Dichloridobis(2-methyl-1,3-benzo­thiazole-κN)zinc(II)

The reaction of 4-[(2-mercaptophen­yl)amino]pent-3-en-2-one with ZnCl₂ in CH₂Cl₂ gives the title complex, [ZnCl₂(C₈H₇NS)₂], as a brown crystalline product in which 4-[(2-mercaptophen­yl)amino]pent-3-en-2-one has been converted into 2-methyl­benzothia­zole. The Zn atom is coordinated by two chloride ions and binds to the N atoms of two 2-methyl­benzothia­zole ligands in a distorted tetra­hedral arrangement.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.026
• wR factor = 0.076
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C16
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  S1      ..       3.50 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn          (2)       1.85

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Benzothiazole derivatives and their complexes (Duff et al., 1969; Peyronel & Giusti, 1981; Alyea & Malek, 1985; Dey et al., 1995; Mueller et al., 1996) have been reported but the structure of the title compound has not been reported previously. The benzothiazoline derivatives were formed through the cyclocondensation of 2,4-pentanedione with 2-aminobenzenethiol by refluxing in EtOH or DMSO (Alyea & Malek, 1985; Dey et al., 1995). However, the title complex was obtained here by the reaction of the ligand formed by the cyclocondensation of 4-(2-mercaptophenyl)amino-3-penten-2-one with ZnCl₂. The geometry around the zinc atom is a distorted tetrahedron containing two nitrogen atoms from 2-methylbenzothiazole ligands and two chloride ions. The planes of the benzothiazoles are almost perpendicular to each other [(83.71 (8)].

Related literature

The synthesis of the complex is described by Peyronel & Giusti (1981). For other benzothiazole derivatives, see: Duff et al. (1969); Alyea & Malek (1985); Dey et al. (1995); Mueller et al. (1996).

S2. Experimental

To a solution of ZnCl₂ (0.08 g, 0.59 mmol) in CH₂Cl₂ (25 ml) was added dropwise a solution of 4-(2-mercaptophenyl)amino-3-penten-2-one (0.12 g, 1.2 mmol) in CH₂Cl₂ (25 ml). The mixture was stirred for 48 h at room temperature. The brown solution was filtered off and dried in vacuo. The residue was washed with ether to give a brown solid. Diffusion of n-hexane into a brown solution in CH₂Cl₂ gave brown crystals within two weeks. Yield; 0.13 g (51%). Anal. Calcd. for C₁₆H₁₄Cl₂N₂S₂Zn: C, 44.21; H, 3.25; N, 6.44; S, 14.75. Found: C, 44.01; H, 3.27; N, 6.52; S, 14.74. ¹H NMR (CDCl₃); 7.48(d, 1H, 2-benz, J = 8.1 Hz), 7.42(d, 1H, 7-benz, J = 7.8 Hz), 7.01(m, 1H, 6-benz), 6.92(m, 1H, 5-benz), 2.21(s, 3H, CH₃).

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, U_iso = 1.2U_eq(C) for aromatic and 0.96 Å, U_iso = 1.5U_eq(C) for CH₃ atoms.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD (McArdle, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of Dichlorobis(2-methylbenzothiazole-κN)zinc(II). Displacement ellipsoids are drawn at the 40% probability level.

Dichloridobis(2-methyl-1,3-benzothiazole-κN)zinc(II)

Crystal data

[ZnCl2(C8H7NS)2]	Z = 2
Mr = 434.72	F(000) = 440
Triclinic, P1	Dx = 1.651 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4063 (4) Å	Cell parameters from 25 reflections
b = 9.0758 (7) Å	θ = 9.6–13.1°
c = 12.8451 (6) Å	µ = 1.95 mm^−1
α = 72.820 (4)°	T = 293 K
β = 78.778 (4)°	Block, light brown
γ = 69.938 (5)°	0.45 × 0.40 × 0.35 mm
V = 874.70 (9) Å^3

