0.013 (3)	0.007 (3)	0.018 (3)
C5	0.060 (4)	0.041 (4)	0.050 (4)	0.009 (3)	0.008 (3)	−0.012 (3)
N1	0.046 (3)	0.043 (3)	0.042 (3)	0.003 (2)	0.008 (2)	0.000 (2)
C3	0.030 (4)	0.041 (4)	0.056 (4)	−0.005 (3)	0.010 (3)	0.003 (3)
C6	0.034 (4)	0.048 (4)	0.055 (4)	0.002 (3)	0.007 (3)	0.005 (3)
C4	0.054 (4)	0.051 (4)	0.029 (3)	0.001 (3)	−0.003 (3)	0.000 (3)
C2	0.070 (5)	0.047 (4)	0.058 (4)	0.014 (3)	0.018 (4)	0.004 (4)
C8	0.078 (6)	0.078 (6)	0.060 (5)	0.004 (4)	0.000 (4)	0.013 (5)
N4	0.070 (4)	0.057 (4)	0.070 (4)	0.016 (3)	0.007 (3)	0.019 (3)
C1	0.068 (5)	0.051 (4)	0.045 (4)	0.007 (4)	0.013 (3)	−0.005 (4)
C7	0.071 (5)	0.056 (5)	0.050 (4)	−0.006 (4)	0.006 (4)	−0.005 (4)
C14	0.049 (4)	0.042 (4)	0.044 (4)	0.014 (3)	−0.011 (3)	−0.004 (3)
N6	0.066 (4)	0.068 (4)	0.075 (5)	0.022 (3)	−0.032 (3)	−0.032 (4)
N5	0.058 (4)	0.061 (4)	0.056 (4)	−0.002 (3)	−0.011 (3)	−0.021 (3)
C16	0.106 (7)	0.066 (5)	0.042 (4)	0.030 (5)	0.005 (5)	−0.003 (4)
C15	0.082 (5)	0.046 (4)	0.044 (4)	0.003 (4)	−0.003 (4)	−0.005 (3)
N2	0.046 (3)	0.045 (3)	0.038 (3)	−0.004 (3)	−0.004 (2)	−0.005 (2)
C12	0.051 (4)	0.043 (4)	0.045 (4)	−0.001 (3)	0.012 (3)	−0.001 (3)
C11	0.033 (4)	0.038 (4)	0.051 (4)	0.002 (3)	−0.005 (3)	0.003 (3)
C13	0.039 (4)	0.048 (4)	0.051 (4)	−0.003 (3)	0.002 (3)	−0.007 (3)
C9	0.059 (5)	0.074 (5)	0.054 (4)	−0.011 (4)	0.015 (4)	−0.020 (4)
C10	0.042 (4)	0.068 (5)	0.061 (5)	−0.014 (3)	−0.001 (4)	−0.016 (4)

Zn1—N1	2.041 (4)	C1—H1	0.9300
Zn1—N2	2.032 (4)	C7—H7	0.9300
Zn1—Cl1	2.2395 (17)	C14—N5	1.344 (7)
Zn1—Cl2	2.2241 (18)	C14—C15	1.394 (8)
N3—C6	1.337 (7)	C14—C11	1.468 (7)
N3—N4	1.342 (6)	N6—N5	1.337 (6)
C5—N1	1.349 (6)	N6—C16	1.341 (8)
C5—C4	1.370 (7)	N6—H6	0.8600
C5—H5	0.9300	C16—C15	1.357 (8)
N1—C1	1.345 (7)	C16—H16	0.9300
C3—C4	1.374 (7)	C15—H15	0.9300
C3—C2	1.387 (8)	N2—C13	1.326 (6)
C3—C6	1.464 (7)	N2—C9	1.344 (7)
C6—C7	1.395 (8)	C12—C13	1.371 (7)
C4—H4	0.9300	C12—C11	1.376 (7)
C2—C1	1.366 (7)	C12—H12	0.9300
C2—H2	0.9300	C11—C10	1.372 (8)
C8—N4	1.341 (8)	C13—H13	0.9300
C8—C7	1.363 (8)	C9—C10	1.372 (8)
C8—H8	0.9300	C9—H9	0.9300
N4—H4A	0.8600	C10—H10	0.9300
N2—Zn1—N1	106.01 (19)	C8—C7—C6	104.5 (6)
N2—Zn1—Cl2	107.64 (15)	C8—C7—H7	127.8
N1—Zn1—Cl2	109.55 (14)	C6—C7—H7	127.8
N2—Zn1—Cl1	106.16 (15)	N5—C14—C15	110.9 (6)
N1—Zn1—Cl1	107.60 (13)	N5—C14—C11	119.6 (6)
Cl2—Zn1—Cl1	119.11 (7)	C15—C14—C11	129.5 (6)
C6—N3—N4	103.4 (5)	N5—N6—C16	113.6 (6)
N1—C5—C4	122.1 (5)	N5—N6—H6	123.2
N1—C5—H5	119.0	C16—N6—H6	123.2
C4—C5—H5	119.0	N6—N5—C14	103.6 (5)
C1—N1—C5	116.5 (5)	N6—C16—C15	106.2 (6)
C1—N1—Zn1	121.7 (4)	N6—C16—H16	126.9
C5—N1—Zn1	121.7 (4)	C15—C16—H16	126.9
C4—C3—C2	116.0 (5)	C16—C15—C14	105.7 (6)
C4—C3—C6	122.7 (6)	C16—C15—H15	127.2
C2—C3—C6	121.2 (6)	C14—C15—H15	127.2
N3—C6—C7	112.0 (5)	C13—N2—C9	115.4 (5)
N3—C6—C3	118.7 (6)	C13—N2—Zn1	123.0 (4)
C7—C6—C3	129.3 (6)	C9—N2—Zn1	121.5 (4)
C5—C4—C3	121.6 (5)	C13—C12—C11	119.4 (6)
C5—C4—H4	119.2	C13—C12—H12	120.3
C3—C4—H4	119.2	C11—C12—H12	120.3
C1—C2—C3	120.2 (6)	C10—C11—C12	117.6 (6)
C1—C2—H2	119.9	C10—C11—C14	121.1 (6)
C3—C2—H2	119.9	C12—C11—C14	121.4 (6)
N4—C8—C7	106.9 (6)	N2—C13—C12	124.3 (6)
N4—C8—H8	126.5	N2—C13—H13	117.8
C7—C8—H8	126.5	C12—C13—H13	117.8
C8—N4—N3	113.2 (5)	N2—C9—C10	124.2 (6)
C8—N4—H4A	123.4	N2—C9—H9	117.9
N3—N4—H4A	123.4	C10—C9—H9	117.9
N1—C1—C2	123.5 (6)	C9—C10—C11	119.1 (6)
N1—C1—H1	118.2	C9—C10—H10	120.4
C2—C1—H1	118.2	C11—C10—H10	120.4

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N5i	0.86	2.23	2.945 (8)	140.
N6—H6···Cl1ii	0.86	2.46	3.266 (5)	156.

Table 1

Selected bond lengths (Å)

Zn1—N1	2.041 (4)
Zn1—N2	2.032 (4)
Zn1—Cl1	2.2395 (17)
Zn1—Cl2	2.2241 (18)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N5i	0.86	2.23	2.945 (8)	140
N6—H6⋯Cl1ii	0.86	2.46	3.266 (5)	156

Symmetry codes: (i) ; (ii) .