2-Iso­propyl-4-methyl-4-phenyl-1,2,3,4-tetra­hydro­iso­quinoline-1-thione

The title compound, C₁₉H₂₁NS, is the photoproduct obtained from N-iso­propyl-N-[(E)-2-phenyl­propenyl]­thio­benz­amide. Recrystallization showed a spontaneous resolution.

S1. Experimental

The title compound 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 < 30°) and for +h,-k,-l (θ < 15°). The chiral space group and Flack parameter of 0.1 (1) suggested a spontaneous resolution of the title compound. All H-atom positional parameters were calculated geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom).

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.

2-Isopropyl-4-methyl-4-phenyl-3,4-dihydro-2H-isoquinoline-1-thione

Crystal data

C19H21NS	Dx = 1.204 Mg m^−3
Mr = 295.44	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 11.166 (1) Å	θ = 14.0–14.8°
b = 13.423 (1) Å	µ = 0.19 mm^−1
c = 10.878 (1) Å	T = 298 K
V = 1630.4 (2) Å^3	Prism, yellow
Z = 4	0.55 × 0.4 × 0.3 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.006
θ–2θ scans	θmax = 30.0°, θmin = 2.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→16
Tmin = 0.928, Tmax = 0.947	k = −10→19
3090 measured reflections	l = −8→16
2684 independent reflections	3 standard reflections every 150 reflections
1963 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0601P)^2 + 0.1846P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.043	(Δ/σ)max = 0.001
wR(F^2) = 0.124	Δρmax = 0.15 e Å^−3
S = 1.06	Δρmin = −0.27 e Å^−3
2684 reflections	Absolute structure: Flack (1983), no Friedel pairs
190 parameters	Absolute structure parameter: 0.1 (1)
H-atom parameters not refined

