Dichlorido{2-hydroxy­imino-N′-[1-(2-pyrid­yl)ethyl­idene]propanohydrazide-κ3N,N′,O}zinc(II) hemihydrate

Moroz, Y.S.; Sliva, T.Yu.; Kulon, K.; Kozłowski, H.; Fritsky, I.O.

doi:10.1107/S160053680706535X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m353-m354

doi:10.1107/S160053680706535X

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Dichlorido{2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazide-κ³N,N′,O}zinc(II) hemihydrate

Yurii S. Moroz,^a ^* Tetyana Yu. Sliva,^a Kinga Kulon,^b Henryk Kozłowski ^b and Igor O. Fritsky ^a

^aNational Taras Shevchenko University, Department of Chemistry, Volodymyrska str. 64, 01033 Kyiv, Ukraine, and ^bFaculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie str., 50-383 Wrocław, Poland
^*Correspondence e-mail: ysmoroz@yahoo.com

(Received 21 November 2007; accepted 4 December 2007; online 16 January 2008)

The title compound, [ZnCl₂(C₁₀H₁₂N₄O₂)]·0.5H₂O, was readily prepared by the reaction between ZnCl₂ and 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazide. The Zn atom has a distorted trigonal–bipyramidal geometry with two Cl atoms and one azomethine N atom in the equatorial plane and one pyridine N atom and one amide O atom in the axial positions. In the crystal structure, complex molecules are connected in pairs by N—H⋯Cl hydrogen bonds, formed between the amide NH of one molecule and the Cl atom of a neighboring one. Molecular pairs are connected by hydrogen bonds involving the uncoordinated water molecule, which lies on a twofold axis.

Related literature

For details of the structure and biological activity of zinc(II) complexes, see: Canary et al. (1998 ); Comba et al. (2002 ); Kasuga et al. (2003 ); Panosyan et al. (2003 ); Rodriuez-Argüelles et al. (1995 ); Sousa et al. (2003 ). For the preparation of 2-(oximato)propanehydrazide, see: Fritsky et al. (1998 ).

Experimental

Crystal data

[ZnCl₂(C₁₀H₁₂N₄O₂)]·0.5H₂O
M_r = 365.51
Monoclinic, C 2/c
a = 14.5666 (8) Å
b = 12.9898 (8) Å
c = 15.8671 (8) Å
β = 109.873 (5)°
V = 2823.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 100 (2) K
0.5 × 0.1 × 0.05 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer
Absorption correction: multi-scan (PLATON; Spek, 2003 ) T_min = 0.774, T_max = 0.891
17382 measured reflections
3373 independent reflections
3069 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.070
S = 1.21
3373 reflections
191 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N1	2.1409 (19)
Zn1—N2	2.1142 (18)
Zn1—O1	2.2348 (16)
Zn1—Cl2	2.2513 (6)
Zn1—Cl3	2.2195 (6)

N2—Zn1—N1	74.71 (7)
N2—Zn1—O1	72.57 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2⋯Cl3ⁱ	0.80 (3)	2.59 (3)	3.310 (2)	150 (3)
O1W—H1W⋯Cl2ⁱⁱ	0.81 (3)	2.44 (3)	3.182 (2)	153 (3)
O2—H1⋯O1Wⁱⁱⁱ	0.88 (3)	1.89 (4)	2.7015 (19)	153 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (ii) -x+1, -y+1, -z+1; (iii) x+1, y, z+1.

Data collection: KM-4 CCD Software (Kuma, 1999 $[Kuma (1999). KM-4 CCD Software. Version 1.61. Kuma Diffraction, Wrocław, Poland.]$ ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680706535X/hy2108sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680706535X/hy2108Isup2.hkl

checkCIF report

Comment top

In the past few decades mononuclear zinc(II) complexes attract a lot of attention because of their biological and catalytical activity (Kasuga et al., 2003; Panosyan et al., 2003; Rodriuez-Argüelles et al., 1995; Sousa et al., 2003). On the other hand, many zinc mononuclear complexes containing additional vacant donor sets and chelate centers are taken as ligands for building of homo- and heteropolynuclear systems, which are widely used in bioinorganic modeling and catalysis. The properties of the obtained compounds are closely connected with their structure, so the best results one could obtain using well designed ligand systems. We report here the synthesis and structure of a zinc complex, [ZnCl₂(C₁₀H₁₂N₄O₂)].0.5H₂O, based on a novel polynucleative ligand 2-(oximato)-N'-(1-(pyridin-2-yl)ethylidene)propanehydrazide (L).

