X-ray diffraction studies carried out on single crystals of the monomeric,
viz. 5,6-dimethoxy-2
H-furo[2,3-
h][1]benzopyran-2-one, C
13H
10O
5, and dimeric,
viz. 5,5',6,6'-tetramethoxy-3,3',4,4'-tetrahydro-2
H,2'
H-3,3':4,4'-bi(furo[2,3-
h][1]benzopyran)-2,2'-dione, C
26H
20O
10, forms of pimpinellin have revealed that, following cyclodimerization, the carbonyl groups are head-to-head with respect to one another. In the monomer, the heterocyclic ring is planar, but it exhibits a twisted-boat conformation in the dimer. Both the monomer and the dimer interact through C-H
O interactions.
Supporting information
CCDC references: 259050; 259051
Crystalline material for X-ray diffraction studies was obtained from a mixture of pimpinellin monomer and dimer isolated from the C6H14 fraction from roots of Esenbeckia grandiflora. Crystals were grown at room temperature from a CHCl3 solution in liquid diffusion with C6H14 for the monomer, and by slow evaporation from a CHCl3 solution for the dimer.
H atoms were located on stereochemical grounds and refined with fixed geometry, each riding on a carrier atom, with a Uiso(H) value of 1.5 (for hydroxy H atoms) or 1.2 (for all other H atoms) times Ueq of the carrier atom.
For both compounds, data collection: Collect (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(I) 5,6-dimethoxy-2
H-furo[2,3-
h]-1-benzopyran-2-one
top
Crystal data top
C13H10O5 | F(000) = 512 |
Mr = 246.21 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9069 (1) Å | Cell parameters from 2383 reflections |
b = 13.4984 (5) Å | θ = 1.0–27.5° |
c = 20.9360 (9) Å | µ = 0.12 mm−1 |
β = 91.733 (2)° | T = 293 K |
V = 1103.59 (7) Å3 | Irregular, colourless |
Z = 4 | 0.30 × 0.23 × 0.20 mm |
Data collection top
Nonius KappaCCD diffractometer | 1609 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.029 |
Horizonally mounted graphite crystal monochromator | θmax = 27.5°, θmin = 3.2° |
Detector resolution: 9 pixels mm-1 | h = −5→5 |
CCD rotation images,thick slices scans | k = −16→17 |
4519 measured reflections | l = −27→27 |
2491 independent reflections | |
Refinement top
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0642P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3 |
2491 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C13H10O5 | V = 1103.59 (7) Å3 |
Mr = 246.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 3.9069 (1) Å | µ = 0.12 mm−1 |
b = 13.4984 (5) Å | T = 293 K |
c = 20.9360 (9) Å | 0.30 × 0.23 × 0.20 mm |
β = 91.733 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 1609 reflections with I > 2σ(I) |
4519 measured reflections | Rint = 0.029 |
2491 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
2491 reflections | Δρmin = −0.17 e Å−3 |
163 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.1010 (4) | 0.07361 (12) | 0.32582 (8) | 0.0696 (5) | |
O2 | 0.4243 (4) | 0.18375 (10) | 0.51332 (6) | 0.0544 (4) | |
O3 | 0.7100 (5) | 0.22720 (13) | 0.60130 (8) | 0.0786 (5) | |
O4 | −0.1060 (4) | 0.42473 (11) | 0.37492 (8) | 0.0711 (5) | |
O5 | −0.3036 (4) | 0.27488 (13) | 0.28805 (7) | 0.0699 (5) | |
C1 | 0.5346 (6) | 0.25514 (17) | 0.55638 (10) | 0.0582 (5) | |
C2 | 0.4344 (6) | 0.35532 (17) | 0.54245 (11) | 0.0613 (6) | |
H2 | 0.4918 | 0.4049 | 0.5717 | 0.074* | |
C3 | 0.2607 (5) | 0.37929 (15) | 0.48852 (10) | 0.0565 (5) | |
H3 | 0.2056 | 0.4452 | 0.4804 | 0.068* | |
C4 | 0.1588 (5) | 0.30507 (14) | 0.44328 (9) | 0.0475 (5) | |
C5 | −0.0196 (5) | 0.32681 (15) | 0.38513 (10) | 0.0530 (5) | |
C6 | −0.1146 (5) | 0.25349 (16) | 0.34247 (9) | 0.0539 (5) | |
C7 | −0.0244 (5) | 0.15693 (16) | 0.36050 (9) | 0.0527 (5) | |
C8 | 0.0289 (7) | −0.00418 (18) | 0.36185 (13) | 0.0763 (7) | |
H8 | 0.0115 | −0.0702 | 0.3495 | 0.092* | |
C9 | 0.1813 (6) | 0.02544 (16) | 0.41607 (11) | 0.0634 (6) | |
H9 | 0.2866 | −0.0142 | 0.4472 | 0.076* | |
C10 | 0.1501 (5) | 0.13148 (14) | 0.41669 (9) | 0.0496 (5) | |
C11 | 0.2426 (5) | 0.20780 (14) | 0.45801 (9) | 0.0463 (5) | |
C12 | 0.0408 (7) | 0.4709 (2) | 0.32075 (14) | 0.0838 (8) | |
H12A | −0.0345 | 0.5385 | 0.3180 | 0.126* | |
H12B | −0.0304 | 0.4362 | 0.2826 | 0.126* | |
H12C | 0.2860 | 0.4691 | 0.3253 | 0.126* | |
C13 | −0.1518 (7) | 0.2463 (2) | 0.22933 (11) | 0.0842 (8) | |
H13A | −0.3020 | 0.2641 | 0.1940 | 0.126* | |
H13B | −0.1152 | 0.1760 | 0.2292 | 0.126* | |
