Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010001180X/vj1108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010001180X/vj1108Isup2.hkl |
CCDC reference: 156155
To a stirred solution of β-naphthol (8 mmoles) in glacial acetic acid (10 ml) at 333–353 K, concentrated HCl (1 ml) was added dropwise. The mixture was stirred at that temperature for 15 min. A solution of 6-methyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde in glacial acetic acid (8 ml) was added dropwise to the reaction mixture which gradually turned red. The deep red solution solidified on stirring at 333–353 K within 1 h. The whole mass was poured into crushed ice (200 g). The solid obtained was filtered, washed with water, dried in air, and digested with chloroform. The major red insoluble mass obtained after the chloroform extraction was digested with methanol. The methanolic solution produced a white crystalline compound, (I), in more than 50% yield. The compound was recrystallized by slow evaporation at room temperature from a solution in an ethanol/chloroform mixture.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PARST93 (Nardelli, 1993).
Fig. 1. Molecular structure showing 30% probability displacement ellipsoids (Farrugia, 1997). |
C32H24O4 | F(000) = 496 |
Mr = 472.51 | Dx = 1.316 Mg m−3 |
Triclinic, P1 | Melting point: 248° K |
a = 10.191 (7) Å | Cu Kα radiation, λ = 1.54180 Å |
b = 10.963 (10) Å | Cell parameters from 25 reflections |
c = 12.6210 (11) Å | θ = 15–20° |
α = 102.23 (6)° | µ = 0.69 mm−1 |
β = 114.58 (3)° | T = 293 K |
γ = 100.64 (6)° | Irregular, colourless |
V = 1192.7 (14) Å3 | 0.35 × 0.27 × 0.23 mm |
Z = 2 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 70.0°, θmin = 4.1° |
Graphite monochromator | h = −12→11 |
ω–2θ scans | k = 0→13 |
4396 measured reflections | l = −15→15 |
4396 independent reflections | 2 standard reflections every 60 min |
3505 reflections with I > 2σ(I) | intensity decay: 0.3 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0968P)2 + 0.1715P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.030 |
4396 reflections | Δρmax = 0.21 e Å−3 |
328 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0060 (19) |
C32H24O4 | γ = 100.64 (6)° |
Mr = 472.51 | V = 1192.7 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.191 (7) Å | Cu Kα radiation |
b = 10.963 (10) Å | µ = 0.69 mm−1 |
c = 12.6210 (11) Å | T = 293 K |
α = 102.23 (6)° | 0.35 × 0.27 × 0.23 mm |
β = 114.58 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
