N-Benzyl-N-(4-methoxy­phenyl)­cyclo­hex-1-ene­carbothio­amide

The crystal structure of the title thio­amide, C₂₁H₂₃NOS, was determined to investigate the relationship between the photostability in the solid state and the structure.

S1. Experimental

The title compound, (I), was prepared by one of the authors (HA) in a study on photocyclization of enamides and thioamides in the solid state (Aoyama, 2000). Crystals were grown from a hexane solution.

S2. Refinement

X-ray intensity data were measured for −h,+k,+l (θ < 75°) and for −h,+k,-l (θ < 30°). The completeness of symmetry unique reflections (θ < 75°) was 92.7%, which was due to the blind region of the low-temperature apparatus. All H-atom positional parameters were calculated geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom). For the cyclohexene ring, the C5—C6 and C5═C10 axes were assigned to be single and double bonds, respectively, based on the bond lengths [1.481 (5) and 1.351 (5) Å, respectively]. The short C7—C8 bond length of 1.366 (13) Å may be an artifact due to the conformational disorder of the six-membered ring.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

Cyclohex-1-enecarbothioic acid benzyl-(4-methoxy-phenyl)-amide

Crystal data

C21H23NOS	Dx = 1.177 Mg m^−3
Mr = 337.48	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 25 reflections
a = 10.880 (2) Å	θ = 28.5–29.6°
b = 16.458 (2) Å	µ = 1.54 mm^−1
c = 21.261 (2) Å	T = 248 K
V = 3807.1 (8) Å^3	Sphere, pale yellow
Z = 8	0.25 mm (radius)

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.044
θ–2θ scans	θmax = 75.0°, θmin = 2.5°
Absorption correction: for a sphere (International Tables for X-ray Crystallography)	h = −14→0
Tmin = 0.566, Tmax = 0.598	k = 0→21
4142 measured reflections	l = −13→27
3630 independent reflections	3 standard reflections every 150 reflections
2723 reflections with I > 2σ(I)	intensity decay: 1.6%

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 2.P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.168	(Δ/σ)max = 0.001
S = 1.24	Δρmax = 0.31 e Å^−3
3630 reflections	Δρmin = −0.25 e Å^−3
217 parameters

