(±)-N-[4-Acetyl-5-methyl-5-(4-methyl-cyclo-hex-3-en-yl)-4,5-dihydro-1,3,4-thia-diazol-2-yl]acetamide.

The new title thiadiazole compound, C(14)H(21)N(3)O(2)S, was semi-synthesized starting from 1-(4-methyl-cyclo-hex-3-en-yl)ethanone, a natural product isolated from Cedrus atlantica essential oil. The stereochemistry has been confirmed by single-crystal X-ray diffraction. The thia-diazo-line ring is roughly planar, although it may be regarded as having a half-chair conformation. The cyclo-hexenyl ring has a half-chair conformation. The most inter-esting feature is the formation of a pseudo-ring formed by four mol-ecules associated through N-H⋯O hydrogen bonds around a fourfold inversion axis, forming an R(4) (4)(28) motif.

Related literature

For related literature, see: Aly et al. (2007 ▶); Beatriz et al. (2002 ▶); Bernstein et al. (1995 ▶); Cremer & Pople (1975 ▶); Demirbas et al. (2005 ▶); Etter et al. (1990 ▶); Farghaly et al. (2006 ▶); Invidiata et al. (1996 ▶); Kubota et al. (1982 ▶); Nizamuddin et al. (1999 ▶); Ourhriss et al. (2005 ▶); Paolo et al. (2005 ▶); Radul et al. (2005 ▶); Sun et al. (1999 ▶); Udupi et al. (2000 ▶).

Experimental

Crystal data

C14H21N3O2S

M = 295.40

Tetragonal,

a = 16.6855 (3) Å

c = 21.8961 (8) Å

V = 6096.0 (3) Å3

Z = 16

Mo Kα radiation

μ = 0.22 mm−1

T = 180 (2) K

0.29 × 0.24 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: none

87517 measured reflections

4637 independent reflections

3849 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.113

S = 1.11

4637 reflections

185 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1993 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004728/bg2164sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004728/bg2164Isup2.hkl

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

C14H21N3O2S	Z = 16
Mr = 295.40	F000 = 2528
Tetragonal, I41/a	Dx = 1.287 Mg m−3
Hall symbol: -I 4ad	Mo Kα radiation λ = 0.71073 Å
a = 16.6855 (3) Å	Cell parameters from 9915 reflections
b = 16.6855 (3) Å	θ = 2.5–36.1º
c = 21.8961 (8) Å	µ = 0.22 mm−1
α = 90º	T = 180 (2) K
β = 90º	Platelet, colourless
γ = 90º	0.29 × 0.24 × 0.08 mm
V = 6096.0 (3) Å3

Bruker APEXII CCD area-detector diffractometer	3849 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Monochromator: graphite	θmax = 30.5º
T = 180(2) K	θmin = 2.4º
φ and ω scans	h = −23→23
Absorption correction: none	k = −23→23
87517 measured reflections	l = −31→31
4637 independent reflections

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.0505P)2 + 5.869P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
4637 reflections	Δρmax = 0.39 e Å−3
185 parameters	Δρmin = −0.26 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
C1	0.65060 (7)	0.64068 (7)	0.33934 (6)	0.0214 (2)
C2	0.64575 (8)	0.56723 (8)	0.29765 (6)	0.0287 (3)
H2A	0.6800	0.5755	0.2618	0.043*
H2B	0.5902	0.5594	0.2844	0.043*
H2C	0.6639	0.5197	0.3200	0.043*
C3	0.68632 (7)	0.78535 (7)	0.31834 (6)	0.0211 (2)
C11	0.79352 (7)	0.62428 (7)	0.37378 (6)	0.0235 (2)
C12	0.87096 (7)	0.66585 (8)	0.38792 (7)	0.0281 (3)
H12A	0.9094	0.6270	0.4043	0.042*
H12B	0.8615	0.7081	0.4182	0.042*
H12C	0.8926	0.6897	0.3505	0.042*
C31	0.62901 (8)	0.90880 (8)	0.27886 (6)	0.0270 (2)
C32	0.64169 (10)	0.99767 (9)	0.27574 (10)	0.0446 (4)
H32A	0.6634	1.0120	0.2356	0.067*
H32B	0.6796	1.0140	0.3076	0.067*
H32C	0.5904	1.0252	0.2820	0.067*
C1'	0.61004 (7)	0.62529 (7)	0.40168 (6)	0.0230 (2)
H1'	0.6342	0.5754	0.4190	0.028*
C2'	0.52001 (8)	0.61027 (9)	0.39510 (6)	0.0298 (3)
H2E	0.4950	0.6567	0.3743	0.036*
H2F	0.5114	0.5624	0.3693	0.036*
C3'	0.47984 (9)	0.59770 (10)	0.45606 (7)	0.0360 (3)
H3'	0.4307	0.5690	0.4578	0.043*
C4'	0.51280 (9)	0.62689 (10)	0.50920 (7)	0.0351 (3)
C5'	0.58895 (11)	0.66893 (12)	0.50955 (7)	0.0433 (4)
H5A	0.6287	0.6349	0.5309	0.052*
H5B	0.5825	0.7184	0.5340	0.052*
C6'	0.62334 (9)	0.69185 (9)	0.44820 (6)	0.0309 (3)
H6A	0.6815	0.7023	0.4524	0.037*
H6B	0.5975	0.7417	0.4336	0.037*
C7'	0.47125 (12)	0.61447 (13)	0.56956 (8)	0.0504 (4)
H71	0.4231	0.5818	0.5634	0.076*
H72	0.4561	0.6665	0.5867	0.076*
H73	0.5076	0.5869	0.5978	0.076*
S1	0.604309 (17)	0.726031 (18)	0.298610 (14)	0.02284 (9)
O1	0.78216 (6)	0.55218 (6)	0.38435 (5)	0.0313 (2)
O2	0.57194 (6)	0.87583 (6)	0.25536 (5)	0.0338 (2)
N1	0.73445 (6)	0.66905 (6)	0.34821 (5)	0.0224 (2)
N2	0.74763 (6)	0.75163 (6)	0.34255 (5)	0.0231 (2)
N3	0.68691 (6)	0.86761 (6)	0.31029 (5)	0.0251 (2)
H3	0.7268	0.8951	0.3263	0.030*

