Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100002705/qb0188sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100002705/qb0188Isup2.hkl |
CCDC reference: 144696
Crystals were kindly provided by Professor O. Sticher (ETH, Zürich), having been crystallized from a methanol–water mixture.
The absolute configuration was determined by refinement of the Flack (1983) parameter, based on 1040 Friedel pairs. The reported configuration yielded x = -0.06 (15), while the inverse configuration yielded x = 1.06 (15). The OH and H2O H atoms were refined isotropically. Other H atoms were placed in calculated positions with C—H distances of 0.93 (Csp2), 0.97 (CH2) and 0.96 Å (CH3), and Uiso = 1.2Ueq of the attached C atom (1.5 for methyl), and thereafter treated as riding. A torsional parameter was refined for the methyl group.
Data collection: CAD-4 Software (Enraf-Nonius, 1994); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
C14H14O5·H2O | F(000) = 296 |
Mr = 280.27 | Dx = 1.403 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54184 Å |
a = 7.1304 (4) Å | Cell parameters from 25 reflections |
b = 6.9381 (4) Å | θ = 13.0–44.0° |
c = 13.4150 (7) Å | µ = 0.93 mm−1 |
β = 90.901 (4)° | T = 297 K |
V = 663.58 (6) Å3 | Lath, colorless |
Z = 2 | 0.58 × 0.18 × 0.05 mm |
Enraf-Nonius CAD-4 diffractometer | 2428 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 74.8°, θmin = 3.3° |
θ/2θ scans | h = −8→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −8→8 |
Tmin = 0.614, Tmax = 0.954 | l = −16→16 |
3733 measured reflections | 3 standard reflections every 120 min |
2519 independent reflections | intensity decay: 0.8% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0682P)2 + 0.0326P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max = 0.003 |
S = 1.07 | Δρmax = 0.25 e Å−3 |
2519 reflections | Δρmin = −0.21 e Å−3 |
200 parameters | Extinction correction: Zachariasen (1963), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0075 (12) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.06 (15) |
C14H14O5·H2O | V = 663.58 (6) Å3 |
Mr = 280.27 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 7.1304 (4) Å | µ = 0.93 mm−1 |
b = 6.9381 (4) Å | T = 297 K |
c = 13.4150 (7) Å | 0.58 × 0.18 × 0.05 mm |
β = 90.901 (4)° |
Enraf-Nonius CAD-4 diffractometer | 2428 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.013 |
Tmin = 0.614, Tmax = 0.954 | 3 standard reflections every 120 min |
3733 measured reflections | intensity decay: 0.8% |
2519 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | Δρmax = 0.25 e Å−3 |
S = 1.07 | Δρmin = −0.21 e Å−3 |
2519 reflections | Absolute structure: Flack (1983) |
200 parameters | Absolute structure parameter: −0.06 (15) |
1 restraint |
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 | 0.26752 (14) | 0.53354 (18) | 0.48838 (7) | 0.0456 (3) | |
C1 | 0.27148 (18) | 0.5208 (2) | 0.26446 (10) | 0.0405 (3) | |
H1A | 0.3411 | 0.4016 | 0.2726 | 0.049* | |
H1B | 0.3558 | 0.6290 | 0.2748 | 0.049* | |
O1W | 0.5131 (2) | −0.0559 (2) | 0.17145 (10) | 0.0558 (3) | |
H2W | 0.536 (3) | −0.039 (3) | 0.2375 (17) | 0.058 (6)* | |
