Dichloridobis[2-(1-hydrazinylideneeth-yl)pyrazine-κN(1)]zinc.

In the structure of the title complex, [ZnCl(2)(C(6)H(8)N(4))(2)], the Zn(II) atom has a distorted octa-hedral geometry. Two cis Cl(-) ions and four N atoms belonging to two different 2-(1-hydrazinylideneeth-yl)pyrazine ligands coordinate the Zn(II) atom, forming two five-membered Zn-N-C-C-N rings. The dihedral angle between the planes of these metallocycles is 88.13 (4)°. The organic ligands are essentially planar (r.m.s. deviations from planarity = 0.072 and 0.040 Å). Inter-molecular N-H⋯N and N-H⋯Cl inter-actions join the mol-ecules into a three-dimensional framework.

Related literature

For the biochemical applications of complexes based on ligands containing pyrazine, see: Ha et al. (1999 ▶); Blackstock et al. (2000 ▶); Adams et al. (2002 ▶); Lee et al. (2012 ▶). For the preparation of the ligand, see: Stadler et al. (2010 ▶).

Experimental

Crystal data

[ZnCl2(C6H8N4)2]

M = 408.60

Monoclinic,

a = 8.4289 (8) Å

b = 15.1128 (14) Å

c = 13.4196 (13) Å

β = 104.077 (1)°

V = 1658.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.81 mm−1

T = 296 K

0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.713, T max = 0.773

11576 measured reflections

4132 independent reflections

3456 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.078

S = 1.03

4132 reflections

223 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; 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 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812016418/pk2404sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016418/pk2404Isup2.hkl

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

[ZnCl2(C6H8N4)2]	F(000) = 832
Mr = 408.60	Dx = 1.637 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4411 reflections
a = 8.4289 (8) Å	θ = 2.7–28.2°
b = 15.1128 (14) Å	µ = 1.81 mm−1
c = 13.4196 (13) Å	T = 296 K
β = 104.077 (1)°	Block, colourless
V = 1658.1 (3) Å3	0.20 × 0.18 × 0.15 mm
Z = 4

Bruker APEXII CCD diffractometer	4132 independent reflections
Radiation source: fine-focus sealed tube	3456 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→11
Tmin = 0.713, Tmax = 0.773	k = −18→20
11576 measured reflections	l = −9→17

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.042P)2 + 0.3057P] where P = (Fo2 + 2Fc2)/3
4132 reflections	(Δ/σ)max = 0.009
223 parameters	Δρmax = 0.42 e Å−3
4 restraints	Δρmin = −0.21 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	0.79801 (2)	0.074400 (13)	0.764996 (15)	0.03098 (8)
Cl1	0.74457 (6)	0.17192 (3)	0.89354 (4)	0.04074 (12)
Cl2	0.61902 (6)	−0.03984 (4)	0.78802 (4)	0.04526 (13)
N1	1.2922 (2)	0.25410 (13)	0.75292 (16)	0.0535 (5)
N2	1.00732 (17)	0.16076 (10)	0.75046 (11)	0.0322 (3)
N3	1.01610 (18)	0.01092 (10)	0.85368 (11)	0.0331 (3)
N4	1.0037 (3)	−0.06823 (12)	0.89868 (16)	0.0478 (5)
H1N4	1.076 (3)	−0.0850 (16)	0.9461 (18)	0.057*
H2N4	0.909 (3)	−0.0860 (17)	0.892 (2)	0.057*
N5	0.8091 (3)	−0.09261 (13)	0.44379 (15)	0.0533 (5)
N6	0.82991 (18)	−0.00119 (10)	0.62587 (11)	0.0327 (3)
N7	0.65102 (18)	0.14165 (10)	0.63190 (12)	0.0330 (3)
N8	0.5788 (2)	0.22084 (12)	0.64252 (16)	0.0473 (4)
H1N8	0.493 (3)	0.2340 (17)	0.5969 (17)	0.057*
H2N8	0.568 (3)	0.2228 (17)	0.7042 (15)	0.057*
C1	1.1478 (3)	0.28105 (15)	0.69904 (19)	0.0508 (5)
H1	1.1414	0.3328	0.6607	0.061*
C2	1.0057 (2)	0.23502 (12)	0.69773 (16)	0.0405 (4)
H2	0.9065	0.2567	0.6589	0.049*
C3	1.1533 (2)	0.13197 (12)	0.80650 (14)	0.0329 (4)
C4	1.2941 (2)	0.18004 (14)	0.80619 (18)	0.0459 (5)
H4	1.3939	0.1593	0.8451	0.055*
C5	1.1551 (2)	0.05001 (13)	0.86525 (14)	0.0333 (4)
C6	1.3119 (2)	0.01689 (16)	0.93253 (16)	0.0478 (5)
H6A	1.2922	−0.0376	0.9643	0.072*
H6B	1.3546	0.0600	0.9847	0.072*
H6C	1.3894	0.0070	0.8919	0.072*
C7	0.9003 (3)	−0.12098 (14)	0.53299 (17)	0.0476 (5)
H7	0.9594	−0.1731	0.5344	0.057*
C8	0.9103 (3)	−0.07594 (12)	0.62350 (17)	0.0405 (4)
H8	0.9752	−0.0986	0.6843	0.049*
C9	0.7363 (2)	0.02954 (12)	0.53650 (14)	0.0321 (4)
C10	0.7270 (3)	−0.01761 (14)	0.44637 (15)	0.0433 (5)
H10	0.6608	0.0040	0.3854	0.052*
C11	0.6464 (2)	0.11247 (12)	0.54143 (14)	0.0332 (4)
C12	0.5611 (3)	0.15970 (16)	0.44551 (17)	0.0542 (6)
H12A	0.4486	0.1689	0.4459	0.081*
H12B	0.5671	0.1247	0.3868	0.081*
H12C	0.6128	0.2159	0.4422	0.081*