4396 measured reflections | 2 standard reflections every 60 min |
4396 independent reflections | intensity decay: 0.3 |
3505 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.21 e Å−3 |
4396 reflections | Δρmin = −0.22 e Å−3 |
328 parameters |
Experimental. θ scan width (1.2 + 1.4θ)° |
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 | ||
C1 | 0.5534 (2) | 0.91517 (18) | 0.67123 (17) | 0.0516 (4) | |
H1 | 0.5883 | 0.8592 | 0.6307 | 0.062* | |
C2 | 0.5695 (2) | 1.03949 (19) | 0.66477 (19) | 0.0610 (5) | |
H2 | 0.6148 | 1.0665 | 0.6197 | 0.073* | |
C3 | 0.5188 (2) | 1.12687 (19) | 0.7250 (2) | 0.0665 (6) | |
H3 | 0.5314 | 1.2115 | 0.7205 | 0.080* | |
C4 | 0.4515 (2) | 1.08757 (18) | 0.7897 (2) | 0.0598 (5) | |
H4 | 0.4190 | 1.1463 | 0.8300 | 0.072* | |
C4A | 0.42937 (19) | 0.95886 (16) | 0.79740 (16) | 0.0476 (4) | |
C5 | 0.3493 (2) | 0.91408 (17) | 0.85679 (16) | 0.0518 (4) | |
H5 | 0.3207 | 0.9731 | 0.9009 | 0.062* | |
C6 | 0.3131 (2) | 0.78666 (17) | 0.85089 (15) | 0.0496 (4) | |
H6 | 0.2537 | 0.7572 | 0.8852 | 0.060* | |
C6A | 0.36634 (19) | 0.69919 (16) | 0.79228 (14) | 0.0429 (4) | |
C6B | 0.45968 (18) | 0.74027 (15) | 0.74465 (14) | 0.0406 (4) | |
C6C | 0.48445 (18) | 0.87000 (15) | 0.73863 (14) | 0.0426 (4) | |
O7 | 0.31670 (15) | 0.57111 (11) | 0.78547 (11) | 0.0509 (3) | |
C7A | 0.3403 (2) | 0.46687 (16) | 0.71026 (15) | 0.0445 (4) | |
C7B | 0.1969 (2) | 0.35453 (17) | 0.64277 (16) | 0.0484 (4) | |
C8 | 0.1518 (2) | 0.27384 (17) | 0.70107 (18) | 0.0520 (4) | |
H8 | 0.2111 | 0.2926 | 0.7853 | 0.062* | |
C9 | 0.0222 (2) | 0.16700 (19) | 0.6382 (2) | 0.0595 (5) | |
C10 | −0.0663 (2) | 0.1436 (2) | 0.5130 (2) | 0.0664 (6) | |
H10 | −0.1549 | 0.0731 | 0.4689 | 0.080* | |
C11 | −0.0264 (2) | 0.2219 (2) | 0.4528 (2) | 0.0671 (6) | |
H11 | −0.0885 | 0.2046 | 0.3692 | 0.080* | |
C11A | 0.1061 (2) | 0.32665 (18) | 0.51627 (17) | 0.0552 (5) | |
O12 | 0.14453 (17) | 0.39520 (13) | 0.44872 (12) | 0.0667 (4) | |
C13 | 0.2582 (2) | 0.52019 (17) | 0.51599 (15) | 0.0475 (4) | |
H13 | 0.2160 | 0.5851 | 0.5451 | 0.057* | |
C13A | 0.39196 (19) | 0.51037 (16) | 0.62346 (14) | 0.0436 (4) | |
H13A | 0.4303 | 0.4436 | 0.5917 | 0.052* | |
C13B | 0.52295 (19) | 0.63722 (16) | 0.69998 (14) | 0.0421 (4) | |
H13B | 0.5673 | 0.6651 | 0.6502 | 0.050* | |
C13C | 0.64161 (19) | 0.61160 (16) | 0.80950 (14) | 0.0421 (4) | |
C13D | 0.79745 (19) | 0.69091 (16) | 0.87501 (15) | 0.0443 (4) | |
C14 | 0.8556 (2) | 0.79546 (19) | 0.84275 (18) | 0.0554 (5) | |
H14 | 0.7909 | 0.8147 | 0.7752 | 0.066* | |
C15 | 1.0043 (2) | 0.8693 (2) | 0.9079 (2) | 0.0621 (5) | |
