N-[4-Acetyl-5-isobutyl-5-(2-p-tolyl-prop-yl)-4,5-dihydro-1,3,4-thia-diazol-2-yl]acetamide ethyl acetate hemisolvate.

The racemic title compound, a new terpenoid, C(20)H(29)N(3)O(2)S·0.5C(4)H(8)O(2), was synthesized from Cedrus Atlantica essential oil. The compound crystallizes with a disordered ethyl acetate solvent mol-ecule. The thia-diazole ring is almost planar, with a maximum deviation from the mean plane of 0.015 (2) Å for the C atom connected to the isobutyl group and has a puckering amplitude of 0.026 (2) Å. The dihedral angle between the benzene and thia-diazole rings is 18.32 (8)°. The crystal packing involves inter-molecular N-H⋯O hydrogen bonds.

Related literature

For 1,3,4-thia­diazole derivatives and their biological activity, see: Abdou et al. (1991 ▶); Sakthivel et al. (2008 ▶); Tehranchian et al. (2005 ▶); Wang et al. (1999 ▶, 2004 ▶). For preparative methods, see: Beatriz et al., 2002 ▶; Mohammed et al. (2008 ▶); For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C20H29N3O2S·0.5C4H8O2

M = 419.57

Monoclinic,

a = 7.8713 (3) Å

b = 12.7587 (5) Å

c = 22.9688 (9) Å

β = 90.937 (2)°

V = 2306.39 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.17 mm−1

T = 295 K

0.5 × 0.4 × 0.3 mm

Data collection

Bruker X8 APEX CCD area-detector diffractometer

Absorption correction: none

27541 measured reflections

7243 independent reflections

6688 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.143

S = 1.23

7243 reflections

298 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia,1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039998/fj2168sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039998/fj2168Isup2.hkl

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

C20H29N3O2S·0.5C4H8O2	F(000) = 904
Mr = 419.57	Dx = 1.208 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13322 reflections
a = 7.8713 (3) Å	θ = 2.6–31.5°
b = 12.7587 (5) Å	µ = 0.17 mm−1
c = 22.9688 (9) Å	T = 295 K
β = 90.937 (2)°	Prism, colourless
V = 2306.39 (16) Å3	0.5 × 0.4 × 0.3 mm
Z = 4

Bruker X8 APEX CCD area-detector diffractometer	6688 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
graphite	θmax = 32.0°, θmin = 1.8°
φ and ω scans	h = −11→11
27541 measured reflections	k = −16→18
7243 independent reflections	l = −33→30