Data collection

Enraf–Nonius CAD-4 four-circle diffractometer	2798 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.009
Graphite monochromator	θmax = 25.5°, θmin = 1.7°
scintillation counter scans	h = −10→9
Absorption correction: ψ scan (ABSCALC; McArdle & Daly, 1999)	k = −10→0
Tmin = 0.433, Tmax = 0.506	l = −15→14
3567 measured reflections	3 standard reflections every 60 min
3236 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 0.2584P] where P = (Fo^2 + 2Fc^2)/3
3236 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn	0.27503 (3)	0.27750 (3)	0.228264 (19)	0.03207 (10)
Cl1	0.15138 (7)	0.51803 (6)	0.12194 (5)	0.04421 (15)
Cl2	0.52890 (7)	0.26472 (8)	0.26501 (5)	0.04639 (16)
N1	0.2735 (2)	0.0927 (2)	0.16511 (14)	0.0304 (4)
C1	0.4131 (3)	−0.0405 (2)	0.14713 (17)	0.0307 (4)
C2	0.5815 (3)	−0.0633 (3)	0.15698 (19)	0.0380 (5)
H2	0.6124	0.0123	0.1776	0.046*
C3	0.7029 (3)	−0.2024 (3)	0.1351 (2)	0.0430 (5)
H3	0.8169	−0.2198	0.1409	0.052*
C4	0.6574 (3)	−0.3154 (3)	0.1050 (2)	0.0472 (6)
H4	0.7415	−0.4079	0.0917	0.057*
C5	0.4921 (3)	−0.2947 (3)	0.0942 (2)	0.0463 (6)
H5	0.4627	−0.3708	0.0732	0.056*
C6	0.3691 (3)	−0.1555 (3)	0.11590 (18)	0.0347 (5)
S1	0.15172 (7)	−0.09114 (7)	0.10699 (5)	0.04242 (15)
C7	0.1320 (3)	0.0818 (2)	0.14470 (17)	0.0329 (4)
C8	−0.0381 (3)	0.2062 (3)	0.1512 (2)	0.0433 (5)
H8A	−0.0530	0.2452	0.2154	0.065*
H8B	−0.1257	0.1586	0.1553	0.065*
H8C	−0.0449	0.2947	0.0872	0.065*
N2	0.1375 (2)	0.2211 (2)	0.38233 (15)	0.0345 (4)
C9	−0.0114 (3)	0.3256 (3)	0.42531 (18)	0.0356 (5)
C10	−0.1195 (3)	0.4644 (3)	0.3654 (2)	0.0479 (6)
H10	−0.0964	0.4991	0.2900	0.058*
C11	−0.2629 (3)	0.5499 (4)	0.4209 (2)	0.0544 (7)
H11	−0.3380	0.6422	0.3817	0.065*
C12	−0.2970 (3)	0.5017 (4)	0.5329 (2)	0.0545 (7)
H12	−0.3931	0.5631	0.5680	0.065*
C13	−0.1922 (4)	0.3656 (4)	0.5930 (2)	0.0558 (7)
H13	−0.2153	0.3338	0.6687	0.067*
C14	−0.0490 (3)	0.2747 (3)	0.53832 (19)	0.0429 (5)
S2	0.10126 (9)	0.09379 (9)	0.58910 (5)	0.05466 (19)