H15 | 1.0389 | 0.9381 | 0.8845 | 0.075* | |
C16 | 1.1061 (2) | 0.8433 (2) | 1.00995 (19) | 0.0604 (5) | |
H16 | 1.2070 | 0.8951 | 1.0548 | 0.072* | |
C17 | 1.0552 (2) | 0.7416 (2) | 1.04213 (17) | 0.0572 (5) | |
H17 | 1.1231 | 0.7229 | 1.1085 | 0.069* | |
C17A | 0.9016 (2) | 0.66299 (18) | 0.97767 (16) | 0.0497 (4) | |
C18 | 0.8483 (2) | 0.55849 (19) | 1.01279 (17) | 0.0574 (5) | |
H18 | 0.9156 | 0.5405 | 1.0799 | 0.069* | |
C19 | 0.7017 (2) | 0.48430 (18) | 0.95103 (17) | 0.0552 (5) | |
H19 | 0.6684 | 0.4157 | 0.9754 | 0.066* | |
C19A | 0.5988 (2) | 0.51136 (16) | 0.84899 (15) | 0.0463 (4) | |
O20 | 0.45309 (14) | 0.42633 (11) | 0.79345 (11) | 0.0508 (3) | |
O21 | 0.30724 (15) | 0.55631 (13) | 0.43687 (11) | 0.0571 (4) | |
C22 | 0.1957 (3) | 0.5867 (3) | 0.33994 (19) | 0.0730 (6) | |
H22A | 0.2398 | 0.6193 | 0.2935 | 0.109* | |
H22B | 0.1611 | 0.6522 | 0.3747 | 0.109* | |
H22C | 0.1116 | 0.5089 | 0.2867 | 0.109* | |
C23 | −0.0195 (3) | 0.0778 (2) | 0.7027 (3) | 0.0790 (7) | |
H23A | 0.0706 | 0.0657 | 0.7606 | 0.118* | |
H23B | −0.0873 | −0.0056 | 0.6431 | 0.118* | |
H23C | −0.0683 | 0.1164 | 0.7454 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0563 (10) | 0.0533 (10) | 0.0468 (10) | 0.0198 (8) | 0.0232 (9) | 0.0193 (8) |
C2 | 0.0606 (11) | 0.0573 (11) | 0.0586 (12) | 0.0125 (9) | 0.0215 (10) | 0.0257 (9) |
C3 | 0.0663 (12) | 0.0415 (10) | 0.0768 (14) | 0.0141 (9) | 0.0203 (11) | 0.0215 (9) |
C4 | 0.0560 (11) | 0.0429 (9) | 0.0660 (13) | 0.0178 (8) | 0.0193 (10) | 0.0083 (8) |
C4A | 0.0431 (8) | 0.0421 (9) | 0.0439 (9) | 0.0149 (7) | 0.0113 (7) | 0.0060 (7) |
C5 | 0.0522 (10) | 0.0511 (10) | 0.0465 (10) | 0.0217 (8) | 0.0221 (8) | 0.0031 (7) |
C6 | 0.0519 (10) | 0.0567 (10) | 0.0408 (9) | 0.0204 (8) | 0.0239 (8) | 0.0096 (7) |
C6A | 0.0517 (9) | 0.0453 (9) | 0.0318 (8) | 0.0187 (7) | 0.0185 (7) | 0.0118 (6) |
C6B | 0.0474 (9) | 0.0455 (8) | 0.0295 (8) | 0.0198 (7) | 0.0165 (7) | 0.0118 (6) |
C6C | 0.0427 (8) | 0.0434 (8) | 0.0346 (8) | 0.0156 (7) | 0.0124 (7) | 0.0099 (6) |
O7 | 0.0740 (8) | 0.0460 (7) | 0.0442 (7) | 0.0215 (6) | 0.0369 (6) | 0.0149 (5) |
C7A | 0.0561 (10) | 0.0440 (9) | 0.0351 (8) | 0.0231 (7) | 0.0192 (8) | 0.0141 (7) |
C7B | 0.0549 (10) | 0.0460 (9) | 0.0435 (10) | 0.0222 (8) | 0.0208 (8) | 0.0121 (7) |
C8 | 0.0590 (10) | 0.0511 (10) | 0.0520 (10) | 0.0230 (8) | 0.0299 (9) | 0.0151 (8) |
C9 | 0.0625 (11) | 0.0527 (10) | 0.0712 (13) | 0.0231 (9) | 0.0393 (11) | 0.0143 (9) |
C10 | 0.0599 (12) | 0.0531 (11) | 0.0715 (14) | 0.0133 (9) | 0.0259 (11) | 0.0067 (10) |
