Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004029/qa0250sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004029/qa0250Isup2.hkl |
CCDC reference: 144710
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 < 75°) and for +h,-k,±l (θ < 30°). The completeness of symmetry unique reflections (θ < 75°) was 93.3%, which was due to the blind region of the low-temperature apparatus.
All H-atom positional parameters were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(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 [1.486 (3) Å and 1.340 (3) Å, respectively]. The short C7—C8 bond length of 1.366 (5) Å may be an artifact due to the conformational disorder of the six-membered ring.
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.
C21H23NO2 | Dx = 1.208 Mg m−3 |
Mr = 321.42 | Cu Kα radiation, λ = 1.54184 Å |
Monoclinic, P21/n | Cell parameters from 25 reflections |
a = 10.485 (3) Å | θ = 28.8–30.0° |
b = 8.179 (1) Å | µ = 0.61 mm−1 |
c = 20.985 (1) Å | T = 248 K |
β = 100.98 (1)° | Plate-like, colourless |
V = 1766.7 (6) Å3 | 0.5 × 0.5 × 0.05 mm |
Z = 4 |
Rigaku AFC-7R diffractometer | Rint = 0.010 |
θ–2θ scans | θmax = 75.0°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = 0→13 |
Tmin = 0.765, Tmax = 0.969 | k = −5→10 |
4069 measured reflections | l = −26→26 |
3388 independent reflections | 3 standard reflections every 150 reflections |
2631 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.055 | w = 1/[σ2(Fo2) + (0.0708P)2 + 0.9854P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.159 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.48 e Å−3 |
3388 reflections | Δρmin = −0.46 e Å−3 |
217 parameters |
C21H23NO2 | V = 1766.7 (6) Å3 |
Mr = 321.42 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 10.485 (3) Å | µ = 0.61 mm−1 |
b = 8.179 (1) Å | T = 248 K |
c = 20.985 (1) Å | 0.5 × 0.5 × 0.05 mm |
β = 100.98 (1)° |
Rigaku AFC-7R diffractometer | 2631 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.010 |
Tmin = 0.765, Tmax = 0.969 | 3 standard reflections every 150 reflections |
4069 measured reflections | intensity decay: none |
3388 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 217 parameters |
wR(F2) = 0.159 | H-atom parameters not refined |
S = 1.04 | Δρmax = 0.48 e Å−3 |
3388 reflections | Δρmin = −0.46 e Å−3 |
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 | ||
O1 | 0.1455 (2) | 0.5217 (2) | 0.21606 (7) | 0.0542 (4) | |
O2 | −0.1286 (2) | 0.7791 (2) | 0.03870 (7) | 0.0548 (4) | |
N3 | 0.0690 (2) | 0.7132 (2) | 0.14063 (8) | 0.0414 (4) | |
C4 | 0.0776 (2) | 0.6423 (2) | 0.20037 (9) | 0.0402 (4) | |
