metal-organic compounds
Dichloridobis(5-m-tolyl-1,3,4-thiadiazol-2-ylamine-κN3)zinc(II)
aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China
*Correspondence e-mail: rwan@njut.edu.cn
In the molecule of the title compound, [ZnCl2(C9H9N3S)2], the ZnII atom is four-coordinated by two N atoms from two 5-m-tolyl-1,3,4-thiadiazol-2-ylamine ligands and two Cl anions in a distorted tetrahedral geometry. Intramolecular N—H⋯N, N—H⋯Cl and C—H⋯S hydrogen bonds result in the formation of one planar and one non-planar five-membered, one non-planar six-membered and one non-planar seven-membered ring. The six- and seven-membered rings have twist conformations, while the non-planar five-membered ring adopts an with the S atom displaced by 0.541 (3) Å from the plane of the other ring atoms. The planar five-membered ring is oriented at dihedral angles of 1.74 (3) and 1.08 (3)°, respectively, with respect to the adjacent aromatic and thiadiazole rings. In the intermolecular N—H⋯Cl hydrogen bonds link the molecules into a three-dimensional network.
Related literature
For general background, see: Alzuet et al. (2003); Shen et al. (2004). For ring puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S160053680801057X/hk2454sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053680801057X/hk2454Isup2.hkl
For the preparation of the title compound, the solution of ZnCl2 (0.5 mmol) in ethanol (20 ml) was added slowly to a solution of 5-m-tolyl-[1,3,4]- thiadiazol-2-ylamine (1.0 mmol) in ethanol (20 ml), and then heated under reflux for 2 h. The reaction mixture was left to cool to room temperature, and then filtered. The solid was recrystallized from ethanol to give the title compound, (I), (m.p. 453 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.
H atoms were positioned geometrically, with N-H = 0.86 Å (for NH2) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. | |
Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines. |
[ZnCl2(C9H9N3S)2] | F(000) = 1056 |
Mr = 518.77 | Dx = 1.584 Mg m−3 |
Monoclinic, P21/c | Melting point: 453 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.826 (2) Å | Cell parameters from 25 reflections |
b = 11.233 (2) Å | θ = 10–13° |
c = 17.892 (4) Å | µ = 1.58 mm−1 |
β = 90.10 (3)° | T = 298 K |
V = 2175.8 (7) Å3 | Block, yellow |
Z = 4 | 0.20 × 0.10 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 2310 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.2°, θmin = 1.9° |