H1W | 0.407 (4) | −0.002 (4) | 0.1588 (18) | 0.078 (8)* | |
C2 | 0.10989 (18) | 0.5295 (2) | 0.33353 (10) | 0.0388 (3) | |
O2 | 0.42801 (19) | 0.5295 (3) | 0.62891 (9) | 0.0695 (4) | |
O3 | −0.02807 (14) | 0.5136 (2) | 0.17890 (8) | 0.0496 (3) | |
C3 | 0.10038 (19) | 0.5328 (2) | 0.43561 (10) | 0.0400 (3) | |
C4 | 0.2727 (2) | 0.5319 (3) | 0.59073 (11) | 0.0512 (4) | |
O4 | 0.19535 (16) | 0.18773 (16) | 0.13091 (8) | 0.0460 (3) | |
H4O | 0.075 (3) | 0.174 (3) | 0.1231 (15) | 0.056 (5)* | |
O5 | 0.16511 (16) | 0.55321 (17) | −0.06744 (8) | 0.0465 (3) | |
H5O | 0.270 (3) | 0.541 (4) | −0.0981 (15) | 0.058 (5)* | |
C5 | 0.0960 (3) | 0.5349 (3) | 0.64153 (12) | 0.0557 (4) | |
H5 | 0.0954 | 0.5359 | 0.7108 | 0.067* | |
C6 | −0.0675 (2) | 0.5363 (3) | 0.59070 (13) | 0.0536 (4) | |
H6 | −0.1795 | 0.5390 | 0.6253 | 0.064* | |
C7 | −0.0721 (2) | 0.5336 (3) | 0.48410 (12) | 0.0472 (3) | |
C8 | −0.2363 (2) | 0.5312 (3) | 0.42468 (14) | 0.0550 (4) | |
H8 | −0.3523 | 0.5328 | 0.4554 | 0.066* | |
C9 | −0.2300 (2) | 0.5264 (3) | 0.32227 (14) | 0.0547 (4) | |
H9 | −0.3395 | 0.5248 | 0.2836 | 0.066* | |
C10 | −0.0553 (2) | 0.5240 (2) | 0.27859 (11) | 0.0431 (3) | |
C11 | 0.17334 (19) | 0.5309 (2) | 0.16101 (10) | 0.0392 (3) | |
H11 | 0.1982 | 0.6571 | 0.1312 | 0.047* | |
C12 | 0.23284 (19) | 0.3736 (2) | 0.08852 (10) | 0.0375 (3) | |
C13 | 0.1255 (2) | 0.3843 (2) | −0.01131 (11) | 0.0429 (3) | |
H13A | 0.1567 | 0.2720 | −0.0508 | 0.052* | |
H13B | −0.0080 | 0.3798 | 0.0014 | 0.052* | |
C14 | 0.4433 (2) | 0.3885 (2) | 0.07371 (11) | 0.0432 (3) | |
H14A | 0.4787 | 0.3088 | 0.0186 | 0.065* | |
H14B | 0.5080 | 0.3462 | 0.1331 | 0.065* | |
H14C | 0.4761 | 0.5200 | 0.0601 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0385 (5) | 0.0605 (6) | 0.0377 (5) | −0.0012 (5) | 0.0006 (4) | −0.0023 (5) |
C1 | 0.0317 (6) | 0.0531 (8) | 0.0367 (6) | 0.0004 (6) | −0.0002 (5) | −0.0033 (7) |
O1W | 0.0612 (8) | 0.0615 (7) | 0.0448 (6) | 0.0083 (6) | 0.0003 (6) | 0.0021 (5) |
C2 | 0.0315 (6) | 0.0404 (6) | 0.0445 (7) | 0.0008 (6) | 0.0003 (6) | −0.0023 (6) |
O2 | 0.0564 (7) | 0.1104 (11) | 0.0417 (5) | −0.0026 (8) | −0.0076 (5) | 0.0008 (8) |
O3 | 0.0330 (5) | 0.0699 (8) | 0.0457 (5) | 0.0052 (5) | −0.0054 (4) | −0.0047 (5) |
C3 | 0.0340 (6) | 0.0408 (7) | 0.0452 (7) | 0.0001 (6) | 0.0006 (6) | −0.0009 (6) |
C4 | 0.0542 (9) | 0.0606 (9) | 0.0388 (7) | 0.0000 (8) | 0.0018 (7) | −0.0010 (8) |
O4 | 0.0435 (6) | 0.0384 (5) | 0.0559 (7) | −0.0040 (4) | −0.0061 (5) | 0.0090 (5) |
O5 | 0.0466 (5) | 0.0486 (6) | 0.0442 (5) | 0.0047 (4) | 0.0007 (5) | 0.0080 (5) |
C5 | 0.0630 (9) | 0.0636 (10) | 0.0406 (7) | −0.0009 (9) | 0.0101 (7) | −0.0022 (8) |
C6 | 0.0517 (8) | 0.0556 (9) | 0.0540 (8) | −0.0007 (8) | 0.0173 (7) | −0.0007 (8) |
C7 | 0.0408 (7) | 0.0473 (7) | 0.0539 (8) | 0.0002 (7) | 0.0108 (7) | −0.0033 (8) |
C8 | 0.0344 (7) | 0.0655 (10) | 0.0655 (9) | 0.0001 (7) | 0.0111 (7) | −0.0056 (10) |
C9 | 0.0294 (6) | 0.0688 (10) | 0.0657 (9) | 0.0030 (8) | −0.0017 (7) | −0.0080 (10) |
C10 | 0.0360 (7) | 0.0457 (7) | 0.0476 (7) | 0.0030 (6) | −0.0016 (6) | −0.0023 (7) |
C11 | 0.0345 (6) | 0.0424 (7) | 0.0406 (6) | 0.0005 (6) | −0.0026 (5) | 0.0000 (6) |
