1-(5-Benzyl-sulfanyl-2,2-dimethyl-2,3-dihydro-1,3,4-thia-diazol-3-yl)-2,2-dimethyl-propan-1-one.

In the title compound, C(16)H(22)N(2)OS(2), the S atom of the thia-diazole 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 thia-diazole ring is in a twist conformation in both disorder components. The mean plane through the thia-diazole ring makes dihedral angles of 77.39 (8) (major component) and 67.45 (11)° (minor component) with the benzene ring. Intra-molecular C-H⋯N inter-actions generate two S(6) ring motifs. In the crystal, mol-ecules 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 = 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

Δρmax = 0.38 e Å−3

Δρmin = −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 ▶).

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

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

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

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

C16H22N2OS2	F(000) = 688
Mr = 322.48	Dx = 1.274 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6904 reflections
a = 16.6174 (2) Å	θ = 2.9–32.3°
b = 10.5178 (1) Å	µ = 0.32 mm−1
c = 9.6758 (1) Å	T = 100 K
β = 96.345 (1)°	Block, colourless
V = 1680.76 (3) Å3	0.26 × 0.19 × 0.12 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5972 independent reflections
Radiation source: fine-focus sealed tube	4678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 32.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −25→13
Tmin = 0.922, Tmax = 0.962	k = −15→15
22216 measured reflections	l = −12→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0355P)2 + 0.5012P] where P = (Fo2 + 2Fc2)/3
5972 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.36774 (15)	0.26997 (19)	0.2500 (3)	0.0233 (4)	0.641 (11)
S1X	0.3827 (2)	0.28188 (18)	0.2089 (6)	0.0216 (6)	0.359 (11)
S2	0.214397 (18)	0.34659 (3)	0.07503 (3)	0.01843 (7)
O1	0.41502 (5)	−0.14077 (8)	0.14798 (9)	0.02125 (18)
N1	0.28175 (6)	0.11644 (9)	0.08318 (10)	0.01500 (18)
N2	0.34822 (6)	0.04481 (9)	0.13754 (10)	0.01761 (19)
C1	0.09412 (8)	0.41815 (12)	−0.21819 (12)	0.0227 (2)
H1A	0.1467	0.4243	−0.2475	0.027*
C2	0.03192 (8)	0.49319 (13)	−0.28083 (14)	0.0279 (3)
H2A	0.0420	0.5505	−0.3528	0.033*
C3	−0.04488 (8)	0.48490 (12)	−0.23872 (14)	0.0250 (3)
H3A	−0.0875	0.5360	−0.2822	0.030*
C4	−0.05940 (7)	0.40174 (11)	−0.13292 (13)	0.0223 (2)
H4A	−0.1120	0.3961	−0.1036	0.027*
C5	0.00308 (7)	0.32658 (11)	−0.06983 (12)	0.0193 (2)
H5A	−0.0070	0.2701	0.0029	0.023*
C6	0.08002 (7)	0.33358 (10)	−0.11244 (11)	0.0166 (2)
C7	0.14763 (7)	0.25122 (11)	−0.04636 (12)	0.0183 (2)
H7A	0.1786	0.2155	−0.1190	0.022*
H7B	0.1250	0.1798	0.0036	0.022*
C8	0.28772 (7)	0.23196 (10)	0.12453 (11)	0.0161 (2)
C9	0.41461 (7)	0.11385 (10)	0.22346 (11)	0.0159 (2)
C10	0.4419 (3)	0.0577 (4)	0.3624 (4)	0.0267 (7)	0.641 (11)
H10A	0.4695	−0.0232	0.3500	0.040*	0.641 (11)
H10B	0.3949	0.0431	0.4131	0.040*	0.641 (11)
H10C	0.4794	0.1165	0.4153	0.040*	0.641 (11)
C10X	0.4118 (6)	0.0686 (8)	0.3771 (8)	0.0296 (14)	0.359 (11)
H10D	0.4294	−0.0202	0.3860	0.044*	0.359 (11)
H10E	0.3563	0.0760	0.4016	0.044*	0.359 (11)
H10F	0.4479	0.1218	0.4397	0.044*	0.359 (11)
C11	0.4847 (2)	0.1317 (4)	0.1339 (4)	0.0252 (7)	0.641 (11)
H11A	0.5099	0.0491	0.1195	0.038*	0.641 (11)
H11B	0.5251	0.1892	0.1814	0.038*	0.641 (11)
H11C	0.4639	0.1680	0.0438	0.038*	0.641 (11)
C11X	0.4988 (4)	0.1030 (7)	0.1826 (10)	0.0275 (14)	0.359 (11)
H11D	0.5184	0.0158	0.1986	0.041*	0.359 (11)
H11E	0.5346	0.1620	0.2385	0.041*	0.359 (11)
H11F	0.4983	0.1242	0.0839	0.041*	0.359 (11)
C12	0.35519 (7)	−0.08096 (10)	0.10018 (11)	0.0146 (2)
C13	0.28826 (7)	−0.14282 (10)	−0.00111 (11)	0.0147 (2)
C14	0.28175 (7)	−0.07640 (11)	−0.14377 (11)	0.0178 (2)
H14A	0.3346	−0.0783	−0.1799	0.027*
H14B	0.2648	0.0120	−0.1336	0.027*
H14C	0.2417	−0.1207	−0.2086	0.027*
C15	0.20567 (7)	−0.14025 (11)	0.05629 (12)	0.0202 (2)
H15A	0.1667	−0.1908	−0.0041	0.030*
H15B	0.1865	−0.0523	0.0592	0.030*
H15C	0.2112	−0.1760	0.1504	0.030*
C16	0.31270 (8)	−0.28173 (10)	−0.02075 (13)	0.0210 (2)
H16A	0.3649	−0.2846	−0.0588	0.031*
H16B	0.2715	−0.3239	−0.0852	0.031*
H16C	0.3173	−0.3255	0.0692	0.031*