ω/2θ scans | h = −12→12 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→13 |
Tmin = 0.742, Tmax = 0.858 | l = 0→21 |
3917 measured reflections | 3 standard reflections every 120 min |
3917 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.086 | H-atom parameters constrained |
wR(F2) = 0.211 | w = 1/[σ2(Fo2) + (0.05P)2 + 19P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3917 reflections | Δρmax = 0.62 e Å−3 |
256 parameters | Δρmin = −0.97 e Å−3 |
Primary atom site location: structure-invariant direct methods |
[ZnCl2(C9H9N3S)2] | V = 2175.8 (7) Å3 |
Mr = 518.77 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.826 (2) Å | µ = 1.58 mm−1 |
b = 11.233 (2) Å | T = 298 K |
c = 17.892 (4) Å | 0.20 × 0.10 × 0.10 mm |
β = 90.10 (3)° |
Enraf–Nonius CAD-4 diffractometer | 2310 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.742, Tmax = 0.858 | 3 standard reflections every 120 min |
3917 measured reflections | intensity decay: none |
3917 independent reflections |
R[F2 > 2σ(F2)] = 0.086 | H-atom parameters constrained |
wR(F2) = 0.211 | w = 1/[σ2(Fo2) + (0.05P)2 + 19P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | Δρmax = 0.62 e Å−3 |
3917 reflections | Δρmin = −0.97 e Å−3 |
256 parameters |
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 > 2sigma(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 | 0.06433 (12) | 0.26059 (8) | 0.14033 (6) | 0.0679 (4) | |
Cl1 | 0.1115 (3) | 0.1322 (2) | 0.05026 (15) | 0.0820 (8) | |
Cl2 | 0.1997 (3) | 0.26430 (19) | 0.23734 (15) | 0.0794 (8) | |
S1 | 0.0144 (3) | 0.65934 (18) | 0.09796 (14) | 0.0734 (8) | |
S2 | −0.2594 (3) | 0.06983 (19) | 0.25635 (15) | 0.0797 (9) | |
N1 | 0.1364 (8) | 0.4722 (6) | 0.0595 (4) | 0.065 (2) | |
N2 | 0.0424 (7) | 0.4353 (6) | 0.1087 (4) | 0.065 (2) | |
N3 | −0.1161 (10) | 0.5103 (6) | 0.1810 (5) | 0.083 (3) | |
H3B | −0.1321 | 0.4410 | 0.1990 | 0.099* | |
H3C | −0.1588 | 0.5710 | 0.1948 | 0.099* | |
N4 | −0.1619 (7) | 0.2723 (6) | 0.2312 (4) | 0.0616 (19) | |
N5 | −0.0944 (7) | 0.1933 (6) | 0.1914 (4) | 0.0612 (19) | |
N6 | −0.0809 (9) | −0.0115 (6) | 0.1629 (5) | 0.088 (3) | |
H6B | −0.0187 | 0.0009 | 0.1341 | 0.106* | |
H6C | −0.1088 | −0.0826 | 0.1688 | 0.106* | |
C1 | 0.4997 (13) | 0.5883 (12) | −0.1215 (8) | 0.114 (5) | |
H1B | 0.4935 | 0.5048 | −0.1107 | 0.171* | |
H1C | 0.5790 | 0.6171 | −0.1058 | 0.171* | |
H1D | 0.4903 | 0.6007 | −0.1743 | 0.171* | |
C2 | 0.4016 (12) | 0.6533 (9) | −0.0812 (6) | 0.082 (3) | |
C3 | 0.3158 (11) | 0.5948 (9) | −0.0373 (6) | 0.080 (3) | |