H13C | 0.0635 | 0.2797 | 0.2254 | 0.126* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0798 (10) | 0.0614 (10) | 0.0667 (10) | −0.0030 (8) | −0.0127 (8) | −0.0093 (8) |
O2 | 0.0633 (8) | 0.0502 (8) | 0.0495 (8) | 0.0029 (6) | −0.0036 (6) | 0.0021 (6) |
O3 | 0.0926 (12) | 0.0841 (12) | 0.0578 (10) | 0.0045 (9) | −0.0177 (9) | −0.0002 (8) |
O4 | 0.0817 (11) | 0.0557 (9) | 0.0761 (11) | 0.0201 (8) | 0.0035 (8) | 0.0138 (8) |
O5 | 0.0613 (9) | 0.0907 (12) | 0.0572 (9) | 0.0150 (8) | −0.0089 (7) | 0.0086 (8) |
C1 | 0.0640 (13) | 0.0621 (13) | 0.0486 (12) | −0.0022 (10) | 0.0029 (10) | −0.0035 (10) |
C2 | 0.0681 (13) | 0.0579 (13) | 0.0582 (13) | −0.0009 (10) | 0.0039 (11) | −0.0124 (10) |
C3 | 0.0607 (12) | 0.0455 (11) | 0.0638 (13) | 0.0048 (9) | 0.0088 (10) | −0.0022 (10) |
C4 | 0.0466 (10) | 0.0446 (10) | 0.0517 (11) | 0.0046 (8) | 0.0070 (8) | −0.0001 (8) |
C5 | 0.0512 (11) | 0.0492 (11) | 0.0590 (12) | 0.0101 (9) | 0.0065 (9) | 0.0082 (10) |
C6 | 0.0483 (11) | 0.0633 (13) | 0.0501 (11) | 0.0057 (9) | 0.0001 (9) | 0.0073 (10) |
C7 | 0.0523 (11) | 0.0557 (12) | 0.0500 (11) | −0.0004 (9) | 0.0007 (9) | −0.0040 (9) |
C8 | 0.0931 (18) | 0.0508 (13) | 0.0842 (18) | −0.0008 (12) | −0.0115 (15) | −0.0077 (12) |
C9 | 0.0750 (14) | 0.0467 (12) | 0.0681 (14) | 0.0021 (10) | −0.0049 (11) | −0.0005 (10) |
C10 | 0.0518 (10) | 0.0459 (11) | 0.0513 (11) | 0.0011 (8) | 0.0039 (9) | 0.0014 (9) |
C11 | 0.0457 (10) | 0.0474 (11) | 0.0459 (10) | 0.0029 (8) | 0.0043 (8) | 0.0026 (8) |
C12 | 0.0845 (17) | 0.0694 (16) | 0.097 (2) | 0.0014 (13) | −0.0056 (15) | 0.0274 (15) |
C13 | 0.0858 (18) | 0.113 (2) | 0.0535 (14) | 0.0137 (16) | −0.0088 (12) | −0.0014 (14) |
Geometric parameters (Å, º) top
O1—C7 | 1.367 (3) | C4—C5 | 1.415 (3) |
O1—C8 | 1.381 (3) | C5—C6 | 1.376 (3) |
O2—C11 | 1.379 (2) | C6—C7 | 1.399 (3) |
O2—C1 | 1.380 (3) | C7—C10 | 1.385 (3) |
O3—C1 | 1.207 (2) | C8—C9 | 1.327 (3) |
O4—C5 | 1.379 (2) | C8—H8 | 0.9300 |
O4—C12 | 1.430 (3) | C9—C10 | 1.437 (3) |
O5—C6 | 1.370 (2) | C9—H9 | 0.9300 |
O5—C13 | 1.434 (3) | C10—C11 | 1.386 (3) |
C1—C2 | 1.435 (3) | C12—H12A | 0.9600 |
C2—C3 | 1.339 (3) | C12—H12B | 0.9600 |
C2—H2 | 0.9300 | C12—H12C | 0.9600 |
C3—C4 | 1.427 (3) | C13—H13A | 0.9600 |
C3—H3 | 0.9300 | C13—H13B | 0.9600 |
C4—C11 | 1.386 (3) | C13—H13C | 0.9600 |
| | | |
C7—O1—C8 | 105.34 (17) | C9—C8—O1 | 112.7 (2) |
C11—O2—C1 | 121.80 (16) | C9—C8—H8 | 123.6 |
C5—O4—C12 | 116.03 (18) | O1—C8—H8 | 123.6 |
C6—O5—C13 | 115.47 (17) | C8—C9—C10 | 105.8 (2) |
O3—C1—O2 | 116.7 (2) | C8—C9—H9 | 127.1 |
O3—C1—C2 | 126.7 (2) | C10—C9—H9 | 127.1 |
O2—C1—C2 | 116.58 (18) | C7—C10—C11 | 117.25 (18) |
C3—C2—C1 | 121.8 (2) | C7—C10—C9 | 106.21 (18) |
C3—C2—H2 | 119.1 | C11—C10—C9 | 136.53 (19) |
C1—C2—H2 | 119.1 | O2—C11—C4 | 121.48 (18) |
C2—C3—C4 | 120.9 (2) | O2—C11—C10 | 117.83 (17) |
C2—C3—H3 | 119.5 | C4—C11—C10 | 120.67 (18) |
C4—C3—H3 | 119.5 | O4—C12—H12A | 109.5 |
C11—C4—C5 | 119.66 (18) | O4—C12—H12B | 109.5 |
C11—C4—C3 | 117.28 (18) | H12A—C12—H12B | 109.5 |
C5—C4—C3 | 123.06 (18) | O4—C12—H12C | 109.5 |
C6—C5—O4 | 121.91 (18) | H12A—C12—H12C | 109.5 |
C6—C5—C4 | 121.68 (18) | H12B—C12—H12C | 109.5 |
O4—C5—C4 | 116.35 (19) | O5—C13—H13A | 109.5 |
O5—C6—C5 | 121.08 (19) | O5—C13—H13B | 109.5 |
O5—C6—C7 | 123.09 (19) | H13A—C13—H13B | 109.5 |
C5—C6—C7 | 115.72 (18) | O5—C13—H13C | 109.5 |
O1—C7—C10 | 109.96 (18) | H13A—C13—H13C | 109.5 |
O1—C7—C6 | 125.02 (18) | H13B—C13—H13C | 109.5 |
C10—C7—C6 | 125.01 (19) | | |
| | | |
C11—O2—C1—O3 | −175.50 (19) | C5—C6—C7—O1 | 178.46 (19) |
C11—O2—C1—C2 | 3.3 (3) | O5—C6—C7—C10 | −176.34 (18) |
O3—C1—C2—C3 | 174.7 (2) | C5—C6—C7—C10 | −0.2 (3) |
O2—C1—C2—C3 | −3.9 (3) | C7—O1—C8—C9 | −0.3 (3) |
C1—C2—C3—C4 | 1.9 (3) | O1—C8—C9—C10 | 0.3 (3) |
C2—C3—C4—C11 | 0.9 (3) | O1—C7—C10—C11 | −179.02 (17) |
C2—C3—C4—C5 | −178.8 (2) | C6—C7—C10—C11 | −0.2 (3) |
C12—O4—C5—C6 | −64.7 (3) | O1—C7—C10—C9 | 0.0 (2) |
C12—O4—C5—C4 | 118.1 (2) | C6—C7—C10—C9 | 178.8 (2) |
C11—C4—C5—C6 | 0.3 (3) | C8—C9—C10—C7 | −0.1 (3) |
C3—C4—C5—C6 | −179.94 (19) | C8—C9—C10—C11 | 178.6 (3) |
C11—C4—C5—O4 | 177.51 (18) | C1—O2—C11—C4 | −0.6 (3) |
C3—C4—C5—O4 | −2.7 (3) | C1—O2—C11—C10 | 178.31 (17) |
C13—O5—C6—C5 | 122.7 (2) | C5—C4—C11—O2 | 178.20 (17) |
C13—O5—C6—C7 | −61.4 (3) | C3—C4—C11—O2 | −1.6 (3) |