	U11	U22	U33	U12	U13	U23
S1	0.0205 (5)	0.0179 (4)	0.0287 (7)	0.0056 (3)	−0.0097 (5)	−0.0087 (4)
S1X	0.0196 (8)	0.0125 (4)	0.0302 (13)	−0.0001 (4)	−0.0078 (8)	−0.0024 (6)
S2	0.01715 (14)	0.01447 (12)	0.02242 (14)	0.00448 (10)	−0.00341 (11)	−0.00322 (10)
O1	0.0199 (4)	0.0168 (4)	0.0253 (4)	0.0047 (3)	−0.0053 (3)	−0.0004 (3)
N1	0.0120 (4)	0.0150 (4)	0.0175 (4)	0.0024 (3)	−0.0007 (3)	0.0005 (3)
N2	0.0152 (5)	0.0142 (4)	0.0215 (5)	0.0033 (3)	−0.0065 (4)	−0.0029 (3)
C1	0.0196 (6)	0.0273 (6)	0.0219 (6)	0.0068 (5)	0.0048 (5)	0.0048 (5)
C2	0.0276 (7)	0.0321 (7)	0.0243 (6)	0.0092 (5)	0.0042 (5)	0.0108 (5)
C3	0.0204 (6)	0.0257 (6)	0.0277 (6)	0.0078 (5)	−0.0030 (5)	0.0033 (5)
C4	0.0147 (5)	0.0203 (5)	0.0314 (6)	0.0012 (4)	0.0002 (5)	−0.0008 (5)
C5	0.0177 (6)	0.0171 (5)	0.0227 (5)	−0.0007 (4)	0.0003 (4)	0.0007 (4)
C6	0.0167 (5)	0.0152 (5)	0.0168 (5)	0.0029 (4)	−0.0024 (4)	−0.0018 (4)
C7	0.0169 (5)	0.0163 (5)	0.0204 (5)	0.0027 (4)	−0.0037 (4)	−0.0021 (4)
C8	0.0149 (5)	0.0157 (5)	0.0171 (5)	0.0023 (4)	−0.0013 (4)	−0.0013 (4)
C9	0.0143 (5)	0.0144 (4)	0.0180 (5)	0.0018 (4)	−0.0029 (4)	−0.0025 (4)
C10	0.037 (2)	0.0245 (11)	0.0163 (13)	−0.0004 (14)	−0.0060 (14)	−0.0003 (9)
C10X	0.043 (4)	0.025 (2)	0.020 (2)	−0.009 (3)	0.001 (3)	0.0002 (17)
C11	0.0236 (14)	0.0246 (14)	0.0280 (16)	−0.0058 (10)	0.0061 (12)	−0.0046 (11)
C11X	0.020 (2)	0.024 (2)	0.040 (4)	−0.0046 (18)	0.007 (2)	−0.010 (2)
C12	0.0162 (5)	0.0134 (4)	0.0142 (5)	0.0011 (4)	0.0018 (4)	0.0008 (4)
C13	0.0153 (5)	0.0136 (4)	0.0149 (5)	−0.0005 (4)	0.0007 (4)	−0.0004 (4)
C14	0.0199 (6)	0.0182 (5)	0.0147 (5)	−0.0004 (4)	−0.0004 (4)	−0.0001 (4)
C15	0.0178 (6)	0.0202 (5)	0.0229 (5)	−0.0037 (4)	0.0043 (5)	−0.0005 (4)
C16	0.0258 (6)	0.0142 (5)	0.0223 (5)	0.0004 (4)	−0.0004 (5)	−0.0015 (4)