The title compound consists of neutral complex molecules and solvated water molecules (Fig. 1). The Zn atom has a distorted trigonal-bipyramidal geometry, defined by two Cl atoms and one azomethine N atom at the equatorial plane and a pyridine N atom and an amide O atom at the axial positions. The Zn—N, Zn—O and Zn—Cl bond lengths are comparable to previously reported zinc complexes with thiosemicarbasone and semicarbasone derivatives (Kasuga et al., 2003) and with pyridine complexed to the metal ion (Canary et al., 1998; Comba et al., 2002) (Table 1). The bite angles around the central atom deviate from an ideal square-planar configuration [e.g. N2—Zn1—O1 = 72.57 (6)°, N2—Zn1—N1 = 74.71 (7)°], that is a consequence of the formation of two almost flat five-membered chelate rings. In the crystal packing, the molecules are connected in pairs by N—H···Cl hydrogen bonds (Fig. 2), where the protonated amide group from one molecule acts as a donor and the Cl atom from the neighboring molecule as an acceptor (Table 2). The weak π-stacking interaction is observed between the pyridine ring and oximic group. The molecular pairs are connected to each other by hydrogen bonds involving the solvated water molecules, resulting in an extensive three-dimensional system (Fig. 3).

Related literature top

For details of the structure and biological activity of zinc(II) complexes, see: Canary et al. (1998); Comba et al. (2002); Kasuga et al. (2003); Panosyan et al. (2003); Rodriuez-Argüelles et al. (1995); Sousa et al. (2003). For thepreparation of 2-(oximato)propanehydrazide, see: Fritsky et al. (1998).

Experimental top

2-(Oximato)-N'-(1-(pyridin-2-yl)ethylidene)propanehydrazide (L) was prepared according to early reported method (Fritsky et al., 1998). 2-Acetylpyridine (1.2 ml, 0.0107 mol) was added to a stirred warm ethanol/water solution (20 ml) of 2-(oximato)propanehydrazide (1.17 g, 0.01 mol). After stirring at 333 k for 6 h, the solution was cooled and a white precipitate was formed immediately. It was filtered off, washed with water and acetone and dried under vacuum (yield 72%, 1.59 g). ¹H NMR, 400.13 MHz, (DMSO-d6): 12.118 (s, 1H, N—OH), 10.242 (s, 1H, NH), 8.608 (dt, 1H, py-6, J6,5 = 4.8 Hz, J6,4 = 1.8 Hz), 8.066 (d, 1H, py-3, J3,4 = 7.8 Hz), 7.861 (td, 1H, py-4, J4,5,3 = 7.8 Hz, J4,6 = 1.8 Hz), 7.415 (ddd, 1H, py-5, J5,6 = 4.8 Hz, J5,4 = 7.8 Hz, J = 1.2 Hz), 2.376 (s, 3H, CH₃(py)), 1.985(s, 3H, CH₃). IR (KBr, cm^-1): 1660 (CO_amid), 1030 (NO_oxim), 3340 (NH_as). Analysis calculated for C₁₀H₁₂N₄O₂: C 54.54, H 5.49, N 25.44%; found: C 54.41, H 5.62, N 25.42%.

Zinc(II) chloride (0.014 g, 0.1 mmol) in H₂O (5 ml) was added to 10 ml of hot methanol solution of L (0.022 g, 0.1 mmol). The solution was left for slow evaporation at room temperature. After 5 days cubic crystals of the title compound suitable for X-ray analysis were obtained.

