Abstract
In the crystal structure of the title compound, C5H3Cl3N4S, two molecules related by a centre of symmetry demonstrate extremely short intermolecular S⋯N contacts of 2.783 (2) Å. The crystal packing also exhibits π–π interactions indicated by a short distance of 3.340 (1) Å between the centroids of the triazole rings of neighbouring molecules.
Related literature
For the antimicrobial and anti-inflammatory activity of 1,2,4-triazole and 1,3,4-thiodiazole derivatives, see: Karabasanagouda et al. (2007 ▶); Mathew et al. (2007 ▶); For related structures, see: Du et al. (2008 ▶); Khan et al. (2009 ▶); Haugwitz et al. (1977 ▶). 
Experimental
Crystal data
C5H3Cl3N4S
M r = 257.52
Monoclinic,
a = 5.8732 (12) Å
b = 9.4164 (19) Å
c = 16.750 (3) Å
β = 91.82 (3)°
V = 925.9 (3) Å3
Z = 4
Mo Kα radiation
μ = 1.17 mm−1
T = 153 K
0.30 × 0.20 × 0.10 mm
Data collection
Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.721, T max = 0.892
9841 measured reflections
2196 independent reflections
1934 reflections with I > 2σ(I)
R int = 0.038
Refinement
R[F 2 > 2σ(F 2)] = 0.029
wR(F 2) = 0.113
S = 1.24
2196 reflections
120 parameters
H-atom parameters constrained
Δρmax = 0.49 e Å−3
Δρmin = −0.44 e Å−3
Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.
Supplementary Material
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012748/cv5070sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012748/cv5070Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
We gratefully acknowledge financial support by the Key Laboratory Project of Liaoning Province (grant No. 2008S127) and the Doctor Starting Foundation of Liaoning Province (grant No. 20071103).
supplementary crystallographic information
Comment
1,2,4-Triazole and 1,3,4-thiodiazole derivatives demonstrate various activities such as antimicrobial (Karabasanagouda et al., 2007) and anti-inflammatory (Mathew et al., 2007) activities. Herewith we report the synthesis and crystal structure of the title compound (I), a new derivative from the aforementioned family.
In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related structures (Du et al., 2008; Khan et al., 2009). The triazolothiadiazole ring system is essentially planar with an r.m.s derivation of 0.0087 (2)Å and maximum deviation of 0.0037 (2)Å for atom C2. In the crystal structure, π-π interactions (Table 1) consolidate the crystal packing, which exhibits short intermolecular S···N contacts of 2.783 (2) Å observed eralier in the related structure (Haugwitz et al., 1977).
Experimental
The title compound was synthesized by the reaction of 4-amino-3-methyl-4H-1,2,4-triazole-5-thiol (2.0 mmol) and trichloroacetic acid (2.0 mmol) in phosphoryl trichloride for 24 h. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1).
Refinement
H atoms were positioned geometrically (C—H = 0.98 Å) and refined as riding, with Uiso(H) = 1.5Ueq(parent).
Figures
Fig. 1.
View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 60% probability level.
Crystal data
| C5H3Cl3N4S | F(000) = 512 |