C11 | 0.0661 (12) | 0.0594 (12) | 0.0517 (12) | 0.0175 (10) | 0.0128 (10) | 0.0057 (9) |
C11A | 0.0643 (11) | 0.0493 (10) | 0.0449 (10) | 0.0215 (9) | 0.0196 (9) | 0.0115 (8) |
O12 | 0.0794 (10) | 0.0599 (8) | 0.0363 (7) | 0.0112 (7) | 0.0114 (7) | 0.0123 (6) |
C13 | 0.0603 (10) | 0.0508 (9) | 0.0346 (9) | 0.0253 (8) | 0.0222 (8) | 0.0134 (7) |
C13A | 0.0555 (10) | 0.0462 (9) | 0.0347 (8) | 0.0259 (7) | 0.0222 (8) | 0.0126 (7) |
C13B | 0.0531 (9) | 0.0486 (9) | 0.0351 (8) | 0.0260 (8) | 0.0244 (8) | 0.0176 (7) |
C13C | 0.0513 (9) | 0.0479 (9) | 0.0332 (8) | 0.0246 (7) | 0.0215 (7) | 0.0131 (7) |
C13D | 0.0525 (9) | 0.0501 (9) | 0.0380 (9) | 0.0269 (8) | 0.0251 (8) | 0.0117 (7) |
C14 | 0.0541 (10) | 0.0683 (12) | 0.0547 (11) | 0.0254 (9) | 0.0306 (9) | 0.0246 (9) |
C15 | 0.0571 (11) | 0.0738 (13) | 0.0667 (13) | 0.0222 (10) | 0.0361 (10) | 0.0280 (10) |
C16 | 0.0495 (10) | 0.0713 (13) | 0.0574 (12) | 0.0203 (9) | 0.0268 (9) | 0.0110 (9) |
C17 | 0.0543 (10) | 0.0683 (12) | 0.0440 (10) | 0.0267 (9) | 0.0187 (9) | 0.0116 (9) |
C17A | 0.0546 (10) | 0.0553 (10) | 0.0386 (9) | 0.0264 (8) | 0.0204 (8) | 0.0097 (7) |
C18 | 0.0615 (11) | 0.0609 (11) | 0.0408 (10) | 0.0260 (9) | 0.0127 (9) | 0.0176 (8) |
C19 | 0.0682 (12) | 0.0531 (10) | 0.0432 (10) | 0.0240 (9) | 0.0200 (9) | 0.0223 (8) |
C19A | 0.0544 (10) | 0.0462 (9) | 0.0379 (9) | 0.0211 (8) | 0.0196 (8) | 0.0131 (7) |
O20 | 0.0558 (7) | 0.0487 (7) | 0.0436 (7) | 0.0181 (6) | 0.0161 (6) | 0.0208 (5) |
O21 | 0.0710 (8) | 0.0784 (9) | 0.0373 (7) | 0.0395 (7) | 0.0290 (6) | 0.0264 (6) |
C22 | 0.0953 (16) | 0.1011 (17) | 0.0489 (12) | 0.0591 (14) | 0.0371 (12) | 0.0426 (11) |
C23 | 0.0875 (16) | 0.0661 (13) | 0.0949 (18) | 0.0158 (12) | 0.0589 (15) | 0.0215 (12) |
C1—C2 | 1.366 (3) | O12—C13 | 1.429 (3) |
C1—C6C | 1.418 (2) | C13—O21 | 1.383 (2) |
C1—H1 | 0.9300 | C13—C13A | 1.512 (2) |
C2—C3 | 1.401 (3) | C13—H13 | 0.9800 |
C2—H2 | 0.9300 | C13A—C13B | 1.524 (3) |
C3—C4 | 1.352 (3) | C13A—H13A | 0.9800 |
C3—H3 | 0.9300 | C13B—C13C | 1.533 (2) |
C4—C4A | 1.418 (3) | C13B—H13B | 0.9800 |
C4—H4 | 0.9300 | C13C—C19A | 1.372 (3) |
C4A—C5 | 1.409 (3) | C13C—C13D | 1.434 (3) |
C4A—C6C | 1.434 (2) | C13D—C14 | 1.406 (3) |
C5—C6 | 1.355 (3) | C13D—C17A | 1.429 (2) |
C5—H5 | 0.9300 | C14—C15 | 1.362 (3) |
C6—C6A | 1.409 (2) | C14—H14 | 0.9300 |
C6—H6 | 0.9300 | C15—C16 | 1.403 (3) |
C6A—O7 | 1.373 (2) | C15—H15 | 0.9300 |
C6A—C6B | 1.379 (2) | C16—C17 | 1.353 (3) |
C6B—C6C | 1.422 (3) | C16—H16 | 0.9300 |