Computing details top

Data collection: KM-4 CCD Software (Kuma, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are shown at the 40% probability level. Water molecule is not shown.
	Fig. 2. A view of a pair of the complex molecules. Displacement ellipsoids are shown at the 40% probability level. Hydrogen bonds are indicated by dashed lines.
	Fig. 3. A packing diagram of the title compound along the b-axis direction. Hydrogen bonds are indicated by dashed lines. H atoms have been omitted for clarity.

Dichlorido[2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene]propanohydrazide- κ³N,N',O]zinc(II) monohydrate top

Crystal data top

[ZnCl₂(C₁₀H₁₂N₄O₂)]·0.5H₂O	F(000) = 1480
M_r = 365.51	D_x = 1.720 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3373 reflections
a = 14.5666 (8) Å	θ = 3.1–28.5°
b = 12.9898 (8) Å	µ = 2.13 mm⁻¹
c = 15.8671 (8) Å	T = 100 K
β = 109.873 (5)°	Cubic, yellow
V = 2823.5 (3) Å³	0.5 × 0.1 × 0.05 mm
Z = 8

Data collection top

Kum KM4 CCD area-detector diffractometer	3373 independent reflections
Radiation source: fine-focus sealed tube	3069 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 28.5°, θ_min = 3.1°
Absorption correction: multi-scan (PLATON; Spek, 2003)	h = −19→19
T_min = 0.774, T_max = 0.891	k = −16→16
17382 measured reflections	l = −20→21

Refinement top

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0282P)² + 3.185P] where P = (F_o² + 2F_c²)/3
3373 reflections	(Δ/σ)_max = 0.002
191 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[ZnCl₂(C₁₀H₁₂N₄O₂)]·0.5H₂O	V = 2823.5 (3) Å³
M_r = 365.51	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.5666 (8) Å	µ = 2.13 mm⁻¹
b = 12.9898 (8) Å	T = 100 K
c = 15.8671 (8) Å	0.5 × 0.1 × 0.05 mm
β = 109.873 (5)°

