Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004054/qa0254sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004054/qa0254Isup2.hkl |
CCDC reference: 144714
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.
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 Uiso(H) = 1.2Ueq(parent atom).
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.
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) Å3 | Prism, yellow |
Z = 4 | 0.55 × 0.4 × 0.3 mm |
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 on F2 | w = 1/[σ2(Fo2) + (0.0601P)2 + 0.1846P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.043 | (Δ/σ)max = 0.001 |
wR(F2) = 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 |
C19H21NS | V = 1630.4 (2) Å3 |
Mr = 295.44 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.166 (1) Å | µ = 0.19 mm−1 |
b = 13.423 (1) Å | T = 298 K |
c = 10.878 (1) Å | 0.55 × 0.4 × 0.3 mm |
Rigaku AFC-7R diffractometer | 1963 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.006 |
Tmin = 0.928, Tmax = 0.947 | 3 standard reflections every 150 reflections |
3090 measured reflections | intensity decay: none |
2684 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters not refined |
wR(F2) = 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) |
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). |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
Experimental details
Crystal data | |
Chemical formula | C19H21NS |
Mr | 295.44 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 11.166 (1), 13.423 (1), 10.878 (1) |
V (Å3) | 1630.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.55 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.928, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3090, 2684, 1963 |
Rint | 0.006 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.124, 1.06 |
No. of reflections | 2684 |
No. of parameters | 190 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.15, −0.27 |
Absolute structure | Flack (1983), no Friedel pairs |
Absolute structure parameter | 0.1 (1) |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), TEXSAN.
S1—C3 | 1.681 (2) | C9—C14 | 1.510 (3) |
N2—C3 | 1.326 (3) | C13—C14 | 1.533 (4) |
N2—C13 | 1.470 (3) |