Dichlorido{2-hydroxy-imino-N'-[1-(2-pyrid-yl)ethyl-idene]propanohydrazide-κN,N',O}zinc(II) hemihydrate.

The title compound, [ZnCl(2)(C(10)H(12)N(4)O(2))]·0.5H(2)O, was readily prepared by the reaction between ZnCl(2) and 2-hydroxy-imino-N'-[1-(2-pyrid-yl)ethyl-idene]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 mol-ecules are connected in pairs by N-H⋯Cl hydrogen bonds, formed between the amide NH of one mol-ecule and the Cl atom of a neighboring one. Mol-ecular pairs are connected by hydrogen bonds involving the uncoordinated water mol-ecule, 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 = 365.51

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.070

S = 1.21

3373 reflections

191 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.37 e Å−3

Data collection: KM-4 CCD Software (Kuma, 1999 ▶); 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 ▶).

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

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

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

[ZnCl2(C10H12N4O2)]·0.5H2O	F000 = 1480
Mr = 365.51	Dx = 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 = 3.1–28.5º
b = 12.9898 (8) Å	µ = 2.13 mm−1
c = 15.8671 (8) Å	T = 100 (2) K
β = 109.873 (5)º	Cubic, yellow
V = 2823.5 (3) Å3	0.5 × 0.1 × 0.05 mm
Z = 8

Kum KM4 CCD area-detector diffractometer	3373 independent reflections
Radiation source: fine-focus sealed tube	3069 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.043
T = 100(2) K	θmax = 28.5º
ω scans	θmin = 3.1º
Absorption correction: multi-scan(PLATON; Spek, 2003)	h = −19→19
Tmin = 0.774, Tmax = 0.891	k = −16→16
17382 measured reflections	l = −20→21

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0282P)2 + 3.185P] where P = (Fo2 + 2Fc2)/3
S = 1.21	(Δ/σ)max = 0.002
3373 reflections	Δρmax = 0.45 e Å−3
191 parameters	Δρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

	x	y	z	Uiso*/Ueq
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)*

	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

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)

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)

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) ; (ii) ; (iii) .