Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052026/hk2346sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052026/hk2346Isup2.hkl |
CCDC reference: 667460
For the preparation of the title compound, (I), dibenzo[a,d]cyclohepta-1,4,6-triene-5-one (620 mg, 2 mmol) and dimethylaminopropyl magnesium (690 mg, 5 mmol) were added in a flask (25 ml) and reacted in an oil bath (363 K) for 6 h. After cooling and filtering, crude compound (I) was obtained. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetone solution (m.p. 480 K).
H atoms were positioned geometrically, with O—H = 0.85 Å (for OH) and C—H = 0.93, 0.97 and 0.96 Å, for aromatic, methylene and methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Triene derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996; Wang et al., 1999). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). We report herein the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular O—H···N hydrogen bond (Table 1) causes to the formation of a non-planar seven-membered ring A (N/C3–C6/O/H0A). Rings B (C7–C12) and D (C15–C20) are nearly planar and they are oriented at a dihedral angle of 51.37 (3)°. The seven-membered ring C (C6/C7/C12–C15/C20) is not-planar.
In the crystal packing (Fig. 2), the molecules are stacked along the a axis.
For related literature, see: Nakagawa et al. (1996); Wang et al. (1999). For bond-length data, see: Allen et al. (1987).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
C20H23NO | Dx = 1.176 Mg m−3 |
Mr = 293.39 | Melting point: 480 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 11.127 (2) Å | θ = 9–12° |
b = 11.325 (2) Å | µ = 0.07 mm−1 |
c = 13.155 (3) Å | T = 298 K |
V = 1657.7 (6) Å3 | Plate, colourless |
Z = 4 | 0.40 × 0.10 × 0.10 mm |
F(000) = 632 |
Enraf–Nonius CAD-4 diffractometer | 1113 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 26.0°, θmin = 2.4° |
ω/2θ scans | h = 0→13 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→13 |
Tmin = 0.952, Tmax = 0.963 | l = 0→16 |
1858 measured reflections | 3 standard reflections every 120 min |
1858 independent reflections | intensity decay: none |
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)] = 0.080 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.201 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.06P)2 + 2P] where P = (Fo2 + 2Fc2)/3 |
1858 reflections | (Δ/σ)max < 0.001 |
175 parameters | Δρmax = 0.28 e Å−3 |
53 restraints | Δρmin = −0.25 e Å−3 |
