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Acta Cryst. (2007). E63, m2334    [ doi:10.1107/S1600536807039104 ]

Dichloridobis(2-methyl-1,3-benzothiazole-[kappa]N)zinc(II)

S.-G. Roh and J. H. Jeong

Abstract top

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.

Comment top

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 top

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).

Experimental top

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).

Refinement top

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

Computing details top

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 top
[Figure 1] 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) top
Crystal data top
[ZnCl2(C8H7NS)2]Z = 2
Mr = 434.72F000 = 440
Triclinic, P1Dx = 1.651 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.4063 (4) ÅCell parameters from 25 reflections
b = 9.0758 (7) Åθ = 9.6–13.1º
c = 12.8451 (6) ŵ = 1.95 mm−1
α = 72.820 (4)ºT = 293 (2) K
β = 78.778 (4)ºBlock, light brown
γ = 69.938 (5)º0.45 × 0.40 × 0.35 mm
V = 874.70 (9) Å3
Data collection top
Enraf–Nonius CAD-4 four-circle
diffractometer		2798 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.009
Monochromator: graphiteθmax = 25.5º
T = 293(2) Kθmin = 1.7º
scintillation counter scansh = −10→9
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)		k = −10→0
Tmin = 0.433, Tmax = 0.506l = −15→14
3567 measured reflections3 standard reflections
3236 independent reflections every 60 min
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.0463P)2 + 0.2584P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
3236 reflectionsΔρmax = 0.44 e Å−3
209 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[ZnCl2(C8H7NS)2]γ = 69.938 (5)º
Mr = 434.72V = 874.70 (9) Å3
Triclinic, P1Z = 2
a = 8.4063 (4) ÅMo Kα
b = 9.0758 (7) ŵ = 1.95 mm−1
c = 12.8451 (6) ÅT = 293 (2) K
α = 72.820 (4)º0.45 × 0.40 × 0.35 mm
β = 78.778 (4)º
Data collection top
Enraf–Nonius CAD-4 four-circle
diffractometer		2798 reflections with I > 2σ(I)
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)		Rint = 0.009
Tmin = 0.433, Tmax = 0.5063 standard reflections
3567 measured reflections every 60 min
3236 independent reflections intensity decay: ?
Refinement top
R[F2 > 2σ(F2)] = 0.026209 parameters
wR(F2) = 0.076H-atom parameters constrained
S = 1.07Δρmax = 0.44 e Å−3
3236 reflectionsΔρmin = −0.37 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn0.27503 (3)0.27750 (3)0.228264 (19)0.03207 (10)
Cl10.15138 (7)0.51803 (6)0.12194 (5)0.04421 (15)
Cl20.52890 (7)0.26472 (8)0.26501 (5)0.04639 (16)
N10.2735 (2)0.0927 (2)0.16511 (14)0.0304 (4)
C10.4131 (3)−0.0405 (2)0.14713 (17)0.0307 (4)
C20.5815 (3)−0.0633 (3)0.15698 (19)0.0380 (5)
H20.61240.01230.17760.046*
C30.7029 (3)−0.2024 (3)0.1351 (2)0.0430 (5)
H30.8169−0.21980.14090.052*
C40.6574 (3)−0.3154 (3)0.1050 (2)0.0472 (6)
H40.7415−0.40790.09170.057*
C50.4921 (3)−0.2947 (3)0.0942 (2)0.0463 (6)
H50.4627−0.37080.07320.056*
C60.3691 (3)−0.1555 (3)0.11590 (18)0.0347 (5)
S10.15172 (7)−0.09114 (7)0.10699 (5)0.04242 (15)
C70.1320 (3)0.0818 (2)0.14470 (17)0.0329 (4)