Data collection top

Kum KM4 CCD area-detector diffractometer	3373 independent reflections
Absorption correction: multi-scan (PLATON; Spek, 2003)	3069 reflections with I > 2σ(I)
T_min = 0.774, T_max = 0.891	R_int = 0.043
17382 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.45 e Å⁻³
3373 reflections	Δρ_min = −0.37 e Å⁻³
191 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8446 (2)	0.45584 (19)	0.90460 (16)	0.0300 (6)
H1A	0.8849	0.3958	0.9225	0.045*
H1B	0.8500	0.4827	0.8501	0.045*
H1C	0.7778	0.4378	0.8949	0.045*
C2	0.87720 (17)	0.53560 (17)	0.97658 (14)	0.0155 (4)
C3	0.86291 (17)	0.64543 (17)	0.95017 (14)	0.0149 (4)
C4	0.89866 (16)	0.89516 (17)	1.03894 (14)	0.0127 (4)
C5	0.96032 (18)	0.89213 (18)	1.13564 (14)	0.0187 (5)
H5A	0.9937	0.8272	1.1490	0.028*
H5B	0.9197	0.9003	1.1718	0.028*
H5C	1.0073	0.9469	1.1483	0.028*
C6	0.86661 (16)	0.99579 (17)	0.99301 (14)	0.0124 (4)
C7	0.89136 (17)	1.08943 (18)	1.03628 (15)	0.0163 (5)
H7	0.9293	1.0921	1.0967	0.020*
C8	0.85855 (19)	1.17985 (18)	0.98807 (16)	0.0194 (5)
H8	0.8745	1.2437	1.0157	0.023*
C9	0.80194 (19)	1.17314 (18)	0.89857 (16)	0.0203 (5)
H9	0.7788	1.2323	0.8650	0.024*
C10	0.78027 (17)	1.07659 (18)	0.85973 (15)	0.0181 (5)
H10	0.7424	1.0722	0.7994	0.022*
N1	0.81153 (14)	0.98950 (15)	0.90538 (12)	0.0140 (4)
N2	0.86837 (14)	0.81687 (14)	0.98712 (12)	0.0127 (4)
N3	0.88998 (14)	0.71758 (14)	1.01651 (13)	0.0144 (4)
N4	0.91703 (14)	0.51964 (14)	1.06044 (12)	0.0161 (4)
O1	0.82753 (14)	0.67055 (12)	0.87067 (10)	0.0213 (4)
O2	0.92836 (13)	0.41557 (13)	1.08008 (11)	0.0211 (4)
Cl2	0.88241 (4)	0.85938 (4)	0.75864 (3)	0.01726 (13)
Cl3	0.63307 (4)	0.81753 (5)	0.78506 (4)	0.01874 (13)
Zn1	0.793127 (19)	0.838156 (19)	0.848619 (16)	0.01239 (8)
H1	0.954 (3)	0.413 (3)	1.139 (2)	0.048 (10)*
O1W	0.0000	0.34448 (19)	0.2500	0.0206 (5)
H1W	0.045 (2)	0.308 (3)	0.250 (2)	0.048 (11)*
H2	0.905 (2)	0.699 (2)	1.068 (2)	0.024 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0471 (17)	0.0123 (12)	0.0180 (12)	−0.0014 (11)	−0.0052 (11)	−0.0005 (9)
C2	0.0178 (11)	0.0114 (11)	0.0162 (11)	−0.0004 (9)	0.0045 (9)	0.0004 (8)
C3	0.0163 (11)	0.0135 (11)	0.0150 (10)	−0.0008 (9)	0.0054 (9)	−0.0011 (8)
C4	0.0134 (11)	0.0124 (11)	0.0129 (10)	−0.0022 (8)	0.0054 (8)	−0.0001 (8)
C5	0.0235 (13)	0.0145 (12)	0.0138 (10)	−0.0020 (9)	0.0005 (9)	0.0002 (9)
C6	0.0122 (10)	0.0130 (11)	0.0135 (10)	0.0006 (8)	0.0063 (8)	0.0016 (8)
C7	0.0181 (12)	0.0163 (11)	0.0141 (10)	−0.0019 (9)	0.0050 (9)	−0.0016 (8)
C8	0.0256 (13)	0.0108 (11)	0.0220 (12)	−0.0017 (9)	0.0086 (10)	−0.0027 (9)
C9	0.0243 (13)	0.0140 (12)	0.0211 (12)	0.0019 (9)	0.0058 (10)	0.0033 (9)
C10	0.0196 (12)	0.0179 (12)	0.0152 (11)	0.0031 (9)	0.0039 (9)	0.0019 (9)
N1	0.0153 (9)	0.0132 (9)	0.0130 (9)	−0.0003 (7)	0.0042 (7)	−0.0008 (7)
N2	0.0150 (9)	0.0103 (9)	0.0130 (9)	0.0011 (7)	0.0051 (7)	0.0016 (7)
N3	0.0202 (10)	0.0115 (9)	0.0097 (9)	−0.0001 (8)	0.0028 (8)	0.0021 (7)
N4	0.0208 (10)	0.0103 (9)	0.0169 (9)	0.0011 (8)	0.0062 (8)	0.0019 (7)
O1	0.0333 (10)	0.0136 (8)	0.0122 (7)	0.0026 (7)	0.0015 (7)	0.0002 (6)
O2	0.0322 (10)	0.0126 (8)	0.0164 (8)	0.0014 (7)	0.0054 (7)	0.0043 (6)
Cl2	0.0152 (3)	0.0210 (3)	0.0172 (3)	−0.0004 (2)	0.0076 (2)	−0.0007 (2)
Cl3	0.0154 (3)	0.0255 (3)	0.0158 (3)	−0.0057 (2)	0.0059 (2)	−0.0026 (2)
Zn1	0.01436 (14)	0.01195 (13)	0.01015 (12)	−0.00066 (10)	0.00323 (9)	−0.00064 (9)
O1W	0.0272 (14)	0.0137 (12)	0.0202 (12)	0.000	0.0070 (11)	0.000