C20H23NO | V = 1657.7 (6) Å3 |
Mr = 293.39 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.127 (2) Å | µ = 0.07 mm−1 |
b = 11.325 (2) Å | T = 298 K |
c = 13.155 (3) Å | 0.40 × 0.10 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 1113 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.952, Tmax = 0.963 | 3 standard reflections every 120 min |
1858 measured reflections | intensity decay: none |
1858 independent reflections |
R[F2 > 2σ(F2)] = 0.080 | 53 restraints |
wR(F2) = 0.201 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.28 e Å−3 |
1858 reflections | Δρmin = −0.25 e Å−3 |
175 parameters |
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 | ||
O | 0.1483 (3) | 0.9481 (4) | 0.1297 (3) | 0.0623 (12) | |
H0A | 0.0960 | 0.9318 | 0.1746 | 0.075* | |
N | −0.0027 (5) | 1.0514 (7) | 0.2639 (5) | 0.092 (2) | |
C1 | −0.1191 (7) | 0.9969 (8) | 0.2686 (7) | 0.106 | |
H1A | −0.1597 | 1.0074 | 0.2048 | 0.159* | |
H1B | −0.1654 | 1.0328 | 0.3219 | 0.159* | |
H1C | −0.1101 | 0.9141 | 0.2823 | 0.159* | |
C2 | −0.0201 (8) | 1.1710 (7) | 0.2385 (7) | 0.108 | |
H2A | 0.0563 | 1.2076 | 0.2262 | 0.162* | |
H2B | −0.0599 | 1.2106 | 0.2935 | 0.162* | |
H2C | −0.0687 | 1.1762 | 0.1783 | 0.162* | |
C3 | 0.0684 (8) | 1.0329 (7) | 0.3559 (6) | 0.102 | |
H3A | 0.0616 | 0.9511 | 0.3770 | 0.122* | |
H3B | 0.0371 | 1.0821 | 0.4101 | 0.122* | |
C4 | 0.2023 (7) | 1.0633 (7) | 0.3378 (7) | 0.094 | |
H4A | 0.2072 | 1.1355 | 0.2984 | 0.113* | |
H4B | 0.2405 | 1.0778 | 0.4029 | 0.113* | |
C5 | 0.2718 (5) | 0.9653 (5) | 0.2820 (4) | 0.0548 (15) | |
H5A | 0.2398 | 0.8896 | 0.3032 | 0.066* | |
H5B | 0.3552 | 0.9684 | 0.3034 | 0.066* | |
C6 | 0.2681 (5) | 0.9710 (6) | 0.1624 (4) | 0.0464 (14) | |
C7 | 0.3438 (5) | 0.8681 (6) | 0.1212 (4) | 0.0520 (14) | |
C8 | 0.2919 (6) | 0.7768 (6) | 0.0715 (4) | 0.0604 (16) | |
H8A | 0.2094 | 0.7793 | 0.0604 | 0.072* | |
C9 | 0.3542 (7) | 0.6811 (7) | 0.0370 (5) | 0.0734 (19) | |
H9A | 0.3132 | 0.6208 | 0.0038 | 0.088* | |
C10 | 0.4754 (7) | 0.6721 (6) | 0.0501 (6) | 0.080 (2) | |
H10A | 0.5179 | 0.6074 | 0.0254 | 0.096* | |
C11 | 0.5326 (6) | 0.7614 (6) | 0.1010 (5) | 0.0702 (18) | |
H11A | 0.6145 | 0.7544 | 0.1139 | 0.084* | |
C12 | 0.4697 (5) | 0.8675 (6) | 0.1358 (4) | 0.0589 (15) | |
C13 | 0.5424 (6) | 0.9602 (8) | 0.1862 (5) | 0.0655 (19) | |
H13A | 0.6102 | 0.9355 | 0.2216 | 0.079* | |
C14 | 0.5207 (6) | 1.0687 (8) | 0.1853 (5) | 0.073 (2) | |
H14A | 0.5766 | 1.1134 | 0.2212 | 0.088* | |
