Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803016945/ww6104sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803016945/ww6104Isup2.hkl |
CCDC reference: 217032
The title compound, (I), was prepared by the reaction of 3,4-methylenedioxylbenzaldehyde, 5,5-dimethyl-1,3-cyclohexandione and isopropylidene malonate in the presence of triethylbenzylammonium chloride in water at 348 K for 6 h (m.p. 427–429 K). The single crystals suitable for X-ray diffraction were obtained by slow evaporation of ethanol solution.
The positions of all H atoms were fixed geometrically and refined as riding (C—H = 0.93–0.98 Å).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure drawing for (I), showing 50% probability of displacement ellipsoids and the atom-numbering scheme. |
C18H18O5 | Z = 2 |
Mr = 314.32 | F(000) = 332 |
Triclinic, P1 | Dx = 1.347 Mg m−3 |
Hall symbol: -P 1 | Melting point = 427–429 K |
a = 6.963 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.957 (2) Å | Cell parameters from 28 reflections |
c = 13.594 (3) Å | θ = 3.3–17.0° |
α = 90.16 (2)° | µ = 0.10 mm−1 |
β = 103.11 (2)° | T = 296 K |
γ = 109.60 (2)° | Block, colorless |
V = 775.0 (3) Å3 | 0.54 × 0.48 × 0.24 mm |
Siemens P4 diffractometer | Rint = 0.014 |
Radiation source: normal-focus sealed tube | θmax = 25.0°, θmin = 1.5° |
Graphite monochromator | h = 0→8 |
ω scans | k = −10→9 |
3072 measured reflections | l = −16→15 |
2731 independent reflections | 3 standard reflections every 97 reflections |
1937 reflections with I > 2σ(I) | intensity decay: 6.0% |
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0542P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2731 reflections | Δρmax = 0.17 e Å−3 |
211 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.041 (5) |
C18H18O5 | γ = 109.60 (2)° |
Mr = 314.32 | V = 775.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.963 (1) Å | Mo Kα radiation |
b = 8.957 (2) Å | µ = 0.10 mm−1 |
c = 13.594 (3) Å | T = 296 K |
α = 90.16 (2)° | 0.54 × 0.48 × 0.24 mm |
β = 103.11 (2)° |
Siemens P4 diffractometer | Rint = 0.014 |
3072 measured reflections | 3 standard reflections every 97 reflections |
2731 independent reflections | intensity decay: 6.0% |
1937 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
2731 reflections | Δρmin = −0.16 e Å−3 |
211 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 | ||
O1 | 0.13514 (18) | 0.54308 (14) | 0.13021 (8) | 0.0545 (3) | |
O2 | 0.85495 (19) | 1.14456 (14) | 0.50051 (9) | 0.0620 (4) | |
O3 | 1.01742 (19) | 1.20478 (14) | 0.36817 (10) | 0.0675 (4) | |
O4 | 0.5954 (2) | 0.40580 (17) | 0.39569 (9) | 0.0783 (4) | |
O5 | 0.0147 (2) | 0.73684 (16) | 0.14565 (10) | 0.0705 (4) | |