O4—C5—C6—O5 | −0.7 (3) | C5—C4—C11—C10 | −0.7 (3) |
C4—C5—C6—O5 | 176.35 (18) | C3—C4—C11—C10 | 179.51 (18) |
O4—C5—C6—C7 | −176.90 (18) | C7—C10—C11—O2 | −178.31 (17) |
C4—C5—C6—C7 | 0.2 (3) | C9—C10—C11—O2 | 3.1 (4) |
C8—O1—C7—C10 | 0.2 (2) | C7—C10—C11—C4 | 0.6 (3) |
C8—O1—C7—C6 | −178.7 (2) | C9—C10—C11—C4 | −178.0 (2) |
O5—C6—C7—O1 | 2.4 (3) | | |
(II) 5,5',6,6'-tetramethoxy-3,3',4,4'-tetrahydro-2H,2'H-3,3':4,4'- bi(furo[2,3-
h]-1-benzopyran)-2,2'-dione
top
Crystal data top
C26H20O10 | Z = 4 |
Mr = 492.44 | F(000) = 1024 |
Triclinic, P1 | Dx = 1.431 Mg m−3 |
a = 9.205 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.285 (4) Å | Cell parameters from 7179 reflections |
c = 17.978 (5) Å | θ = 1.0–27.5° |
α = 84.00 (1)° | µ = 0.11 mm−1 |
β = 83.28 (1)° | T = 293 K |
γ = 77.66 (1)° | Irregular, colorless |
V = 2285.8 (10) Å3 | 0.30 × 0.25 × 0.20 mm |
Data collection top
Nonius KappaCCD diffractometer | 4472 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.050 |
Horizonally mounted graphite crystal monochromator | θmax = 27.6°, θmin = 2.3° |
Detector resolution: 9 pixels mm-1 | h = −11→11 |
CCD rotation images,thick slices scans | k = −18→18 |
15850 measured reflections | l = −23→20 |
10555 independent reflections | |
Refinement top
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)] = 0.076 | H-atom parameters constrained |
wR(F2) = 0.183 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.6753P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
10375 reflections | Δρmax = 0.19 e Å−3 |
650 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (10) |
Crystal data top
C26H20O10 | γ = 77.66 (1)° |
Mr = 492.44 | V = 2285.8 (10) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.205 (2) Å | Mo Kα radiation |
b = 14.285 (4) Å | µ = 0.11 mm−1 |
c = 17.978 (5) Å | T = 293 K |
α = 84.00 (1)° | 0.30 × 0.25 × 0.20 mm |
β = 83.28 (1)° | |
Data collection top
Nonius KappaCCD diffractometer | 4472 reflections with I > 2σ(I) |
15850 measured reflections | Rint = 0.050 |
10555 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.19 e Å−3 |
10375 reflections | Δρmin = −0.18 e Å−3 |
650 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O11 | 0.1363 (3) | −0.07631 (17) | 0.28667 (15) | 0.0760 (8) | |
O12 | −0.0940 (2) | 0.13640 (16) | 0.46223 (13) | 0.0616 (6) | |
O13 | −0.2096 (3) | 0.22030 (18) | 0.55433 (15) | 0.0814 (8) | |
O14 | 0.3969 (3) | 0.16166 (17) | 0.34640 (16) | 0.0743 (8) | |
O15 | 0.4048 (3) | 0.00133 (16) | 0.26544 (15) | 0.0774 (8) | |
O21 | −0.4282 (3) | 0.32275 (18) | 0.24859 (14) | 0.0725 (7) | |
O22 | −0.2644 (2) | 0.41263 (15) | 0.45686 (12) | 0.0583 (6) | |
O23 | −0.2133 (3) | 0.45160 (18) | 0.56403 (14) | 0.0757 (8) | |
O24 | 0.1064 (3) | 0.27966 (18) | 0.26368 (13) | 0.0749 (8) | |
O25 | −0.1301 (3) | 0.2582 (2) | 0.17901 (14) | 0.0837 (8) | |
C101 | −0.0996 (4) | 0.2032 (2) | 0.5120 (2) | 0.0585 (9) | |
C102 | 0.0307 (4) | 0.2515 (2) | 0.51132 (19) | 0.0573 (9) | |
H102 | 0.0802 | 0.2355 | 0.5577 | 0.069* | |
C103 | 0.1419 (4) | 0.2423 (2) | 0.44061 (18) | 0.0523 (8) | |
H103 | 0.2408 | 0.2481 | 0.4523 | 0.063* | |
C104 | 0.1527 (4) | 0.1531 (2) | 0.40286 (18) | 0.0501 (8) | |
C105 | 0.2796 (4) | 0.1152 (2) | 0.3548 (2) | 0.0565 (9) | |
C106 | 0.2844 (4) | 0.0379 (2) | 0.31426 (19) | 0.0586 (9) | |
C107 | 0.1583 (4) | −0.0017 (2) | 0.3243 (2) | 0.0603 (10) | |
C108 | −0.0027 (5) | −0.0902 (3) | 0.3133 (3) | 0.0789 (12) | |
H108 | −0.0459 | −0.1367 | 0.2972 | 0.095* | |
C109 | −0.0710 (4) | −0.0304 (2) | 0.3650 (2) | 0.0677 (10) | |
H109 | −0.1657 | −0.0279 | 0.3903 | 0.081* | |
C110 | 0.0331 (4) | 0.0292 (2) | 0.37317 (19) | 0.0564 (9) | |
C111 | 0.0345 (4) | 0.1076 (2) | 0.41359 (18) | 0.0513 (8) | |
C112 | 0.5182 (5) | 0.1160 (4) | 0.3880 (4) | 0.149 (3) | |
H12A | 0.5956 | 0.1526 | 0.3792 | 0.223* | |
H12B | 0.5568 | 0.0524 | 0.3724 | 0.223* | |
H12C | 0.4844 | 0.1120 | 0.4406 | 0.223* | |
C113 | 0.4260 (8) | 0.0603 (4) | 0.1989 (3) | 0.165 (3) | |
H13A | 0.5117 | 0.0296 | 0.1682 | 0.247* | |
H13B | 0.4414 | 0.1210 | 0.2112 | 0.247* | |
H13C | 0.3391 | 0.0706 | 0.1719 | 0.247* | |
C201 | −0.1663 (4) | 0.4127 (2) | 0.5078 (2) | 0.0556 (9) | |
C202 | −0.0088 (4) | 0.3628 (2) | 0.48951 (18) | 0.0542 (9) | |
H202 | 0.0584 | 0.3945 | 0.5117 | 0.065* | |
C203 | 0.0529 (4) | 0.3432 (2) | 0.40739 (18) | 0.0518 (8) | |