H3A | 0.3226 | 0.5125 | −0.0335 | 0.096* | |
C4 | 0.2196 (12) | 0.6500 (8) | 0.0019 (5) | 0.077 (3) | |
C5 | 0.2031 (9) | 0.7744 (8) | −0.0049 (6) | 0.068 (3) | |
H5A | 0.1390 | 0.8141 | 0.0191 | 0.081* | |
C6 | 0.2915 (11) | 0.8363 (10) | −0.0513 (7) | 0.085 (3) | |
H6A | 0.2846 | 0.9181 | −0.0579 | 0.102* | |
C7 | 0.3826 (13) | 0.7774 (10) | −0.0845 (7) | 0.086 (3) | |
H7A | 0.4386 | 0.8218 | −0.1123 | 0.104* | |
C8 | 0.1285 (11) | 0.5868 (7) | 0.0515 (5) | 0.071 (3) | |
C9 | −0.0319 (12) | 0.5226 (7) | 0.1353 (6) | 0.068 (3) | |
C10 | −0.6334 (10) | 0.2481 (11) | 0.4112 (7) | 0.092 | |
H10A | −0.6745 | 0.2995 | 0.4461 | 0.138* | |
H10B | −0.6150 | 0.1735 | 0.4350 | 0.138* | |
H10C | −0.6861 | 0.2344 | 0.3689 | 0.138* | |
C11 | −0.5168 (9) | 0.3049 (9) | 0.3860 (6) | 0.069 (2) | |
C12 | −0.4872 (10) | 0.4201 (9) | 0.4035 (5) | 0.071 (2) | |
H12A | −0.5399 | 0.4636 | 0.4341 | 0.085* | |
C13 | −0.3872 (10) | 0.4703 (9) | 0.3782 (6) | 0.079 (3) | |
H13A | −0.3711 | 0.5494 | 0.3901 | 0.095* | |
C14 | −0.3029 (10) | 0.4072 (8) | 0.3333 (6) | 0.071 (3) | |
H14A | −0.2292 | 0.4407 | 0.3169 | 0.085* | |
C15 | −0.3377 (9) | 0.2900 (7) | 0.3149 (5) | 0.060 (2) | |
C16 | −0.4505 (10) | 0.2402 (8) | 0.3390 (5) | 0.070 (2) | |
H16A | −0.4769 | 0.1658 | 0.3227 | 0.084* | |
C17 | −0.2499 (9) | 0.2250 (7) | 0.2652 (5) | 0.057 (2) | |
C18 | −0.1351 (9) | 0.0809 (8) | 0.1990 (6) | 0.063 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.1219 (10) | 0.0225 (5) | 0.0593 (7) | 0.0009 (5) | −0.0147 (6) | 0.0037 (5) |
Cl1 | 0.134 (2) | 0.0377 (12) | 0.0743 (17) | 0.0062 (14) | −0.0046 (16) | −0.0073 (11) |
Cl2 | 0.134 (2) | 0.0332 (11) | 0.0712 (16) | −0.0054 (13) | −0.0253 (15) | 0.0062 (11) |
S1 | 0.134 (2) | 0.0210 (10) | 0.0646 (15) | 0.0045 (12) | −0.0170 (15) | 0.0042 (10) |
S2 | 0.146 (3) | 0.0255 (11) | 0.0671 (16) | −0.0043 (13) | −0.0155 (16) | 0.0022 (11) |
N1 | 0.114 (7) | 0.035 (4) | 0.046 (4) | −0.009 (4) | −0.003 (4) | 0.001 (3) |
N2 | 0.114 (7) | 0.022 (3) | 0.059 (5) | 0.010 (4) | −0.013 (5) | −0.003 (3) |
N3 | 0.159 (9) | 0.024 (4) | 0.066 (6) | −0.001 (5) | −0.011 (6) | 0.004 (4) |
N4 | 0.084 (5) | 0.037 (3) | 0.064 (4) | −0.002 (3) | −0.003 (4) | −0.001 (3) |
N5 | 0.095 (5) | 0.033 (3) | 0.055 (4) | 0.004 (3) | −0.002 (4) | 0.000 (3) |
N6 | 0.130 (8) | 0.025 (4) | 0.110 (7) | 0.000 (4) | −0.002 (6) | −0.008 (4) |
C1 | 0.130 (11) | 0.082 (9) | 0.130 (12) | 0.000 (8) | 0.006 (9) | −0.015 (9) |
C2 | 0.125 (10) | 0.058 (6) | 0.064 (6) | −0.028 (6) | 0.014 (6) | 0.005 (5) |