C6B—C13B | 1.520 (2) | C17—C17A | 1.414 (3) |
O7—C7A | 1.448 (2) | C17—H17 | 0.9300 |
C7A—O20 | 1.416 (2) | C17A—C18 | 1.411 (3) |
C7A—C7B | 1.495 (3) | C18—C19 | 1.347 (3) |
C7A—C13A | 1.521 (2) | C18—H18 | 0.9300 |
C7B—C8 | 1.394 (3) | C19—C19A | 1.414 (2) |
C7B—C11A | 1.399 (3) | C19—H19 | 0.9300 |
C8—C9 | 1.382 (3) | C19A—O20 | 1.382 (3) |
C8—H8 | 0.9300 | O21—C22 | 1.433 (2) |
C9—C10 | 1.391 (3) | C22—H22A | 0.9600 |
C9—C23 | 1.507 (3) | C22—H22B | 0.9600 |
C10—C11 | 1.371 (3) | C22—H22C | 0.9600 |
C10—H10 | 0.9300 | C23—H23A | 0.9600 |
C11—C11A | 1.386 (3) | C23—H23B | 0.9600 |
C11—H11 | 0.9300 | C23—H23C | 0.9600 |
C11A—O12 | 1.373 (2) | ||
C2—C1—C6C | 121.21 (18) | O21—C13—H13 | 110.3 |
C2—C1—H1 | 119.4 | O12—C13—H13 | 110.3 |
C6C—C1—H1 | 119.4 | C13A—C13—H13 | 110.3 |
C1—C2—C3 | 121.1 (2) | C13—C13A—C7A | 109.47 (15) |
C1—C2—H2 | 119.5 | C13—C13A—C13B | 115.12 (15) |
C3—C2—H2 | 119.5 | C7A—C13A—C13B | 107.00 (14) |
C4—C3—C2 | 119.69 (18) | C13—C13A—H13A | 108.4 |
C4—C3—H3 | 120.2 | C7A—C13A—H13A | 108.4 |
C2—C3—H3 | 120.2 | C13B—C13A—H13A | 108.4 |
C3—C4—C4A | 121.55 (19) | C6B—C13B—C13A | 107.35 (15) |
C3—C4—H4 | 119.2 | C6B—C13B—C13C | 110.42 (13) |
C4A—C4—H4 | 119.2 | C13A—C13B—C13C | 107.80 (14) |
C5—C4A—C4 | 121.85 (17) | C6B—C13B—H13B | 110.4 |
C5—C4A—C6C | 119.05 (16) | C13A—C13B—H13B | 110.4 |
C4—C4A—C6C | 119.04 (18) | C13C—C13B—H13B | 110.4 |
C6—C5—C4A | 121.23 (16) | C19A—C13C—C13D | 117.98 (16) |
C6—C5—H5 | 119.4 | C19A—C13C—C13B | 119.76 (17) |
C4A—C5—H5 | 119.4 | C13D—C13C—C13B | 122.24 (15) |
C5—C6—C6A | 119.47 (17) | C14—C13D—C17A | 117.27 (18) |
C5—C6—H6 | 120.3 | C14—C13D—C13C | 123.37 (17) |
C6A—C6—H6 | 120.3 | C17A—C13D—C13C | 119.35 (17) |
O7—C6A—C6B | 123.19 (15) | C15—C14—C13D | 121.63 (19) |
O7—C6A—C6 | 114.85 (16) | C15—C14—H14 | 119.2 |
C6B—C6A—C6 | 121.96 (16) | C13D—C14—H14 | 119.2 |
C6A—C6B—C6C | 118.56 (15) | C14—C15—C16 | 121.1 (2) |
C6A—C6B—C13B | 114.89 (15) | C14—C15—H15 | 119.4 |
C6C—C6B—C13B | 126.53 (15) | C16—C15—H15 | 119.4 |
C1—C6C—C6B | 123.57 (16) | C17—C16—C15 | 119.0 (2) |
C1—C6C—C4A | 117.41 (16) | C17—C16—H16 | 120.5 |
C6B—C6C—C4A | 118.92 (16) | C15—C16—H16 | 120.5 |
C6A—O7—C7A | 121.06 (13) | C16—C17—C17A | 121.80 (19) |
O20—C7A—O7 | 105.96 (14) | C16—C17—H17 | 119.1 |
O20—C7A—C7B | 107.79 (15) | C17A—C17—H17 | 119.1 |
O7—C7A—C7B | 107.91 (15) | C18—C17A—C17 | 121.69 (18) |
O20—C7A—C13A | 109.80 (14) | C18—C17A—C13D | 119.14 (18) |
O7—C7A—C13A | 112.98 (14) | C17—C17A—C13D | 119.16 (18) |
C7B—C7A—C13A | 112.09 (15) | C19—C18—C17A | 121.30 (18) |