H203 | 0.1181 | 0.3865 | 0.3844 | 0.062* | |
C204 | −0.0711 (4) | 0.3401 (2) | 0.36153 (17) | 0.0476 (8) | |
C205 | −0.0430 (4) | 0.3052 (2) | 0.28933 (18) | 0.0577 (9) | |
C206 | −0.1568 (4) | 0.2956 (2) | 0.24786 (18) | 0.0617 (10) | |
C207 | −0.3005 (4) | 0.3262 (2) | 0.28030 (19) | 0.0579 (9) | |
C208 | −0.5440 (5) | 0.3622 (3) | 0.3000 (2) | 0.0732 (11) | |
H208 | −0.6445 | 0.3695 | 0.2931 | 0.088* | |
C209 | −0.4963 (4) | 0.3886 (2) | 0.3601 (2) | 0.0605 (9) | |
H209 | −0.5542 | 0.4165 | 0.4011 | 0.073* | |
C210 | −0.3359 (4) | 0.3649 (2) | 0.34810 (18) | 0.0518 (8) | |
C211 | −0.2196 (4) | 0.3708 (2) | 0.38889 (17) | 0.0488 (8) | |
C212 | 0.1523 (5) | 0.3132 (3) | 0.1910 (2) | 0.0882 (13) | |
H12D | 0.2579 | 0.2903 | 0.1805 | 0.132* | |
H12E | 0.1303 | 0.3823 | 0.1866 | 0.132* | |
H12F | 0.1002 | 0.2903 | 0.1557 | 0.132* | |
C213 | −0.1053 (7) | 0.1568 (4) | 0.1824 (3) | 0.129 (2) | |
H13D | −0.0876 | 0.1363 | 0.1324 | 0.194* | |
H13E | −0.1917 | 0.1356 | 0.2079 | 0.194* | |
H13F | −0.0199 | 0.1296 | 0.2093 | 0.194* | |
O31 | 1.1132 (3) | 0.55959 (18) | 0.14649 (14) | 0.0745 (7) | |
O32 | 0.7939 (2) | 0.61357 (17) | 0.36240 (12) | 0.0606 (6) | |
O33 | 0.6603 (3) | 0.64528 (18) | 0.46903 (13) | 0.0708 (7) | |
O34 | 0.5831 (3) | 0.58153 (17) | 0.13647 (14) | 0.0743 (8) | |
O35 | 0.8728 (3) | 0.5524 (2) | 0.05773 (15) | 0.0870 (9) | |
O41 | 0.6624 (5) | 0.9076 (2) | −0.01745 (19) | 0.1163 (13) | |
O42 | 0.6859 (3) | 0.83816 (16) | 0.23727 (15) | 0.0644 (7) | |
O43 | 0.6918 (3) | 0.8372 (2) | 0.35888 (16) | 0.0899 (9) | |
O44 | 0.3052 (3) | 0.73708 (18) | 0.12272 (15) | 0.0797 (8) | |
O45 | 0.4057 (4) | 0.8216 (2) | −0.01807 (16) | 0.1148 (12) | |
C301 | 0.6592 (4) | 0.6424 (2) | 0.4030 (2) | 0.0540 (9) | |
C302 | 0.5248 (4) | 0.6704 (2) | 0.36085 (18) | 0.0533 (9) | |
H302 | 0.4367 | 0.6579 | 0.3933 | 0.064* | |
C303 | 0.5262 (4) | 0.6330 (2) | 0.28328 (18) | 0.0502 (8) | |
H303 | 0.4659 | 0.5841 | 0.2839 | 0.060* | |
C304 | 0.6816 (4) | 0.6039 (2) | 0.24727 (17) | 0.0482 (8) | |
C305 | 0.7076 (4) | 0.5835 (2) | 0.17100 (19) | 0.0565 (9) | |
C306 | 0.8482 (4) | 0.5695 (2) | 0.13287 (19) | 0.0631 (10) | |
C307 | 0.9656 (4) | 0.5716 (2) | 0.1741 (2) | 0.0597 (9) | |
C308 | 1.1872 (5) | 0.5656 (3) | 0.2083 (2) | 0.0768 (11) | |
H308 | 1.2902 | 0.5596 | 0.2063 | 0.092* | |
C309 | 1.0953 (4) | 0.5807 (3) | 0.2702 (2) | 0.0665 (10) | |
H309 | 1.1213 | 0.5871 | 0.3177 | 0.080* | |
C310 | 0.9481 (4) | 0.5854 (2) | 0.24967 (19) | 0.0544 (9) | |
C311 | 0.8027 (4) | 0.6023 (2) | 0.28560 (17) | 0.0500 (8) | |
C312 | 0.5833 (5) | 0.4990 (3) | 0.0987 (3) | 0.0918 (14) | |
H12G | 0.4907 | 0.5069 | 0.0769 | 0.138* | |
H12H | 0.5947 | 0.4432 | 0.1339 | 0.138* | |
H12I | 0.6647 | 0.4912 | 0.0598 | 0.138* | |
C313 | 0.8991 (8) | 0.6329 (4) | 0.0089 (3) | 0.158 (3) | |
H13G | 0.9144 | 0.6159 | −0.0421 | 0.237* | |
H13H | 0.9863 | 0.6523 | 0.0213 | 0.237* | |
H13I | 0.8143 | 0.6850 | 0.0144 | 0.237* | |
C401 | 0.6274 (4) | 0.8195 (2) | 0.3092 (2) | 0.0607 (10) | |
C402 | 0.4920 (4) | 0.7761 (2) | 0.32350 (18) | 0.0524 (8) | |
H402 | 0.4087 | 0.8173 | 0.3511 | 0.063* | |
C403 | 0.4431 (4) | 0.7378 (2) | 0.25545 (18) | 0.0499 (8) | |
H403 | 0.3346 | 0.7425 | 0.2607 | 0.060* | |
C404 | 0.4926 (4) | 0.7845 (2) | 0.18145 (19) | 0.0533 (9) | |
C405 | 0.4235 (5) | 0.7833 (2) | 0.1157 (2) | 0.0657 (10) | |
C406 | 0.4733 (6) | 0.8221 (3) | 0.0458 (2) | 0.0805 (13) | |
C407 | 0.5952 (6) | 0.8648 (3) | 0.0450 (2) | 0.0826 (13) | |
C408 | 0.7740 (8) | 0.9417 (4) | 0.0091 (4) | 0.128 (2) | |
H408 | 0.8367 | 0.9760 | −0.0215 | 0.154* | |
C409 | 0.7839 (5) | 0.9210 (3) | 0.0825 (3) | 0.0957 (15) | |
H409 | 0.8522 | 0.9361 | 0.1112 | 0.115* | |
C410 | 0.6665 (5) | 0.8706 (2) | 0.1073 (2) | 0.0697 (11) | |
C411 | 0.6117 (4) | 0.8293 (2) | 0.1759 (2) | 0.0575 (9) | |
C412 | 0.1623 (5) | 0.7990 (3) | 0.1142 (3) | 0.1086 (17) | |
H12J | 0.0866 | 0.7611 | 0.1198 | 0.163* | |
H12K | 0.1637 | 0.8330 | 0.0653 | 0.163* | |
H12L | 0.1409 | 0.8442 | 0.1519 | 0.163* | |
C413 | 0.4359 (8) | 0.7329 (4) | −0.0498 (3) | 0.142 (2) | |
H13J | 0.3849 | 0.7393 | −0.0943 | 0.213* | |
H13K | 0.4020 | 0.6854 | −0.0142 | 0.213* | |
H13L | 0.5416 | 0.7135 | −0.0627 | 0.213* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O11 | 0.091 (2) | 0.0567 (15) | 0.0799 (18) | −0.0114 (14) | −0.0041 (16) | −0.0164 (13) |