C3 | 0.127 (9) | 0.041 (5) | 0.072 (7) | 0.003 (6) | −0.010 (7) | −0.017 (5) |
C4 | 0.146 (10) | 0.037 (5) | 0.047 (5) | −0.014 (6) | −0.032 (6) | 0.004 (4) |
C5 | 0.074 (6) | 0.040 (5) | 0.090 (7) | 0.000 (4) | −0.013 (5) | 0.007 (5) |
C6 | 0.094 (8) | 0.049 (6) | 0.112 (9) | −0.024 (6) | −0.020 (7) | 0.029 (6) |
C7 | 0.119 (10) | 0.055 (6) | 0.085 (8) | −0.006 (7) | −0.020 (7) | 0.019 (6) |
C8 | 0.131 (9) | 0.030 (4) | 0.052 (5) | −0.009 (5) | −0.030 (6) | 0.008 (4) |
C9 | 0.129 (9) | 0.024 (4) | 0.051 (6) | −0.002 (5) | −0.022 (6) | 0.002 (4) |
C10 | 0.092 | 0.092 | 0.092 | 0.000 | 0.000 | 0.000 |
C11 | 0.072 (5) | 0.059 (5) | 0.077 (6) | −0.006 (4) | −0.020 (4) | 0.004 (4) |
C12 | 0.084 (6) | 0.060 (5) | 0.069 (6) | 0.007 (4) | −0.007 (4) | −0.007 (4) |
C13 | 0.091 (6) | 0.056 (5) | 0.090 (6) | 0.001 (4) | −0.004 (5) | −0.013 (5) |
C14 | 0.094 (6) | 0.043 (4) | 0.076 (6) | −0.002 (4) | −0.002 (5) | −0.002 (4) |
C15 | 0.094 (5) | 0.037 (4) | 0.049 (5) | 0.017 (4) | −0.011 (4) | −0.004 (4) |
C16 | 0.105 (6) | 0.045 (4) | 0.061 (5) | −0.003 (4) | −0.014 (4) | 0.002 (4) |
C17 | 0.094 (5) | 0.034 (4) | 0.043 (4) | −0.003 (4) | −0.006 (4) | −0.007 (3) |
C18 | 0.074 (5) | 0.037 (4) | 0.077 (5) | 0.003 (4) | −0.025 (4) | −0.004 (4) |
Zn—Cl1 | 2.223 (3) | C3—H3A | 0.9300 |
Zn—Cl2 | 2.270 (3) | C4—C5 | 1.414 (12) |
Zn—N2 | 2.056 (6) | C4—C8 | 1.505 (14) |
Zn—N5 | 2.089 (8) | C5—C6 | 1.446 (14) |
S1—C8 | 1.698 (11) | C5—H5A | 0.9300 |
S1—C9 | 1.748 (9) | C6—C7 | 1.328 (15) |
S2—C18 | 1.699 (11) | C6—H6A | 0.9300 |
S2—C17 | 1.753 (8) | C7—H7A | 0.9300 |
N1—N2 | 1.410 (8) | C9—N3 | 1.234 (13) |
N1—C8 | 1.298 (11) | C10—C11 | 1.485 (14) |
N2—C9 | 1.355 (12) | C10—H10A | 0.9600 |
N3—H3B | 0.8600 | C10—H10B | 0.9600 |
N3—H3C | 0.8600 | C10—H10C | 0.9600 |
N4—C17 | 1.250 (11) | C11—C16 | 1.324 (11) |
N5—N4 | 1.353 (10) | C11—C12 | 1.370 (13) |
N5—C18 | 1.344 (11) | C12—C13 | 1.302 (14) |
N6—H6B | 0.8600 | C12—H12A | 0.9300 |
N6—H6C | 0.8600 | C13—C14 | 1.409 (13) |
C1—C2 | 1.478 (16) | C13—H13A | 0.9300 |
C1—H1B | 0.9600 | C14—C15 | 1.408 (12) |
C1—H1C | 0.9600 | C14—H14A | 0.9300 |
C1—H1D | 0.9600 | C15—C16 | 1.411 (13) |
C2—C3 | 1.383 (14) | C15—C17 | 1.494 (12) |
C2—C7 | 1.411 (15) | C16—H16A | 0.9300 |
C3—C4 | 1.402 (15) | C18—N6 | 1.357 (12) |
N2—Zn—N5 | 111.8 (3) | C7—C6—H6A | 119.7 |
N2—Zn—Cl1 | 116.5 (2) | C5—C6—H6A | 119.7 |
N5—Zn—Cl1 | 105.8 (2) | C6—C7—C2 | 125.6 (12) |
N2—Zn—Cl2 | 105.5 (2) | C6—C7—H7A | 117.2 |