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	0.53579 (9)	−0.13551 (6)	−0.08369 (7)	0.0790 (3)
N2	0.6122 (2)	−0.0496 (2)	0.1220 (2)	0.0552 (5)
C3	0.5208 (3)	−0.0816 (2)	0.0550 (2)	0.0533 (6)
C4	0.3996 (2)	−0.0670 (2)	0.1092 (2)	0.0502 (5)
C5	0.3052 (3)	−0.1315 (2)	0.0786 (3)	0.0663 (8)
C6	0.1932 (3)	−0.1184 (2)	0.1312 (3)	0.0730 (9)
C7	0.1721 (3)	−0.0401 (3)	0.2103 (3)	0.0703 (8)
C8	0.2642 (2)	0.0242 (2)	0.2395 (3)	0.0584 (6)
C9	0.3790 (2)	0.0111 (2)	0.1922 (2)	0.0475 (5)
C10	0.7400 (3)	−0.0672 (3)	0.0899 (3)	0.0767 (9)
C11	0.8042 (4)	0.0294 (3)	0.0652 (4)	0.106 (1)
C12	0.8002 (3)	−0.1288 (3)	0.1885 (5)	0.106 (1)
C13	0.5899 (2)	0.0029 (2)	0.2383 (2)	0.0550 (6)
C14	0.4845 (2)	0.0755 (2)	0.2269 (2)	0.0489 (5)
C15	0.4665 (3)	0.1232 (3)	0.3543 (3)	0.0682 (7)
C16	0.5105 (2)	0.1557 (2)	0.1302 (2)	0.0511 (5)
C17	0.5992 (3)	0.2267 (2)	0.1516 (4)	0.0763 (9)
C18	0.6243 (3)	0.2995 (2)	0.0665 (5)	0.092 (1)
C19	0.5647 (4)	0.3018 (2)	−0.0447 (5)	0.088 (1)
C20	0.4782 (3)	0.2330 (2)	−0.0675 (4)	0.0810 (9)
C21	0.4501 (3)	0.1606 (2)	0.0186 (3)	0.0616 (7)
H5	0.3211	−0.1853	0.0205	0.0813*
H6	0.1269	−0.1638	0.1146	0.0900*
H7	0.0925	−0.0292	0.2471	0.0834*
H8	0.2494	0.0799	0.2963	0.0707*
H10	0.7426	−0.1066	0.0161	0.0901*
H11A	0.8845	0.0185	0.0407	0.1286*
H11B	0.7623	0.0651	−0.0007	0.1286*
H11C	0.8019	0.0713	0.1373	0.1286*
H12A	0.7546	−0.1897	0.2041	0.1244*
H12B	0.8798	−0.1445	0.1703	0.1244*
H12C	0.7982	−0.0913	0.2676	0.1244*
H13A	0.5734	−0.0460	0.3009	0.0686*
H13B	0.6613	0.0390	0.2607	0.0686*
H15A	0.5365	0.1585	0.3787	0.0843*
H15B	0.3994	0.1697	0.3508	0.0843*
H15C	0.4476	0.0729	0.4143	0.0843*
H17	0.6435	0.2237	0.2299	0.0910*
H18	0.6831	0.3505	0.0874	0.1151*
H19	0.5865	0.3522	−0.1063	0.1028*
H20	0.4357	0.2345	−0.1470	0.1000*
H21	0.3852	0.1137	0.0026	0.0760*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.1199 (7)	0.0659 (4)	0.0513 (3)	0.0217 (5)	−0.0125 (4)	−0.0219 (3)
N2	0.058 (1)	0.061 (1)	0.046 (1)	0.017 (1)	−0.0051 (10)	−0.0136 (10)
C3	0.079 (2)	0.0371 (9)	0.043 (1)	0.011 (1)	−0.011 (1)	−0.0051 (8)
C4	0.063 (1)	0.041 (1)	0.047 (1)	0.000 (1)	−0.016 (1)	0.0056 (9)
C5	0.092 (2)	0.045 (1)	0.062 (1)	−0.007 (1)	−0.030 (2)	0.012 (1)
C6	0.070 (2)	0.069 (2)	0.080 (2)	−0.021 (2)	−0.027 (2)	0.029 (2)
C7	0.055 (1)	0.079 (2)	0.077 (2)	−0.010 (2)	−0.008 (1)	0.028 (2)
C8	0.053 (1)	0.061 (1)	0.062 (1)	0.001 (1)	0.000 (1)	0.007 (1)
C9	0.049 (1)	0.048 (1)	0.046 (1)	0.000 (1)	−0.005 (1)	0.004 (1)
C10	0.069 (2)	0.090 (2)	0.072 (2)	0.022 (2)	0.007 (2)	−0.030 (2)
C11	0.095 (3)	0.115 (3)	0.107 (3)	0.005 (2)	0.049 (2)	0.000 (2)
C12	0.074 (2)	0.101 (3)	0.143 (4)	0.038 (2)	−0.012 (2)	−0.007 (3)
C13	0.053 (1)	0.068 (1)	0.043 (1)	0.008 (1)	−0.006 (1)	−0.016 (1)
C14	0.049 (1)	0.054 (1)	0.044 (1)	0.004 (1)	0.000 (1)	−0.0141 (10)
C15	0.063 (2)	0.088 (2)	0.054 (1)	0.008 (2)	0.000 (1)	−0.029 (1)
C16	0.049 (1)	0.043 (1)	0.062 (1)	−0.001 (1)	0.006 (1)	−0.0158 (10)
C17	0.070 (2)	0.066 (2)	0.093 (2)	−0.019 (2)	0.000 (2)	−0.025 (2)
C18	0.073 (2)	0.058 (2)	0.144 (4)	−0.024 (2)	0.018 (2)	−0.015 (2)
C19	0.085 (2)	0.051 (2)	0.127 (3)	−0.009 (2)	0.029 (2)	0.011 (2)
C20	0.094 (2)	0.061 (2)	0.088 (2)	−0.012 (2)	0.001 (2)	0.019 (2)
C21	0.061 (2)	0.053 (1)	0.070 (2)	−0.013 (1)	−0.005 (1)	0.005 (1)

Geometric parameters (Å, º)