C1 | 0.2442 (2) | 0.44709 (18) | 0.17532 (12) | 0.0440 (4) | |
C2 | 0.2199 (3) | 0.3133 (2) | 0.10370 (13) | 0.0556 (5) | |
H2A | 0.2192 | 0.3505 | 0.0367 | 0.067* | |
H2B | 0.0853 | 0.2307 | 0.0999 | 0.067* | |
C3 | 0.3937 (3) | 0.2418 (2) | 0.13387 (13) | 0.0532 (5) | |
C4 | 0.4296 (3) | 0.2229 (2) | 0.24763 (14) | 0.0611 (5) | |
H4A | 0.3063 | 0.1418 | 0.2600 | 0.073* | |
H4B | 0.5473 | 0.1858 | 0.2687 | 0.073* | |
C5 | 0.4729 (3) | 0.3733 (2) | 0.31177 (13) | 0.0527 (4) | |
C6 | 0.3592 (2) | 0.47907 (18) | 0.27140 (11) | 0.0430 (4) | |
C7 | 0.3631 (2) | 0.61509 (19) | 0.33727 (11) | 0.0451 (4) | |
H7 | 0.3727 | 0.5829 | 0.4066 | 0.054* | |
C8 | 0.1511 (3) | 0.6401 (2) | 0.30052 (12) | 0.0515 (4) | |
H8A | 0.0418 | 0.5526 | 0.3187 | 0.062* | |
H8B | 0.1573 | 0.7374 | 0.3347 | 0.062* | |
C9 | 0.0961 (3) | 0.6501 (2) | 0.18920 (13) | 0.0501 (4) | |
C10 | 0.5462 (2) | 0.77008 (19) | 0.34060 (11) | 0.0423 (4) | |
C11 | 0.6075 (2) | 0.88055 (19) | 0.42492 (11) | 0.0444 (4) | |
H11 | 0.5429 | 0.8588 | 0.4786 | 0.053* | |
C12 | 0.7650 (2) | 1.02084 (19) | 0.42544 (11) | 0.0435 (4) | |
C13 | 0.8631 (2) | 1.05607 (19) | 0.34699 (13) | 0.0488 (4) | |
C14 | 0.8088 (3) | 0.9507 (2) | 0.26496 (13) | 0.0594 (5) | |
H14 | 0.8764 | 0.9739 | 0.2123 | 0.071* | |
C15 | 0.6475 (3) | 0.8062 (2) | 0.26271 (13) | 0.0537 (5) | |
H15 | 0.6070 | 0.7321 | 0.2072 | 0.064* | |
C16 | 0.9975 (3) | 1.2682 (2) | 0.45983 (14) | 0.0588 (5) | |
H16A | 0.9450 | 1.3555 | 0.4466 | 0.071* | |
H16B | 1.1334 | 1.3081 | 0.5079 | 0.071* | |
C17 | 0.3261 (4) | 0.0808 (2) | 0.07398 (17) | 0.0780 (6) | |
H17A | 0.3036 | 0.0949 | 0.0028 | 0.094* | |
H17B | 0.1981 | 0.0114 | 0.0879 | 0.094* | |
H17C | 0.4340 | 0.0349 | 0.0936 | 0.094* | |
C18 | 0.5966 (3) | 0.3507 (3) | 0.11116 (19) | 0.0847 (7) | |
H18A | 0.5749 | 0.3613 | 0.0396 | 0.102* | |
H18B | 0.7053 | 0.3061 | 0.1328 | 0.102* | |
H18C | 0.6377 | 0.4535 | 0.1468 | 0.102* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0605 (8) | 0.0604 (7) | 0.0408 (6) | 0.0271 (6) | −0.0005 (5) | 0.0020 (5) |
O2 | 0.0675 (8) | 0.0537 (7) | 0.0547 (7) | 0.0078 (6) | 0.0153 (6) | −0.0092 (6) |
O3 | 0.0609 (8) | 0.0563 (8) | 0.0749 (9) | 0.0015 (7) | 0.0253 (7) | −0.0061 (7) |
O4 | 0.0792 (10) | 0.1013 (11) | 0.0519 (8) | 0.0464 (9) | −0.0122 (7) | 0.0011 (7) |
O5 | 0.0756 (9) | 0.0720 (9) | 0.0688 (9) | 0.0395 (8) | 0.0057 (7) | 0.0086 (7) |
C1 | 0.0412 (9) | 0.0449 (9) | 0.0415 (9) | 0.0121 (7) | 0.0054 (7) | 0.0052 (7) |
C2 | 0.0559 (11) | 0.0534 (10) | 0.0482 (10) | 0.0136 (9) | 0.0022 (8) | −0.0037 (8) |
C3 | 0.0522 (10) | 0.0492 (10) | 0.0545 (10) | 0.0124 (9) | 0.0136 (8) | −0.0006 (8) |