N5—Zn—Cl2 | 101.7 (2) | C2—C7—H7A | 117.2 |
Cl1—Zn—Cl2 | 114.67 (12) | N1—C8—C4 | 119.3 (10) |
C8—S1—C9 | 88.6 (5) | N1—C8—S1 | 118.0 (8) |
C18—S2—C17 | 86.3 (4) | C4—C8—S1 | 122.7 (7) |
C8—N1—N2 | 108.2 (8) | N3—C9—N2 | 126.2 (9) |
C9—N2—N1 | 115.8 (7) | N3—C9—S1 | 124.4 (8) |
C9—N2—Zn | 131.5 (6) | N2—C9—S1 | 109.4 (8) |
N1—N2—Zn | 111.7 (5) | C11—C10—H10A | 109.5 |
C9—N3—H3B | 120.0 | C11—C10—H10B | 109.5 |
C9—N3—H3C | 120.0 | H10A—C10—H10B | 109.5 |
H3B—N3—H3C | 120.0 | C11—C10—H10C | 109.5 |
C17—N4—N5 | 112.9 (7) | H10A—C10—H10C | 109.5 |
C18—N5—N4 | 112.7 (8) | H10B—C10—H10C | 109.5 |
C18—N5—Zn | 130.8 (7) | C16—C11—C12 | 122.4 (10) |
N4—N5—Zn | 116.0 (5) | C16—C11—C10 | 114.8 (10) |
C18—N6—H6B | 120.0 | C12—C11—C10 | 122.4 (10) |
C18—N6—H6C | 120.0 | C13—C12—C11 | 121.7 (10) |
H6B—N6—H6C | 120.0 | C13—C12—H12A | 119.2 |
C2—C1—H1B | 109.5 | C11—C12—H12A | 119.2 |
C2—C1—H1C | 109.5 | C12—C13—C14 | 121.3 (10) |
H1B—C1—H1C | 109.5 | C12—C13—H13A | 119.3 |
C2—C1—H1D | 109.5 | C14—C13—H13A | 119.3 |
H1B—C1—H1D | 109.5 | C15—C14—C13 | 115.5 (10) |
H1C—C1—H1D | 109.5 | C15—C14—H14A | 122.3 |
C3—C2—C7 | 113.3 (11) | C13—C14—H14A | 122.3 |
C3—C2—C1 | 121.8 (10) | C14—C15—C16 | 122.0 (9) |
C7—C2—C1 | 124.9 (11) | C14—C15—C17 | 115.2 (9) |
C2—C3—C4 | 125.1 (10) | C16—C15—C17 | 122.7 (8) |
C2—C3—H3A | 117.5 | C11—C16—C15 | 116.6 (9) |
C4—C3—H3A | 117.5 | C11—C16—H16A | 121.7 |
C3—C4—C5 | 119.2 (10) | C15—C16—H16A | 121.7 |
C3—C4—C8 | 125.1 (9) | N4—C17—C15 | 124.6 (8) |
C5—C4—C8 | 115.7 (10) | N4—C17—S2 | 115.1 (7) |
C4—C5—C6 | 116.1 (10) | C15—C17—S2 | 120.2 (7) |
C4—C5—H5A | 121.9 | N5—C18—N6 | 121.9 (9) |
C6—C5—H5A | 121.9 | N5—C18—S2 | 113.0 (7) |
C7—C6—C5 | 120.7 (10) | N6—C18—S2 | 125.1 (7) |
N5—Zn—N2—C9 | 25.7 (10) | C9—S1—C8—C4 | −179.4 (8) |
Cl1—Zn—N2—C9 | 147.6 (8) | N1—N2—C9—N3 | −177.0 (10) |
Cl2—Zn—N2—C9 | −84.0 (9) | Zn—N2—C9—N3 | −9.3 (16) |
N5—Zn—N2—N1 | −166.2 (5) | N1—N2—C9—S1 | 0.3 (10) |
Cl1—Zn—N2—N1 | −44.4 (6) | Zn—N2—C9—S1 | 167.9 (5) |
Cl2—Zn—N2—N1 | 84.1 (5) | C8—S1—C9—N3 | 176.8 (10) |
N2—Zn—N5—C18 | 156.5 (8) | C8—S1—C9—N2 | −0.5 (7) |
Cl1—Zn—N5—C18 | 28.7 (9) | C16—C11—C12—C13 | −4.5 (13) |
Cl2—Zn—N5—C18 | −91.4 (8) | C10—C11—C12—C13 | −177.0 (10) |
N2—Zn—N5—N4 | −32.2 (7) | C11—C12—C13—C14 | −1.7 (13) |
Cl1—Zn—N5—N4 | −160.0 (6) | C12—C13—C14—C15 | 3.2 (14) |
Cl2—Zn—N5—N4 | 79.9 (6) | C13—C14—C15—C16 | 0.9 (14) |
C8—N1—N2—C9 | 0.2 (11) | C13—C14—C15—C17 | 178.1 (8) |
C8—N1—N2—Zn | −169.9 (6) | C12—C11—C16—C15 | 8.2 (14) |