	U11	U22	U33	U12	U13	U23
C1	0.0182 (5)	0.0197 (5)	0.0262 (5)	−0.0009 (4)	−0.0014 (4)	−0.0010 (4)
C2	0.0296 (6)	0.0251 (6)	0.0312 (6)	−0.0016 (5)	−0.0005 (5)	−0.0063 (5)
C3	0.0177 (5)	0.0211 (5)	0.0245 (5)	−0.0012 (4)	0.0000 (4)	0.0011 (4)
C11	0.0200 (5)	0.0228 (5)	0.0277 (6)	0.0034 (4)	−0.0003 (4)	0.0000 (4)
C12	0.0202 (5)	0.0264 (6)	0.0376 (7)	0.0022 (4)	−0.0047 (5)	0.0019 (5)
C31	0.0242 (6)	0.0267 (6)	0.0302 (6)	0.0032 (4)	0.0007 (5)	0.0060 (5)
C32	0.0397 (8)	0.0253 (7)	0.0687 (12)	0.0039 (6)	−0.0089 (8)	0.0114 (7)
C1'	0.0211 (5)	0.0236 (5)	0.0244 (5)	−0.0011 (4)	−0.0006 (4)	0.0008 (4)
C2'	0.0239 (6)	0.0370 (7)	0.0287 (6)	−0.0066 (5)	−0.0005 (5)	0.0027 (5)
C3'	0.0288 (7)	0.0432 (8)	0.0359 (7)	−0.0025 (6)	0.0059 (5)	0.0077 (6)
C4'	0.0340 (7)	0.0396 (8)	0.0318 (7)	0.0040 (6)	0.0066 (6)	0.0060 (6)
C5'	0.0507 (9)	0.0514 (9)	0.0278 (7)	−0.0088 (7)	0.0052 (6)	−0.0059 (6)
C6'	0.0320 (7)	0.0322 (7)	0.0286 (6)	−0.0054 (5)	0.0009 (5)	−0.0046 (5)
C7'	0.0547 (11)	0.0607 (11)	0.0360 (8)	−0.0001 (9)	0.0146 (8)	0.0057 (8)
S1	0.01844 (14)	0.02350 (15)	0.02657 (15)	−0.00176 (10)	−0.00422 (10)	0.00242 (10)
O1	0.0263 (4)	0.0217 (4)	0.0460 (6)	0.0025 (3)	−0.0046 (4)	0.0038 (4)
O2	0.0284 (5)	0.0368 (5)	0.0361 (5)	0.0003 (4)	−0.0088 (4)	0.0073 (4)
N1	0.0171 (4)	0.0185 (4)	0.0316 (5)	0.0000 (3)	−0.0017 (4)	0.0015 (4)
N2	0.0183 (4)	0.0195 (4)	0.0314 (5)	−0.0011 (3)	−0.0014 (4)	0.0024 (4)
N3	0.0200 (5)	0.0208 (5)	0.0345 (6)	−0.0007 (4)	−0.0038 (4)	0.0035 (4)