C12 | 0.0383 (7) | 0.0345 (6) | 0.0396 (6) | −0.0013 (5) | −0.0013 (6) | 0.0023 (5) |
C13 | 0.0446 (7) | 0.0443 (7) | 0.0398 (7) | −0.0033 (6) | −0.0036 (6) | 0.0006 (6) |
C14 | 0.0383 (7) | 0.0460 (8) | 0.0456 (7) | 0.0006 (6) | 0.0017 (6) | −0.0009 (6) |
O1—C4 | 1.3730 (16) | C5—C6 | 1.341 (3) |
O1—C3 | 1.3766 (17) | C5—H5 | 0.9300 |
C1—C2 | 1.4911 (18) | C6—C7 | 1.430 (2) |
C1—C11 | 1.5460 (18) | C6—H6 | 0.9300 |
C1—H1A | 0.9700 | C7—C8 | 1.406 (2) |
C1—H1B | 0.9700 | C8—C9 | 1.376 (3) |
O1W—H2W | 0.91 (2) | C8—H8 | 0.9300 |
O1W—H1W | 0.85 (3) | C9—C10 | 1.385 (2) |
C2—C3 | 1.3724 (19) | C9—H9 | 0.9300 |
C2—C10 | 1.3799 (19) | C11—C12 | 1.526 (2) |
O2—C4 | 1.213 (2) | C11—H11 | 0.9800 |
O3—C10 | 1.3563 (18) | C12—C14 | 1.5206 (19) |
O3—C11 | 1.4647 (16) | C12—C13 | 1.5338 (19) |
C3—C7 | 1.400 (2) | C13—H13A | 0.9700 |
C4—C5 | 1.442 (3) | C13—H13B | 0.9700 |
O4—C12 | 1.4364 (17) | C14—H14A | 0.9600 |
O4—H4O | 0.87 (2) | C14—H14B | 0.9600 |
O5—C13 | 1.4236 (19) | C14—H14C | 0.9600 |
O5—H5O | 0.86 (2) | ||
C4—O1—C3 | 121.57 (11) | C7—C8—H8 | 119.1 |
C2—C1—C11 | 102.28 (10) | C8—C9—C10 | 117.80 (14) |
C2—C1—H1A | 111.3 | C8—C9—H9 | 121.1 |
C11—C1—H1A | 111.3 | C10—C9—H9 | 121.1 |
C2—C1—H1B | 111.3 | O3—C10—C2 | 113.21 (12) |
C11—C1—H1B | 111.3 | O3—C10—C9 | 124.14 (13) |
H1A—C1—H1B | 109.2 | C2—C10—C9 | 122.65 (14) |
H2W—O1W—H1W | 106 (2) | O3—C11—C12 | 109.19 (11) |
C3—C2—C10 | 118.57 (12) | O3—C11—C1 | 106.28 (11) |
C3—C2—C1 | 132.18 (11) | C12—C11—C1 | 114.40 (12) |
C10—C2—C1 | 109.17 (12) | O3—C11—H11 | 108.9 |
C10—O3—C11 | 108.23 (10) | C12—C11—H11 | 108.9 |
C2—C3—O1 | 117.21 (12) | C1—C11—H11 | 108.9 |
C2—C3—C7 | 121.41 (13) | O4—C12—C14 | 107.64 (11) |
O1—C3—C7 | 121.38 (13) | O4—C12—C11 | 109.54 (11) |
O2—C4—O1 | 115.61 (14) | C14—C12—C11 | 108.63 (11) |
O2—C4—C5 | 126.82 (14) | O4—C12—C13 | 107.20 (11) |
O1—C4—C5 | 117.57 (13) | C14—C12—C13 | 111.26 (11) |
C12—O4—H4O | 103.9 (15) | C11—C12—C13 | 112.45 (12) |
C13—O5—H5O | 110.6 (16) | O5—C13—C12 | 113.65 (12) |
C6—C5—C4 | 121.25 (14) | O5—C13—H13A | 108.8 |
C6—C5—H5 | 119.4 | C12—C13—H13A | 108.8 |
C4—C5—H5 | 119.4 | O5—C13—H13B | 108.8 |
C5—C6—C7 | 120.93 (14) | C12—C13—H13B | 108.8 |
C5—C6—H6 | 119.5 | H13A—C13—H13B | 107.7 |
C7—C6—H6 | 119.5 | C12—C14—H14A | 109.5 |
C3—C7—C8 | 117.79 (15) | C12—C14—H14B | 109.5 |
C3—C7—C6 | 117.28 (14) | H14A—C14—H14B | 109.5 |
C8—C7—C6 | 124.93 (14) | C12—C14—H14C | 109.5 |
C9—C8—C7 | 121.77 (14) | H14A—C14—H14C | 109.5 |
C9—C8—H8 | 119.1 | H14B—C14—H14C | 109.5 |
C11—C1—C2—C3 | −177.66 (16) | C11—O3—C10—C2 | −5.58 (19) |
C11—C1—C2—C10 | 5.65 (17) | C11—O3—C10—C9 | 175.27 (17) |
C10—C2—C3—O1 | 178.47 (13) | C3—C2—C10—O3 | −177.56 (13) |
C1—C2—C3—O1 | 2.0 (2) | C1—C2—C10—O3 | −0.3 (2) |
C10—C2—C3—C7 | −1.0 (2) | C3—C2—C10—C9 | 1.6 (2) |
C1—C2—C3—C7 | −177.40 (17) | C1—C2—C10—C9 | 178.82 (17) |
C4—O1—C3—C2 | −178.34 (14) | C8—C9—C10—O3 | 177.95 (17) |
C4—O1—C3—C7 | 1.1 (2) | C8—C9—C10—C2 | −1.1 (3) |
C3—O1—C4—O2 | 178.82 (17) | C10—O3—C11—C12 | 132.77 (13) |
C3—O1—C4—C5 | −1.7 (2) | C10—O3—C11—C1 | 8.90 (16) |
O2—C4—C5—C6 | −179.6 (2) | C2—C1—C11—O3 | −8.62 (15) |
O1—C4—C5—C6 | 1.0 (3) | C2—C1—C11—C12 | −129.19 (13) |
