Bis(2-amino-1,3-benzothia-zole-κN)dichloridozinc(II) ethanol hemisolvate.

In the title compound, [ZnCl(2)(C(7)H(6)N(2)S)(2)]·0.5CH(3)CH(2)OH, the Zn(II) atom is coordinated by two N atoms of two 2-amino-benzothia-zole ligands and two Cl atoms within a distorted tetra-hedral geometry. The dihedral angle between the N/Zn/N and Cl/Zn/Cl planes is 86.22 (7)°. The benzothia-zole mol-ecules are almost perpendicular to each other, forming a dihedral angle of 80.20 (8)°. The mol-ecular structure is stabilized by intra-molecular N-H⋯Cl hydrogen bonds. In the crystal, inter-molecular N-H⋯Cl hydrogen bonds link the mol-ecules into a three-dimensional network. The SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155] was used to model a disordered ethanol solvent mol-ecule; the calculated unit-cell data allow for the presence of half of this mol-ecule in the asymmetric unit.

Related literature

For the synthesis and structures of related ZnII and HgII metal complexes, see: Kim et al. (2007 ▶, 2010 ▶, 2011 ▶); Seo et al. (2009 ▶); Kim & Kang (2010 ▶). For the biological and photochemical properties of benzothia­zole compounds, see: Khan et al. (2011 ▶); Pavlovic et al. (2007 ▶); Raposo et al. (2011 ▶); Saeed et al. (2010 ▶); Zajac et al. (2008 ▶).

Experimental

Crystal data

[ZnCl2(C7H6N2S)2]·0.5C2H6O

M = 459.72

Orthorhombic,

a = 21.0129 (10) Å

b = 11.6013 (5) Å

c = 16.6025 (8) Å

V = 4047.3 (3) Å3

Z = 8

Mo Kα radiation

μ = 1.69 mm−1

T = 296 K

0.13 × 0.10 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.813, T max = 0.881

16706 measured reflections

4956 independent reflections

2612 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.136

S = 0.88

4956 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812001560/tk5044sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001560/tk5044Isup2.hkl

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

[ZnCl2(C7H6N2S)2]·0.5C2H6O	F(000) = 1760
Mr = 459.72	Dx = 1.509 Mg m−3
Orthorhombic, Pcca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ac	Cell parameters from 1986 reflections
a = 21.0129 (10) Å	θ = 3.0–24.3°
b = 11.6013 (5) Å	µ = 1.69 mm−1
c = 16.6025 (8) Å	T = 296 K
V = 4047.3 (3) Å3	Block, colourless
Z = 8	0.13 × 0.1 × 0.07 mm

Bruker SMART CCD area-detector diffractometer	2612 reflections with I > 2σ(I)
graphite	Rint = 0.058
φ and ω scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −27→8
Tmin = 0.813, Tmax = 0.881	k = −15→12
16706 measured reflections	l = −19→21
4956 independent reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136	H-atom parameters constrained
S = 0.88	w = 1/[σ2(Fo2) + (0.0724P)2] where P = (Fo2 + 2Fc2)/3
4956 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.34 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	0.387172 (17)	0.61071 (4)	0.10299 (3)	0.04953 (16)
Cl2	0.33663 (4)	0.61006 (11)	0.22239 (6)	0.0701 (3)
Cl3	0.42382 (4)	0.43298 (9)	0.06892 (7)	0.0598 (3)
N4	0.32592 (12)	0.6503 (3)	0.01289 (18)	0.0477 (7)
C5	0.34802 (15)	0.6653 (3)	−0.0662 (2)	0.0462 (8)
C6	0.41141 (18)	0.6731 (4)	−0.0882 (2)	0.0569 (10)
H6	0.4435	0.6673	−0.0499	0.068*
C7	0.42565 (19)	0.6899 (4)	−0.1684 (3)	0.0624 (11)
H7	0.4681	0.6945	−0.184	0.075*
C8	0.3791 (2)	0.6999 (4)	−0.2255 (3)	0.0766 (13)
H8	0.3899	0.7119	−0.2791	0.092*
C9	0.3160 (2)	0.6922 (4)	−0.2033 (3)	0.0758 (13)
H9	0.2841	0.6989	−0.2418	0.091*
C10	0.30062 (17)	0.6744 (4)	−0.1237 (3)	0.0565 (10)
S11	0.22578 (4)	0.66284 (11)	−0.07852 (7)	0.0681 (3)
C12	0.26227 (15)	0.6488 (3)	0.0152 (2)	0.0519 (9)
N13	0.22837 (13)	0.6396 (3)	0.0822 (2)	0.0682 (10)
H13A	0.2473	0.6342	0.128	0.082*
H13B	0.1875	0.6391	0.0799	0.082*
N14	0.45956 (13)	0.7257 (3)	0.11147 (19)	0.0510 (8)
C15	0.45232 (18)	0.8447 (4)	0.1039 (2)	0.0563 (10)
C16	0.3996 (2)	0.9016 (4)	0.0752 (4)	0.0839 (15)
H16	0.3638	0.8601	0.0595	0.101*
C17	0.3998 (3)	1.0218 (5)	0.0695 (4)	0.1028 (18)
H17	0.3648	1.0607	0.0486	0.123*
C18	0.4536 (4)	1.0833 (5)	0.0957 (4)	0.1039 (19)
H18	0.4536	1.1635	0.0936	0.125*
C19	0.5060 (3)	1.0260 (5)	0.1243 (4)	0.0920 (16)
H19	0.542	1.0665	0.1408	0.11*
C20	0.5045 (2)	0.9079 (4)	0.1283 (3)	0.0689 (12)
S21	0.56461 (5)	0.81677 (11)	0.16229 (8)	0.0794 (4)
C22	0.51607 (16)	0.6994 (4)	0.1405 (2)	0.0526 (9)
N23	0.53666 (14)	0.5938 (3)	0.1541 (2)	0.0673 (10)
H23A	0.5125	0.5358	0.1439	0.081*
H23B	0.5742	0.583	0.1732	0.081*