C15 | 0.4259 (6) | 1.1385 (6) | 0.1395 (4) | 0.0618 (16) | |
C16 | 0.4494 (7) | 1.2484 (7) | 0.1066 (5) | 0.083 (2) | |
H16A | 0.5244 | 1.2805 | 0.1211 | 0.099* | |
C17 | 0.3680 (8) | 1.3173 (7) | 0.0518 (6) | 0.084 (2) | |
H17A | 0.3858 | 1.3946 | 0.0333 | 0.101* | |
C18 | 0.2607 (7) | 1.2657 (8) | 0.0267 (5) | 0.090 (3) | |
H18A | 0.2081 | 1.3061 | −0.0158 | 0.108* | |
C19 | 0.2278 (6) | 1.1554 (6) | 0.0623 (4) | 0.0655 (18) | |
H19A | 0.1505 | 1.1277 | 0.0498 | 0.079* | |
C20 | 0.3088 (5) | 1.0841 (6) | 0.1173 (4) | 0.0597 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O | 0.0347 (19) | 0.103 (3) | 0.049 (2) | −0.008 (2) | −0.0014 (18) | −0.008 (3) |
N | 0.052 (3) | 0.151 (6) | 0.073 (4) | 0.005 (4) | 0.018 (3) | −0.024 (5) |
C1 | 0.106 | 0.106 | 0.106 | 0.000 | 0.000 | 0.000 |
C2 | 0.108 | 0.108 | 0.108 | 0.000 | 0.000 | 0.000 |
C3 | 0.102 | 0.102 | 0.102 | 0.000 | 0.000 | 0.000 |
C4 | 0.094 | 0.094 | 0.094 | 0.000 | 0.000 | 0.000 |
C5 | 0.053 (3) | 0.073 (4) | 0.038 (3) | 0.003 (3) | −0.006 (3) | −0.003 (3) |
C6 | 0.033 (3) | 0.082 (4) | 0.023 (2) | −0.006 (3) | −0.003 (2) | −0.009 (3) |
C7 | 0.044 (3) | 0.089 (4) | 0.023 (2) | −0.001 (3) | 0.006 (2) | 0.003 (3) |
C8 | 0.053 (3) | 0.094 (4) | 0.034 (3) | −0.001 (3) | 0.002 (3) | 0.007 (3) |
C9 | 0.074 (4) | 0.086 (4) | 0.060 (4) | −0.004 (4) | 0.008 (4) | −0.002 (4) |
C10 | 0.078 (4) | 0.087 (4) | 0.073 (4) | 0.027 (4) | 0.006 (4) | 0.008 (4) |
C11 | 0.056 (4) | 0.094 (4) | 0.061 (4) | 0.017 (3) | 0.007 (3) | 0.010 (3) |
C12 | 0.050 (3) | 0.095 (4) | 0.032 (3) | 0.007 (3) | 0.006 (3) | 0.002 (3) |
C13 | 0.042 (3) | 0.117 (6) | 0.037 (3) | 0.003 (4) | 0.002 (3) | 0.006 (4) |
C14 | 0.049 (4) | 0.122 (6) | 0.049 (4) | −0.006 (4) | 0.008 (3) | 0.018 (4) |
C15 | 0.055 (4) | 0.103 (5) | 0.028 (3) | −0.003 (4) | 0.003 (3) | 0.005 (3) |
C16 | 0.080 (5) | 0.109 (6) | 0.058 (5) | −0.016 (5) | 0.010 (4) | −0.012 (5) |
C17 | 0.094 (6) | 0.089 (5) | 0.069 (5) | −0.010 (5) | 0.011 (5) | 0.012 (4) |
C18 | 0.079 (5) | 0.145 (8) | 0.045 (4) | 0.009 (6) | 0.000 (4) | 0.012 (5) |
C19 | 0.060 (4) | 0.102 (5) | 0.035 (3) | 0.011 (4) | −0.004 (3) | −0.005 (4) |
C20 | 0.046 (3) | 0.104 (5) | 0.030 (3) | 0.000 (3) | −0.001 (3) | −0.017 (3) |
O—C6 | 1.424 (6) | C8—C9 | 1.364 (9) |
O—H0A | 0.8500 | C8—H8A | 0.9300 |
N—C2 | 1.409 (10) | C9—C10 | 1.363 (9) |
N—C1 | 1.436 (9) | C9—H9A | 0.9300 |
N—C3 | 1.460 (10) | C10—C11 | 1.369 (7) |
C1—H1A | 0.9600 | C10—H10A | 0.9300 |
C1—H1B | 0.9600 | C11—C12 | 1.465 (9) |