Geometric parameters (Å, º) top

C1—C2	1.495 (3)	C7—H7	0.9300
C1—H1A	0.9600	C8—C9	1.381 (3)
C1—H1B	0.9600	C8—H8	0.9300
C1—H1C	0.9600	C9—C10	1.386 (3)
C2—N4	1.275 (3)	C9—H9	0.9300
C2—C3	1.482 (3)	C10—N1	1.337 (3)
C3—O1	1.233 (3)	C10—H10	0.9300
C3—N3	1.364 (3)	Zn1—N1	2.1409 (19)
C4—N2	1.288 (3)	N2—N3	1.371 (3)
C4—C5	1.492 (3)	Zn1—N2	2.1142 (18)
C4—C6	1.492 (3)	N3—H2	0.80 (3)
C5—H5A	0.9600	N4—O2	1.384 (2)
C5—H5B	0.9600	Zn1—O1	2.2348 (16)
C5—H5C	0.9600	O2—H1	0.88 (3)
C6—N1	1.351 (3)	Zn1—Cl2	2.2513 (6)
C6—C7	1.383 (3)	Zn1—Cl3	2.2195 (6)
C7—C8	1.394 (3)	O1W—H1W	0.81 (3)

C2—C1—H1A	109.5	C7—C8—H8	120.5
C2—C1—H1B	109.5	C8—C9—C10	118.7 (2)
H1A—C1—H1B	109.5	C8—C9—H9	120.6
C2—C1—H1C	109.5	C10—C9—H9	120.6
H1A—C1—H1C	109.5	N1—C10—C9	122.7 (2)
H1B—C1—H1C	109.5	N1—C10—H10	118.6
N4—C2—C3	115.0 (2)	C9—C10—H10	118.6
N4—C2—C1	126.8 (2)	C10—N1—C6	118.69 (19)
C3—C2—C1	118.27 (19)	C10—N1—Zn1	125.33 (15)
O1—C3—N3	121.2 (2)	C6—N1—Zn1	115.73 (15)
O1—C3—C2	120.9 (2)	C4—N2—N3	122.44 (18)
N3—C3—C2	117.88 (19)	C4—N2—Zn1	120.30 (15)
N2—C4—C5	126.3 (2)	N3—N2—Zn1	117.03 (13)
N2—C4—C6	113.42 (18)	C3—N3—N2	114.28 (18)
C5—C4—C6	120.29 (19)	C3—N3—H2	119 (2)
C4—C5—H5A	109.5	N2—N3—H2	125 (2)
C4—C5—H5B	109.5	C2—N4—O2	111.77 (18)
H5A—C5—H5B	109.5	C3—O1—Zn1	114.29 (14)
C4—C5—H5C	109.5	N4—O2—H1	104 (2)
H5A—C5—H5C	109.5	N2—Zn1—N1	74.71 (7)
H5B—C5—H5C	109.5	N2—Zn1—Cl3	123.36 (5)
N1—C6—C7	121.8 (2)	N1—Zn1—Cl3	105.30 (5)
N1—C6—C4	115.30 (19)	N2—Zn1—O1	72.57 (6)
C7—C6—C4	122.86 (19)	N1—Zn1—O1	147.07 (6)
C6—C7—C8	119.1 (2)	Cl3—Zn1—O1	95.66 (5)
C6—C7—H7	120.5	N2—Zn1—Cl2	117.91 (5)
C8—C7—H7	120.5	N1—Zn1—Cl2	97.91 (5)
C9—C8—C7	119.0 (2)	Cl3—Zn1—Cl2	118.08 (2)
C9—C8—H8	120.5	O1—Zn1—Cl2	94.10 (5)