S1—C3	1.681 (2)	C12—H12A	0.98
N2—C3	1.326 (3)	C12—H12B	0.93
N2—C10	1.488 (4)	C12—H12C	1.00
N2—C13	1.470 (3)	C13—C14	1.533 (4)
C3—C4	1.489 (4)	C13—H13A	0.96
C4—C5	1.405 (4)	C13—H13B	0.96
C4—C9	1.402 (3)	C14—C15	1.539 (4)
C5—C6	1.387 (5)	C14—C16	1.533 (3)
C5—H5	0.98	C15—H15A	0.95
C6—C7	1.378 (5)	C15—H15B	0.98
C6—H6	0.98	C15—H15C	0.96
C7—C8	1.380 (4)	C16—C17	1.394 (4)
C7—H7	0.99	C16—C21	1.390 (4)
C8—C9	1.393 (4)	C17—C18	1.375 (6)
C8—H8	0.98	C17—H17	0.99
C9—C14	1.510 (3)	C18—C19	1.381 (7)
C10—C11	1.505 (6)	C18—H18	0.98
C10—C12	1.512 (6)	C19—C20	1.359 (5)
C10—H10	0.96	C19—H19	0.98
C11—H11A	0.95	C20—C21	1.386 (4)
C11—H11B	0.98	C20—H20	0.99
C11—H11C	0.97	C21—H21	0.98
C3—N2—C10	123.9 (2)	H12A—C12—H12B	110
C3—N2—C13	119.9 (2)	H12A—C12—H12C	105
C10—N2—C13	116.2 (2)	H12B—C12—H12C	109
S1—C3—N2	123.8 (2)	N2—C13—C14	111.5 (2)
S1—C3—C4	120.2 (2)	N2—C13—H13A	108
N2—C3—C4	116.1 (2)	N2—C13—H13B	109
C3—C4—C5	120.5 (2)	C14—C13—H13A	110
C3—C4—C9	120.1 (2)	C14—C13—H13B	110
C5—C4—C9	119.4 (2)	H13A—C13—H13B	109
C4—C5—C6	120.0 (3)	C9—C14—C13	104.8 (2)
C4—C5—H5	118	C9—C14—C15	111.2 (2)
C6—C5—H5	122	C9—C14—C16	112.2 (2)
C5—C6—C7	120.6 (3)	C13—C14—C15	107.0 (2)
C5—C6—H6	122	C13—C14—C16	110.9 (2)
C7—C6—H6	118	C15—C14—C16	110.6 (2)
C6—C7—C8	119.6 (3)	C14—C15—H15A	111
C6—C7—H7	121	C14—C15—H15B	109
C8—C7—H7	119	C14—C15—H15C	110
C7—C8—C9	121.4 (3)	H15A—C15—H15B	109
C7—C8—H8	120	H15A—C15—H15C	110
C9—C8—H8	119	H15B—C15—H15C	108
C4—C9—C8	118.9 (2)	C14—C16—C17	120.0 (2)
C4—C9—C14	117.5 (2)	C14—C16—C21	122.7 (2)
C8—C9—C14	123.6 (2)	C17—C16—C21	117.3 (3)
N2—C10—C11	111.2 (3)	C16—C17—C18	121.2 (3)
N2—C10—C12	110.3 (3)	C16—C17—H17	118
N2—C10—H10	108	C18—C17—H17	121
C11—C10—C12	112.7 (3)	C17—C18—C19	120.5 (3)
C11—C10—H10	108	C17—C18—H18	119
C12—C10—H10	106	C19—C18—H18	121
C10—C11—H11A	112	C18—C19—C20	119.1 (4)
C10—C11—H11B	109	C18—C19—H19	120
C10—C11—H11C	110	C20—C19—H19	121
H11A—C11—H11B	109	C19—C20—C21	120.9 (4)
H11A—C11—H11C	110	C19—C20—H20	119
H11B—C11—H11C	107	C21—C20—H20	120
C10—C12—H12A	110	C16—C21—C20	120.9 (3)
C10—C12—H12B	113	C16—C21—H21	119
C10—C12—H12C	109	C20—C21—H21	120