C4—C5—C6—C7 | 0.4 (3) | O3—C11—C12—O4 | −60.54 (14) |
C2—C3—C7—C8 | −0.1 (3) | C1—C11—C12—O4 | 58.39 (15) |
O1—C3—C7—C8 | −179.50 (15) | O3—C11—C12—C14 | −177.86 (11) |
C2—C3—C7—C6 | 179.76 (15) | C1—C11—C12—C14 | −58.93 (15) |
O1—C3—C7—C6 | 0.4 (2) | O3—C11—C12—C13 | 58.54 (15) |
C5—C6—C7—C3 | −1.1 (3) | C1—C11—C12—C13 | 177.47 (12) |
C5—C6—C7—C8 | 178.77 (19) | O4—C12—C13—O5 | −173.63 (12) |
C3—C7—C8—C9 | 0.6 (3) | C14—C12—C13—O5 | −56.19 (16) |
C6—C7—C8—C9 | −179.25 (18) | C11—C12—C13—O5 | 65.93 (16) |
C7—C8—C9—C10 | 0.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O4 | 0.85 (3) | 2.04 (3) | 2.8717 (18) | 165 (3) |
O1W—H2W···O2i | 0.91 (2) | 1.87 (2) | 2.7686 (18) | 173 (2) |
O4—H4O···O5ii | 0.87 (2) | 2.04 (2) | 2.8519 (15) | 156 (2) |
O5—H5O···O1Wiii | 0.86 (2) | 1.97 (2) | 2.8083 (18) | 165 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x, y−1/2, −z; (iii) −x+1, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C14H14O5·H2O |
Mr | 280.27 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 297 |
a, b, c (Å) | 7.1304 (4), 6.9381 (4), 13.4150 (7) |
β (°) | 90.901 (4) |
V (Å3) | 663.58 (6) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.58 × 0.18 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.614, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3733, 2519, 2428 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.097, 1.07 |
No. of reflections | 2519 |
No. of parameters | 200 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.06 (15) |
Computer programs: CAD-4 Software (Enraf-Nonius, 1994), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1996), SHELXS (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O4 | 0.85 (3) | 2.04 (3) | 2.8717 (18) | 165 (3) |
O1W—H2W···O2i | 0.91 (2) | 1.87 (2) | 2.7686 (18) | 173 (2) |
O4—H4O···O5ii | 0.87 (2) | 2.04 (2) | 2.8519 (15) | 156 (2) |
O5—H5O···O1Wiii | 0.86 (2) | 1.97 (2) | 2.8083 (18) | 165 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x, y−1/2, −z; (iii) −x+1, y+1/2, −z. |
Isolation of furocoumarins from the roots of Angelica species has been reported by Harmala et al. (1992). The structure of the title furocoumarin, (I), was studied in order to determine the stereochemistry of the two chiral centers, C11 and C12. The complete sphere of Cu Kα data proved adequate to determine not only the relative configurations of these centers, but also the absolute configurations in the absence of elements heavier than oxygen. Both centers are found to have the S configuration. The bond lengths and angles of the coumarin rings are similar to those found in other recently reported coumarin structures (Chinnakali et al., 1998; Yip et al., 1995). Both six-membered rings are fairly planar, with maximum deviations from their respective rings of 0.0087 (13) Å for O1 and 0.0077 (12) Å for C10. The furan ring is much less planar, having a flattened envelope conformation with C11 at the flap position, lying 0.0541 (9) Å from the best plane of the five-membered ring. All potential donors of the OH groups and H2O are involved in nearly linear intermolecular O—H···O hydrogen bonds, as detailed in Table 1.