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H-atom parameters constrained
S = 1.23	w = 1/[σ2(Fo2) + (0.0435P)2 + 1.5861P] where P = (Fo2 + 2Fc2)/3
7243 reflections	(Δ/σ)max = 0.006
298 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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)
C1'	0.5624 (2)	0.56734 (16)	0.09954 (8)	0.0284 (4)
H1'	0.6130	0.5214	0.0736	0.034*
C2	0.6060 (2)	0.80786 (11)	0.33245 (7)	0.0160 (3)
C2'	0.5345 (2)	0.53523 (13)	0.15666 (8)	0.0231 (3)
H2'	0.5671	0.4681	0.1680	0.028*
C3	0.4619 (2)	0.92243 (12)	0.40282 (7)	0.0189 (3)
C3'	0.4581 (2)	0.60205 (12)	0.19769 (7)	0.0198 (3)
C4'	0.4129 (2)	0.70239 (13)	0.17921 (8)	0.0261 (4)
H4'	0.3636	0.7488	0.2052	0.031*
C4	0.4186 (2)	1.03550 (13)	0.41486 (8)	0.0247 (3)
H41	0.3953	1.0710	0.3788	0.037*
H42	0.5127	1.0687	0.4345	0.037*
H43	0.3202	1.0387	0.4389	0.037*
C5	0.6899 (2)	0.61643 (11)	0.31921 (7)	0.0163 (3)
C5'	0.4414 (3)	0.73375 (16)	0.12186 (9)	0.0334 (4)
H5'	0.4100	0.8011	0.1105	0.040*
C6'	0.5158 (3)	0.66697 (17)	0.08093 (9)	0.0316 (4)
C6	0.5755 (2)	0.53023 (11)	0.29360 (7)	0.0168 (3)
H61	0.6439	0.4869	0.2684	0.020*
H62	0.5382	0.4862	0.3254	0.020*
C7'	0.5422 (3)	0.6998 (2)	0.01806 (10)	0.0496 (6)
H71'	0.4499	0.6741	−0.0058	0.074*
H72'	0.6472	0.6711	0.0046	0.074*
H73'	0.5461	0.7749	0.0157	0.074*
C7	0.4196 (2)	0.56528 (12)	0.25922 (7)	0.0199 (3)
H7	0.3686	0.6241	0.2801	0.024*
C8	0.2898 (2)	0.47506 (15)	0.25783 (9)	0.0280 (4)
H81	0.2646	0.4544	0.2969	0.042*
H82	0.3363	0.4165	0.2372	0.042*
H83	0.1874	0.4980	0.2384	0.042*
C9	0.8420 (2)	0.56432 (12)	0.34917 (7)	0.0203 (3)
H91	0.7995	0.5074	0.3728	0.024*
H92	0.9113	0.5332	0.3192	0.024*
C10	0.9575 (2)	0.63119 (15)	0.38756 (8)	0.0260 (4)
H10	0.8883	0.6640	0.4176	0.031*
C11	1.0522 (2)	0.71819 (16)	0.35485 (11)	0.0358 (5)
H111	0.9721	0.7695	0.3410	0.054*
H112	1.1105	0.6883	0.3224	0.054*
H113	1.1330	0.7510	0.3807	0.054*
C12	1.0842 (3)	0.55835 (18)	0.41726 (9)	0.0389 (5)
H123	1.0243	0.5062	0.4390	0.058*
H121	1.1563	0.5980	0.4432	0.058*
H122	1.1522	0.5247	0.3884	0.058*
C41	0.8340 (2)	0.67172 (12)	0.22639 (7)	0.0182 (3)
C42	0.8709 (3)	0.75771 (13)	0.18334 (8)	0.0259 (4)
H423	0.7761	0.8050	0.1811	0.039*
H421	0.8894	0.7276	0.1457	0.039*
H422	0.9707	0.7953	0.1958	0.039*
O1	0.42441 (18)	0.85144 (10)	0.43626 (6)	0.0281 (3)
O2	0.88630 (16)	0.58120 (9)	0.21879 (5)	0.0211 (2)
N1	0.54896 (18)	0.90516 (10)	0.35115 (6)	0.0174 (3)
H1	0.5686	0.9585	0.3294	0.021*
N3	0.69220 (17)	0.80070 (9)	0.28451 (6)	0.0169 (3)
N4	0.74060 (18)	0.69617 (9)	0.27477 (6)	0.0167 (3)
S1	0.56524 (5)	0.69427 (3)	0.372883 (17)	0.01838 (10)
C1"	0.4182 (8)	0.3287 (4)	0.4750 (2)	0.0377 (11)	0.50
H13"	0.4099	0.3038	0.4357	0.057*	0.50
H12"	0.3115	0.3184	0.4939	0.057*	0.50
H11"	0.5055	0.2906	0.4956	0.057*	0.50
C2"	0.4610 (5)	0.4425 (3)	0.47503 (16)	0.0282 (7)	0.50
C3"	0.4243 (5)	0.6083 (3)	0.52319 (18)	0.0325 (8)	0.50
H32"	0.3404	0.6396	0.5483	0.039*	0.50
H31"	0.4071	0.6367	0.4844	0.039*	0.50
C4"	0.5952 (7)	0.6366 (4)	0.5446 (3)	0.0398 (11)	0.50
H42"	0.6142	0.6066	0.5825	0.060*	0.50
H43"	0.6046	0.7115	0.5470	0.060*	0.50
H41"	0.6784	0.6101	0.5182	0.060*	0.50
O1'	0.5439 (5)	0.4867 (3)	0.43748 (15)	0.0456 (8)	0.50
O2'	0.3987 (4)	0.4949 (2)	0.52147 (12)	0.0326 (6)	0.50