	U11	U22	U33	U12	U13	U23
Zn1	0.02815 (12)	0.03323 (12)	0.02997 (12)	−0.00097 (8)	0.00402 (8)	0.00062 (8)
Cl1	0.0421 (2)	0.0393 (3)	0.0413 (3)	0.00117 (19)	0.01106 (19)	−0.00545 (19)
Cl2	0.0444 (3)	0.0473 (3)	0.0443 (3)	−0.0159 (2)	0.0113 (2)	−0.0026 (2)
N1	0.0427 (10)	0.0487 (11)	0.0738 (14)	−0.0098 (8)	0.0232 (10)	−0.0013 (9)
N2	0.0295 (7)	0.0318 (7)	0.0353 (8)	−0.0001 (6)	0.0078 (6)	−0.0032 (6)
N3	0.0339 (8)	0.0326 (8)	0.0309 (8)	0.0006 (6)	0.0044 (6)	0.0015 (6)
N4	0.0466 (11)	0.0423 (10)	0.0485 (11)	−0.0012 (8)	−0.0003 (9)	0.0142 (8)
N5	0.0660 (13)	0.0522 (11)	0.0441 (11)	0.0055 (9)	0.0181 (9)	−0.0093 (8)
N6	0.0328 (8)	0.0319 (8)	0.0326 (8)	0.0006 (6)	0.0064 (6)	0.0008 (6)
N7	0.0286 (7)	0.0313 (7)	0.0390 (9)	0.0020 (6)	0.0081 (6)	0.0001 (6)
N8	0.0458 (10)	0.0413 (10)	0.0545 (11)	0.0136 (8)	0.0115 (9)	0.0010 (8)
C1	0.0531 (13)	0.0376 (11)	0.0671 (15)	−0.0016 (9)	0.0250 (11)	0.0061 (10)
C2	0.0400 (10)	0.0351 (10)	0.0466 (11)	0.0033 (8)	0.0110 (8)	0.0030 (8)
C3	0.0275 (8)	0.0381 (10)	0.0334 (9)	−0.0009 (7)	0.0084 (7)	−0.0060 (7)
C4	0.0317 (10)	0.0515 (12)	0.0557 (13)	−0.0047 (9)	0.0130 (9)	−0.0018 (10)
C5	0.0290 (9)	0.0412 (10)	0.0284 (9)	0.0034 (7)	0.0047 (7)	−0.0043 (7)
C6	0.0331 (10)	0.0616 (14)	0.0448 (12)	0.0089 (9)	0.0018 (9)	0.0065 (10)
C7	0.0530 (13)	0.0399 (11)	0.0527 (13)	0.0083 (9)	0.0185 (10)	−0.0033 (9)
C8	0.0412 (11)	0.0369 (10)	0.0432 (11)	0.0056 (8)	0.0098 (9)	0.0018 (8)
C9	0.0300 (8)	0.0349 (9)	0.0319 (9)	−0.0030 (7)	0.0083 (7)	0.0019 (7)
C10	0.0498 (12)	0.0462 (11)	0.0330 (10)	0.0011 (9)	0.0079 (9)	−0.0016 (8)
C11	0.0293 (9)	0.0340 (9)	0.0343 (9)	−0.0004 (7)	0.0042 (7)	0.0054 (7)
C12	0.0656 (15)	0.0501 (13)	0.0408 (12)	0.0119 (11)	0.0011 (10)	0.0117 (9)