C15	0.2041 (3)	0.0948 (3)	0.45884 (18)	0.0375 (5)
C16	0.3534 (3)	−0.0466 (3)	0.4400 (2)	0.0475 (6)
H16A	0.3268	−0.0968	0.3923	0.071*
H16B	0.3790	−0.1237	0.5088	0.071*
H16C	0.4503	−0.0100	0.4069	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.03075 (15)	0.02626 (15)	0.03583 (16)	−0.00427 (10)	−0.00148 (10)	−0.00924 (10)
Cl1	0.0497 (3)	0.0269 (3)	0.0462 (3)	−0.0041 (2)	−0.0038 (2)	−0.0043 (2)
Cl2	0.0338 (3)	0.0505 (3)	0.0596 (4)	−0.0116 (2)	−0.0023 (2)	−0.0239 (3)
N1	0.0285 (8)	0.0249 (8)	0.0336 (9)	−0.0036 (7)	−0.0020 (7)	−0.0075 (7)
C1	0.0320 (10)	0.0241 (9)	0.0309 (10)	−0.0030 (8)	−0.0017 (8)	−0.0070 (8)
C2	0.0336 (11)	0.0340 (11)	0.0441 (12)	−0.0041 (9)	−0.0041 (9)	−0.0136 (10)
C3	0.0319 (11)	0.0382 (12)	0.0479 (13)	0.0021 (9)	−0.0019 (9)	−0.0111 (10)
C4	0.0469 (13)	0.0314 (11)	0.0504 (14)	0.0051 (10)	−0.0005 (11)	−0.0144 (10)
C5	0.0538 (14)	0.0303 (11)	0.0521 (15)	−0.0038 (10)	−0.0046 (11)	−0.0178 (10)
C6	0.0384 (11)	0.0270 (10)	0.0353 (11)	−0.0065 (8)	−0.0034 (9)	−0.0070 (8)
S1	0.0403 (3)	0.0349 (3)	0.0560 (4)	−0.0110 (2)	−0.0099 (3)	−0.0144 (3)
C7	0.0344 (11)	0.0281 (10)	0.0328 (11)	−0.0079 (8)	−0.0024 (8)	−0.0052 (8)
C8	0.0309 (11)	0.0375 (12)	0.0556 (14)	−0.0033 (9)	−0.0070 (10)	−0.0099 (11)
N2	0.0345 (9)	0.0321 (9)	0.0340 (9)	−0.0076 (7)	−0.0003 (7)	−0.0089 (7)
C9	0.0326 (10)	0.0393 (12)	0.0362 (11)	−0.0113 (9)	0.0010 (8)	−0.0135 (9)
C10	0.0422 (13)	0.0480 (14)	0.0418 (13)	−0.0029 (11)	0.0028 (10)	−0.0114 (11)
C11	0.0416 (13)	0.0555 (16)	0.0582 (17)	−0.0012 (12)	0.0001 (11)	−0.0219 (13)
C12	0.0441 (14)	0.0626 (17)	0.0605 (17)	−0.0120 (12)	0.0102 (12)	−0.0358 (14)
C13	0.0598 (16)	0.0687 (18)	0.0419 (14)	−0.0254 (14)	0.0141 (12)	−0.0238 (13)
C14	0.0459 (13)	0.0498 (14)	0.0356 (12)	−0.0174 (11)	0.0012 (10)	−0.0144 (10)
S2	0.0637 (4)	0.0547 (4)	0.0338 (3)	−0.0135 (3)	−0.0018 (3)	−0.0013 (3)
C15	0.0418 (12)	0.0370 (11)	0.0338 (11)	−0.0136 (9)	−0.0053 (9)	−0.0062 (9)
C16	0.0481 (14)	0.0349 (12)	0.0513 (14)	−0.0032 (10)	−0.0120 (11)	−0.0051 (10)

