[(E)-But-2-enoato-κO]chlorido(2,2'-diamino-4,4'-bi-1,3-thia-zole-κN,N)zinc(II) monohydrate.

In the title compound, [Zn(C(4)H(5)O(2))Cl(C(6)H(6)N(4)S(2))]·H(2)O, the Zn(II) cation is coordinated by a bidentate diamino-bithia-zole (DABT) ligand, a but-2-enoate anion and a Cl(-) anion in a distorted tetra-hedral geometry. Within the DABT ligand, the two thia-zole rings are twisted to each other at a dihedral angle of 4.38 (10)°. An intra-molecular N-H⋯O inter-action occurs. The centroid-centroid distance of 3.6650 (17) Å and partially overlapped arrangement between nearly parallel thia-zole rings of adjacent complexes indicate the existence of π-π stacking in the crystal structure. Extensive O-H⋯Cl, O-H⋯O, N-H⋯Cl and N-H⋯O hydrogen bonding helps to stabilize the crystal structure.

Related literature

For the potential applications of metal complexes of diamino­bithia­zole in the biological field, see: Waring (1981 ▶); Fisher et al. (1985 ▶). For dihedral angles between thia­zole rings in diamino­bithia­zole complexes, see: Du et al. (2010 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

[Zn(C4H5O2)Cl(C6H6N4S2)]·H2O

M = 402.18

Monoclinic,

a = 7.2782 (13) Å

b = 16.2846 (16) Å

c = 13.237 (2) Å

β = 99.252 (16)°

V = 1548.5 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.04 mm−1

T = 294 K

0.36 × 0.30 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.75, T max = 0.88

7862 measured reflections

2735 independent reflections

2293 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.080

S = 1.05

2735 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −0.45 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); 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/S160053681001113X/ng2750sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001113X/ng2750Isup2.hkl

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

[Zn(C4H5O2)Cl(C6H6N4S2)]·H2O	F(000) = 816
Mr = 402.18	Dx = 1.725 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3446 reflections
a = 7.2782 (13) Å	θ = 2.0–24.6°
b = 16.2846 (16) Å	µ = 2.04 mm−1
c = 13.237 (2) Å	T = 294 K
β = 99.252 (16)°	Block, yellow
V = 1548.5 (4) Å3	0.36 × 0.30 × 0.24 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	2735 independent reflections
Radiation source: fine-focus sealed tube	2293 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.75, Tmax = 0.88	k = −12→19
7862 measured reflections	l = −15→15

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0353P)2 + 1.093P] where P = (Fo2 + 2Fc2)/3
2735 reflections	(Δ/σ)max = 0.002
191 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Zn	0.77894 (5)	0.12724 (2)	0.64617 (2)	0.03260 (13)
Cl1	1.01129 (13)	0.21725 (6)	0.67179 (7)	0.0541 (3)
S1	0.93933 (12)	−0.14538 (5)	0.65212 (7)	0.0433 (2)
S2	0.56191 (12)	0.09881 (5)	0.30033 (6)	0.0418 (2)
N1	0.8456 (3)	0.00649 (15)	0.64140 (17)	0.0314 (6)
N2	0.9835 (4)	−0.03495 (18)	0.8057 (2)	0.0483 (7)
H2A	0.9737	0.0134	0.8305	0.058*
H2B	1.0326	−0.0740	0.8447	0.058*
N3	0.6716 (3)	0.10813 (15)	0.49432 (17)	0.0299 (5)
N4	0.5365 (4)	0.22969 (16)	0.4215 (2)	0.0444 (7)
H4A	0.5508	0.2545	0.4796	0.053*
H4B	0.4859	0.2549	0.3670	0.053*
O1	0.5737 (3)	0.15367 (14)	0.72007 (17)	0.0471 (6)
O2	0.7729 (4)	0.11162 (17)	0.8535 (2)	0.0630 (7)
O1W	0.4071 (4)	0.29467 (17)	0.6138 (2)	0.0726 (8)
H1A	0.2909	0.2835	0.6079	0.087*
H1B	0.4522	0.2592	0.6587	0.087*
C1	0.9224 (4)	−0.04933 (19)	0.7066 (2)	0.0351 (7)
C2	0.8373 (4)	−0.10659 (19)	0.5354 (2)	0.0396 (8)
H2	0.8137	−0.1368	0.4751	0.047*
C3	0.7965 (4)	−0.02684 (18)	0.5437 (2)	0.0316 (7)
C4	0.7091 (4)	0.02855 (18)	0.4637 (2)	0.0309 (7)
C5	0.6607 (4)	0.0136 (2)	0.3637 (2)	0.0386 (7)
H5	0.6782	−0.0363	0.3325	0.046*
C6	0.5924 (4)	0.15275 (19)	0.4159 (2)	0.0333 (7)
C7	0.6148 (5)	0.1325 (2)	0.8138 (3)	0.0448 (8)
C8	0.4511 (6)	0.1316 (2)	0.8698 (3)	0.0541 (9)
H8	0.3377	0.1509	0.8357	0.065*
C9	0.4583 (6)	0.1061 (2)	0.9613 (3)	0.0623 (11)
H9	0.5745	0.0909	0.9963	0.075*
C10	0.2972 (7)	0.0984 (3)	1.0172 (3)	0.0724 (13)
H10A	0.3061	0.1397	1.0696	0.109*
H10B	0.2981	0.0450	1.0479	0.109*
H10C	0.1834	0.1057	0.9702	0.109*