Special details

Refinement. Refinement was based on F² against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F², and conventional R-factor (R) was calculated on F, with F set to zero for negative F². The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	1.17438 (7)	0.04269 (6)	0.56009 (4)	0.0869 (3)
O2	0.5033 (2)	0.1686 (2)	0.6896 (1)	0.0873 (7)
N3	0.9507 (2)	0.1066 (1)	0.5721 (1)	0.0583 (5)
C4	1.0332 (3)	0.0512 (2)	0.5905 (1)	0.0635 (7)
C5	0.9945 (3)	−0.0074 (2)	0.6399 (1)	0.0678 (7)
C6	1.0666 (4)	−0.0096 (3)	0.6990 (2)	0.109 (1)
C7	1.0305 (6)	−0.0770 (7)	0.7411 (3)	0.266 (6)
C8	0.9251 (10)	−0.1208 (4)	0.7326 (3)	0.185 (3)
C9	0.8626 (5)	−0.1235 (3)	0.6727 (3)	0.126 (2)
C10	0.9007 (3)	−0.0592 (2)	0.6285 (2)	0.0827 (9)
C11	0.9748 (3)	0.1636 (2)	0.5199 (1)	0.0675 (7)
C12	0.9965 (2)	0.2488 (2)	0.5429 (1)	0.0596 (6)
C13	0.9098 (3)	0.3087 (2)	0.5353 (2)	0.0743 (8)
C14	0.9327 (4)	0.3870 (2)	0.5554 (2)	0.088 (1)
C15	1.0414 (4)	0.4063 (2)	0.5831 (2)	0.088 (1)
C16	1.1291 (3)	0.3474 (2)	0.5918 (2)	0.0849 (9)
C17	1.1068 (3)	0.2689 (2)	0.5719 (2)	0.0716 (8)
C18	0.8345 (2)	0.1190 (2)	0.6032 (1)	0.0532 (6)
C19	0.8296 (2)	0.1472 (2)	0.6643 (1)	0.0646 (7)
C20	0.7169 (3)	0.1624 (2)	0.6917 (1)	0.0720 (8)
C21	0.6099 (2)	0.1495 (2)	0.6582 (1)	0.0631 (7)
C22	0.6148 (3)	0.1226 (2)	0.5978 (1)	0.0636 (7)
C23	0.7276 (3)	0.1064 (2)	0.5705 (1)	0.0628 (7)
C24	0.3927 (3)	0.1681 (4)	0.6545 (2)	0.126 (2)
H6A	1.1520	−0.0155	0.6877	0.1395*
H6B	1.0555	0.0417	0.7200	0.1395*
H7A	1.0941	−0.1170	0.7401	0.2712*
H7B	1.0242	−0.0549	0.7831	0.2712*
H8A	0.9399	−0.1754	0.7449	0.1990*
H8B	0.8637	−0.0976	0.7620	0.1990*
H9A	0.8744	−0.1771	0.6525	0.1442*
H9B	0.7711	−0.1194	0.6779	0.1442*
H10	0.8598	−0.0534	0.5881	0.0990*
H11A	0.9028	0.1646	0.4922	0.0790*
H11B	1.0439	0.1458	0.4960	0.0790*
H13	0.8313	0.2951	0.5144	0.0860*
H14	0.8719	0.4299	0.5492	0.1008*
H15	1.0540	0.4625	0.5978	0.1031*
H16	1.2068	0.3600	0.6125	0.1036*
H17	1.1697	0.2282	0.5768	0.0852*
H19	0.9032	0.1580	0.6873	0.0742*
H20	0.7121	0.1814	0.7346	0.0815*
H22	0.5397	0.1129	0.5740	0.0760*
H23	0.7316	0.0861	0.5276	0.0734*
H24A	0.3978	0.2054	0.6194	0.1491*
H24B	0.3802	0.1132	0.6354	0.1491*
H24C	0.3230	0.1798	0.6792	0.1491*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0581 (5)	0.1003 (6)	0.1023 (7)	0.0121 (4)	0.0114 (4)	−0.0138 (5)
O2	0.057 (1)	0.130 (2)	0.074 (1)	0.011 (1)	0.009 (1)	0.000 (1)
N3	0.053 (1)	0.064 (1)	0.058 (1)	0.002 (1)	0.003 (1)	−0.002 (1)
C4	0.059 (2)	0.066 (2)	0.066 (2)	0.006 (1)	−0.005 (1)	−0.013 (1)
C5	0.065 (2)	0.069 (2)	0.069 (2)	0.018 (1)	0.000 (1)	−0.005 (1)
C6	0.103 (3)	0.141 (4)	0.081 (2)	0.034 (3)	−0.018 (2)	0.003 (2)
C7	0.133 (5)	0.50 (2)	0.163 (6)	−0.070 (8)	−0.055 (5)	0.202 (9)
C8	0.33 (1)	0.123 (4)	0.102 (4)	−0.019 (6)	0.011 (6)	0.028 (3)
C9	0.143 (4)	0.095 (3)	0.140 (4)	0.008 (3)	0.034 (3)	0.031 (3)
C10	0.096 (2)	0.066 (2)	0.086 (2)	0.008 (2)	0.004 (2)	0.005 (2)
C11	0.066 (2)	0.079 (2)	0.058 (1)	−0.001 (1)	0.008 (1)	0.001 (1)
C12	0.052 (1)	0.069 (2)	0.058 (1)	−0.002 (1)	0.009 (1)	0.004 (1)
C13	0.056 (2)	0.085 (2)	0.082 (2)	0.003 (2)	0.005 (1)	0.005 (2)
C14	0.080 (2)	0.075 (2)	0.109 (3)	0.015 (2)	0.010 (2)	0.003 (2)
C15	0.096 (3)	0.071 (2)	0.097 (2)	−0.004 (2)	0.014 (2)	−0.005 (2)
C16	0.074 (2)	0.088 (2)	0.093 (2)	−0.015 (2)	−0.001 (2)	−0.005 (2)
C17	0.059 (2)	0.075 (2)	0.081 (2)	0.003 (1)	0.002 (1)	0.003 (2)
C18	0.050 (1)	0.055 (1)	0.055 (1)	0.002 (1)	−0.001 (1)	0.001 (1)
C19	0.053 (2)	0.080 (2)	0.061 (2)	0.006 (1)	−0.010 (1)	−0.012 (1)
C20	0.064 (2)	0.098 (2)	0.054 (1)	0.012 (2)	−0.002 (1)	−0.010 (1)
C21	0.051 (1)	0.075 (2)	0.063 (2)	0.008 (1)	0.003 (1)	0.006 (1)
C22	0.052 (1)	0.074 (2)	0.065 (2)	−0.002 (1)	−0.009 (1)	0.002 (1)
C23	0.063 (2)	0.067 (2)	0.058 (1)	0.000 (1)	−0.004 (1)	−0.004 (1)
C24	0.049 (2)	0.225 (5)	0.105 (3)	0.015 (3)	0.003 (2)	−0.010 (3)