O12 | 0.0516 (14) | 0.0617 (14) | 0.0674 (16) | −0.0072 (11) | 0.0067 (12) | −0.0093 (12) |
O13 | 0.0703 (18) | 0.0779 (17) | 0.083 (2) | −0.0035 (14) | 0.0259 (16) | −0.0091 (14) |
O14 | 0.0532 (16) | 0.0624 (15) | 0.105 (2) | −0.0155 (13) | 0.0138 (14) | −0.0138 (14) |
O15 | 0.0790 (18) | 0.0537 (14) | 0.0861 (19) | 0.0005 (13) | 0.0267 (15) | −0.0119 (13) |
O21 | 0.0760 (18) | 0.0821 (17) | 0.0617 (16) | −0.0130 (14) | −0.0213 (15) | −0.0066 (13) |
O22 | 0.0580 (14) | 0.0607 (14) | 0.0541 (14) | 0.0000 (11) | −0.0086 (12) | −0.0165 (11) |
O23 | 0.0791 (18) | 0.0787 (17) | 0.0626 (17) | 0.0139 (14) | −0.0101 (14) | −0.0334 (14) |
O24 | 0.0660 (17) | 0.0970 (19) | 0.0475 (15) | 0.0057 (14) | 0.0055 (12) | 0.0002 (13) |
O25 | 0.095 (2) | 0.101 (2) | 0.0518 (16) | −0.0018 (16) | −0.0113 (14) | −0.0210 (14) |
C101 | 0.063 (2) | 0.051 (2) | 0.053 (2) | 0.0001 (18) | 0.0030 (19) | 0.0016 (16) |
C102 | 0.059 (2) | 0.060 (2) | 0.049 (2) | 0.0003 (18) | −0.0071 (17) | −0.0079 (16) |
C103 | 0.0486 (19) | 0.0529 (19) | 0.053 (2) | −0.0036 (15) | −0.0063 (16) | −0.0056 (15) |
C104 | 0.047 (2) | 0.0470 (18) | 0.054 (2) | −0.0056 (16) | −0.0026 (16) | −0.0058 (15) |
C105 | 0.048 (2) | 0.0471 (19) | 0.069 (2) | −0.0063 (16) | 0.0058 (18) | −0.0036 (16) |
C106 | 0.061 (2) | 0.0457 (19) | 0.062 (2) | −0.0014 (18) | 0.0072 (18) | −0.0050 (16) |
C107 | 0.072 (3) | 0.0416 (19) | 0.064 (2) | −0.0037 (18) | −0.005 (2) | −0.0081 (16) |
C108 | 0.082 (3) | 0.063 (3) | 0.095 (3) | −0.020 (2) | −0.015 (3) | −0.009 (2) |
C109 | 0.062 (2) | 0.055 (2) | 0.085 (3) | −0.0100 (19) | −0.014 (2) | 0.0010 (19) |
C110 | 0.055 (2) | 0.0463 (19) | 0.065 (2) | −0.0052 (17) | −0.0071 (18) | −0.0028 (16) |
C111 | 0.045 (2) | 0.0496 (19) | 0.055 (2) | −0.0023 (16) | −0.0014 (16) | −0.0033 (15) |
C112 | 0.065 (3) | 0.106 (4) | 0.279 (8) | −0.014 (3) | −0.057 (4) | 0.008 (4) |
C113 | 0.226 (7) | 0.089 (4) | 0.119 (5) | 0.031 (4) | 0.093 (5) | 0.017 (3) |
C201 | 0.065 (2) | 0.0470 (19) | 0.053 (2) | −0.0029 (16) | −0.0079 (19) | −0.0125 (16) |
C202 | 0.058 (2) | 0.0517 (19) | 0.054 (2) | −0.0058 (16) | −0.0093 (17) | −0.0134 (15) |
C203 | 0.050 (2) | 0.0483 (18) | 0.056 (2) | −0.0076 (15) | −0.0041 (17) | −0.0064 (15) |
C204 | 0.056 (2) | 0.0402 (17) | 0.0442 (19) | −0.0053 (15) | −0.0066 (16) | −0.0016 (13) |
C205 | 0.064 (2) | 0.056 (2) | 0.045 (2) | 0.0020 (17) | 0.0013 (18) | −0.0031 (15) |
C206 | 0.078 (3) | 0.070 (2) | 0.0348 (19) | −0.0050 (19) | −0.0120 (19) | −0.0093 (16) |
C207 | 0.058 (2) | 0.063 (2) | 0.051 (2) | −0.0048 (18) | −0.0137 (19) | −0.0030 (17) |
C208 | 0.061 (2) | 0.082 (3) | 0.073 (3) | −0.005 (2) | −0.017 (2) | 0.002 (2) |
C209 | 0.061 (2) | 0.058 (2) | 0.059 (2) | −0.0061 (17) | −0.0104 (19) | 0.0026 (17) |
C210 | 0.055 (2) | 0.0476 (18) | 0.050 (2) | −0.0036 (15) | −0.0089 (17) | 0.0000 (15) |
C211 | 0.061 (2) | 0.0415 (17) | 0.0409 (19) | −0.0036 (15) | −0.0056 (17) | −0.0051 (14) |
C212 | 0.095 (3) | 0.113 (3) | 0.056 (3) | −0.027 (3) | 0.004 (2) | −0.001 (2) |
C213 | 0.184 (6) | 0.105 (4) | 0.100 (4) | −0.011 (4) | −0.015 (4) | −0.048 (3) |
O31 | 0.0643 (17) | 0.0913 (18) | 0.0616 (17) | −0.0027 (14) | 0.0015 (14) | −0.0125 (13) |
O32 | 0.0538 (15) | 0.0808 (16) | 0.0463 (14) | −0.0099 (12) | −0.0051 (11) | −0.0080 (11) |
O33 | 0.0748 (17) | 0.0948 (19) | 0.0422 (15) | −0.0152 (14) | −0.0058 (13) | −0.0072 (12) |
O34 | 0.0761 (18) | 0.0713 (16) | 0.0786 (18) | 0.0021 (13) | −0.0283 (15) | −0.0326 (13) |
O35 | 0.096 (2) | 0.104 (2) | 0.0549 (17) | 0.0030 (17) | −0.0039 (15) | −0.0303 (16) |
O41 | 0.170 (4) | 0.087 (2) | 0.070 (2) | −0.008 (2) | 0.024 (2) | 0.0154 (18) |
O42 | 0.0627 (16) | 0.0597 (15) | 0.0710 (18) | −0.0142 (12) | −0.0041 (14) | −0.0059 (12) |
O43 | 0.109 (2) | 0.099 (2) | 0.083 (2) | −0.0559 (18) | −0.0357 (18) | 0.0027 (16) |
O44 | 0.085 (2) | 0.0680 (16) | 0.089 (2) | −0.0048 (15) | −0.0389 (16) | −0.0075 (14) |
O45 | 0.184 (3) | 0.088 (2) | 0.0664 (19) | 0.005 (2) | −0.050 (2) | −0.0045 (16) |
C301 | 0.062 (2) | 0.0531 (19) | 0.047 (2) | −0.0128 (17) | −0.0025 (18) | −0.0061 (16) |
C302 | 0.053 (2) | 0.0551 (19) | 0.051 (2) | −0.0120 (16) | −0.0014 (17) | −0.0039 (15) |
C303 | 0.052 (2) | 0.0484 (18) | 0.053 (2) | −0.0132 (15) | −0.0082 (16) | −0.0079 (14) |
C304 | 0.057 (2) | 0.0422 (17) | 0.0445 (19) | −0.0055 (15) | −0.0094 (17) | −0.0064 (14) |