C5 | −0.0009 (2) | 0.7149 (2) | 0.24562 (9) | 0.0396 (4) | |
C6 | 0.0715 (2) | 0.7562 (3) | 0.3116 (1) | 0.0538 (6) | |
C7 | −0.0139 (3) | 0.8068 (5) | 0.3572 (2) | 0.102 (1) | |
C8 | −0.1367 (3) | 0.8629 (7) | 0.3338 (2) | 0.120 (2) | |
C9 | −0.2133 (2) | 0.7890 (4) | 0.2737 (1) | 0.0699 (7) | |
C10 | −0.1301 (2) | 0.7298 (3) | 0.2281 (1) | 0.0530 (6) | |
C11 | 0.1358 (2) | 0.6327 (3) | 0.0937 (1) | 0.0496 (5) | |
C12 | 0.2727 (2) | 0.6901 (3) | 0.0950 (1) | 0.0448 (5) | |
C13 | 0.3302 (3) | 0.6611 (3) | 0.0413 (1) | 0.0562 (6) | |
C14 | 0.4567 (3) | 0.7111 (4) | 0.0417 (1) | 0.0729 (8) | |
C15 | 0.5267 (3) | 0.7923 (4) | 0.0939 (2) | 0.0729 (8) | |
C16 | 0.4710 (2) | 0.8226 (3) | 0.1473 (1) | 0.0651 (7) | |
C17 | 0.3455 (2) | 0.7701 (3) | 0.1477 (1) | 0.0523 (5) | |
C18 | 0.0237 (2) | 0.8781 (2) | 0.12751 (9) | 0.0389 (4) | |
C19 | 0.0782 (2) | 1.0045 (3) | 0.16678 (9) | 0.0421 (4) | |
C20 | 0.0349 (2) | 1.1635 (3) | 0.1557 (1) | 0.0517 (5) | |
C21 | −0.0625 (2) | 1.1956 (3) | 0.1030 (1) | 0.0567 (6) | |
C22 | −0.1173 (2) | 1.0698 (3) | 0.0626 (1) | 0.0519 (5) | |
C23 | −0.0758 (2) | 0.9114 (3) | 0.07480 (9) | 0.0431 (5) | |
C24 | −0.2178 (2) | 0.8132 (4) | −0.0198 (1) | 0.0604 (6) | |
H6A | 0.1237 | 0.6620 | 0.3289 | 0.0580* | |
H6B | 0.1299 | 0.8456 | 0.3082 | 0.0580* | |
H7A | −0.0244 | 0.7052 | 0.3827 | 0.1193* | |
H7B | 0.0357 | 0.8813 | 0.3880 | 0.1193* | |
H8A | −0.1897 | 0.8651 | 0.3664 | 0.1291* | |
H8B | −0.1270 | 0.9832 | 0.3222 | 0.1291* | |
H9A | −0.2768 | 0.8647 | 0.2509 | 0.0800* | |
H9B | −0.2595 | 0.6960 | 0.2870 | 0.0800* | |
H10 | −0.1719 | 0.7022 | 0.1841 | 0.0555* | |
H11A | 0.1392 | 0.5176 | 0.1026 | 0.0532* | |
H11B | 0.0869 | 0.6514 | 0.0507 | 0.0532* | |
H13 | 0.2829 | 0.6015 | 0.0042 | 0.0606* | |
H14 | 0.4951 | 0.6885 | 0.0046 | 0.0799* | |
H15 | 0.6143 | 0.8343 | 0.0928 | 0.0777* | |
H16 | 0.5209 | 0.8782 | 0.1856 | 0.0735* | |
H17 | 0.3072 | 0.7896 | 0.1854 | 0.0557* | |
H19 | 0.1475 | 0.9815 | 0.2032 | 0.0454* | |
H20 | 0.0722 | 1.2514 | 0.1840 | 0.0557* | |
H21 | −0.0909 | 1.3064 | 0.0945 | 0.0630* | |
H22 | −0.1854 | 1.0938 | 0.0255 | 0.0555* | |
H24A | −0.2914 | 0.8733 | −0.0104 | 0.0672* | |
H24B | −0.2493 | 0.7118 | −0.0409 | 0.0672* | |
H24C | −0.1770 | 0.8761 | −0.0488 | 0.0672* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0663 (10) | 0.0408 (8) | 0.0536 (9) | 0.0105 (7) | 0.0064 (7) | 0.0049 (7) |
O2 | 0.0556 (9) | 0.0578 (10) | 0.0458 (8) | −0.0078 (7) | −0.0032 (7) | −0.0016 (7) |
N3 | 0.0458 (9) | 0.0428 (9) | 0.0354 (8) | 0.0022 (7) | 0.0074 (7) | −0.0001 (7) |
C4 | 0.042 (1) | 0.0368 (10) | 0.0395 (10) | −0.0038 (8) | 0.0010 (8) | 0.0008 (8) |