| Mr = 257.52 | Dx = 1.847 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2918 reflections |
| a = 5.8732 (12) Å | θ = 3.3–27.9° |
| b = 9.4164 (19) Å | µ = 1.17 mm−1 |
| c = 16.750 (3) Å | T = 153 K |
| β = 91.82 (3)° | Prism, colorless |
| V = 925.9 (3) Å3 | 0.30 × 0.20 × 0.10 mm |
| Z = 4 |
Data collection
| Rigaku Saturn CCD area-detector diffractometer | 2196 independent reflections |
| Radiation source: rotating anode | 1934 reflections with I > 2σ(I) |
| multilayer | Rint = 0.038 |
| Detector resolution: 7.31 pixels mm-1 | θmax = 27.9°, θmin = 2.4° |
| φ and ω scans | h = −7→7 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −10→12 |
| Tmin = 0.721, Tmax = 0.892 | l = −22→22 |
| 9841 measured reflections |
Refinement
| 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)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0693P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.24 | (Δ/σ)max < 0.001 |
| 2196 reflections | Δρmax = 0.49 e Å−3 |
| 120 parameters | Δρmin = −0.44 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.071 (6) |
Special details
| 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.13777 (9) | 0.52705 (5) | 0.13657 (3) | 0.01622 (19) | |
| Cl1 | 0.55694 (10) | 0.67616 (5) | 0.27560 (3) | 0.0242 (2) | |
| Cl2 | 0.15047 (9) | 0.53079 (6) | 0.32341 (3) | 0.02410 (19) | |
| Cl3 | 0.58496 (8) | 0.38759 (5) | 0.33267 (3) | 0.01648 (18) | |
| N1 | 0.3533 (3) | 0.30847 (19) | −0.04370 (11) | 0.0193 (4) | |
| N2 | 0.1853 (3) | 0.40411 (19) | −0.01768 (11) | 0.0191 (4) | |
| N3 | 0.4320 (3) | 0.35972 (16) | 0.08095 (10) | 0.0134 (4) | |
| N4 | 0.5132 (3) | 0.37661 (17) | 0.15796 (10) | 0.0133 (4) | |
| C1 | 0.7018 (4) | 0.1903 (2) | 0.01481 (13) | 0.0223 (5) | |
| H1A | 0.7271 | 0.1594 | −0.0401 | 0.033* | |
| H1B | 0.6776 | 0.1070 | 0.0486 | 0.033* | |
| H1C | 0.8353 | 0.2430 | 0.0352 | 0.033* | |
| C2 | 0.4981 (3) | 0.2833 (2) | 0.01591 (12) | 0.0158 (4) | |
| C3 | 0.2385 (3) | 0.4306 (2) | 0.05699 (12) | 0.0151 (4) | |
| C4 | 0.3744 (3) | 0.46089 (19) | 0.19257 (12) | 0.0135 (4) | |
| C5 | 0.4165 (3) | 0.5096 (2) | 0.27709 (11) | 0.0136 (4) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0153 (3) | 0.0166 (3) | 0.0165 (3) | 0.00419 (18) | −0.0027 (2) | −0.00059 (17) |
| Cl1 | 0.0359 (4) | 0.0136 (3) | 0.0227 (3) | −0.0086 (2) | −0.0055 (2) | 0.00025 (18) |
| Cl2 | 0.0186 (3) | 0.0337 (4) | 0.0202 (3) | 0.0075 (2) | 0.0050 (2) | −0.0021 (2) |
| Cl3 | 0.0186 (3) | 0.0164 (3) | 0.0143 (3) | 0.00304 (18) | −0.00199 (19) | 0.00178 (16) |
| N1 | 0.0204 (9) | 0.0206 (9) | 0.0169 (9) | −0.0011 (7) | −0.0001 (7) | −0.0020 (7) |
| N2 | 0.0201 (9) | 0.0214 (9) | 0.0157 (9) | 0.0021 (7) | −0.0023 (7) | −0.0011 (7) |
| N3 | 0.0142 (8) | 0.0127 (8) | 0.0133 (8) | −0.0010 (6) | −0.0022 (6) | 0.0002 (6) |
| N4 | 0.0132 (8) | 0.0145 (8) | 0.0122 (8) | −0.0015 (6) | −0.0015 (6) | 0.0002 (6) |
| C1 | 0.0240 (12) | 0.0254 (11) | 0.0176 (10) | 0.0059 (9) | 0.0015 (8) | −0.0031 (8) |
| C2 | 0.0180 (10) | 0.0155 (9) | 0.0142 (9) | −0.0029 (8) | 0.0017 (7) | −0.0013 (7) |