Zn1—N3	2.1568 (15)	N8—H2N8	0.857 (18)
Zn1—N7	2.1637 (15)	C1—C2	1.382 (3)
Zn1—N2	2.2408 (15)	C1—H1	0.9300
Zn1—N6	2.2600 (15)	C2—H2	0.9300
Zn1—Cl2	2.3620 (5)	C3—C4	1.392 (3)
Zn1—Cl1	2.3934 (5)	C3—C5	1.466 (3)
N1—C1	1.320 (3)	C4—H4	0.9300
N1—C4	1.326 (3)	C5—C6	1.493 (3)
N2—C2	1.325 (2)	C6—H6A	0.9600
N2—C3	1.349 (2)	C6—H6B	0.9600
N3—C5	1.288 (2)	C6—H6C	0.9600
N3—N4	1.355 (2)	C7—C8	1.377 (3)
N4—H1N4	0.806 (19)	C7—H7	0.9300
N4—H2N4	0.827 (19)	C8—H8	0.9300
N5—C7	1.326 (3)	C9—C10	1.389 (3)
N5—C10	1.333 (3)	C9—C11	1.474 (3)
N6—C8	1.322 (2)	C10—H10	0.9300
N6—C9	1.348 (2)	C11—C12	1.494 (3)
N7—C11	1.283 (2)	C12—H12A	0.9600
N7—N8	1.366 (2)	C12—H12B	0.9600
N8—H1N8	0.850 (19)	C12—H12C	0.9600
N3—Zn1—N7	154.76 (6)	N2—C2—H2	119.2
N3—Zn1—N2	73.96 (6)	C1—C2—H2	119.2
N7—Zn1—N2	87.67 (5)	N2—C3—C4	119.51 (18)
N3—Zn1—N6	88.53 (6)	N2—C3—C5	117.46 (16)
N7—Zn1—N6	73.43 (6)	C4—C3—C5	123.03 (17)
N2—Zn1—N6	88.17 (5)	N1—C4—C3	122.96 (19)
N3—Zn1—Cl2	95.08 (4)	N1—C4—H4	118.5
N7—Zn1—Cl2	101.28 (4)	C3—C4—H4	118.5
N2—Zn1—Cl2	168.11 (4)	N3—C5—C3	115.63 (15)
N6—Zn1—Cl2	86.94 (4)	N3—C5—C6	124.36 (18)
N3—Zn1—Cl1	99.25 (4)	C3—C5—C6	120.01 (17)
N7—Zn1—Cl1	97.78 (4)	C5—C6—H6A	109.5
N2—Zn1—Cl1	89.67 (4)	C5—C6—H6B	109.5
N6—Zn1—Cl1	171.02 (4)	H6A—C6—H6B	109.5
Cl2—Zn1—Cl1	96.76 (2)	C5—C6—H6C	109.5
C1—N1—C4	116.34 (18)	H6A—C6—H6C	109.5
C2—N2—C3	117.43 (16)	H6B—C6—H6C	109.5
C2—N2—Zn1	129.32 (13)	N5—C7—C8	122.3 (2)
C3—N2—Zn1	113.23 (12)	N5—C7—H7	118.9
C5—N3—N4	121.17 (16)	C8—C7—H7	118.9
C5—N3—Zn1	119.41 (12)	N6—C8—C7	121.45 (19)
N4—N3—Zn1	119.40 (13)	N6—C8—H8	119.3
N3—N4—H1N4	120.3 (19)	C7—C8—H8	119.3
N3—N4—H2N4	114.6 (18)	N6—C9—C10	119.67 (18)
H1N4—N4—H2N4	120 (3)	N6—C9—C11	116.67 (16)
C7—N5—C10	116.23 (18)	C10—C9—C11	123.65 (17)
C8—N6—C9	117.76 (17)	N5—C10—C9	122.61 (19)
C8—N6—Zn1	128.07 (13)	N5—C10—H10	118.7
C9—N6—Zn1	113.55 (12)	C9—C10—H10	118.7
C11—N7—N8	119.22 (16)	N7—C11—C9	115.91 (15)
C11—N7—Zn1	119.93 (12)	N7—C11—C12	123.24 (18)
N8—N7—Zn1	120.38 (13)	C9—C11—C12	120.81 (18)
N7—N8—H1N8	117.0 (17)	C11—C12—H12A	109.5
N7—N8—H2N8	106.8 (17)	C11—C12—H12B	109.5
H1N8—N8—H2N8	114 (2)	H12A—C12—H12B	109.5
N1—C1—C2	122.2 (2)	C11—C12—H12C	109.5
N1—C1—H1	118.9	H12A—C12—H12C	109.5
C2—C1—H1	118.9	H12B—C12—H12C	109.5
N2—C2—C1	121.55 (19)
N3—Zn1—N2—C2	178.63 (17)	C4—N1—C1—C2	0.0 (3)