	U11	U22	U33	U12	U13	U23
Zn	0.0384 (2)	0.0298 (2)	0.0298 (2)	−0.00060 (15)	0.00584 (14)	−0.00417 (15)
Cl1	0.0597 (6)	0.0545 (6)	0.0507 (5)	−0.0236 (4)	0.0161 (4)	−0.0186 (4)
S1	0.0460 (5)	0.0295 (4)	0.0551 (5)	0.0035 (4)	0.0103 (4)	0.0042 (4)
S2	0.0460 (5)	0.0489 (5)	0.0286 (4)	−0.0057 (4)	0.0004 (3)	−0.0015 (4)
N1	0.0353 (14)	0.0292 (13)	0.0305 (13)	−0.0011 (11)	0.0076 (10)	0.0008 (11)
N2	0.0629 (19)	0.0439 (17)	0.0357 (15)	0.0110 (14)	0.0010 (13)	0.0064 (13)
N3	0.0316 (13)	0.0310 (13)	0.0279 (12)	−0.0041 (11)	0.0069 (10)	−0.0008 (10)
N4	0.0572 (18)	0.0363 (16)	0.0371 (15)	0.0029 (13)	0.0001 (13)	0.0059 (12)
O1	0.0528 (15)	0.0469 (14)	0.0449 (14)	0.0028 (11)	0.0173 (11)	−0.0083 (11)
O2	0.0653 (19)	0.0609 (17)	0.0627 (17)	0.0061 (14)	0.0103 (14)	−0.0015 (14)
O1W	0.0642 (18)	0.072 (2)	0.084 (2)	−0.0139 (15)	0.0188 (15)	−0.0228 (16)
C1	0.0323 (17)	0.0348 (17)	0.0397 (18)	−0.0008 (14)	0.0100 (13)	0.0035 (14)
C2	0.046 (2)	0.0319 (18)	0.0428 (18)	−0.0028 (14)	0.0115 (15)	−0.0064 (14)
C3	0.0298 (16)	0.0315 (17)	0.0353 (16)	−0.0052 (13)	0.0110 (12)	−0.0043 (13)
C4	0.0310 (16)	0.0304 (16)	0.0329 (16)	−0.0055 (13)	0.0098 (12)	−0.0025 (13)
C5	0.0449 (19)	0.0372 (18)	0.0343 (17)	−0.0060 (15)	0.0081 (14)	−0.0069 (14)
C6	0.0337 (17)	0.0347 (17)	0.0309 (16)	−0.0053 (13)	0.0038 (13)	0.0006 (13)
C7	0.056 (2)	0.0315 (18)	0.050 (2)	−0.0028 (16)	0.0166 (17)	−0.0093 (16)
C8	0.062 (2)	0.051 (2)	0.051 (2)	0.0083 (18)	0.0151 (18)	−0.0034 (18)
C9	0.079 (3)	0.050 (2)	0.062 (3)	0.014 (2)	0.022 (2)	0.002 (2)
C10	0.097 (3)	0.063 (3)	0.069 (3)	0.017 (2)	0.048 (3)	0.011 (2)