C18—N5—N4—C17 | −1.7 (12) | C10—C11—C16—C15 | −178.8 (9) |
Zn—N5—N4—C17 | −174.6 (6) | C14—C15—C16—C11 | −6.5 (14) |
C7—C2—C3—C4 | −1.0 (17) | C17—C15—C16—C11 | 176.6 (8) |
C1—C2—C3—C4 | −179.3 (11) | N5—N4—C17—C15 | 178.4 (8) |
C2—C3—C4—C5 | 2.6 (17) | N5—N4—C17—S2 | 2.6 (11) |
C2—C3—C4—C8 | −178.1 (10) | C14—C15—C17—N4 | −11.5 (14) |
C3—C4—C5—C6 | −1.8 (15) | C16—C15—C17—N4 | 165.6 (9) |
C8—C4—C5—C6 | 178.9 (9) | C14—C15—C17—S2 | 164.0 (7) |
C4—C5—C6—C7 | −0.4 (16) | C16—C15—C17—S2 | −18.8 (12) |
C5—C6—C7—C2 | 2 (2) | C18—S2—C17—N4 | −2.2 (8) |
C3—C2—C7—C6 | −1.5 (19) | C18—S2—C17—C15 | −178.2 (8) |
C1—C2—C7—C6 | 176.8 (13) | N4—N5—C18—N6 | 179.1 (9) |
C3—C4—C8—N1 | −0.5 (15) | Zn—N5—C18—N6 | −9.4 (14) |
C5—C4—C8—N1 | 178.8 (9) | N4—N5—C18—S2 | 0.0 (10) |
C3—C4—C8—S1 | 179.6 (8) | Zn—N5—C18—S2 | 171.5 (5) |
C5—C4—C8—S1 | −1.1 (13) | C17—S2—C18—N5 | 1.1 (7) |
C9—S1—C8—N1 | 0.7 (8) | C17—S2—C18—N6 | −178.0 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···N4 | 0.86 | 2.01 | 2.864 (10) | 174 |
N3—H3C···Cl2i | 0.86 | 2.53 | 3.332 (8) | 156 |
N6—H6B···Cl1 | 0.86 | 2.53 | 3.320 (9) | 152 |
N6—H6C···Cl2ii | 0.86 | 2.60 | 3.345 (8) | 146 |
C5—H5A···S1 | 0.93 | 2.62 | 3.040 (10) | 108 |
C10—H10C···Cl2iii | 0.96 | 2.68 | 3.599 (12) | 161 |
C16—H16A···S2 | 0.93 | 2.85 | 3.184 (10) | 103 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C9H9N3S)2] |
Mr | 518.77 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.826 (2), 11.233 (2), 17.892 (4) |
β (°) | 90.10 (3) |
V (Å3) | 2175.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.58 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.742, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3917, 3917, 2310 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.086, 0.211, 1.02 |
No. of reflections | 3917 |
No. of parameters | 256 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.05P)2 + 19P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.62, −0.97 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Zn—Cl1 | 2.223 (3) | Zn—N2 | 2.056 (6) |
Zn—Cl2 | 2.270 (3) | Zn—N5 | 2.089 (8) |
N2—Zn—N5 | 111.8 (3) | N2—Zn—Cl2 | 105.5 (2) |
N2—Zn—Cl1 | 116.5 (2) | N5—Zn—Cl2 | 101.7 (2) |
N5—Zn—Cl1 | 105.8 (2) | Cl1—Zn—Cl2 | 114.67 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···N4 | 0.86 | 2.01 | 2.864 (10) | 174.00 |
N3—H3C···Cl2i | 0.86 | 2.53 | 3.332 (8) | 156.00 |
N6—H6B···Cl1 | 0.86 | 2.53 | 3.320 (9) | 152.00 |
N6—H6C···Cl2ii | 0.86 | 2.60 | 3.345 (8) | 146.00 |