C305 | 0.061 (2) | 0.0521 (19) | 0.055 (2) | 0.0036 (16) | −0.0181 (19) | −0.0154 (16) |
C306 | 0.076 (3) | 0.060 (2) | 0.047 (2) | 0.0044 (19) | −0.009 (2) | −0.0137 (16) |
C307 | 0.056 (2) | 0.062 (2) | 0.055 (2) | −0.0013 (17) | −0.0002 (19) | −0.0071 (17) |
C308 | 0.057 (2) | 0.102 (3) | 0.070 (3) | −0.015 (2) | −0.004 (2) | −0.007 (2) |
C309 | 0.056 (2) | 0.085 (3) | 0.057 (2) | −0.0105 (19) | −0.007 (2) | −0.0058 (19) |
C310 | 0.052 (2) | 0.061 (2) | 0.048 (2) | −0.0036 (16) | −0.0093 (17) | −0.0046 (15) |
C311 | 0.056 (2) | 0.0508 (19) | 0.0416 (19) | −0.0059 (15) | −0.0053 (17) | −0.0075 (14) |
C312 | 0.115 (4) | 0.082 (3) | 0.091 (3) | −0.023 (3) | −0.027 (3) | −0.039 (2) |
C313 | 0.263 (8) | 0.116 (4) | 0.053 (3) | 0.040 (5) | 0.000 (4) | 0.006 (3) |
C401 | 0.068 (3) | 0.050 (2) | 0.067 (3) | −0.0124 (18) | −0.017 (2) | −0.0049 (17) |
C402 | 0.053 (2) | 0.0532 (19) | 0.051 (2) | −0.0081 (16) | −0.0045 (16) | −0.0132 (15) |
C403 | 0.0445 (19) | 0.0489 (18) | 0.056 (2) | −0.0064 (15) | −0.0048 (16) | −0.0085 (15) |
C404 | 0.056 (2) | 0.0446 (18) | 0.055 (2) | 0.0015 (16) | −0.0066 (18) | −0.0084 (15) |
C405 | 0.081 (3) | 0.046 (2) | 0.068 (3) | −0.0001 (19) | −0.020 (2) | −0.0059 (18) |
C406 | 0.125 (4) | 0.057 (2) | 0.051 (3) | 0.004 (3) | −0.017 (3) | −0.0006 (19) |
C407 | 0.116 (4) | 0.056 (2) | 0.061 (3) | 0.002 (2) | 0.003 (3) | 0.005 (2) |
C408 | 0.157 (6) | 0.079 (4) | 0.128 (6) | −0.018 (4) | 0.045 (5) | 0.014 (3) |
C409 | 0.095 (4) | 0.075 (3) | 0.102 (4) | −0.008 (3) | 0.021 (3) | 0.009 (3) |
C410 | 0.074 (3) | 0.049 (2) | 0.073 (3) | 0.0003 (19) | 0.016 (2) | −0.0006 (19) |
C411 | 0.062 (2) | 0.0481 (19) | 0.058 (2) | −0.0008 (18) | −0.0030 (19) | −0.0069 (16) |
C412 | 0.091 (3) | 0.100 (3) | 0.132 (4) | 0.002 (3) | −0.042 (3) | −0.008 (3) |
C413 | 0.210 (7) | 0.123 (4) | 0.093 (4) | 0.000 (4) | −0.049 (4) | −0.043 (3) |
Geometric parameters (Å, º) top
O11—C108 | 1.360 (5) | O31—C307 | 1.372 (4) |
O11—C107 | 1.382 (4) | O31—C308 | 1.388 (4) |
O12—C101 | 1.363 (4) | O32—C301 | 1.368 (4) |
O12—C111 | 1.400 (4) | O32—C311 | 1.398 (4) |
O13—C101 | 1.191 (4) | O33—C301 | 1.193 (4) |
O14—C105 | 1.370 (4) | O34—C305 | 1.373 (4) |
O14—C112 | 1.420 (5) | O34—C312 | 1.420 (4) |
O15—C106 | 1.376 (4) | O35—C306 | 1.382 (4) |
O15—C113 | 1.409 (5) | O35—C313 | 1.418 (6) |
O21—C207 | 1.376 (4) | O41—C407 | 1.368 (5) |
O21—C208 | 1.390 (4) | O41—C408 | 1.377 (7) |
O22—C201 | 1.360 (4) | O42—C401 | 1.363 (4) |
O22—C211 | 1.396 (4) | O42—C411 | 1.394 (4) |
O23—C201 | 1.196 (4) | O43—C401 | 1.204 (4) |
O24—C205 | 1.382 (4) | O44—C405 | 1.377 (5) |
O24—C212 | 1.394 (4) | O44—C412 | 1.434 (5) |
O25—C206 | 1.374 (4) | O45—C406 | 1.370 (5) |
O25—C213 | 1.414 (5) | O45—C413 | 1.404 (5) |
C101—C102 | 1.504 (5) | C301—C302 | 1.487 (5) |
C102—C103 | 1.534 (4) | C302—C303 | 1.542 (4) |
C102—C202 | 1.572 (4) | C302—C402 | 1.569 (4) |
C102—H102 | 0.9800 | C302—H302 | 0.9800 |
C103—C104 | 1.485 (4) | C303—C304 | 1.491 (4) |
C103—C203 | 1.592 (4) | C303—C403 | 1.588 (4) |
C103—H103 | 0.9800 | C303—H303 | 0.9800 |
C104—C111 | 1.368 (5) | C304—C311 | 1.372 (4) |
C104—C105 | 1.413 (4) | C304—C305 | 1.414 (4) |
C105—C106 | 1.376 (5) | C305—C306 | 1.376 (5) |
C106—C107 | 1.381 (5) | C306—C307 | 1.387 (5) |
C107—C110 | 1.387 (5) | C307—C310 | 1.379 (5) |
C108—C109 | 1.337 (5) | C308—C309 | 1.325 (5) |
C108—H108 | 0.9300 | C308—H308 | 0.9300 |
C109—C110 | 1.440 (5) | C309—C310 | 1.433 (5) |
C109—H109 | 0.9300 | C309—H309 | 0.9300 |
C110—C111 | 1.400 (5) | C310—C311 | 1.399 (5) |
C112—H12A | 0.9600 | C312—H12G | 0.9600 |
C112—H12B | 0.9600 | C312—H12H | 0.9600 |
C112—H12C | 0.9600 | C312—H12I | 0.9600 |
C113—H13A | 0.9600 | C313—H13G | 0.9600 |
C113—H13B | 0.9600 | C313—H13H | 0.9600 |
C113—H13C | 0.9600 | C313—H13I | 0.9600 |
C201—C202 | 1.488 (5) | C401—C402 | 1.491 (5) |
C202—C203 | 1.550 (4) | C402—C403 | 1.540 (4) |
C202—H202 | 0.9800 | C402—H402 | 0.9800 |
C203—C204 | 1.495 (4) | C403—C404 | 1.491 (5) |
C203—H203 | 0.9800 | C403—H403 | 0.9800 |
C204—C211 | 1.391 (4) | C404—C411 | 1.372 (5) |
C204—C205 | 1.415 (4) | C404—C405 | 1.409 (5) |
C205—C206 | 1.392 (5) | C405—C406 | 1.387 (6) |
C206—C207 | 1.381 (5) | C406—C407 | 1.386 (6) |
C207—C210 | 1.367 (4) | C407—C410 | 1.381 (6) |
C208—C209 | 1.330 (5) | C408—C409 | 1.331 (7) |