C1—H1C | 0.9600 | C11—H11A | 0.9300 |
C2—H2A | 0.9600 | C12—C13 | 1.481 (9) |
C2—H2B | 0.9600 | C13—C14 | 1.253 (10) |
C2—H2C | 0.9600 | C13—H13A | 0.9300 |
C3—C4 | 1.547 (11) | C14—C15 | 1.450 (9) |
C3—H3A | 0.9700 | C14—H14A | 0.9300 |
C3—H3B | 0.9700 | C15—C16 | 1.344 (9) |
C4—C5 | 1.540 (9) | C15—C20 | 1.470 (8) |
C4—H4A | 0.9700 | C16—C17 | 1.396 (10) |
C4—H4B | 0.9700 | C16—H16A | 0.9300 |
C5—C6 | 1.575 (7) | C17—C18 | 1.370 (10) |
C5—H5A | 0.9700 | C17—H17A | 0.9300 |
C5—H5B | 0.9700 | C18—C19 | 1.383 (8) |
C6—C20 | 1.483 (9) | C18—H18A | 0.9300 |
C6—C7 | 1.537 (8) | C19—C20 | 1.410 (8) |
C7—C8 | 1.353 (8) | C19—H19A | 0.9300 |
C7—C12 | 1.414 (8) | ||
C6—O—H0A | 118.1 | C8—C7—C6 | 121.1 (5) |
C2—N—C1 | 107.4 (7) | C12—C7—C6 | 119.9 (6) |
C2—N—C3 | 114.2 (7) | C7—C8—C9 | 123.5 (7) |
C1—N—C3 | 113.1 (7) | C7—C8—H8A | 118.3 |
N—C1—H1A | 109.5 | C9—C8—H8A | 118.3 |
N—C1—H1B | 109.5 | C8—C9—C10 | 121.3 (8) |
H1A—C1—H1B | 109.5 | C8—C9—H9A | 119.3 |
N—C1—H1C | 109.5 | C10—C9—H9A | 119.3 |
H1A—C1—H1C | 109.5 | C9—C10—C11 | 117.8 (7) |
H1B—C1—H1C | 109.5 | C9—C10—H10A | 121.1 |
N—C2—H2A | 109.5 | C11—C10—H10A | 121.1 |
N—C2—H2B | 109.5 | C10—C11—C12 | 122.5 (6) |
H2A—C2—H2B | 109.5 | C10—C11—H11A | 118.8 |
N—C2—H2C | 109.5 | C12—C11—H11A | 118.8 |
H2A—C2—H2C | 109.5 | C7—C12—C11 | 115.8 (6) |
H2B—C2—H2C | 109.5 | C7—C12—C13 | 126.8 (6) |
N—C3—C4 | 111.3 (7) | C11—C12—C13 | 117.4 (6) |
N—C3—H3A | 109.4 | C14—C13—C12 | 125.9 (7) |
C4—C3—H3A | 109.4 | C14—C13—H13A | 117.1 |
N—C3—H3B | 109.4 | C12—C13—H13A | 117.1 |
C4—C3—H3B | 109.4 | C13—C14—C15 | 132.7 (8) |
H3A—C3—H3B | 108.0 | C13—C14—H14A | 113.6 |
C5—C4—C3 | 113.4 (7) | C15—C14—H14A | 113.6 |
C5—C4—H4A | 108.9 | C16—C15—C14 | 119.8 (7) |
C3—C4—H4A | 108.9 | C16—C15—C20 | 119.8 (7) |
C5—C4—H4B | 108.9 | C14—C15—C20 | 120.0 (6) |
C3—C4—H4B | 108.9 | C15—C16—C17 | 123.9 (8) |
H4A—C4—H4B | 107.7 | C15—C16—H16A | 118.1 |
C4—C5—C6 | 115.7 (6) | C17—C16—H16A | 118.1 |
C4—C5—H5A | 108.4 | C18—C17—C16 | 116.9 (8) |
C6—C5—H5A | 108.4 | C18—C17—H17A | 121.6 |
C4—C5—H5B | 108.4 | C16—C17—H17A | 121.6 |
C6—C5—H5B | 108.4 | C17—C18—C19 | 122.3 (8) |
H5A—C5—H5B | 107.4 | C17—C18—H18A | 118.9 |
O—C6—C20 | 108.8 (5) | C19—C18—H18A | 118.9 |
O—C6—C7 | 105.6 (5) | C18—C19—C20 | 121.4 (7) |
C20—C6—C7 | 110.3 (4) | C18—C19—H19A | 119.3 |
O—C6—C5 | 108.6 (4) | C20—C19—H19A | 119.3 |
C20—C6—C5 | 115.3 (5) | C19—C20—C15 | 115.4 (6) |
C7—C6—C5 | 107.8 (5) | C19—C20—C6 | 120.3 (5) |