N7—Zn1—N2—C2	16.15 (17)	C3—N2—C2—C1	0.6 (3)
N6—Zn1—N2—C2	89.63 (17)	Zn1—N2—C2—C1	178.73 (15)
Cl2—Zn1—N2—C2	155.39 (16)	N1—C1—C2—N2	−0.3 (3)
Cl1—Zn1—N2—C2	−81.65 (16)	C2—N2—C3—C4	−0.5 (3)
N3—Zn1—N2—C3	−3.15 (12)	Zn1—N2—C3—C4	−178.93 (14)
N7—Zn1—N2—C3	−165.63 (13)	C2—N2—C3—C5	179.72 (16)
N6—Zn1—N2—C3	−92.15 (13)	Zn1—N2—C3—C5	1.3 (2)
Cl2—Zn1—N2—C3	−26.4 (3)	C1—N1—C4—C3	0.1 (3)
Cl1—Zn1—N2—C3	96.57 (12)	N2—C3—C4—N1	0.1 (3)
N7—Zn1—N3—C5	50.1 (2)	C5—C3—C4—N1	179.9 (2)
N2—Zn1—N3—C5	5.20 (13)	N4—N3—C5—C3	175.73 (17)
N6—Zn1—N3—C5	93.72 (14)	Zn1—N3—C5—C3	−6.2 (2)
Cl2—Zn1—N3—C5	−179.49 (13)	N4—N3—C5—C6	−4.0 (3)
Cl1—Zn1—N3—C5	−81.77 (14)	Zn1—N3—C5—C6	174.13 (15)
N7—Zn1—N3—N4	−131.82 (16)	N2—C3—C5—N3	3.1 (3)
N2—Zn1—N3—N4	−176.68 (16)	C4—C3—C5—N3	−176.72 (18)
N6—Zn1—N3—N4	−88.16 (15)	N2—C3—C5—C6	−177.23 (17)
Cl2—Zn1—N3—N4	−1.36 (15)	C4—C3—C5—C6	3.0 (3)
Cl1—Zn1—N3—N4	96.35 (15)	C10—N5—C7—C8	0.0 (3)
N3—Zn1—N6—C8	23.01 (17)	C9—N6—C8—C7	0.4 (3)
N7—Zn1—N6—C8	−174.88 (17)	Zn1—N6—C8—C7	170.70 (15)
N2—Zn1—N6—C8	97.01 (17)	N5—C7—C8—N6	−0.5 (3)
Cl2—Zn1—N6—C8	−72.15 (16)	C8—N6—C9—C10	0.3 (3)
N3—Zn1—N6—C9	−166.32 (13)	Zn1—N6—C9—C10	−171.45 (14)
N7—Zn1—N6—C9	−4.21 (12)	C8—N6—C9—C11	179.32 (17)
N2—Zn1—N6—C9	−92.33 (13)	Zn1—N6—C9—C11	7.6 (2)
Cl2—Zn1—N6—C9	98.51 (12)	C7—N5—C10—C9	0.7 (3)
N3—Zn1—N7—C11	46.0 (2)	N6—C9—C10—N5	−0.8 (3)
N2—Zn1—N7—C11	88.76 (14)	C11—C9—C10—N5	−179.8 (2)
N6—Zn1—N7—C11	−0.03 (14)	N8—N7—C11—C9	176.15 (16)
Cl2—Zn1—N7—C11	−83.36 (14)	Zn1—N7—C11—C9	4.0 (2)
Cl1—Zn1—N7—C11	178.11 (14)	N8—N7—C11—C12	−1.8 (3)
N3—Zn1—N7—N8	−126.06 (16)	Zn1—N7—C11—C12	−174.00 (16)
N2—Zn1—N7—N8	−83.33 (14)	N6—C9—C11—N7	−7.9 (2)
N6—Zn1—N7—N8	−172.11 (15)	C10—C9—C11—N7	171.15 (18)
Cl2—Zn1—N7—N8	104.55 (14)	N6—C9—C11—C12	170.15 (18)
Cl1—Zn1—N7—N8	6.02 (14)	C10—C9—C11—C12	−10.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N8—H2N8···Cl1	0.86 (2)	2.73 (2)	3.400 (2)	137 (2)
N8—H2N8···N1i	0.86 (2)	2.60 (2)	3.165 (3)	124 (2)
N4—H2N4···Cl2	0.83 (2)	2.60 (2)	3.250 (2)	137 (2)
N4—H1N4···Cl1ii	0.81 (2)	2.66 (2)	3.4429 (19)	165 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H2N8⋯Cl1	0.86 (2)	2.73 (2)	3.400 (2)	137 (2)
N8—H2N8⋯N1i	0.86 (2)	2.60 (2)	3.165 (3)	124 (2)
N4—H2N4⋯Cl2	0.83 (2)	2.60 (2)	3.250 (2)	137 (2)
N4—H1N4⋯Cl1ii	0.81 (2)	2.66 (2)	3.4429 (19)	165 (2)

Symmetry codes: (i) ; (ii) .