S1—C8	1.7448 (16)	C9—C11	1.539 (3)
S1—C9	1.8473 (15)	C9—C10X	1.566 (8)
S1X—C8	1.774 (2)	C10—H10A	0.9800
S1X—C9	1.846 (2)	C10—H10B	0.9800
S2—C8	1.7432 (11)	C10—H10C	0.9800
S2—C7	1.8245 (12)	C10X—H10D	0.9800
O1—C12	1.2233 (13)	C10X—H10E	0.9800
N1—C8	1.2795 (14)	C10X—H10F	0.9800
N1—N2	1.3913 (13)	C11—H11A	0.9800
N2—C12	1.3796 (14)	C11—H11B	0.9800
N2—C9	1.4942 (14)	C11—H11C	0.9800
C1—C2	1.3857 (17)	C11X—H11D	0.9800
C1—C6	1.3950 (16)	C11X—H11E	0.9800
C1—H1A	0.9500	C11X—H11F	0.9800
C2—C3	1.3847 (18)	C12—C13	1.5428 (15)
C2—H2A	0.9500	C13—C16	1.5339 (15)
C3—C4	1.3878 (18)	C13—C15	1.5365 (16)
C3—H3A	0.9500	C13—C14	1.5401 (15)
C4—C5	1.3912 (17)	C14—H14A	0.9800
C4—H4A	0.9500	C14—H14B	0.9800
C5—C6	1.3880 (16)	C14—H14C	0.9800
C5—H5A	0.9500	C15—H15A	0.9800
C6—C7	1.5042 (16)	C15—H15B	0.9800
C7—H7A	0.9900	C15—H15C	0.9800
C7—H7B	0.9900	C16—H16A	0.9800
C9—C10	1.492 (4)	C16—H16B	0.9800
C9—C11X	1.499 (6)	C16—H16C	0.9800
C8—S1—C9	90.02 (7)	C11X—C9—S1	121.6 (2)
C8—S1X—C9	89.16 (10)	C11—C9—S1	109.09 (13)
C8—S2—C7	98.83 (5)	C10X—C9—S1	94.7 (3)
C8—N1—N2	111.41 (9)	C9—C10—H10A	109.5
C12—N2—N1	120.42 (9)	C9—C10—H10B	109.5
C12—N2—C9	122.25 (9)	C9—C10—H10C	109.5
N1—N2—C9	116.98 (8)	C9—C10X—H10D	109.5
C2—C1—C6	120.42 (12)	C9—C10X—H10E	109.5
C2—C1—H1A	119.8	H10D—C10X—H10E	109.5
C6—C1—H1A	119.8	C9—C10X—H10F	109.5
C3—C2—C1	120.18 (12)	H10D—C10X—H10F	109.5
C3—C2—H2A	119.9	H10E—C10X—H10F	109.5
C1—C2—H2A	119.9	C9—C11—H11A	109.5
C2—C3—C4	119.85 (11)	C9—C11—H11B	109.5
C2—C3—H3A	120.1	C9—C11—H11C	109.5
C4—C3—H3A	120.1	C9—C11X—H11D	109.5
C3—C4—C5	119.98 (12)	C9—C11X—H11E	109.5
C3—C4—H4A	120.0	H11D—C11X—H11E	109.5
C5—C4—H4A	120.0	C9—C11X—H11F	109.5
C6—C5—C4	120.45 (11)	H11D—C11X—H11F	109.5
C6—C5—H5A	119.8	H11E—C11X—H11F	109.5
C4—C5—H5A	119.8	O1—C12—N2	118.84 (10)
C5—C6—C1	119.12 (11)	O1—C12—C13	121.47 (9)
C5—C6—C7	120.83 (10)	N2—C12—C13	119.69 (9)
C1—C6—C7	120.06 (11)	C16—C13—C15	108.72 (9)
C6—C7—S2	109.24 (8)	C16—C13—C14	108.32 (9)
C6—C7—H7A	109.8	C15—C13—C14	109.81 (9)
S2—C7—H7A	109.8	C16—C13—C12	107.35 (9)
C6—C7—H7B	109.8	C15—C13—C12	111.90 (9)
S2—C7—H7B	109.8	C14—C13—C12	110.64 (9)
H7A—C7—H7B	108.3	C13—C14—H14A	109.5
N1—C8—S2	122.90 (9)	C13—C14—H14B	109.5