C1—N1	1.4897 (15)	C32—H32C	0.9800
C1—C2	1.5303 (17)	C1'—C6'	1.5232 (18)
C1—C1'	1.5451 (17)	C1'—C2'	1.5298 (17)
C1—S1	1.8493 (12)	C1'—H1'	1.0000
C2—H2A	0.9800	C2'—C3'	1.508 (2)
C2—H2B	0.9800	C2'—H2E	0.9900
C2—H2C	0.9800	C2'—H2F	0.9900
C3—N2	1.2822 (15)	C3'—C4'	1.376 (2)
C3—N3	1.3839 (15)	C3'—H3'	0.9500
C3—S1	1.7431 (12)	C4'—C5'	1.451 (2)
C11—O1	1.2396 (15)	C4'—C7'	1.507 (2)
C11—N1	1.3577 (15)	C5'—C6'	1.510 (2)
C11—C12	1.4987 (18)	C5'—H5A	0.9900
C12—H12A	0.9800	C5'—H5B	0.9900
C12—H12B	0.9800	C6'—H6A	0.9900
C12—H12C	0.9800	C6'—H6B	0.9900
C31—O2	1.2141 (17)	C7'—H71	0.9800
C31—N3	1.3710 (16)	C7'—H72	0.9800
C31—C32	1.499 (2)	C7'—H73	0.9800
C32—H32A	0.9800	N1—N2	1.4009 (14)
C32—H32B	0.9800	N3—H3	0.8800
N1—C1—C2	112.45 (10)	C3'—C2'—C1'	112.07 (12)
N1—C1—C1'	110.42 (10)	C3'—C2'—H2E	109.2
C2—C1—C1'	111.76 (10)	C1'—C2'—H2E	109.2
N1—C1—S1	102.15 (7)	C3'—C2'—H2F	109.2
C2—C1—S1	107.88 (9)	C1'—C2'—H2F	109.2
C1'—C1—S1	111.79 (8)	H2E—C2'—H2F	107.9
C1—C2—H2A	109.5	C4'—C3'—C2'	121.44 (13)
C1—C2—H2B	109.5	C4'—C3'—H3'	119.3
H2A—C2—H2B	109.5	C2'—C3'—H3'	119.3
C1—C2—H2C	109.5	C3'—C4'—C5'	121.69 (14)
H2A—C2—H2C	109.5	C3'—C4'—C7'	120.61 (15)
H2B—C2—H2C	109.5	C5'—C4'—C7'	117.69 (15)
N2—C3—N3	118.82 (11)	C4'—C5'—C6'	116.78 (14)
N2—C3—S1	118.67 (9)	C4'—C5'—H5A	108.1
N3—C3—S1	122.49 (9)	C6'—C5'—H5A	108.1
O1—C11—N1	119.99 (11)	C4'—C5'—H5B	108.1
O1—C11—C12	122.86 (11)	C6'—C5'—H5B	108.1
N1—C11—C12	117.15 (11)	H5A—C5'—H5B	107.3
C11—C12—H12A	109.5	C5'—C6'—C1'	110.78 (12)
C11—C12—H12B	109.5	C5'—C6'—H6A	109.5
H12A—C12—H12B	109.5	C1'—C6'—H6A	109.5
C11—C12—H12C	109.5	C5'—C6'—H6B	109.5
H12A—C12—H12C	109.5	C1'—C6'—H6B	109.5
H12B—C12—H12C	109.5	H6A—C6'—H6B	108.1
O2—C31—N3	122.57 (12)	C4'—C7'—H71	109.5
O2—C31—C32	122.65 (13)	C4'—C7'—H72	109.5
N3—C31—C32	114.79 (12)	H71—C7'—H72	109.5
C31—C32—H32A	109.5	C4'—C7'—H73	109.5
C31—C32—H32B	109.5	H71—C7'—H73	109.5
H32A—C32—H32B	109.5	H72—C7'—H73	109.5
C31—C32—H32C	109.5	C3—S1—C1	89.42 (5)
H32A—C32—H32C	109.5	C11—N1—N2	117.63 (10)
H32B—C32—H32C	109.5	C11—N1—C1	124.11 (10)
C6'—C1'—C2'	109.00 (11)	N2—N1—C1	116.65 (9)
C6'—C1'—C1	113.93 (10)	C3—N2—N1	110.05 (10)
C2'—C1'—C1	111.97 (10)	C31—N3—C3	123.79 (11)
C6'—C1'—H1'	107.2	C31—N3—H3	118.1
C2'—C1'—H1'	107.2	C3—N3—H3	118.1
C1—C1'—H1'	107.2

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1i	0.88	1.95	2.8223 (14)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1i	0.88	1.95	2.8223 (14)	171

Symmetry code: (i) .