	U11	U22	U33	U12	U13	U23
C1'	0.0218 (9)	0.0388 (10)	0.0247 (9)	0.0006 (7)	−0.0002 (7)	0.0008 (7)
C2	0.0157 (7)	0.0133 (6)	0.0190 (7)	−0.0004 (5)	0.0000 (5)	0.0009 (5)
C2'	0.0214 (8)	0.0239 (7)	0.0239 (8)	0.0030 (6)	−0.0013 (6)	0.0002 (6)
C3	0.0168 (7)	0.0191 (7)	0.0209 (7)	0.0015 (5)	0.0023 (6)	−0.0008 (5)
C3'	0.0163 (7)	0.0189 (7)	0.0241 (8)	0.0009 (5)	−0.0036 (6)	0.0012 (6)
C4'	0.0244 (9)	0.0213 (7)	0.0324 (9)	0.0032 (6)	−0.0063 (7)	0.0017 (6)
C4	0.0287 (9)	0.0182 (7)	0.0274 (9)	0.0056 (6)	0.0075 (7)	−0.0016 (6)
C5	0.0182 (7)	0.0141 (6)	0.0167 (7)	0.0015 (5)	0.0033 (5)	0.0001 (5)
C5'	0.0314 (10)	0.0288 (9)	0.0396 (11)	−0.0015 (7)	−0.0097 (8)	0.0128 (8)
C6'	0.0237 (9)	0.0410 (10)	0.0300 (10)	−0.0049 (8)	−0.0027 (7)	0.0118 (8)
C6	0.0168 (7)	0.0140 (6)	0.0197 (7)	0.0003 (5)	0.0030 (6)	0.0012 (5)
C7'	0.0455 (14)	0.0672 (17)	0.0360 (12)	−0.0024 (12)	0.0003 (10)	0.0221 (11)
C7	0.0163 (7)	0.0200 (7)	0.0236 (8)	0.0021 (6)	0.0019 (6)	−0.0017 (6)
C8	0.0194 (8)	0.0341 (9)	0.0304 (9)	−0.0049 (7)	0.0026 (7)	0.0002 (7)
C9	0.0213 (8)	0.0194 (7)	0.0201 (7)	0.0027 (6)	−0.0006 (6)	−0.0008 (5)
C10	0.0198 (8)	0.0319 (9)	0.0263 (9)	0.0054 (7)	−0.0023 (7)	−0.0096 (7)
C11	0.0186 (9)	0.0334 (9)	0.0552 (13)	−0.0012 (7)	−0.0059 (9)	−0.0046 (9)
C12	0.0381 (12)	0.0469 (12)	0.0312 (10)	0.0131 (9)	−0.0140 (9)	−0.0090 (9)
C41	0.0189 (7)	0.0165 (6)	0.0192 (7)	−0.0032 (5)	0.0020 (6)	−0.0025 (5)
C42	0.0341 (10)	0.0189 (7)	0.0252 (8)	−0.0031 (6)	0.0116 (7)	−0.0002 (6)
O1	0.0367 (8)	0.0199 (5)	0.0280 (7)	0.0030 (5)	0.0130 (6)	0.0025 (5)
O2	0.0224 (6)	0.0179 (5)	0.0231 (6)	0.0007 (4)	0.0039 (5)	−0.0040 (4)
N1	0.0207 (7)	0.0137 (5)	0.0179 (6)	0.0020 (5)	0.0031 (5)	0.0003 (4)
N3	0.0182 (6)	0.0126 (5)	0.0200 (6)	−0.0002 (5)	0.0020 (5)	−0.0003 (4)
N4	0.0202 (6)	0.0126 (5)	0.0175 (6)	−0.0004 (5)	0.0037 (5)	−0.0007 (4)
S1	0.0229 (2)	0.01389 (16)	0.01860 (18)	0.00144 (13)	0.00611 (14)	0.00131 (12)
C1"	0.057 (3)	0.029 (2)	0.027 (2)	−0.001 (2)	0.001 (2)	0.0012 (17)
C2"	0.0284 (19)	0.0352 (18)	0.0210 (17)	0.0066 (15)	−0.0007 (14)	0.0079 (14)
C3"	0.033 (2)	0.0322 (18)	0.032 (2)	0.0021 (16)	−0.0019 (16)	0.0023 (15)
C4"	0.031 (2)	0.039 (3)	0.048 (3)	0.002 (2)	−0.006 (2)	0.000 (2)
O1'	0.063 (2)	0.0384 (16)	0.0367 (18)	0.0035 (15)	0.0194 (16)	0.0102 (13)
O2'	0.0443 (17)	0.0310 (13)	0.0225 (13)	−0.0037 (12)	−0.0010 (12)	0.0033 (10)