C8—C7—C12 | 119.0 (6) | C15—C20—C6 | 123.6 (5) |
C2—N—C3—C4 | −71.8 (9) | C10—C11—C12—C13 | −177.5 (6) |
C1—N—C3—C4 | 165.1 (7) | C7—C12—C13—C14 | −32.6 (11) |
N—C3—C4—C5 | −79.0 (8) | C11—C12—C13—C14 | 150.3 (7) |
C3—C4—C5—C6 | 87.5 (8) | C12—C13—C14—C15 | 0.0 (13) |
C4—C5—C6—O | −67.0 (7) | C13—C14—C15—C16 | −147.4 (8) |
C4—C5—C6—C20 | 55.4 (7) | C13—C14—C15—C20 | 24.8 (11) |
C4—C5—C6—C7 | 179.0 (5) | C14—C15—C16—C17 | 172.8 (6) |
O—C6—C7—C8 | −4.1 (7) | C20—C15—C16—C17 | 0.5 (9) |
C20—C6—C7—C8 | −121.5 (6) | C15—C16—C17—C18 | −3.4 (10) |
C5—C6—C7—C8 | 111.9 (6) | C16—C17—C18—C19 | 6.7 (11) |
O—C6—C7—C12 | 176.5 (5) | C17—C18—C19—C20 | −7.4 (11) |
C20—C6—C7—C12 | 59.1 (6) | C18—C19—C20—C15 | 4.1 (9) |
C5—C6—C7—C12 | −67.5 (7) | C18—C19—C20—C6 | 174.6 (6) |
C12—C7—C8—C9 | 2.1 (10) | C16—C15—C20—C19 | −0.8 (8) |
C6—C7—C8—C9 | −177.3 (6) | C14—C15—C20—C19 | −173.0 (5) |
C7—C8—C9—C10 | −0.5 (11) | C16—C15—C20—C6 | −171.0 (5) |
C8—C9—C10—C11 | 1.2 (12) | C14—C15—C20—C6 | 16.8 (8) |
C9—C10—C11—C12 | −3.6 (11) | O—C6—C20—C19 | 6.6 (7) |
C8—C7—C12—C11 | −4.1 (9) | C7—C6—C20—C19 | 122.0 (6) |
C6—C7—C12—C11 | 175.3 (5) | C5—C6—C20—C19 | −115.6 (6) |
C8—C7—C12—C13 | 178.7 (6) | O—C6—C20—C15 | 176.4 (5) |
C6—C7—C12—C13 | −1.9 (10) | C7—C6—C20—C15 | −68.2 (6) |
C10—C11—C12—C7 | 5.0 (9) | C5—C6—C20—C15 | 54.2 (7) |
Experimental details
Crystal data | |
Chemical formula | C20H23NO |
Mr | 293.39 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 11.127 (2), 11.325 (2), 13.155 (3) |
V (Å3) | 1657.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.952, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1858, 1858, 1113 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.080, 0.201, 1.01 |
No. of reflections | 1858 |
No. of parameters | 175 |
No. of restraints | 53 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.25 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
Triene derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996; Wang et al., 1999). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). We report herein the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular O—H···N hydrogen bond (Table 1) causes to the formation of a non-planar seven-membered ring A (N/C3–C6/O/H0A). Rings B (C7–C12) and D (C15–C20) are nearly planar and they are oriented at a dihedral angle of 51.37 (3)°. The seven-membered ring C (C6/C7/C12–C15/C20) is not-planar.
In the crystal packing (Fig. 2), the molecules are stacked along the a axis.