C4 | 0.0610 (12) | 0.0625 (12) | 0.0646 (12) | 0.0306 (10) | 0.0105 (9) | 0.0100 (9) |
C5 | 0.0486 (10) | 0.0636 (11) | 0.0440 (10) | 0.0200 (9) | 0.0065 (8) | 0.0089 (8) |
C6 | 0.0392 (8) | 0.0464 (9) | 0.0378 (8) | 0.0096 (7) | 0.0066 (7) | 0.0047 (7) |
C7 | 0.0429 (9) | 0.0540 (10) | 0.0334 (8) | 0.0123 (8) | 0.0062 (7) | 0.0032 (7) |
C8 | 0.0437 (9) | 0.0592 (11) | 0.0492 (10) | 0.0128 (8) | 0.0141 (8) | 0.0027 (8) |
C9 | 0.0400 (9) | 0.0520 (10) | 0.0525 (10) | 0.0122 (8) | 0.0054 (8) | 0.0014 (8) |
C10 | 0.0388 (8) | 0.0505 (10) | 0.0373 (8) | 0.0173 (8) | 0.0056 (7) | 0.0033 (7) |
C11 | 0.0434 (9) | 0.0539 (10) | 0.0371 (8) | 0.0178 (8) | 0.0103 (7) | 0.0033 (7) |
C12 | 0.0410 (9) | 0.0489 (10) | 0.0399 (9) | 0.0182 (8) | 0.0044 (7) | −0.0006 (7) |
C13 | 0.0397 (9) | 0.0517 (10) | 0.0531 (10) | 0.0137 (8) | 0.0108 (8) | 0.0041 (8) |
C14 | 0.0590 (12) | 0.0641 (12) | 0.0533 (11) | 0.0110 (10) | 0.0257 (9) | 0.0010 (9) |
C15 | 0.0547 (10) | 0.0570 (11) | 0.0441 (9) | 0.0107 (9) | 0.0148 (8) | −0.0060 (8) |
C16 | 0.0488 (10) | 0.0522 (11) | 0.0665 (12) | 0.0117 (9) | 0.0053 (9) | −0.0026 (9) |
C17 | 0.0876 (15) | 0.0659 (13) | 0.0806 (14) | 0.0277 (12) | 0.0190 (12) | −0.0068 (11) |
C18 | 0.0732 (14) | 0.0807 (15) | 0.1004 (17) | 0.0126 (12) | 0.0430 (13) | −0.0001 (13) |
O1—C9 | 1.381 (2) | C7—C8 | 1.539 (2) |
O1—C1 | 1.3864 (18) | C7—H7 | 0.9800 |
O2—C12 | 1.3784 (19) | C8—C9 | 1.485 (2) |
O2—C16 | 1.426 (2) | C8—H8A | 0.9700 |
O3—C13 | 1.382 (2) | C8—H8B | 0.9700 |
O3—C16 | 1.422 (2) | C10—C15 | 1.382 (2) |
O4—C5 | 1.2264 (19) | C10—C11 | 1.401 (2) |
O5—C9 | 1.192 (2) | C11—C12 | 1.361 (2) |
C1—C6 | 1.341 (2) | C11—H11 | 0.9300 |
C1—C2 | 1.482 (2) | C12—C13 | 1.375 (2) |
C2—C3 | 1.529 (2) | C13—C14 | 1.357 (2) |
C2—H2A | 0.9700 | C14—C15 | 1.395 (2) |
C2—H2B | 0.9700 | C14—H14 | 0.9300 |
C3—C18 | 1.523 (3) | C15—H15 | 0.9300 |
C3—C17 | 1.525 (2) | C16—H16A | 0.9700 |
C3—C4 | 1.529 (2) | C16—H16B | 0.9700 |
C4—C5 | 1.506 (2) | C17—H17A | 0.9600 |
C4—H4A | 0.9700 | C17—H17B | 0.9600 |
C4—H4B | 0.9700 | C17—H17C | 0.9600 |
C5—C6 | 1.461 (2) | C18—H18A | 0.9600 |
C6—C7 | 1.499 (2) | C18—H18B | 0.9600 |
C7—C10 | 1.530 (2) | C18—H18C | 0.9600 |
C9—O1—C1 | 120.18 (12) | H8A—C8—H8B | 107.9 |
C12—O2—C16 | 105.65 (13) | O5—C9—O1 | 116.87 (15) |
C13—O3—C16 | 105.47 (13) | O5—C9—C8 | 126.67 (17) |
C6—C1—O1 | 122.06 (14) | O1—C9—C8 | 116.40 (15) |
C6—C1—C2 | 126.44 (15) | C15—C10—C11 | 119.43 (15) |
O1—C1—C2 | 111.48 (13) | C15—C10—C7 | 122.52 (14) |
C1—C2—C3 | 113.28 (14) | C11—C10—C7 | 118.02 (14) |
C1—C2—H2A | 108.9 | C12—C11—C10 | 117.66 (15) |
C3—C2—H2A | 108.9 | C12—C11—H11 | 121.2 |
C1—C2—H2B | 108.9 | C10—C11—H11 | 121.2 |