| C3 | 0.0133 (10) | 0.0135 (9) | 0.0184 (10) | 0.0013 (8) | −0.0018 (8) | 0.0022 (7) |
| C4 | 0.0145 (10) | 0.0121 (9) | 0.0136 (9) | −0.0009 (7) | −0.0007 (7) | 0.0027 (7) |
| C5 | 0.0138 (9) | 0.0110 (8) | 0.0162 (10) | 0.0023 (7) | 0.0008 (7) | 0.0009 (7) |
Geometric parameters (Å, °)
| S1—C3 | 1.732 (2) | N3—N4 | 1.370 (2) |
| S1—C4 | 1.765 (2) | N3—C2 | 1.372 (3) |
| Cl1—C5 | 1.772 (2) | N4—C4 | 1.289 (3) |
| Cl2—C5 | 1.778 (2) | C1—C2 | 1.483 (3) |
| Cl3—C5 | 1.763 (2) | C1—H1A | 0.9800 |
| N1—C2 | 1.313 (3) | C1—H1B | 0.9800 |
| N1—N2 | 1.415 (2) | C1—H1C | 0.9800 |
| N2—C3 | 1.304 (3) | C4—C5 | 1.501 (3) |
| N3—C3 | 1.367 (3) | ||
| Cg1···Cg1i | 3.340 (1) | Cg1···Cg2i | 3.682 (1) |
| C3—S1—C4 | 86.65 (9) | N1—C2—C1 | 126.9 (2) |
| C2—N1—N2 | 108.78 (17) | N3—C2—C1 | 124.63 (18) |
| C3—N2—N1 | 105.63 (17) | N2—C3—N3 | 111.08 (18) |
| C3—N3—N4 | 118.75 (16) | N2—C3—S1 | 139.59 (16) |
| C3—N3—C2 | 106.06 (17) | N3—C3—S1 | 109.33 (14) |
| N4—N3—C2 | 135.19 (17) | N4—C4—C5 | 121.67 (18) |
| C4—N4—N3 | 106.78 (16) | N4—C4—S1 | 118.48 (15) |
| C2—C1—H1A | 109.5 | C5—C4—S1 | 119.77 (15) |
| C2—C1—H1B | 109.5 | C4—C5—Cl3 | 111.82 (14) |
| H1A—C1—H1B | 109.5 | C4—C5—Cl1 | 108.66 (13) |
| C2—C1—H1C | 109.5 | Cl3—C5—Cl1 | 109.30 (11) |
| H1A—C1—H1C | 109.5 | C4—C5—Cl2 | 108.97 (14) |
| H1B—C1—H1C | 109.5 | Cl3—C5—Cl2 | 109.20 (10) |
| N1—C2—N3 | 108.44 (17) | Cl1—C5—Cl2 | 108.84 (10) |
| C2—N1—N2—C3 | −0.4 (2) | C2—N3—C3—S1 | 178.46 (13) |
| C3—N3—N4—C4 | 0.9 (2) | C4—S1—C3—N2 | 179.8 (3) |
| C2—N3—N4—C4 | −178.6 (2) | C4—S1—C3—N3 | 0.80 (14) |
| N2—N1—C2—N3 | −0.2 (2) | N3—N4—C4—C5 | −176.81 (17) |
| N2—N1—C2—C1 | −179.41 (19) | N3—N4—C4—S1 | −0.2 (2) |
| C3—N3—C2—N1 | 0.6 (2) | C3—S1—C4—N4 | −0.36 (16) |
| N4—N3—C2—N1 | −179.8 (2) | C3—S1—C4—C5 | 176.31 (16) |
| C3—N3—C2—C1 | 179.86 (19) | N4—C4—C5—Cl3 | −25.8 (2) |
| N4—N3—C2—C1 | −0.6 (3) | S1—C4—C5—Cl3 | 157.64 (11) |
| N1—N2—C3—N3 | 0.7 (2) | N4—C4—C5—Cl1 | 94.93 (19) |
| N1—N2—C3—S1 | −178.24 (19) | S1—C4—C5—Cl1 | −81.63 (16) |
| N4—N3—C3—N2 | 179.50 (16) | N4—C4—C5—Cl2 | −146.61 (16) |
| C2—N3—C3—N2 | −0.8 (2) | S1—C4—C5—Cl2 | 36.83 (18) |
| N4—N3—C3—S1 | −1.2 (2) |
Symmetry codes: (i) −x+1, −y+1, −z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV5070).
References
- Du, H., Du, H., An, Y. & Li, S. (2008). Acta Cryst. E64, o1402. [DOI] [PMC free article] [PubMed]
- Haugwitz, R. D., Toeplitz, B. & Gougoutas, J. Z. (1977). J. Chem. Soc. Chem. Commun. pp. 736–737.
- Karabasanagouda, T., Adhikari, A. V. & Shetty, S. N. (2007). Eur. J. Med. Chem. 42, 521–529. [DOI] [PubMed]
- Khan, M.-H., Hameed, S., Tahir, M. N., Bokhari, T. H. & Khan, I. U. (2009). Acta Cryst. E65, o1437. [DOI] [PMC free article] [PubMed]
- Mathew, V., Keshavayya, J., Vaidya, V. P. & Giles, D. (2007). Eur. J. Med. Chem. 42, 823–840. [DOI] [PubMed]
- Rigaku/MSC (2005). CrystalClear Molecular Structure Corporation, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012748/cv5070sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012748/cv5070Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report