	U11	U22	U33	U12	U13	U23
Zn1	0.0339 (2)	0.0592 (3)	0.0555 (3)	−0.00259 (18)	−0.00195 (16)	−0.0009 (2)
Cl2	0.0450 (5)	0.1092 (9)	0.0562 (6)	0.0047 (5)	0.0029 (4)	0.0017 (6)
Cl3	0.0395 (4)	0.0593 (6)	0.0807 (7)	0.0003 (4)	0.0012 (4)	−0.0048 (5)
N4	0.0336 (13)	0.0584 (19)	0.051 (2)	−0.0019 (13)	−0.0030 (12)	−0.0022 (15)
C5	0.0385 (17)	0.044 (2)	0.056 (2)	−0.0035 (15)	−0.0026 (15)	−0.0041 (18)
C6	0.047 (2)	0.063 (3)	0.062 (3)	0.0010 (18)	0.0038 (17)	−0.002 (2)
C7	0.056 (2)	0.069 (3)	0.062 (3)	−0.0080 (19)	0.013 (2)	−0.010 (2)
C8	0.078 (3)	0.098 (4)	0.053 (3)	−0.019 (3)	0.008 (2)	−0.006 (3)
C9	0.070 (3)	0.103 (4)	0.055 (3)	−0.015 (3)	−0.015 (2)	−0.006 (3)
C10	0.043 (2)	0.066 (3)	0.060 (3)	−0.0058 (18)	−0.0032 (16)	0.000 (2)
S11	0.0404 (5)	0.0954 (9)	0.0686 (7)	−0.0065 (5)	−0.0123 (4)	0.0040 (6)
C12	0.0363 (17)	0.057 (2)	0.063 (3)	0.0000 (15)	−0.0028 (16)	−0.003 (2)
N13	0.0321 (15)	0.108 (3)	0.064 (2)	−0.0072 (16)	0.0005 (14)	0.001 (2)
N14	0.0403 (15)	0.053 (2)	0.059 (2)	−0.0049 (14)	−0.0028 (13)	−0.0030 (15)
C15	0.054 (2)	0.056 (3)	0.059 (3)	−0.0036 (19)	0.0036 (18)	−0.002 (2)
C16	0.080 (3)	0.062 (3)	0.109 (4)	−0.001 (2)	−0.017 (3)	−0.006 (3)
C17	0.102 (4)	0.070 (4)	0.136 (5)	0.018 (3)	−0.015 (4)	−0.004 (3)
C18	0.129 (5)	0.055 (3)	0.128 (5)	−0.008 (3)	0.014 (4)	−0.007 (3)
C19	0.083 (4)	0.074 (4)	0.119 (5)	−0.018 (3)	0.000 (3)	−0.010 (3)
C20	0.076 (3)	0.054 (3)	0.077 (3)	−0.015 (2)	0.008 (2)	−0.009 (2)
S21	0.0532 (6)	0.0765 (8)	0.1084 (10)	−0.0193 (5)	−0.0102 (6)	−0.0122 (7)
C22	0.0419 (19)	0.063 (3)	0.053 (2)	−0.0077 (18)	0.0060 (16)	−0.005 (2)
N23	0.0423 (16)	0.068 (3)	0.092 (3)	0.0004 (16)	−0.0166 (17)	−0.005 (2)