C3—C2—H2B | 108.9 | C11—C12—C13 | 122.35 (15) |
H2A—C2—H2B | 107.7 | C11—C12—O2 | 128.05 (15) |
C18—C3—C17 | 108.95 (16) | C13—C12—O2 | 109.57 (15) |
C18—C3—C4 | 109.42 (16) | C14—C13—C12 | 121.28 (16) |
C17—C3—C4 | 110.61 (15) | C14—C13—O3 | 128.78 (16) |
C18—C3—C2 | 110.57 (16) | C12—C13—O3 | 109.92 (14) |
C17—C3—C2 | 109.29 (15) | C13—C14—C15 | 117.36 (16) |
C4—C3—C2 | 108.00 (14) | C13—C14—H14 | 121.3 |
C5—C4—C3 | 114.06 (15) | C15—C14—H14 | 121.3 |
C5—C4—H4A | 108.7 | C10—C15—C14 | 121.90 (16) |
C3—C4—H4A | 108.7 | C10—C15—H15 | 119.1 |
C5—C4—H4B | 108.7 | C14—C15—H15 | 119.1 |
C3—C4—H4B | 108.7 | O3—C16—O2 | 108.29 (13) |
H4A—C4—H4B | 107.6 | O3—C16—H16A | 110.0 |
O4—C5—C6 | 120.57 (17) | O2—C16—H16A | 110.0 |
O4—C5—C4 | 121.93 (17) | O3—C16—H16B | 110.0 |
C6—C5—C4 | 117.48 (14) | O2—C16—H16B | 110.0 |
C1—C6—C5 | 118.22 (15) | H16A—C16—H16B | 108.4 |
C1—C6—C7 | 120.98 (15) | C3—C17—H17A | 109.5 |
C5—C6—C7 | 120.74 (14) | C3—C17—H17B | 109.5 |
C6—C7—C10 | 115.02 (13) | H17A—C17—H17B | 109.5 |
C6—C7—C8 | 107.43 (13) | C3—C17—H17C | 109.5 |
C10—C7—C8 | 110.91 (13) | H17A—C17—H17C | 109.5 |
C6—C7—H7 | 107.7 | H17B—C17—H17C | 109.5 |
C10—C7—H7 | 107.7 | C3—C18—H18A | 109.5 |
C8—C7—H7 | 107.7 | C3—C18—H18B | 109.5 |
C9—C8—C7 | 112.28 (14) | H18A—C18—H18B | 109.5 |
C9—C8—H8A | 109.1 | C3—C18—H18C | 109.5 |
C7—C8—H8A | 109.1 | H18A—C18—H18C | 109.5 |
C9—C8—H8B | 109.1 | H18B—C18—H18C | 109.5 |
C7—C8—H8B | 109.1 | ||
C9—O1—C1—C6 | −16.9 (2) | C1—O1—C9—C8 | −7.8 (2) |
C9—O1—C1—C2 | 164.54 (14) | C7—C8—C9—O5 | −140.99 (18) |
C6—C1—C2—C3 | −19.7 (2) | C7—C8—C9—O1 | 42.0 (2) |
O1—C1—C2—C3 | 158.79 (13) | C6—C7—C10—C15 | 25.4 (2) |
C1—C2—C3—C18 | −75.18 (19) | C8—C7—C10—C15 | −96.77 (18) |
C1—C2—C3—C17 | 164.90 (15) | C6—C7—C10—C11 | −156.64 (14) |
C1—C2—C3—C4 | 44.5 (2) | C8—C7—C10—C11 | 81.21 (17) |
C18—C3—C4—C5 | 66.6 (2) | C15—C10—C11—C12 | 0.6 (2) |
C17—C3—C4—C5 | −173.39 (16) | C7—C10—C11—C12 | −177.43 (14) |
C2—C3—C4—C5 | −53.84 (19) | C10—C11—C12—C13 | 0.0 (2) |
C3—C4—C5—O4 | −144.53 (18) | C10—C11—C12—O2 | −178.04 (14) |
C3—C4—C5—C6 | 36.9 (2) | C16—O2—C12—C11 | −174.70 (16) |
O1—C1—C6—C5 | −178.56 (13) | C16—O2—C12—C13 | 7.04 (18) |
C2—C1—C6—C5 | −0.2 (3) | C11—C12—C13—C14 | −0.8 (3) |
O1—C1—C6—C7 | 4.3 (2) | O2—C12—C13—C14 | 177.59 (15) |
C2—C1—C6—C7 | −177.43 (15) | C11—C12—C13—O3 | −179.33 (14) |
O4—C5—C6—C1 | 173.12 (17) | O2—C12—C13—O3 | −0.95 (19) |
C4—C5—C6—C1 | −8.3 (2) | C16—O3—C13—C14 | 176.03 (18) |
O4—C5—C6—C7 | −9.7 (2) | C16—O3—C13—C12 | −5.57 (18) |
C4—C5—C6—C7 | 168.93 (15) | C12—C13—C14—C15 | 0.9 (3) |
C1—C6—C7—C10 | −95.19 (18) | O3—C13—C14—C15 | 179.10 (16) |
C5—C6—C7—C10 | 87.70 (18) | C11—C10—C15—C14 | −0.5 (3) |
