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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039104/sj2323sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039104/sj2323Isup2.hkl
Contains datablock I

CCDC reference: 660101

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

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.

Structure description 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)].

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).

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 = 434.72F(000) = 440
Triclinic, P1Dx = 1.651 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4063 (4) ÅCell parameters from 25 reflections
b = 9.0758 (7) Åθ = 9.6–13.1°
c = 12.8451 (6) ŵ = 1.95 mm1
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) 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
Graphite monochromatorθmax = 25.5°, θmin = 1.7°
scintillation counter scansh = 109
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)
k = 100
Tmin = 0.433, Tmax = 0.506l = 1514
3567 measured reflections3 standard reflections every 60 min
3236 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0463P)2 + 0.2584P]
where P = (Fo2 + 2Fc2)/3
3236 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
[ZnCl2(C8H7NS)2]γ = 69.938 (5)°
Mr = 434.72V = 874.70 (9) Å3
Triclinic, P1Z = 2
a = 8.4063 (4) ÅMo Kα radiation
b = 9.0758 (7) ŵ = 1.95 mm1
c = 12.8451 (6) ÅT = 293 K
α = 72.820 (4)°0.45 × 0.40 × 0.35 mm
β = 78.778 (4)°
Data collection top
Enraf–Nonius CAD-4 four-circle
diffractometer
3236 independent reflections
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)
2798 reflections with I > 2σ(I)
Tmin = 0.433, Tmax = 0.506Rint = 0.009
3567 measured reflections3 standard reflections every 60 min
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.07Δρmax = 0.44 e Å3
3236 reflectionsΔρmin = 0.37 e Å3
209 parameters
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)
H30.81690.21980.14090.052*
C40.6574 (3)0.3154 (3)0.1050 (2)0.0472 (6)
H40.74150.40790.09170.057*
C50.4921 (3)0.2947 (3)0.0942 (2)0.0463 (6)
H50.46270.37080.07320.056*
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)
C80.0381 (3)0.2062 (3)0.1512 (2)0.0433 (5)
H8A0.05300.24520.21540.065*
H8B0.12570.15860.15530.065*
H8C0.04490.29470.08720.065*
N20.1375 (2)0.2211 (2)0.38233 (15)0.0345 (4)
C90.0114 (3)0.3256 (3)0.42531 (18)0.0356 (5)
C100.1195 (3)0.4644 (3)0.3654 (2)0.0479 (6)
H100.09640.49910.29000.058*
C110.2629 (3)0.5499 (4)0.4209 (2)0.0544 (7)
H110.33800.64220.38170.065*
C120.2970 (3)0.5017 (4)0.5329 (2)0.0545 (7)
H120.39310.56310.56800.065*
C130.1922 (4)0.3656 (4)0.5930 (2)0.0558 (7)
H130.21530.33380.66870.067*
C140.0490 (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)
H16A0.32680.09680.39230.071*
H16B0.37900.12370.50880.071*
H16C0.45030.01000.40690.071*
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, º) 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—C755.77 (17)Cl1—Zn—N2—C15170.73 (15)
Cl2—Zn—N1—C7176.88 (14)Cl2—Zn—N2—C1548.73 (18)
N2—Zn—N1—C1109.69 (17)N1—Zn—N2—C9124.47 (17)
Cl1—Zn—N1—C1129.73 (16)Cl1—Zn—N2—C96.39 (19)
Cl2—Zn—N1—C12.38 (18)Cl2—Zn—N2—C9115.62 (17)
C7—N1—C1—C2177.3 (2)C15—N2—C9—C10175.2 (2)
Zn—N1—C1—C27.7 (3)Zn—N2—C9—C1019.1 (3)
C7—N1—C1—C62.2 (3)C15—N2—C9—C142.4 (3)
Zn—N1—C1—C6172.79 (14)Zn—N2—C9—C14163.21 (16)
C6—C1—C2—C30.1 (3)C14—C9—C10—C110.6 (4)
N1—C1—C2—C3179.6 (2)N2—C9—C10—C11178.1 (2)
C1—C2—C3—C40.3 (4)C9—C10—C11—C121.3 (4)
C2—C3—C4—C50.7 (4)C10—C11—C12—C131.4 (5)
C3—C4—C5—C60.7 (4)C11—C12—C13—C140.4 (4)
C4—C5—C6—C10.3 (4)C10—C9—C14—C132.3 (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—S21.0 (3)
C2—C1—C6—S1178.33 (17)C12—C13—C14—C92.2 (4)
N1—C1—C6—S11.2 (2)C12—C13—C14—S2176.7 (2)
C5—C6—S1—C7178.3 (2)C9—C14—S2—C150.39 (18)
C1—C6—S1—C70.02 (16)C13—C14—S2—C15178.6 (3)
C1—N1—C7—C8177.4 (2)C9—N2—C15—C16174.5 (2)
Zn—N1—C7—C87.3 (3)Zn—N2—C15—C1619.0 (3)
C1—N1—C7—S12.2 (2)C9—N2—C15—S22.8 (2)
Zn—N1—C7—S1173.10 (9)Zn—N2—C15—S2163.76 (11)
C6—S1—C7—N11.28 (17)C14—S2—C15—N21.89 (19)
C6—S1—C7—C8178.31 (19)C14—S2—C15—C16175.5 (2)

Experimental details

Crystal data
Chemical formula[ZnCl2(C8H7NS)2]
Mr434.72
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)8.4063 (4), 9.0758 (7), 12.8451 (6)
α, β, γ (°)72.820 (4), 78.778 (4), 69.938 (5)
V3)874.70 (9)
Z2
Radiation typeMo Kα
µ (mm1)1.95
Crystal size (mm)0.45 × 0.40 × 0.35
Data collection
DiffractometerEnraf–Nonius CAD-4 four-circle
Absorption correctionψ scan
(ABSCALC; McArdle & Daly, 1999)
Tmin, Tmax0.433, 0.506
No. of measured, independent and
observed [I > 2σ(I)] reflections
3567, 3236, 2798
Rint0.009
(sin θ/λ)max1)0.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.076, 1.07
No. of reflections3236
No. of parameters209
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.44, 0.37

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CAD-4 Software, XCAD (McArdle, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), SHELXL97.

 

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