C5 | 0.043 (1) | 0.0370 (10) | 0.0378 (10) | −0.0043 (8) | 0.0061 (8) | 0.0048 (8) |
C6 | 0.052 (1) | 0.062 (1) | 0.046 (1) | 0.001 (1) | 0.0043 (10) | −0.001 (1) |
C7 | 0.073 (2) | 0.167 (4) | 0.062 (2) | 0.017 (2) | 0.004 (1) | −0.049 (2) |
C8 | 0.066 (2) | 0.216 (5) | 0.080 (2) | 0.017 (3) | 0.016 (2) | −0.061 (3) |
C9 | 0.044 (1) | 0.098 (2) | 0.069 (2) | −0.004 (1) | 0.014 (1) | −0.006 (1) |
C10 | 0.048 (1) | 0.065 (1) | 0.045 (1) | −0.012 (1) | 0.0069 (9) | 0.000 (1) |
C11 | 0.058 (1) | 0.051 (1) | 0.040 (1) | 0.003 (1) | 0.0088 (9) | −0.0072 (9) |
C12 | 0.052 (1) | 0.043 (1) | 0.040 (1) | 0.0108 (9) | 0.0115 (9) | 0.0054 (9) |
C13 | 0.069 (1) | 0.061 (1) | 0.041 (1) | 0.013 (1) | 0.015 (1) | 0.005 (1) |
C14 | 0.075 (2) | 0.089 (2) | 0.064 (2) | 0.015 (2) | 0.037 (1) | 0.015 (1) |
C15 | 0.057 (1) | 0.085 (2) | 0.081 (2) | 0.001 (1) | 0.023 (1) | 0.009 (2) |
C16 | 0.053 (1) | 0.070 (2) | 0.072 (2) | 0.003 (1) | 0.010 (1) | −0.004 (1) |
C17 | 0.048 (1) | 0.061 (1) | 0.048 (1) | 0.007 (1) | 0.0094 (10) | −0.005 (1) |
C18 | 0.042 (1) | 0.040 (1) | 0.0368 (9) | −0.0013 (8) | 0.0125 (8) | 0.0034 (8) |
C19 | 0.043 (1) | 0.045 (1) | 0.0393 (10) | −0.0034 (9) | 0.0090 (8) | 0.0014 (9) |
C20 | 0.060 (1) | 0.041 (1) | 0.056 (1) | −0.0056 (10) | 0.016 (1) | −0.0050 (10) |
C21 | 0.063 (1) | 0.045 (1) | 0.064 (1) | 0.007 (1) | 0.016 (1) | 0.009 (1) |
C22 | 0.049 (1) | 0.055 (1) | 0.050 (1) | 0.005 (1) | 0.0056 (10) | 0.012 (1) |
C23 | 0.043 (1) | 0.048 (1) | 0.0391 (10) | −0.0040 (9) | 0.0101 (8) | 0.0026 (9) |
C24 | 0.048 (1) | 0.082 (2) | 0.047 (1) | −0.005 (1) | 0.0002 (10) | −0.004 (1) |
O1—C4 | 1.224 (2) | C12—C13 | 1.395 (3) |
O2—C23 | 1.375 (3) | C12—C17 | 1.384 (3) |
O2—C24 | 1.422 (3) | C13—C14 | 1.387 (4) |
N3—C4 | 1.369 (3) | C13—H13 | 0.97 |
N3—C11 | 1.468 (3) | C14—C15 | 1.368 (4) |
N3—C18 | 1.439 (3) | C14—H14 | 0.96 |
C4—C5 | 1.493 (3) | C15—C16 | 1.382 (4) |
C5—C6 | 1.486 (3) | C15—H15 | 0.98 |
C5—C10 | 1.340 (3) | C16—C17 | 1.385 (4) |
C6—C7 | 1.488 (4) | C16—H16 | 0.98 |
C6—H6A | 0.97 | C17—H17 | 0.97 |
C6—H6B | 0.97 | C18—C19 | 1.377 (3) |
C7—C8 | 1.366 (5) | C18—C23 | 1.395 (3) |
C7—H7A | 1.01 | C19—C20 | 1.383 (3) |
C7—H7B | 0.97 | C19—H19 | 0.97 |
C8—C9 | 1.488 (4) | C20—C21 | 1.379 (3) |
C8—H8A | 0.96 | C20—H20 | 0.97 |
C8—H8B | 1.02 | C21—C22 | 1.387 (3) |
C9—C10 | 1.493 (4) | C21—H21 | 0.96 |
C9—H9A | 0.97 | C22—C23 | 1.375 (3) |
C9—H9B | 0.97 | C22—H22 | 0.97 |
C10—H10 | 0.97 | C24—H24A | 0.97 |
C11—C12 | 1.506 (3) | C24—H24B | 0.97 |
C11—H11A | 0.96 | C24—H24C | 0.96 |
C11—H11B | 0.96 | ||
C23—O2—C24 | 116.8 (2) | C11—C12—C13 | 119.3 (2) |