C1—C6—C7—C8 | 28.8 (2) | C7—C10—C15—C14 | 177.42 (15) |
C5—C6—C7—C8 | −148.29 (14) | C13—C14—C15—C10 | −0.2 (3) |
C6—C7—C8—C9 | −50.09 (18) | C13—O3—C16—O2 | 9.87 (18) |
C10—C7—C8—C9 | 76.39 (17) | C12—O2—C16—O3 | −10.46 (18) |
C1—O1—C9—O5 | 174.88 (14) |
Experimental details
Crystal data | |
Chemical formula | C18H18O5 |
Mr | 314.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 6.963 (1), 8.957 (2), 13.594 (3) |
α, β, γ (°) | 90.16 (2), 103.11 (2), 109.60 (2) |
V (Å3) | 775.0 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.54 × 0.48 × 0.24 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3072, 2731, 1937 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.102, 1.03 |
No. of reflections | 2731 |
No. of parameters | 211 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Sheldrick, 1997), SHELXTL.
O1—C9 | 1.381 (2) | C1—C6 | 1.341 (2) |
O1—C1 | 1.3864 (18) | C5—C6 | 1.461 (2) |
O4—C5 | 1.2264 (19) | C8—C9 | 1.485 (2) |
O5—C9 | 1.192 (2) | ||
C6—C1—O1 | 122.06 (14) | C6—C7—C8 | 107.43 (13) |
C6—C1—C2 | 126.44 (15) | O5—C9—O1 | 116.87 (15) |
C1—C6—C5 | 118.22 (15) | O1—C9—C8 | 116.40 (15) |
C6—C7—C10 | 115.02 (13) | ||
C9—O1—C1—C6 | −16.9 (2) | C4—C5—C6—C1 | −8.3 (2) |
C2—C1—C6—C5 | −0.2 (3) | C1—C6—C7—C8 | 28.8 (2) |
Coumarin and coumarin derivatives are natural compounds and are important chemicals in the perfume, cosmetic and pharmaceutical industrial production (Soine, 1964). As part of our program aimed at developing new and environmental friendly methodologies for the preparation of fine chemicals (Shi et al., 2003). We performed the synthesis of coumarin derivatives through a three-component reaction employing water as the reaction medium.
We report here the crystal structure of 4-(3,4-methylenedioxyphenyl)-7,7-dimethyl-5-oxo-3,4,5,6,7,8-hexahydrocoumarin, (I), synthesized by the reaction of 3,4-methylenedioxylbenzaldehyde, 5,5-dimethyl-1,3-cyclohexandione and isopropylidene malonate in the presence of triethylbenzylammonium chloride in water.
In (I), atoms O1, C1, C6, C7, C8 and C9 form a pyran ring, and the O1—C1, O1—C9 and C1—C6 bond lengths of 1.386 (2), 1.381 (2) and 1.341 (2) Å, respectively, are slightly longer than those of 2-amino-7,7-dimethyl-4-phenyl-5-oxo-5,6,7,8-tetrahydro- 4H-chromene-3-carbonitrile (Gao et al., 2001). In addition, this pyran ring adopts a distorted boat conformation; atoms O1, C1, C6 and C7 are on one plane, while atoms C8 and C9 deviate from the plane by 0.77 and 0.28 Å, respectively. X-Ray analysis reveals that the six-membered C1–C6 ring adopts a distorted boat conformation which is different from the envelope conformation (Tu et al., 2001).