C1'—C6'	1.389 (3)	C8—H83	0.9600
C1'—C2'	1.395 (3)	C9—C10	1.519 (2)
C1'—H1'	0.9300	C9—H91	0.9700
C2—N3	1.306 (2)	C9—H92	0.9700
C2—N1	1.3904 (19)	C10—C12	1.517 (3)
C2—S1	1.7537 (15)	C10—C11	1.540 (3)
C2'—C3'	1.413 (2)	C10—H10	0.9800
C2'—H2'	0.9300	C11—H111	0.9600
C3—O1	1.227 (2)	C11—H112	0.9600
C3—N1	1.398 (2)	C11—H113	0.9600
C3—C4	1.509 (2)	C12—H123	0.9600
C3'—C4'	1.393 (2)	C12—H121	0.9600
C3'—C7	1.524 (2)	C12—H122	0.9600
C4'—C5'	1.398 (3)	C41—O2	1.2394 (18)
C4'—H4'	0.9300	C41—N4	1.378 (2)
C4—H41	0.9600	C41—C42	1.508 (2)
C4—H42	0.9600	C42—H423	0.9600
C4—H43	0.9600	C42—H421	0.9600
C5—N4	1.4998 (19)	C42—H422	0.9600
C5—C9	1.524 (2)	N1—H1	0.8600
C5—C6	1.533 (2)	N3—N4	1.4058 (17)
C5—S1	1.8732 (15)	C1"—C2"	1.490 (6)
C5'—C6'	1.404 (3)	C1"—H13"	0.9600
C5'—H5'	0.9300	C1"—H12"	0.9600
C6'—C7'	1.521 (3)	C1"—H11"	0.9600
C6—C7	1.516 (2)	C2"—O1'	1.227 (5)
C6—H61	0.9700	C2"—O2'	1.358 (5)
C6—H62	0.9700	C3"—O2'	1.461 (5)
C7'—H71'	0.9600	C3"—C4"	1.470 (7)
C7'—H72'	0.9600	C3"—H32"	0.9700
C7'—H73'	0.9600	C3"—H31"	0.9700
C7—C8	1.539 (2)	C4"—H42"	0.9600
C7—H7	0.9800	C4"—H43"	0.9600
C8—H81	0.9600	C4"—H41"	0.9600
C8—H82	0.9600
C6'—C1'—C2'	120.88 (18)	H81—C8—H82	109.5
C6'—C1'—H1'	119.6	C7—C8—H83	109.5
C2'—C1'—H1'	119.6	H81—C8—H83	109.5
N3—C2—N1	119.84 (13)	H82—C8—H83	109.5
N3—C2—S1	119.38 (11)	C10—C9—C5	118.40 (13)
N1—C2—S1	120.77 (12)	C10—C9—H91	107.7
C1'—C2'—C3'	121.70 (16)	C5—C9—H91	107.7
C1'—C2'—H2'	119.2	C10—C9—H92	107.7
C3'—C2'—H2'	119.2	C5—C9—H92	107.7
O1—C3—N1	122.80 (14)	H91—C9—H92	107.1
O1—C3—C4	122.25 (15)	C12—C10—C9	107.44 (15)
N1—C3—C4	114.95 (14)	C12—C10—C11	109.96 (17)
C4'—C3'—C2'	117.43 (16)	C9—C10—C11	114.31 (16)
C4'—C3'—C7	120.79 (16)	C12—C10—H10	108.3
C2'—C3'—C7	121.74 (14)	C9—C10—H10	108.3