C4—N3—C11 | 117.8 (2) | C11—C12—C17 | 122.7 (2) |
C4—N3—C18 | 122.3 (2) | C13—C12—C17 | 117.9 (2) |
C11—N3—C18 | 118.3 (2) | C12—C13—C14 | 120.3 (2) |
O1—C4—N3 | 121.4 (2) | C12—C13—H13 | 120 |
O1—C4—C5 | 120.8 (2) | C14—C13—H13 | 120 |
N3—C4—C5 | 117.7 (2) | C13—C14—C15 | 121.0 (3) |
C4—C5—C6 | 116.0 (2) | C13—C14—H14 | 119 |
C4—C5—C10 | 120.9 (2) | C15—C14—H14 | 120 |
C6—C5—C10 | 123.0 (2) | C14—C15—C16 | 119.4 (3) |
C5—C6—C7 | 113.5 (2) | C14—C15—H15 | 121 |
C5—C6—H6A | 109 | C16—C15—H15 | 120 |
C5—C6—H6B | 109 | C15—C16—C17 | 119.9 (2) |
C7—C6—H6A | 110 | C15—C16—H16 | 120 |
C7—C6—H6B | 108 | C17—C16—H16 | 120 |
H6A—C6—H6B | 108 | C12—C17—C16 | 121.5 (2) |
C6—C7—C8 | 120.3 (3) | C12—C17—H17 | 119 |
C6—C7—H7A | 105 | C16—C17—H17 | 120 |
C6—C7—H7B | 107 | N3—C18—C19 | 120.3 (2) |
C8—C7—H7A | 106 | N3—C18—C23 | 120.3 (2) |
C8—C7—H7B | 112 | C19—C18—C23 | 119.4 (2) |
H7A—C7—H7B | 105 | C18—C19—C20 | 121.3 (2) |
C7—C8—C9 | 119.1 (4) | C18—C19—H19 | 119 |
C7—C8—H8A | 113 | C20—C19—H19 | 119 |
C7—C8—H8B | 106 | C19—C20—C21 | 118.9 (2) |
C9—C8—H8A | 109 | C19—C20—H20 | 121 |
C9—C8—H8B | 105 | C21—C20—H20 | 120 |
H8A—C8—H8B | 104 | C20—C21—C22 | 120.4 (2) |
C8—C9—C10 | 112.8 (2) | C20—C21—H21 | 119 |
C8—C9—H9A | 112 | C22—C21—H21 | 121 |
C8—C9—H9B | 107 | C21—C22—C23 | 120.4 (2) |
C10—C9—H9A | 109 | C21—C22—H22 | 120 |
C10—C9—H9B | 108 | C23—C22—H22 | 120 |
H9A—C9—H9B | 108 | O2—C23—C18 | 116.4 (2) |
C5—C10—C9 | 122.5 (2) | O2—C23—C22 | 124.0 (2) |
C5—C10—H10 | 119 | C18—C23—C22 | 119.6 (2) |
C9—C10—H10 | 118 | O2—C24—H24A | 110 |
N3—C11—C12 | 115.0 (2) | O2—C24—H24B | 110 |
N3—C11—H11A | 108 | O2—C24—H24C | 111 |
N3—C11—H11B | 109 | H24A—C24—H24B | 108 |
C12—C11—H11A | 108 | H24A—C24—H24C | 109 |
C12—C11—H11B | 108 | H24B—C24—H24C | 109 |
H11A—C11—H11B | 109 |
Experimental details
Crystal data | |
Chemical formula | C21H23NO2 |
Mr | 321.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 248 |
a, b, c (Å) | 10.485 (3), 8.179 (1), 20.985 (1) |
β (°) | 100.98 (1) |
V (Å3) | 1766.7 (6) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.5 × 0.5 × 0.05 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.765, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4069, 3388, 2631 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.159, 1.04 |
No. of reflections | 3388 |
No. of parameters | 217 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.48, −0.46 |
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.
O1—C4 | 1.224 (2) | C6—C7 | 1.488 (4) |
N3—C4 | 1.369 (3) | C7—C8 | 1.366 (5) |
C4—C5 | 1.493 (3) | C8—C9 | 1.488 (4) |
C5—C6 | 1.486 (3) | C9—C10 | 1.493 (4) |
C5—C10 | 1.340 (3) |