1-(5-Benzyl­sulfanyl-2,2-dimethyl-2,3-dihydro-1,3,4-thia­diazol-3-yl)-2,2-dimethyl­propan-1-one

Mohd Sukeri Mohd Yusof; Fatimah Abdul Mutalib; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536812012639

. 2012 Mar 31;68(Pt 4):o1228. doi: 10.1107/S1600536812012639

1-(5-Benzylsulfanyl-2,2-dimethyl-2,3-dihydro-1,3,4-thiadiazol-3-yl)-2,2-dimethylpropan-1-one

Mohd Sukeri Mohd Yusof ^a, Fatimah Abdul Mutalib ^a, Suhana Arshad ^b, Ibrahim Abdul Razak ^b,^*,^‡

PMCID: PMC3344160 PMID: 22606163

Abstract

In the title compound, C₁₆H₂₂N₂OS₂, the S atom of the thiadiazole ring and the attached methyl groups are disordered over two orientations with a refined site-occupancy ratio of 0.641 (11):0.359 (11). The thiadiazole ring is in a twist conformation in both disorder components. The mean plane through the thiadiazole ring makes dihedral angles of 77.39 (8) (major component) and 67.45 (11)° (minor component) with the benzene ring. Intramolecular C—H⋯N interactions generate two S(6) ring motifs. In the crystal, molecules are linked by C—H⋯O hydrogen bonds into zigzag chains parallel to the b axis.

Related literature

For background to the pharmacological properties of thiadiazole derivatives, see: Noolvi et al. (2011 ▶); Yusuf et al. (2008 ▶). For a related structure, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₆H₂₂N₂OS₂
M _r = 322.48
Monoclinic,
a = 16.6174 (2) Å
b = 10.5178 (1) Å
c = 9.6758 (1) Å
β = 96.345 (1)°
V = 1680.76 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 100 K
0.26 × 0.19 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.922, T _max = 0.962
22216 measured reflections
5972 independent reflections
4678 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.092
S = 1.02
5972 reflections
225 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812012639/rz2718sup1.cif

e-68-o1228-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012639/rz2718Isup2.hkl

e-68-o1228-Isup2.hkl^{(292.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812012639/rz2718Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯N1	0.98	2.36	2.9893 (15)	122
C15—H15B⋯N1	0.98	2.37	2.9803 (15)	120
C11—H11B⋯O1ⁱ	0.98	2.56	3.490 (4)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Malaysian Government, Universiti Malaysia Terengganu and Universiti Sains Malaysia for research facilities and the Fundamental Research Grant Scheme (FRGS) Nos. 203/PFIZIK/6711171 and FRGS 59166 to conduct this work.

supplementary crystallographic information

Comment

Thiadiazole derivatives have been reported to posses anti-cancer (Noolvi et al., 2011) and anti-depressant activity (Yusuf et al., 2008). The title compound is one of these thiadiazole derivatives, and its crystal structure is reported herein.

In the molecule of the title compound (Fig. 1), the S atom of the thiadiazole ring and the attached dimethyl groups (C10/C10X and C11/C11X) are disordered over two orientations with a refined site-occupancy ratio of 0.641 (11):0.359 (11). The disordered thiadiazole (S1/N1/N2/C8/C9 and S1X/N1/N2/C8/C9) rings are both in twist conformation (Cremer & Pople, 1975) in which the ring is twisted about the C9–S1 bond [puckering parameters: Q = 0.1477 (19) Å and φ= 167.7 (5)°] and about the S1X–C8 bond [puckering parameters: Q = 0.131 (2) Å and φ= 298.6 (8)°], respectively. The mean plane through the thiadiazole rings make dihedral angles of 77.39 (8) and 67.45 (11)°, respectively, with the benzene (C1–C6) ring. Intramolecular C14—H14B···N1 and C15—H15B···N1 interactions (Table 1) generate two S(6) ring motifs (Bernstein et al., 1995). The bond lengths and angles are within normal ranges and are comparable to those reported in a related structure (Fun et al., 2011). The crystal packing is shown in Fig. 2. Intermolecular C11—H11B···O1 (Table 1) hydrogen bonds link the molecules into one dimensional zigzag chains parallel to the b axis.

Experimental

A solution of pivaloylisothiocyanate (1.0 g, 8 mmol) in 30 ml acetone was added into a flask containing 30 ml acetone solution of s-benzyldithiocarbazate (1.5 g, 8.00 mmol). The mixture was refluxed for 4 h, then, the solution was filtered-off and left to evaporate at room temperature. Colourless crystals suitable for X-ray analyisis were obtained after one day on slow evaporation of the solvent (yield 60%, M.p. 503.5–504.5 K, IR(KBr)cm^-1: 1334.72 (ν_C—N), 1547.95 (ν_C_═_N), 1647.08 (ν_C_═_O), 8944.79 (ν_C—S). ¹H NMR (CDCl₃)δp.p.m. 1.289 (s, 9H, -(CH₃)₃), 2.004 (s, 6H, -(CH₃)₂), 4.330 (s, 2H, –CH₂), 7.35–7.45 (m, 2H, ar-H). ¹³C NMR (CDCl₃)δp.p.m. 127.86–135.40 (6 C, ar-C), 144.57 (thiadiazole carbon), 176.72 (C═O), 27.06–37.50(4 C, –C-(CH₃)₃). Anal. Found (calc.) for C₁₆H₂₂N₂OS₂ (%): C, 59.59(58.98); H, 6.88(6.86); N, 8.69(8.66); S, 19.89(19.86).