Geometric parameters (Å, º)

S1—C4	1.672 (3)	C12—C13	1.374 (4)
O2—C21	1.374 (3)	C12—C17	1.389 (4)
O2—C24	1.416 (4)	C13—C14	1.381 (5)
N3—C4	1.338 (4)	C13—H13	0.99
N3—C11	1.477 (4)	C14—C15	1.358 (6)
N3—C18	1.442 (3)	C14—H14	0.98
C4—C5	1.487 (4)	C15—C16	1.374 (5)
C5—C6	1.481 (5)	C15—H15	0.99
C5—C10	1.351 (5)	C16—C17	1.380 (5)
C6—C7	1.479 (11)	C16—H16	0.98
C6—H6A	0.97	C17—H17	0.96
C6—H6B	0.96	C18—C19	1.380 (4)
C7—C8	1.366 (13)	C18—C23	1.371 (4)
C7—H7A	0.96	C19—C20	1.380 (4)
C7—H7B	0.97	C19—H19	0.96
C8—C9	1.443 (9)	C20—C21	1.381 (4)
C8—H8A	0.95	C20—H20	0.97
C8—H8B	0.99	C21—C22	1.359 (4)
C9—C10	1.475 (6)	C22—C23	1.384 (4)
C9—H9A	0.99	C22—H22	0.98
C9—H9B	1.01	C23—H23	0.97
C10—H10	0.973	C24—H24A	0.97
C11—C12	1.504 (4)	C24—H24B	1.00
C11—H11A	0.98	C24—H24C	0.94
C11—H11B	0.95
C21—O2—C24	117.4 (3)	C11—C12—C13	121.5 (3)
C4—N3—C11	122.3 (2)	C11—C12—C17	120.1 (3)
C4—N3—C18	123.4 (2)	C13—C12—C17	118.4 (3)
C11—N3—C18	114.2 (2)	C12—C13—C14	120.6 (3)
S1—C4—N3	124.0 (2)	C12—C13—H13	119
S1—C4—C5	118.6 (2)	C14—C13—H13	120
N3—C4—C5	117.3 (2)	C13—C14—C15	120.6 (3)
C4—C5—C6	117.7 (3)	C13—C14—H14	121
C4—C5—C10	119.8 (3)	C15—C14—H14	119
C6—C5—C10	122.4 (3)	C14—C15—C16	119.9 (3)
C5—C6—C7	113.0 (4)	C14—C15—H15	119
C5—C6—H6A	108	C16—C15—H15	121
C5—C6—H6B	108	C15—C16—C17	119.8 (3)
C7—C6—H6A	109	C15—C16—H16	121
C7—C6—H6B	110	C17—C16—H16	119
H6A—C6—H6B	109	C12—C17—C16	120.7 (3)
C6—C7—C8	122.6 (6)	C12—C17—H17	120
C6—C7—H7A	108	C16—C17—H17	120
C6—C7—H7B	107	N3—C18—C19	120.8 (2)
C8—C7—H7A	104	N3—C18—C23	119.3 (2)
C8—C7—H7B	105	C19—C18—C23	119.8 (2)
H7A—C7—H7B	109	C18—C19—C20	119.5 (2)
C7—C8—C9	121.9 (6)	C18—C19—H19	121
C7—C8—H8A	109	C20—C19—H19	120
C7—C8—H8B	106	C19—C20—C21	120.2 (3)
C9—C8—H8A	107	C19—C20—H20	120
C9—C8—H8B	105	C21—C20—H20	119
H8A—C8—H8B	108	O2—C21—C20	115.2 (2)
C8—C9—C10	114.0 (5)	O2—C21—C22	124.5 (2)
C8—C9—H9A	110	C20—C21—C22	120.2 (3)
C8—C9—H9B	112	C21—C22—C23	119.6 (3)
C10—C9—H9A	109	C21—C22—H22	121
C10—C9—H9B	107	C23—C22—H22	120
H9A—C9—H9B	104	C18—C23—C22	120.6 (3)
C5—C10—C9	123.4 (4)	C18—C23—H23	119
C5—C10—H10	116	C22—C23—H23	120
C9—C10—H10	120	O2—C24—H24A	111
N3—C11—C12	112.0 (2)	O2—C24—H24B	110
N3—C11—H11A	109	O2—C24—H24C	113
N3—C11—H11B	110	H24A—C24—H24B	106
C12—C11—H11A	108	H24A—C24—H24C	110
C12—C11—H11B	110	H24B—C24—H24C	108
H11A—C11—H11B	109