N4—C2—C3—O1	178.0 (2)	Zn1—N2—N3—C3	2.7 (2)
C1—C2—C3—O1	−2.0 (4)	C3—C2—N4—O2	−179.79 (19)
N4—C2—C3—N3	−2.1 (3)	C1—C2—N4—O2	0.2 (4)
C1—C2—C3—N3	177.9 (2)	N3—C3—O1—Zn1	−8.3 (3)
N2—C4—C6—N1	0.0 (3)	C2—C3—O1—Zn1	171.56 (16)
C5—C4—C6—N1	179.6 (2)	C4—N2—Zn1—N1	−6.55 (17)
N2—C4—C6—C7	−179.8 (2)	N3—N2—Zn1—N1	178.85 (17)
C5—C4—C6—C7	−0.1 (3)	C4—N2—Zn1—Cl3	−105.03 (17)
N1—C6—C7—C8	0.0 (3)	N3—N2—Zn1—Cl3	80.36 (16)
C4—C6—C7—C8	179.7 (2)	C4—N2—Zn1—O1	169.73 (19)
C6—C7—C8—C9	0.3 (4)	N3—N2—Zn1—O1	−4.88 (15)
C7—C8—C9—C10	−0.4 (4)	C4—N2—Zn1—Cl2	84.41 (17)
C8—C9—C10—N1	0.3 (4)	N3—N2—Zn1—Cl2	−90.20 (15)
C9—C10—N1—C6	−0.1 (3)	C10—N1—Zn1—N2	−179.8 (2)
C9—C10—N1—Zn1	−173.99 (18)	C6—N1—Zn1—N2	6.09 (15)
C7—C6—N1—C10	−0.1 (3)	C10—N1—Zn1—Cl3	−58.74 (19)
C4—C6—N1—C10	−179.9 (2)	C6—N1—Zn1—Cl3	127.17 (14)
C7—C6—N1—Zn1	174.42 (17)	C10—N1—Zn1—O1	173.63 (16)
C4—C6—N1—Zn1	−5.4 (2)	C6—N1—Zn1—O1	−0.5 (2)
C5—C4—N2—N3	0.4 (3)	C10—N1—Zn1—Cl2	63.31 (19)
C6—C4—N2—N3	179.97 (19)	C6—N1—Zn1—Cl2	−110.78 (15)
C5—C4—N2—Zn1	−173.95 (18)	C3—O1—Zn1—N2	6.96 (17)
C6—C4—N2—Zn1	5.7 (3)	C3—O1—Zn1—N1	13.6 (2)
O1—C3—N3—N2	4.1 (3)	C3—O1—Zn1—Cl3	−116.27 (17)
C2—C3—N3—N2	−175.80 (19)	C3—O1—Zn1—Cl2	124.96 (17)
C4—N2—N3—C3	−171.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2···Cl3ⁱ	0.80 (3)	2.59 (3)	3.310 (2)	150 (3)
O1W—H1W···Cl2ⁱⁱ	0.81 (3)	2.44 (3)	3.182 (2)	153 (3)
O2—H1···O1Wⁱⁱⁱ	0.88 (3)	1.89 (4)	2.7015 (19)	153 (3)

Symmetry codes: (i) −x+3/2, −y+3/2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₀H₁₂N₄O₂)]·0.5H₂O
M_r	365.51
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	14.5666 (8), 12.9898 (8), 15.8671 (8)
β (°)	109.873 (5)
V (Å³)	2823.5 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.5 × 0.1 × 0.05

Data collection
Diffractometer	Kum KM4 CCD area-detector diffractometer
Absorption correction	Multi-scan (PLATON; Spek, 2003)
T_min, T_max	0.774, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	17382, 3373, 3069
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.070, 1.21
No. of reflections	3373
No. of parameters	191
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.37

Computer programs: KM-4 CCD Software (Kuma, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn1—N1	2.1409 (19)	Zn1—Cl2	2.2513 (6)
Zn1—N2	2.1142 (18)	Zn1—Cl3	2.2195 (6)
Zn1—O1	2.2348 (16)

N2—Zn1—N1	74.71 (7)	N2—Zn1—O1	72.57 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2···Cl3ⁱ	0.80 (3)	2.59 (3)	3.310 (2)	150 (3)
O1W—H1W···Cl2ⁱⁱ	0.81 (3)	2.44 (3)	3.182 (2)	153 (3)
O2—H1···O1Wⁱⁱⁱ	0.88 (3)	1.89 (4)	2.7015 (19)	153 (3)

Symmetry codes: (i) −x+3/2, −y+3/2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z+1.

Acknowledgements

The authors are grateful to NATO for financial support (grant CBP. NUKR. CLG 982019).

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