C8—C7B—C11A | 118.47 (19) | C19—C18—H18 | 119.3 |
C8—C7B—C7A | 122.14 (17) | C17A—C18—H18 | 119.3 |
C11A—C7B—C7A | 119.37 (17) | C18—C19—C19A | 119.58 (18) |
C9—C8—C7B | 122.36 (19) | C18—C19—H19 | 120.2 |
C9—C8—H8 | 118.8 | C19A—C19—H19 | 120.2 |
C7B—C8—H8 | 118.8 | C13C—C19A—O20 | 124.07 (16) |
C8—C9—C10 | 117.5 (2) | C13C—C19A—C19 | 122.64 (18) |
C8—C9—C23 | 121.1 (2) | O20—C19A—C19 | 113.29 (16) |
C10—C9—C23 | 121.4 (2) | C19A—O20—C7A | 115.02 (14) |
C11—C10—C9 | 121.8 (2) | C13—O21—C22 | 113.59 (15) |
C11—C10—H10 | 119.1 | O21—C22—H22A | 109.5 |
C9—C10—H10 | 119.1 | O21—C22—H22B | 109.5 |
C10—C11—C11A | 120.2 (2) | H22A—C22—H22B | 109.5 |
C10—C11—H11 | 119.9 | O21—C22—H22C | 109.5 |
C11A—C11—H11 | 119.9 | H22A—C22—H22C | 109.5 |
O12—C11A—C11 | 117.12 (18) | H22B—C22—H22C | 109.5 |
O12—C11A—C7B | 123.13 (19) | C9—C23—H23A | 109.5 |
C11—C11A—C7B | 119.7 (2) | C9—C23—H23B | 109.5 |
C11A—O12—C13 | 116.80 (15) | H23A—C23—H23B | 109.5 |
O21—C13—O12 | 107.24 (15) | C9—C23—H23C | 109.5 |
O21—C13—C13A | 108.34 (15) | H23A—C23—H23C | 109.5 |
O12—C13—C13A | 110.36 (16) | H23B—C23—H23C | 109.5 |
C6C—C1—C2—C3 | 0.2 (3) | O12—C13—C13A—C7A | −61.24 (18) |
C1—C2—C3—C4 | −0.6 (3) | O21—C13—C13A—C13B | 61.09 (18) |
C2—C3—C4—C4A | −0.6 (3) | O12—C13—C13A—C13B | 178.22 (13) |
C3—C4—C4A—C5 | −175.14 (19) | O20—C7A—C13A—C13 | 165.64 (13) |
C3—C4—C4A—C6C | 2.2 (3) | O7—C7A—C13A—C13 | −76.32 (19) |
C4—C4A—C5—C6 | 171.98 (17) | C7B—C7A—C13A—C13 | 45.86 (18) |
C6C—C4A—C5—C6 | −5.3 (3) | O20—C7A—C13A—C13B | −69.00 (17) |
C4A—C5—C6—C6A | 4.9 (3) | O7—C7A—C13A—C13B | 49.05 (18) |
C5—C6—C6A—O7 | −176.66 (15) | C7B—C7A—C13A—C13B | 171.22 (12) |
C5—C6—C6A—C6B | 2.7 (3) | C6A—C6B—C13B—C13A | 46.13 (18) |
O7—C6A—C6B—C6C | 169.90 (15) | C6C—C6B—C13B—C13A | −132.09 (17) |
C6—C6A—C6B—C6C | −9.4 (2) | C6A—C6B—C13B—C13C | −71.13 (19) |
O7—C6A—C6B—C13B | −8.5 (2) | C6C—C6B—C13B—C13C | 110.65 (19) |
C6—C6A—C6B—C13B | 172.28 (15) | C13—C13A—C13B—C6B | 56.68 (17) |
C2—C1—C6C—C6B | 177.56 (17) | C7A—C13A—C13B—C6B | −65.20 (15) |
C2—C1—C6C—C4A | 1.3 (3) | C13—C13A—C13B—C13C | 175.65 (13) |
C6A—C6B—C6C—C1 | −167.59 (16) | C7A—C13A—C13B—C13C | 53.76 (16) |
C13B—C6B—C6C—C1 | 10.6 (3) | C6B—C13B—C13C—C19A | 93.70 (19) |
C6A—C6B—C6C—C4A | 8.6 (2) | C13A—C13B—C13C—C19A | −23.28 (19) |
C13B—C6B—C6C—C4A | −173.26 (14) | C6B—C13B—C13C—C13D | −85.02 (19) |
C5—C4A—C6C—C1 | 174.90 (16) | C13A—C13B—C13C—C13D | 158.00 (14) |
C4—C4A—C6C—C1 | −2.5 (2) | C19A—C13C—C13D—C14 | 179.29 (15) |
C5—C4A—C6C—C6B | −1.5 (2) | C13B—C13C—C13D—C14 | −2.0 (2) |