Geometric parameters (Å, º)

Zn—N1	2.0725 (17)	C8—H8B	0.9600
Zn—N2	2.1054 (18)	C8—H8C	0.9600
Zn—Cl1	2.2239 (6)	N2—C15	1.304 (3)
Zn—Cl2	2.2317 (6)	N2—C9	1.413 (3)
N1—C7	1.307 (3)	C9—C10	1.385 (3)
N1—C1	1.406 (2)	C9—C14	1.395 (3)
C1—C2	1.385 (3)	C10—C11	1.383 (3)
C1—C6	1.398 (3)	C10—H10	0.9300
C2—C3	1.389 (3)	C11—C12	1.378 (4)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.381 (4)	C12—C13	1.361 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.366 (4)	C13—C14	1.398 (4)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.393 (3)	C14—S2	1.727 (3)
C5—H5	0.9300	S2—C15	1.726 (2)
C6—S1	1.733 (2)	C15—C16	1.497 (3)
S1—C7	1.722 (2)	C16—H16A	0.9600
C7—C8	1.493 (3)	C16—H16B	0.9600
C8—H8A	0.9600	C16—H16C	0.9600
N1—Zn—N2	99.81 (7)	C7—C8—H8C	109.5
N1—Zn—Cl1	110.72 (5)	H8A—C8—H8C	109.5
N2—Zn—Cl1	114.11 (5)	H8B—C8—H8C	109.5
N1—Zn—Cl2	115.46 (5)	C15—N2—C9	111.04 (19)
N2—Zn—Cl2	105.13 (5)	C15—N2—Zn	121.06 (15)
Cl1—Zn—Cl2	111.12 (3)	C9—N2—Zn	126.32 (14)
C7—N1—C1	111.33 (18)	C10—C9—C14	120.0 (2)
C7—N1—Zn	121.60 (14)	C10—C9—N2	126.0 (2)
C1—N1—Zn	126.88 (14)	C14—C9—N2	113.9 (2)
C2—C1—C6	120.16 (19)	C11—C10—C9	118.2 (2)
C2—C1—N1	126.06 (19)	C11—C10—H10	120.9
C6—C1—N1	113.77 (18)	C9—C10—H10	120.9
C1—C2—C3	118.0 (2)	C12—C11—C10	121.5 (3)
C1—C2—H2	121.0	C12—C11—H11	119.3
C3—C2—H2	121.0	C10—C11—H11	119.3
C4—C3—C2	121.1 (2)	C13—C12—C11	121.1 (2)
C4—C3—H3	119.4	C13—C12—H12	119.5
C2—C3—H3	119.4	C11—C12—H12	119.5
C5—C4—C3	121.7 (2)	C12—C13—C14	118.4 (2)
C5—C4—H4	119.1	C12—C13—H13	120.8
C3—C4—H4	119.1	C14—C13—H13	120.8
C4—C5—C6	117.6 (2)	C9—C14—C13	120.7 (2)
C4—C5—H5	121.2	C9—C14—S2	109.57 (17)
C6—C5—H5	121.2	C13—C14—S2	129.7 (2)
C5—C6—C1	121.3 (2)	C15—S2—C14	90.28 (11)
C5—C6—S1	129.17 (19)	N2—C15—C16	125.0 (2)
C1—C6—S1	109.50 (15)	N2—C15—S2	115.14 (17)
C7—S1—C6	90.15 (10)	C16—C15—S2	119.83 (17)
N1—C7—C8	125.0 (2)	C15—C16—H16A	109.5
N1—C7—S1	115.20 (15)	C15—C16—H16B	109.5
C8—C7—S1	119.79 (16)	H16A—C16—H16B	109.5
C7—C8—H8A	109.5	C15—C16—H16C	109.5
C7—C8—H8B	109.5	H16A—C16—H16C	109.5
H8A—C8—H8B	109.5	H16B—C16—H16C	109.5
N2—Zn—N1—C7	64.80 (17)	N1—Zn—N2—C15	71.18 (18)
Cl1—Zn—N1—C7	−55.77 (17)	Cl1—Zn—N2—C15	−170.73 (15)
Cl2—Zn—N1—C7	176.88 (14)	Cl2—Zn—N2—C15	−48.73 (18)
N2—Zn—N1—C1	−109.69 (17)	N1—Zn—N2—C9	−124.47 (17)
Cl1—Zn—N1—C1	129.73 (16)	Cl1—Zn—N2—C9	−6.39 (19)
Cl2—Zn—N1—C1	2.38 (18)	Cl2—Zn—N2—C9	115.62 (17)
C7—N1—C1—C2	177.3 (2)	C15—N2—C9—C10	−175.2 (2)
Zn—N1—C1—C2	−7.7 (3)	Zn—N2—C9—C10	19.1 (3)
C7—N1—C1—C6	−2.2 (3)	C15—N2—C9—C14	2.4 (3)
Zn—N1—C1—C6	172.79 (14)	Zn—N2—C9—C14	−163.21 (16)
C6—C1—C2—C3	−0.1 (3)	C14—C9—C10—C11	0.6 (4)
N1—C1—C2—C3	−179.6 (2)	N2—C9—C10—C11	178.1 (2)
C1—C2—C3—C4	−0.3 (4)	C9—C10—C11—C12	1.3 (4)
C2—C3—C4—C5	0.7 (4)	C10—C11—C12—C13	−1.4 (5)
C3—C4—C5—C6	−0.7 (4)	C11—C12—C13—C14	−0.4 (4)
C4—C5—C6—C1	0.3 (4)	C10—C9—C14—C13	−2.3 (4)
C4—C5—C6—S1	178.36 (19)	N2—C9—C14—C13	179.8 (2)
C2—C1—C6—C5	0.1 (3)	C10—C9—C14—S2	176.8 (2)
N1—C1—C6—C5	179.7 (2)	N2—C9—C14—S2	−1.0 (3)
C2—C1—C6—S1	−178.33 (17)	C12—C13—C14—C9	2.2 (4)
N1—C1—C6—S1	1.2 (2)	C12—C13—C14—S2	−176.7 (2)
C5—C6—S1—C7	−178.3 (2)	C9—C14—S2—C15	−0.39 (18)
C1—C6—S1—C7	−0.02 (16)	C13—C14—S2—C15	178.6 (3)
C1—N1—C7—C8	−177.4 (2)	C9—N2—C15—C16	174.5 (2)
Zn—N1—C7—C8	7.3 (3)	Zn—N2—C15—C16	−19.0 (3)
C1—N1—C7—S1	2.2 (2)	C9—N2—C15—S2	−2.8 (2)
Zn—N1—C7—S1	−173.10 (9)	Zn—N2—C15—S2	163.76 (11)
C6—S1—C7—N1	−1.28 (17)	C14—S2—C15—N2	1.89 (19)
C6—S1—C7—C8	178.31 (19)	C14—S2—C15—C16	−175.5 (2)