C5—H5A···S1 | 0.93 | 2.62 | 3.040 (10) | 108.00 |
C10—H10C···Cl2iii | 0.96 | 2.68 | 3.599 (12) | 161.00 |
C16—H16A···S2 | 0.93 | 2.85 | 3.184 (10) | 103.00 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x−1, y, z. |
Acknowledgements
The authors thank Professor Hua-Qin Wang, Analysis Centre, Nanjing University, for performing the X-ray crystallographic analysis.
References
Alzuet, G., Borras, J., Estevan, F., Liu-Gonzalez, M. & Sanz-Ruiz, F. (2003). Inorg. Chim. Acta, 343, 56–60. Web of Science CSD CrossRef CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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As a series of superior ligands, thiadiazoles and their derivatives can coordinate to many metal ions with nitrogen or sulfur atoms of the five-membered ring. In particular N,N'-linkage ligands, such as 1,3,4-thiadiazoles, are very versatile compounds that are able to bridge a wide range of inter-metallic separations through two close adjacent N donors (Alzuet et al., 2003). These complexes have received considerable attention in the past few years, due to their certain antibacterial and antifungal activities (Shen et al., 2004).
In the molecule of (I), (Fig. 1), ZnII atom is four-coordinated by two N atoms from two 5-m-tolyl-[1,3,4]thiadiazol-2-ylamine ligands and two Cl anions. It has a distorted tetrahedral coordination geometry (Table 1). Rings A (C2-C7), B (N1/N2/S1/C8/C9), C (N4/N5/S2/C17/C18) and D (C11-C16) are, of course, planar. The dihedral angles between them are A/B = 1.87 (3)°, A/C = 14.55 (3)°, A/D = 27.98 (4)°, B/C = 14.63 (4)°, B/D = 28.43 (3)° and C/D = 14.21 (3)°. The intramolecular N-H···N, N-H···Cl and C-H···S hydrogen bonds (Table 2) result in the formation of one planar F (S1/C4/C5/H5A/C8) and one non-planar G (S2/C15-C17/H16A) five-membered, one non-planar H (Zn/Cl1/N5/N6/H6B/C18) six-membered and one non-planar E (Zn/N2-N5/H3B/C9) seven-membered rings. Ring F is oriented with respect to the adjacent rings A and B at dihedral angles of A/F = 1.74 (3)° and B/F = 1.08 (3)°. So, rings A, B and F are nearly coplanar. Rings E and H have twisted conformations, having total puckering amplitudes, QT, of 0.712 (3) and 0.424 (2) Å, respectively (Cremer & Pople, 1975). Ring G adopts envelope conformation with sulfur atom displaced by -0.541 (3) Å from the plane of the other ring atoms.
In the crystal structure, intermolecular N-H···Cl hydrogen bonds (Table 2) link the molecules to form a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.