C4—C4A—C6C—C6B | −178.88 (15) | C19A—C13C—C13D—C17A | 0.2 (2) |
C6B—C6A—O7—C7A | −9.9 (2) | C13B—C13C—C13D—C17A | 178.92 (13) |
C6—C6A—O7—C7A | 169.42 (14) | C17A—C13D—C14—C15 | −1.4 (3) |
C6A—O7—C7A—O20 | 108.17 (17) | C13C—C13D—C14—C15 | 179.48 (16) |
C6A—O7—C7A—C7B | −136.59 (15) | C13D—C14—C15—C16 | 0.4 (3) |
C6A—O7—C7A—C13A | −12.1 (2) | C14—C15—C16—C17 | 1.1 (3) |
O20—C7A—C7B—C8 | 39.7 (2) | C15—C16—C17—C17A | −1.6 (3) |
O7—C7A—C7B—C8 | −74.28 (19) | C16—C17—C17A—C18 | −178.82 (17) |
C13A—C7A—C7B—C8 | 160.69 (15) | C16—C17—C17A—C13D | 0.6 (3) |
O20—C7A—C7B—C11A | −138.60 (16) | C14—C13D—C17A—C18 | −179.67 (15) |
O7—C7A—C7B—C11A | 107.37 (18) | C13C—C13D—C17A—C18 | −0.5 (2) |
C13A—C7A—C7B—C11A | −17.7 (2) | C14—C13D—C17A—C17 | 0.9 (2) |
C11A—C7B—C8—C9 | 0.8 (3) | C13C—C13D—C17A—C17 | −179.91 (14) |
C7A—C7B—C8—C9 | −177.58 (15) | C17—C17A—C18—C19 | 179.84 (17) |
C7B—C8—C9—C10 | −1.7 (3) | C13D—C17A—C18—C19 | 0.5 (3) |
C7B—C8—C9—C23 | 176.99 (17) | C17A—C18—C19—C19A | −0.1 (3) |
C8—C9—C10—C11 | 0.9 (3) | C13D—C13C—C19A—O20 | −179.04 (13) |
C23—C9—C10—C11 | −177.80 (19) | C13B—C13C—C19A—O20 | 2.2 (2) |
C9—C10—C11—C11A | 0.8 (3) | C13D—C13C—C19A—C19 | 0.2 (2) |
C10—C11—C11A—O12 | 175.51 (17) | C13B—C13C—C19A—C19 | −178.55 (15) |
C10—C11—C11A—C7B | −1.8 (3) | C18—C19—C19A—C13C | −0.3 (3) |
C8—C7B—C11A—O12 | −176.13 (16) | C18—C19—C19A—O20 | 179.05 (16) |
C7A—C7B—C11A—O12 | 2.3 (3) | C13C—C19A—O20—C7A | −14.6 (2) |
C8—C7B—C11A—C11 | 1.0 (3) | C19—C19A—O20—C7A | 166.11 (14) |
C7A—C7B—C11A—C11 | 179.42 (17) | O7—C7A—O20—C19A | −74.65 (18) |
C11—C11A—O12—C13 | 165.15 (16) | C7B—C7A—O20—C19A | 170.03 (13) |
C7B—C11A—O12—C13 | −17.6 (3) | C13A—C7A—O20—C19A | 47.67 (18) |
C11A—O12—C13—O21 | 164.91 (15) | O12—C13—O21—C22 | 69.1 (2) |
C11A—O12—C13—C13A | 47.1 (2) | C13A—C13—O21—C22 | −171.78 (15) |
O21—C13—C13A—C7A | −178.37 (13) |
Experimental details
Crystal data | |
Chemical formula | C32H24O4 |
Mr | 472.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.191 (7), 10.963 (10), 12.6210 (11) |
α, β, γ (°) | 102.23 (6), 114.58 (3), 100.64 (6) |
V (Å3) | 1192.7 (14) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.35 × 0.27 × 0.23 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4396, 4396, 3505 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.151, 1.04 |
No. of reflections | 4396 |
No. of parameters | 328 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, NRCVAX (Gabe et al., 1989), SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and PARST93 (Nardelli, 1993).