C208—H208 | 0.9300 | C408—H408 | 0.9300 |
C209—C210 | 1.438 (5) | C409—C410 | 1.428 (6) |
C209—H209 | 0.9300 | C409—H409 | 0.9300 |
C210—C211 | 1.388 (4) | C410—C411 | 1.398 (5) |
C212—H12D | 0.9600 | C412—H12J | 0.9600 |
C212—H12E | 0.9600 | C412—H12K | 0.9600 |
C212—H12F | 0.9600 | C412—H12L | 0.9600 |
C213—H13D | 0.9600 | C413—H13J | 0.9600 |
C213—H13E | 0.9600 | C413—H13K | 0.9600 |
C213—H13F | 0.9600 | C413—H13L | 0.9600 |
| | | |
C108—O11—C107 | 105.3 (3) | C307—O31—C308 | 104.4 (3) |
C101—O12—C111 | 121.1 (3) | C301—O32—C311 | 121.2 (3) |
C105—O14—C112 | 114.5 (3) | C305—O34—C312 | 117.9 (3) |
C106—O15—C113 | 114.9 (3) | C306—O35—C313 | 114.1 (3) |
C207—O21—C208 | 104.3 (3) | C407—O41—C408 | 104.4 (5) |
C201—O22—C211 | 122.0 (3) | C401—O42—C411 | 121.4 (3) |
C205—O24—C212 | 118.2 (3) | C405—O44—C412 | 114.9 (3) |
C206—O25—C213 | 114.5 (3) | C406—O45—C413 | 115.1 (3) |
O13—C101—O12 | 117.3 (4) | O33—C301—O32 | 117.1 (3) |
O13—C101—C102 | 123.1 (3) | O33—C301—C302 | 125.6 (3) |
O12—C101—C102 | 119.6 (3) | O32—C301—C302 | 117.3 (3) |
C101—C102—C103 | 115.6 (3) | C301—C302—C303 | 120.2 (3) |
C101—C102—C202 | 113.3 (3) | C301—C302—C402 | 116.4 (3) |
C103—C102—C202 | 88.2 (2) | C303—C302—C402 | 89.3 (2) |
C101—C102—H102 | 112.5 | C301—C302—H302 | 109.8 |
C103—C102—H102 | 112.5 | C303—C302—H302 | 109.8 |
C202—C102—H102 | 112.5 | C402—C302—H302 | 109.8 |
C104—C103—C102 | 114.2 (3) | C304—C303—C302 | 111.5 (3) |
C104—C103—C203 | 121.2 (3) | C304—C303—C403 | 114.3 (3) |
C102—C103—C203 | 88.5 (2) | C302—C303—C403 | 88.0 (2) |
C104—C103—H103 | 110.4 | C304—C303—H303 | 113.6 |
C102—C103—H103 | 110.4 | C302—C303—H303 | 113.6 |
C203—C103—H103 | 110.4 | C403—C303—H303 | 113.6 |
C111—C104—C105 | 119.0 (3) | C311—C304—C305 | 118.3 (3) |
C111—C104—C103 | 118.9 (3) | C311—C304—C303 | 121.0 (3) |
C105—C104—C103 | 122.1 (3) | C305—C304—C303 | 120.6 (3) |
O14—C105—C106 | 120.3 (3) | O34—C305—C306 | 121.9 (3) |
O14—C105—C104 | 117.5 (3) | O34—C305—C304 | 115.8 (3) |
C106—C105—C104 | 122.2 (3) | C306—C305—C304 | 122.3 (3) |
O15—C106—C105 | 123.3 (4) | C305—C306—O35 | 122.2 (3) |
O15—C106—C107 | 120.7 (3) | C305—C306—C307 | 116.6 (3) |
C105—C106—C107 | 116.0 (3) | O35—C306—C307 | 121.2 (3) |
C106—C107—O11 | 125.6 (3) | O31—C307—C310 | 110.8 (3) |
C106—C107—C110 | 124.6 (3) | O31—C307—C306 | 125.5 (3) |
O11—C107—C110 | 109.7 (3) | C310—C307—C306 | 123.7 (3) |
C109—C108—O11 | 113.4 (4) | C309—C308—O31 | 112.7 (4) |
C109—C108—H108 | 123.3 | C309—C308—H308 | 123.7 |
O11—C108—H108 | 123.3 | O31—C308—H308 | 123.7 |
C108—C109—C110 | 105.4 (4) | C308—C309—C310 | 106.3 (3) |
C108—C109—H109 | 127.3 | C308—C309—H309 | 126.8 |
C110—C109—H109 | 127.3 | C310—C309—H309 | 126.8 |
C107—C110—C111 | 117.0 (3) | C307—C310—C311 | 117.7 (3) |
C107—C110—C109 | 106.1 (3) | C307—C310—C309 | 105.8 (3) |
C111—C110—C109 | 136.8 (3) | C311—C310—C309 | 136.4 (3) |
C104—C111—C110 | 120.9 (3) | C304—C311—O32 | 124.2 (3) |
C104—C111—O12 | 123.9 (3) | C304—C311—C310 | 121.2 (3) |
C110—C111—O12 | 115.2 (3) | O32—C311—C310 | 114.5 (3) |
O14—C112—H12A | 109.5 | O34—C312—H12G | 109.5 |
O14—C112—H12B | 109.5 | O34—C312—H12H | 109.5 |
H12A—C112—H12B | 109.5 | H12G—C312—H12H | 109.5 |
O14—C112—H12C | 109.5 | O34—C312—H12I | 109.5 |
H12A—C112—H12C | 109.5 | H12G—C312—H12I | 109.5 |
H12B—C112—H12C | 109.5 | H12H—C312—H12I | 109.5 |
O15—C113—H13A | 109.5 | O35—C313—H13G | 109.5 |
O15—C113—H13B | 109.5 | O35—C313—H13H | 109.5 |
H13A—C113—H13B | 109.5 | H13G—C313—H13H | 109.5 |
O15—C113—H13C | 109.5 | O35—C313—H13I | 109.5 |
H13A—C113—H13C | 109.5 | H13G—C313—H13I | 109.5 |
H13B—C113—H13C | 109.5 | H13H—C313—H13I | 109.5 |
O23—C201—O22 | 117.7 (3) | O43—C401—O42 | 117.1 (4) |
O23—C201—C202 | 125.1 (3) | O43—C401—C402 | 122.8 (4) |
O22—C201—C202 | 117.1 (3) | O42—C401—C402 | 120.0 (3) |
C201—C202—C203 | 120.9 (3) | C401—C402—C403 | 116.3 (3) |
C201—C202—C102 | 117.0 (3) | C401—C402—C302 | 113.2 (3) |
C203—C202—C102 | 88.7 (2) | C403—C402—C302 | 88.7 (2) |
C201—C202—H202 | 109.5 | C401—C402—H402 | 112.2 |
C203—C202—H202 | 109.5 | C403—C402—H402 | 112.2 |
C102—C202—H202 | 109.5 | C302—C402—H402 | 112.2 |
C204—C203—C202 | 110.7 (3) | C404—C403—C402 | 114.0 (3) |
C204—C203—C103 | 116.4 (3) | C404—C403—C303 | 120.5 (2) |
C202—C203—C103 | 86.9 (2) | C402—C403—C303 | 88.7 (2) |