Zn—O1	1.961 (2)	O1—C7	1.275 (4)
Zn—N1	2.029 (2)	O2—C7	1.234 (4)
Zn—N3	2.060 (2)	O1W—H1A	0.8564
Zn—Cl1	2.2223 (9)	O1W—H1B	0.8550
S1—C2	1.723 (3)	C2—C3	1.340 (4)
S1—C1	1.735 (3)	C2—H2	0.9300
S2—C5	1.718 (3)	C3—C4	1.457 (4)
S2—C6	1.747 (3)	C4—C5	1.336 (4)
N1—C1	1.315 (4)	C5—H5	0.9300
N1—C3	1.395 (4)	C7—C8	1.502 (5)
N2—C1	1.336 (4)	C8—C9	1.273 (5)
N2—H2A	0.8600	C8—H8	0.9300
N2—H2B	0.8600	C9—C10	1.490 (5)
N3—C6	1.321 (4)	C9—H9	0.9300
N3—C4	1.398 (4)	C10—H10A	0.9600
N4—C6	1.323 (4)	C10—H10B	0.9600
N4—H4A	0.8600	C10—H10C	0.9600
N4—H4B	0.8600
O1—Zn—N1	115.69 (10)	C2—C3—N1	115.2 (3)
O1—Zn—N3	108.68 (10)	C2—C3—C4	128.1 (3)
N1—Zn—N3	83.01 (9)	N1—C3—C4	116.7 (2)
O1—Zn—Cl1	113.65 (7)	C5—C4—N3	115.0 (3)
N1—Zn—Cl1	117.66 (7)	C5—C4—C3	128.5 (3)
N3—Zn—Cl1	114.11 (7)	N3—C4—C3	116.5 (2)
C2—S1—C1	89.60 (15)	C4—C5—S2	111.1 (2)
C5—S2—C6	89.66 (15)	C4—C5—H5	124.5
C1—N1—C3	111.0 (2)	S2—C5—H5	124.5
C1—N1—Zn	136.7 (2)	N3—C6—N4	125.2 (3)
C3—N1—Zn	112.28 (18)	N3—C6—S2	112.9 (2)
C1—N2—H2A	120.0	N4—C6—S2	121.9 (2)
C1—N2—H2B	120.0	O2—C7—O1	123.1 (3)
H2A—N2—H2B	120.0	O2—C7—C8	123.1 (3)
C6—N3—C4	111.3 (2)	O1—C7—C8	113.7 (3)
C6—N3—Zn	137.1 (2)	C9—C8—C7	124.0 (4)
C4—N3—Zn	111.23 (18)	C9—C8—H8	118.0
C6—N4—H4A	120.0	C7—C8—H8	118.0
C6—N4—H4B	120.0	C8—C9—C10	125.8 (4)
H4A—N4—H4B	120.0	C8—C9—H9	117.1
C7—O1—Zn	110.3 (2)	C10—C9—H9	117.1
H1A—O1W—H1B	100.6	C9—C10—H10A	109.5
N1—C1—N2	124.2 (3)	C9—C10—H10B	109.5
N1—C1—S1	113.6 (2)	H10A—C10—H10B	109.5
N2—C1—S1	122.1 (2)	C9—C10—H10C	109.5
C3—C2—S1	110.6 (2)	H10A—C10—H10C	109.5
C3—C2—H2	124.7	H10B—C10—H10C	109.5
S1—C2—H2	124.7

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···Cl1i	0.86	2.56	3.345 (3)	152
O1W—H1B···O1	0.86	2.04	2.859 (4)	160
N2—H2A···O2	0.86	2.22	2.959 (4)	144
N2—H2B···O1Wii	0.86	2.23	3.032 (4)	154
N4—H4A···O1W	0.86	2.30	3.043 (4)	145
N4—H4B···Cl1iii	0.86	2.66	3.393 (3)	144

Table 1

Selected bond lengths (Å)

Zn—O1	1.961 (2)
Zn—N1	2.029 (2)
Zn—N3	2.060 (2)
Zn—Cl1	2.2223 (9)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯Cl1i	0.86	2.56	3.345 (3)	152
O1W—H1B⋯O1	0.86	2.04	2.859 (4)	160
N2—H2A⋯O2	0.86	2.22	2.959 (4)	144
N2—H2B⋯O1Wii	0.86	2.23	3.032 (4)	154
N4—H4A⋯O1W	0.86	2.30	3.043 (4)	145
N4—H4B⋯Cl1iii	0.86	2.66	3.393 (3)	144

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