O7—C6A—C6B—C13B | −8.5 (2) | O20—C7A—C13A—C13B | −69.00 (17) |
C6B—C6A—O7—C7A | −9.9 (2) | O7—C7A—C13A—C13B | 49.05 (18) |
C6A—O7—C7A—C13A | −12.1 (2) | C6A—C6B—C13B—C13A | 46.13 (18) |
C13A—C7A—C7B—C11A | −17.7 (2) | C7A—C13A—C13B—C6B | −65.20 (15) |
C7A—C7B—C11A—O12 | 2.3 (3) | C7A—C13A—C13B—C13C | 53.76 (16) |
C7B—C11A—O12—C13 | −17.6 (3) | C13A—C13B—C13C—C19A | −23.28 (19) |
C11A—O12—C13—C13A | 47.1 (2) | C13B—C13C—C19A—O20 | 2.2 (2) |
O12—C13—C13A—C7A | −61.24 (18) | C13C—C19A—O20—C7A | −14.6 (2) |
C7B—C7A—C13A—C13 | 45.86 (18) | C13A—C7A—O20—C19A | 47.67 (18) |
Recently, some coumarin-based inhibitors of HIV-integrase (Zhao et al., 1997) have been synthesized which have some structural resemblance to the compounds obtained by the reaction of β-naphthol with simple aldehydes (Sirkecioglue et al., 1995), and by the reaction of 4-hydroxycoumarins with vinyl acetate (Balasubramanian et al., 1996) and with isatin (Jain et al., 1997). The synthesis of an analogous chromone-based compound by reacting 6-methyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde with β-naphthol was attempted. The present study has revealed that the structure of the compound as determined by spectroscopic analysis and reported earlier (Bandyopadhyay & Sur, 2000) was erroneous. Here we describe the actual structure of the compound, (I), as determined by X-ray crystal structure analysis. \sch
The compound contains three fused dihydropyran rings. Two of these dihydropyran rings (B and C) are attached to naphthalene rings and the third (A) is attached to a benzene ring. According to ring puckering parameters [Q = 0.480 (2) Å, ϕ = −92.8 (4)°, θ = 131.3 (3)°] (Cremer & Pople, 1975) and ring torsion angles (Nashipuri, 1991) (Table 1), the dihydropyran ring A adopts a half-chair conformation with atoms C13 and C13A out of the best plane containing the remaining atoms by 0.346 (3) Å and −0.390 (3) Å, respectively. The asymmetry parameter (Nardelli, 1983) ΔC2(C13—C13A) = 0.008 (1) also reveals the half-chair conformation with a twofold pseudoaxis passing through the midpoints of the C13—C13A and C7B—C11A bonds. The best plane through the fused dihydropyran ring forms a dihedral angle of 5.1 (1)° with the benzene ring.
The half-chair conformation of ring B (O20,C19A,C13C,C13B,C13A,C7A) is evident from the ring puckering parameters [Q = 0.544 (2) Å, ϕ = −101.5 (3)°, θ = 49.0 (2)°] and also from the torsion angles (Table 1). The asymmetry parameter ΔC2(C13C—C19A) = 0.043 (1) indicates the presence of a twofold pseudoaxis passing through the midpoints of C13C– C19A and C7A—C13A bonds. The fused naphthalene ring makes a dihedral angle of 5.2 (1)° with the best plane through ring B.
Ring C adopts a distorted half-boat conformation [ring puckering parameters: Q = 0.556 (2) Å, ϕ = 147.0 (2)°, θ = 56.7 (2)°]. The atoms C13A and C7A are out of the best plane passing through the remaining atoms of the ring by −0.938 (3) Å and −0.375 (3) Å, respectively. The asymmetry parameter ΔC2(O7—C6A) = 0.013 (1) indicates the presence of the twofold pseudoaxis across the O7—C6A and C13A—C13B bonds.
The torsion angle C7B—C7A—C13A—C13B of 171.2 (1)° indicates that the A/B ring junction is trans. The angles between the best planes through rings A and B, rings B and C, and rings A and C are 18.0 (1), 94.1 (1) and 112.1 (1)°, respectively.