N1—C8—S1	117.51 (10)	H14A—C14—H14B	109.5
S2—C8—S1	119.24 (7)	C13—C14—H14C	109.5
N1—C8—S1X	117.33 (12)	H14A—C14—H14C	109.5
S2—C8—S1X	118.74 (9)	H14B—C14—H14C	109.5
C10—C9—N2	116.2 (2)	C13—C15—H15A	109.5
C10—C9—C11X	90.4 (3)	C13—C15—H15B	109.5
N2—C9—C11X	118.0 (3)	H15A—C15—H15B	109.5
C10—C9—C11	112.43 (18)	C13—C15—H15C	109.5
N2—C9—C11	107.73 (16)	H15A—C15—H15C	109.5
N2—C9—C10X	106.4 (3)	H15B—C15—H15C	109.5
C11X—C9—C10X	110.7 (3)	C13—C16—H16A	109.5
N2—C9—S1X	103.56 (9)	C13—C16—H16B	109.5
C11X—C9—S1X	108.7 (2)	H16A—C16—H16B	109.5
C10X—C9—S1X	109.0 (3)	C13—C16—H16C	109.5
C10—C9—S1	108.51 (15)	H16A—C16—H16C	109.5
N2—C9—S1	102.27 (8)	H16B—C16—H16C	109.5
C8—N1—N2—C12	−176.95 (10)	N1—N2—C9—C11	−103.8 (2)
C8—N1—N2—C9	−3.69 (13)	C12—N2—C9—C10X	−77.1 (4)
C6—C1—C2—C3	0.1 (2)	N1—N2—C9—C10X	109.8 (4)
C1—C2—C3—C4	0.4 (2)	C12—N2—C9—S1X	168.1 (2)
C2—C3—C4—C5	−0.26 (19)	N1—N2—C9—S1X	−5.0 (3)
C3—C4—C5—C6	−0.34 (18)	C12—N2—C9—S1	−175.75 (17)
C4—C5—C6—C1	0.79 (17)	N1—N2—C9—S1	11.12 (18)
C4—C5—C6—C7	−179.04 (11)	C8—S1X—C9—C10	−123.1 (4)
C2—C1—C6—C5	−0.66 (18)	C8—S1X—C9—N2	8.7 (3)
C2—C1—C6—C7	179.17 (12)	C8—S1X—C9—C11X	135.0 (5)
C5—C6—C7—S2	−103.10 (11)	C8—S1X—C9—C11	118.0 (4)
C1—C6—C7—S2	77.07 (12)	C8—S1X—C9—C10X	−104.3 (5)
C8—S2—C7—C6	−176.36 (8)	C8—S1X—C9—S1	−78.5 (3)
N2—N1—C8—S2	179.94 (8)	C8—S1—C9—C10	−134.8 (3)
N2—N1—C8—S1	−7.0 (2)	C8—S1—C9—N2	−11.51 (19)
N2—N1—C8—S1X	11.7 (3)	C8—S1—C9—C11X	122.7 (5)
C7—S2—C8—N1	−4.34 (11)	C8—S1—C9—C11	102.4 (3)
C7—S2—C8—S1	−177.32 (18)	C8—S1—C9—C10X	−119.5 (4)
C7—S2—C8—S1X	163.8 (3)	C8—S1—C9—S1X	84.9 (3)
C9—S1—C8—N1	11.8 (2)	N1—N2—C12—O1	178.79 (10)
C9—S1—C8—S2	−174.86 (9)	C9—N2—C12—O1	5.89 (16)
C9—S1—C8—S1X	−81.9 (3)	N1—N2—C12—C13	−0.76 (15)
C9—S1X—C8—N1	−12.7 (3)	C9—N2—C12—C13	−173.67 (9)
C9—S1X—C8—S2	178.57 (12)	O1—C12—C13—C16	1.05 (14)
C9—S1X—C8—S1	82.3 (3)	N2—C12—C13—C16	−179.41 (10)
C12—N2—C9—C10	−57.8 (3)	O1—C12—C13—C15	120.25 (11)
N1—N2—C9—C10	129.1 (2)	N2—C12—C13—C15	−60.21 (13)
C12—N2—C9—C11X	48.0 (5)	O1—C12—C13—C14	−116.95 (11)
N1—N2—C9—C11X	−125.2 (4)	N2—C12—C13—C14	62.59 (13)
C12—N2—C9—C11	69.4 (2)

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

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

Symmetry code: (i) .