Zn1—N4	2.026 (3)	N13—H13A	0.86
Zn1—N14	2.028 (3)	N13—H13B	0.86
Zn1—Cl2	2.2489 (11)	N14—C22	1.317 (4)
Zn1—Cl3	2.2726 (11)	N14—C15	1.395 (5)
N4—C12	1.338 (4)	C15—C16	1.374 (6)
N4—C5	1.404 (5)	C15—C20	1.380 (6)
C5—C10	1.384 (5)	C16—C17	1.399 (7)
C5—C6	1.384 (5)	C16—H16	0.93
C6—C7	1.378 (5)	C17—C18	1.405 (8)
C6—H6	0.93	C17—H17	0.93
C7—C8	1.368 (6)	C18—C19	1.373 (8)
C7—H7	0.93	C18—H18	0.93
C8—C9	1.379 (6)	C19—C20	1.372 (6)
C8—H8	0.93	C19—H19	0.93
C9—C10	1.375 (6)	C20—S21	1.741 (5)
C9—H9	0.93	S21—C22	1.740 (4)
C10—S11	1.748 (4)	C22—N23	1.318 (5)
S11—C12	1.742 (4)	N23—H23A	0.86
C12—N13	1.326 (5)	N23—H23B	0.86
N4—Zn1—N14	112.24 (12)	C12—N13—H13A	120
N4—Zn1—Cl2	110.59 (8)	C12—N13—H13B	120
N14—Zn1—Cl2	107.17 (9)	H13A—N13—H13B	120
N4—Zn1—Cl3	103.73 (9)	C22—N14—C15	111.1 (3)
N14—Zn1—Cl3	111.09 (9)	C22—N14—Zn1	123.3 (3)
Cl2—Zn1—Cl3	112.11 (5)	C15—N14—Zn1	124.3 (2)
C12—N4—C5	111.0 (3)	C16—C15—C20	119.2 (4)
C12—N4—Zn1	127.7 (3)	C16—C15—N14	126.5 (4)
C5—N4—Zn1	120.6 (2)	C20—C15—N14	114.4 (4)
C10—C5—C6	120.4 (4)	C15—C16—C17	120.0 (5)
C10—C5—N4	114.7 (3)	C15—C16—H16	120
C6—C5—N4	125.0 (3)	C17—C16—H16	120
C7—C6—C5	118.2 (4)	C16—C17—C18	119.2 (5)
C7—C6—H6	120.9	C16—C17—H17	120.4
C5—C6—H6	120.9	C18—C17—H17	120.4
C8—C7—C6	121.8 (4)	C19—C18—C17	120.5 (5)
C8—C7—H7	119.1	C19—C18—H18	119.8
C6—C7—H7	119.1	C17—C18—H18	119.8
C7—C8—C9	119.8 (4)	C20—C19—C18	118.8 (5)
C7—C8—H8	120.1	C20—C19—H19	120.6
C9—C8—H8	120.1	C18—C19—H19	120.6
C10—C9—C8	119.5 (4)	C19—C20—C15	122.3 (5)
C10—C9—H9	120.2	C19—C20—S21	127.2 (4)
C8—C9—H9	120.2	C15—C20—S21	110.4 (3)
C9—C10—C5	120.3 (3)	C22—S21—C20	89.0 (2)
C9—C10—S11	129.5 (3)	N14—C22—N23	125.0 (3)
C5—C10—S11	110.2 (3)	N14—C22—S21	115.0 (3)
C12—S11—C10	89.70 (17)	N23—C22—S21	119.9 (3)
N13—C12—N4	124.2 (3)	C22—N23—H23A	120
N13—C12—S11	121.4 (3)	C22—N23—H23B	120
N4—C12—S11	114.4 (3)	H23A—N23—H23B	120

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13A···Cl2	0.86	2.46	3.273 (3)	157
N13—H13B···Cl3i	0.86	2.49	3.314 (3)	161
N23—H23A···Cl3	0.86	2.54	3.333 (3)	154
N23—H23B···Cl2ii	0.86	2.57	3.366 (3)	154

Zn1—N4	2.026 (3)
Zn1—N14	2.028 (3)
Zn1—Cl2	2.2489 (11)
Zn1—Cl3	2.2726 (11)

N4—Zn1—N14	112.24 (12)
Cl2—Zn1—Cl3	112.11 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13A⋯Cl2	0.86	2.46	3.273 (3)	157
N13—H13B⋯Cl3i	0.86	2.49	3.314 (3)	161
N23—H23A⋯Cl3	0.86	2.54	3.333 (3)	154
N23—H23B⋯Cl2ii	0.86	2.57	3.366 (3)	154

Symmetry codes: (i) ; (ii) .