C8−0.0381 (3)0.2062 (3)0.1512 (2)0.0433 (5)
H8A−0.05300.24520.21540.065*
H8B−0.12570.15860.15530.065*
H8C−0.04490.29470.08720.065*
N20.1375 (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)
H10−0.09640.49910.29000.058*
C11−0.2629 (3)0.5499 (4)0.4209 (2)0.0544 (7)
H11−0.33800.64220.38170.065*
C12−0.2970 (3)0.5017 (4)0.5329 (2)0.0545 (7)
H12−0.39310.56310.56800.065*
C13−0.1922 (4)0.3656 (4)0.5930 (2)0.0558 (7)
H13−0.21530.33380.66870.067*
C14−0.0490 (3)0.2747 (3)0.53832 (19)0.0429 (5)
S20.10126 (9)0.09379 (9)0.58910 (5)0.05466 (19)
C150.2041 (3)0.0948 (3)0.45884 (18)0.0375 (5)
C160.3534 (3)−0.0466 (3)0.4400 (2)0.0475 (6)
H16A0.3268−0.09680.39230.071*
H16B0.3790−0.12370.50880.071*
H16C0.4503−0.01000.40690.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.03075 (15)0.02626 (15)0.03583 (16)−0.00427 (10)−0.00148 (10)−0.00924 (10)
Cl10.0497 (3)0.0269 (3)0.0462 (3)−0.0041 (2)−0.0038 (2)−0.0043 (2)
Cl20.0338 (3)0.0505 (3)0.0596 (4)−0.0116 (2)−0.0023 (2)−0.0239 (3)
N10.0285 (8)0.0249 (8)0.0336 (9)−0.0036 (7)−0.0020 (7)−0.0075 (7)
C10.0320 (10)0.0241 (9)0.0309 (10)−0.0030 (8)−0.0017 (8)−0.0070 (8)
C20.0336 (11)0.0340 (11)0.0441 (12)−0.0041 (9)−0.0041 (9)−0.0136 (10)
C30.0319 (11)0.0382 (12)0.0479 (13)0.0021 (9)−0.0019 (9)−0.0111 (10)
C40.0469 (13)0.0314 (11)0.0504 (14)0.0051 (10)−0.0005 (11)−0.0144 (10)
C50.0538 (14)0.0303 (11)0.0521 (15)−0.0038 (10)−0.0046 (11)−0.0178 (10)
C60.0384 (11)0.0270 (10)0.0353 (11)−0.0065 (8)−0.0034 (9)−0.0070 (8)
S10.0403 (3)0.0349 (3)0.0560 (4)−0.0110 (2)−0.0099 (3)−0.0144 (3)
C70.0344 (11)0.0281 (10)0.0328 (11)−0.0079 (8)−0.0024 (8)−0.0052 (8)
C80.0309 (11)0.0375 (12)0.0556 (14)−0.0033 (9)−0.0070 (10)−0.0099 (11)
N20.0345 (9)0.0321 (9)0.0340 (9)−0.0076 (7)−0.0003 (7)−0.0089 (7)
C90.0326 (10)0.0393 (12)0.0362 (11)−0.0113 (9)0.0010 (8)−0.0135 (9)
C100.0422 (13)0.0480 (14)0.0418 (13)−0.0029 (11)0.0028 (10)−0.0114 (11)
C110.0416 (13)0.0555 (16)0.0582 (17)−0.0012 (12)0.0001 (11)−0.0219 (13)
C120.0441 (14)0.0626 (17)0.0605 (17)−0.0120 (12)0.0102 (12)−0.0358 (14)
C130.0598 (16)0.0687 (18)0.0419 (14)−0.0254 (14)0.0141 (12)−0.0238 (13)
C140.0459 (13)0.0498 (14)0.0356 (12)−0.0174 (11)0.0012 (10)−0.0144 (10)
S20.0637 (4)0.0547 (4)0.0338 (3)−0.0135 (3)−0.0018 (3)−0.0013 (3)
C150.0418 (12)0.0370 (11)0.0338 (11)−0.0136 (9)−0.0053 (9)−0.0062 (9)
C160.0481 (14)0.0349 (12)0.0513 (14)−0.0032 (10)−0.0120 (11)−0.0051 (10)
Geometric parameters (Å, °) top
Zn—N12.0725 (17)C8—H8B0.9600
Zn—N22.1054 (18)C8—H8C0.9600
Zn—Cl12.2239 (6)N2—C151.304 (3)
Zn—Cl22.2317 (6)N2—C91.413 (3)
N1—C71.307 (3)C9—C101.385 (3)
N1—C11.406 (2)C9—C141.395 (3)
C1—C21.385 (3)C10—C111.383 (3)
C1—C61.398 (3)C10—H100.9300
C2—C31.389 (3)C11—C121.378 (4)
C2—H20.9300C11—H110.9300
C3—C41.381 (4)C12—C131.361 (4)
C3—H30.9300C12—H120.9300
C4—C51.366 (4)C13—C141.398 (4)
C4—H40.9300C13—H130.9300
C5—C61.393 (3)C14—S21.727 (3)
C5—H50.9300S2—C151.726 (2)
C6—S11.733 (2)C15—C161.497 (3)
S1—C71.722 (2)C16—H16A0.9600
C7—C81.493 (3)C16—H16B0.9600
C8—H8A0.9600C16—H16C0.9600
N1—Zn—N299.81 (7)C7—C8—H8C109.5
N1—Zn—Cl1110.72 (5)H8A—C8—H8C109.5
N2—Zn—Cl1114.11 (5)H8B—C8—H8C109.5