C3'—C4'—C5'	120.40 (18)	C11—C10—H10	108.3
C3'—C4'—H4'	119.8	C10—C11—H111	109.5
C5'—C4'—H4'	119.8	C10—C11—H112	109.5
C3—C4—H41	109.5	H111—C11—H112	109.5
C3—C4—H42	109.5	C10—C11—H113	109.5
H41—C4—H42	109.5	H111—C11—H113	109.5
C3—C4—H43	109.5	H112—C11—H113	109.5
H41—C4—H43	109.5	C10—C12—H123	109.5
H42—C4—H43	109.5	C10—C12—H121	109.5
N4—C5—C9	112.80 (13)	H123—C12—H121	109.5
N4—C5—C6	112.75 (12)	C10—C12—H122	109.5
C9—C5—C6	108.21 (12)	H123—C12—H122	109.5
N4—C5—S1	103.67 (9)	H121—C12—H122	109.5
C9—C5—S1	110.51 (11)	O2—C41—N4	120.49 (14)
C6—C5—S1	108.79 (11)	O2—C41—C42	121.15 (15)
C4'—C5'—C6'	122.16 (17)	N4—C41—C42	118.36 (13)
C4'—C5'—H5'	118.9	C41—C42—H423	109.5
C6'—C5'—H5'	118.9	C41—C42—H421	109.5
C1'—C6'—C5'	117.43 (18)	H423—C42—H421	109.5
C1'—C6'—C7'	120.3 (2)	C41—C42—H422	109.5
C5'—C6'—C7'	122.3 (2)	H423—C42—H422	109.5
C7—C6—C5	116.99 (12)	H421—C42—H422	109.5
C7—C6—H61	108.1	C2—N1—C3	124.63 (13)
C5—C6—H61	108.1	C2—N1—H1	117.7
C7—C6—H62	108.1	C3—N1—H1	117.7
C5—C6—H62	108.1	C2—N3—N4	110.27 (12)
H61—C6—H62	107.3	C41—N4—N3	119.50 (12)
C6'—C7'—H71'	109.5	C41—N4—C5	123.13 (12)
C6'—C7'—H72'	109.5	N3—N4—C5	117.36 (12)
H71'—C7'—H72'	109.5	C2—S1—C5	89.27 (7)
C6'—C7'—H73'	109.5	O1'—C2"—O2'	121.9 (4)
H71'—C7'—H73'	109.5	O1'—C2"—C1"	124.8 (4)
H72'—C7'—H73'	109.5	O2'—C2"—C1"	113.3 (4)
C6—C7—C3'	113.72 (14)	O2'—C3"—C4"	112.2 (4)
C6—C7—C8	108.77 (13)	O2'—C3"—H32"	109.2
C3'—C7—C8	110.65 (14)	C4"—C3"—H32"	109.2
C6—C7—H7	107.8	O2'—C3"—H31"	109.2
C3'—C7—H7	107.8	C4"—C3"—H31"	109.2
C8—C7—H7	107.8	H32"—C3"—H31"	107.9
C7—C8—H81	109.5	C2"—O2'—C3"	117.3 (3)
C7—C8—H82	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.86	1.95	2.812 (2)	179

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	1.95	2.812 (2)	179

Symmetry code: (i) .