N1—Zn—Cl2115.46 (5)C15—N2—C9111.04 (19)
N2—Zn—Cl2105.13 (5)C15—N2—Zn121.06 (15)
Cl1—Zn—Cl2111.12 (3)C9—N2—Zn126.32 (14)
C7—N1—C1111.33 (18)C10—C9—C14120.0 (2)
C7—N1—Zn121.60 (14)C10—C9—N2126.0 (2)
C1—N1—Zn126.88 (14)C14—C9—N2113.9 (2)
C2—C1—C6120.16 (19)C11—C10—C9118.2 (2)
C2—C1—N1126.06 (19)C11—C10—H10120.9
C6—C1—N1113.77 (18)C9—C10—H10120.9
C1—C2—C3118.0 (2)C12—C11—C10121.5 (3)
C1—C2—H2121.0C12—C11—H11119.3
C3—C2—H2121.0C10—C11—H11119.3
C4—C3—C2121.1 (2)C13—C12—C11121.1 (2)
C4—C3—H3119.4C13—C12—H12119.5
C2—C3—H3119.4C11—C12—H12119.5
C5—C4—C3121.7 (2)C12—C13—C14118.4 (2)
C5—C4—H4119.1C12—C13—H13120.8
C3—C4—H4119.1C14—C13—H13120.8
C4—C5—C6117.6 (2)C9—C14—C13120.7 (2)
C4—C5—H5121.2C9—C14—S2109.57 (17)
C6—C5—H5121.2C13—C14—S2129.7 (2)
C5—C6—C1121.3 (2)C15—S2—C1490.28 (11)
C5—C6—S1129.17 (19)N2—C15—C16125.0 (2)
C1—C6—S1109.50 (15)N2—C15—S2115.14 (17)
C7—S1—C690.15 (10)C16—C15—S2119.83 (17)
N1—C7—C8125.0 (2)C15—C16—H16A109.5
N1—C7—S1115.20 (15)C15—C16—H16B109.5
C8—C7—S1119.79 (16)H16A—C16—H16B109.5
C7—C8—H8A109.5C15—C16—H16C109.5
C7—C8—H8B109.5H16A—C16—H16C109.5
H8A—C8—H8B109.5H16B—C16—H16C109.5
N2—Zn—N1—C764.80 (17)N1—Zn—N2—C1571.18 (18)
Cl1—Zn—N1—C7−55.77 (17)Cl1—Zn—N2—C15−170.73 (15)
Cl2—Zn—N1—C7176.88 (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—C1129.73 (16)Cl1—Zn—N2—C9−6.39 (19)
Cl2—Zn—N1—C12.38 (18)Cl2—Zn—N2—C9115.62 (17)
C7—N1—C1—C2177.3 (2)C15—N2—C9—C10−175.2 (2)
Zn—N1—C1—C2−7.7 (3)Zn—N2—C9—C1019.1 (3)
C7—N1—C1—C6−2.2 (3)C15—N2—C9—C142.4 (3)
Zn—N1—C1—C6172.79 (14)Zn—N2—C9—C14−163.21 (16)
C6—C1—C2—C3−0.1 (3)C14—C9—C10—C110.6 (4)
N1—C1—C2—C3−179.6 (2)N2—C9—C10—C11178.1 (2)
C1—C2—C3—C4−0.3 (4)C9—C10—C11—C121.3 (4)
C2—C3—C4—C50.7 (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—C10.3 (4)C10—C9—C14—C13−2.3 (4)
C4—C5—C6—S1178.36 (19)N2—C9—C14—C13179.8 (2)
C2—C1—C6—C50.1 (3)C10—C9—C14—S2176.8 (2)
N1—C1—C6—C5179.7 (2)N2—C9—C14—S2−1.0 (3)
C2—C1—C6—S1−178.33 (17)C12—C13—C14—C92.2 (4)
N1—C1—C6—S11.2 (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—C15178.6 (3)
C1—N1—C7—C8−177.4 (2)C9—N2—C15—C16174.5 (2)
Zn—N1—C7—C87.3 (3)Zn—N2—C15—C16−19.0 (3)
C1—N1—C7—S12.2 (2)C9—N2—C15—S2−2.8 (2)
Zn—N1—C7—S1−173.10 (9)Zn—N2—C15—S2163.76 (11)
C6—S1—C7—N1−1.28 (17)C14—S2—C15—N21.89 (19)
C6—S1—C7—C8178.31 (19)C14—S2—C15—C16−175.5 (2)
references
References top

Alyea, E. C. & Malek, A. (1985). J. Heterocycl. Chem. 22, 1325–1327.

Dey, K., Bandyopadhyay, D., Chakraborty, K., Mallick, A. K. & Mondal, K. (1995). Synth. React. Inorg. Met.-Org. Chem. 25, 1429–1454.

Duff, E. J., Hughes, M. N. & Rutt, K. J. (1969). J. Chem. Soc. A, 14, 2101–2105.

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

McArdle, P. (1995). J. Appl. Cryst. 28, 65–?.

McArdle, P. (1999). XCAD. National University of Ireland Galway, Ireland.

McArdle, P. & Daly, P. (1999). ABSCALC. National University of Ireland Galway, Ireland.

Mueller, A., Johannes, K. U., Plass, W., Boegge, H., Krahn, E. & Schneider, K. (1996). Z. Anorg. Allg. Chem. 622, 1765–1772.

Peyronel, G. & Giusti, A. (1981). Spectrochim. Acta Part A, 37(2), 71–75.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.