C204—C203—H203 | 113.4 | C404—C403—H403 | 110.6 |
C202—C203—H203 | 113.4 | C402—C403—H403 | 110.6 |
C103—C203—H203 | 113.4 | C303—C403—H403 | 110.6 |
C211—C204—C205 | 117.3 (3) | C411—C404—C405 | 117.9 (3) |
C211—C204—C203 | 120.9 (3) | C411—C404—C403 | 119.4 (3) |
C205—C204—C203 | 121.8 (3) | C405—C404—C403 | 122.7 (3) |
O24—C205—C206 | 122.5 (3) | O44—C405—C406 | 120.0 (4) |
O24—C205—C204 | 114.8 (3) | O44—C405—C404 | 116.7 (3) |
C206—C205—C204 | 122.7 (3) | C406—C405—C404 | 123.2 (4) |
O25—C206—C207 | 121.3 (3) | O45—C406—C407 | 121.4 (4) |
O25—C206—C205 | 123.0 (3) | O45—C406—C405 | 123.4 (5) |
C207—C206—C205 | 115.7 (3) | C407—C406—C405 | 115.2 (4) |
C210—C207—O21 | 110.5 (3) | O41—C407—C410 | 110.1 (5) |
C210—C207—C206 | 124.7 (3) | O41—C407—C406 | 125.1 (5) |
O21—C207—C206 | 124.8 (3) | C410—C407—C406 | 124.8 (4) |
C209—C208—O21 | 113.0 (3) | C409—C408—O41 | 113.8 (5) |
C209—C208—H208 | 123.5 | C409—C408—H408 | 123.1 |
O21—C208—H208 | 123.5 | O41—C408—H408 | 123.1 |
C208—C209—C210 | 105.3 (3) | C408—C409—C410 | 104.7 (6) |
C208—C209—H209 | 127.3 | C408—C409—H409 | 127.7 |
C210—C209—H209 | 127.3 | C410—C409—H409 | 127.7 |
C207—C210—C211 | 118.0 (3) | C407—C410—C411 | 117.2 (4) |
C207—C210—C209 | 106.8 (3) | C407—C410—C409 | 107.0 (4) |
C211—C210—C209 | 135.1 (3) | C411—C410—C409 | 135.9 (5) |
C210—C211—C204 | 121.5 (3) | C404—C411—O42 | 123.3 (3) |
C210—C211—O22 | 114.7 (3) | C404—C411—C410 | 121.7 (4) |
C204—C211—O22 | 123.8 (3) | O42—C411—C410 | 115.0 (4) |
O24—C212—H12D | 109.5 | O44—C412—H12J | 109.5 |
O24—C212—H12E | 109.5 | O44—C412—H12K | 109.5 |
H12D—C212—H12E | 109.5 | H12J—C412—H12K | 109.5 |
O24—C212—H12F | 109.5 | O44—C412—H12L | 109.5 |
H12D—C212—H12F | 109.5 | H12J—C412—H12L | 109.5 |
H12E—C212—H12F | 109.5 | H12K—C412—H12L | 109.5 |
O25—C213—H13D | 109.5 | O45—C413—H13J | 109.5 |
O25—C213—H13E | 109.5 | O45—C413—H13K | 109.5 |
H13D—C213—H13E | 109.5 | H13J—C413—H13K | 109.5 |
O25—C213—H13F | 109.5 | O45—C413—H13L | 109.5 |
H13D—C213—H13F | 109.5 | H13J—C413—H13L | 109.5 |
H13E—C213—H13F | 109.5 | H13K—C413—H13L | 109.5 |
| | | |
C111—O12—C101—O13 | −176.0 (3) | C311—O32—C301—O33 | 176.1 (3) |
C111—O12—C101—C102 | 4.0 (4) | C311—O32—C301—C302 | −5.9 (4) |
O13—C101—C102—C103 | −163.7 (3) | O33—C301—C302—C303 | −159.5 (3) |
O12—C101—C102—C103 | 16.3 (4) | O32—C301—C302—C303 | 22.7 (4) |
O13—C101—C102—C202 | −64.1 (4) | O33—C301—C302—C402 | 94.6 (4) |
O12—C101—C102—C202 | 116.0 (3) | O32—C301—C302—C402 | −83.2 (4) |
C101—C102—C103—C104 | −29.3 (4) | C301—C302—C303—C304 | −22.4 (4) |
C202—C102—C103—C104 | −144.4 (3) | C402—C302—C303—C304 | 98.2 (3) |
C101—C102—C103—C203 | 94.4 (3) | C301—C302—C303—C403 | −137.7 (3) |
C202—C102—C103—C203 | −20.6 (2) | C402—C302—C303—C403 | −17.2 (2) |
C102—C103—C104—C111 | 24.0 (4) | C302—C303—C304—C311 | 6.8 (4) |
C203—C103—C104—C111 | −79.8 (4) | C403—C303—C304—C311 | 104.5 (3) |
C102—C103—C104—C105 | −157.7 (3) | C302—C303—C304—C305 | −168.9 (3) |
C203—C103—C104—C105 | 98.6 (4) | C403—C303—C304—C305 | −71.1 (4) |
C112—O14—C105—C106 | −81.2 (5) | C312—O34—C305—C306 | 54.3 (5) |
C112—O14—C105—C104 | 102.1 (4) | C312—O34—C305—C304 | −127.6 (4) |
C111—C104—C105—O14 | −178.8 (3) | C311—C304—C305—O34 | 177.0 (3) |
C103—C104—C105—O14 | 2.8 (5) | C303—C304—C305—O34 | −7.3 (4) |
C111—C104—C105—C106 | 4.6 (5) | C311—C304—C305—C306 | −5.0 (5) |
C103—C104—C105—C106 | −173.8 (3) | C303—C304—C305—C306 | 170.8 (3) |
C113—O15—C106—C105 | −70.7 (6) | O34—C305—C306—O35 | −0.1 (5) |
C113—O15—C106—C107 | 108.4 (5) | C304—C305—C306—O35 | −178.1 (3) |
O14—C105—C106—O15 | 1.6 (5) | O34—C305—C306—C307 | −178.9 (3) |
C104—C105—C106—O15 | 178.1 (3) | C304—C305—C306—C307 | 3.1 (5) |
O14—C105—C106—C107 | −177.5 (3) | C313—O35—C306—C305 | 103.4 (5) |
C104—C105—C106—C107 | −1.0 (5) | C313—O35—C306—C307 | −77.8 (5) |
O15—C106—C107—O11 | −2.4 (5) | C308—O31—C307—C310 | 0.6 (4) |
C105—C106—C107—O11 | 176.7 (3) | C308—O31—C307—C306 | −178.9 (3) |
O15—C106—C107—C110 | 178.8 (3) | C305—C306—C307—O31 | −179.7 (3) |
C105—C106—C107—C110 | −2.2 (5) | O35—C306—C307—O31 | 1.5 (6) |
C108—O11—C107—C106 | −179.1 (3) | C305—C306—C307—C310 | 0.9 (5) |
C108—O11—C107—C110 | −0.1 (4) | O35—C306—C307—C310 | −178.0 (3) |
C107—O11—C108—C109 | 0.0 (4) | C307—O31—C308—C309 | −0.4 (4) |
O11—C108—C109—C110 | 0.2 (4) | O31—C308—C309—C310 | 0.0 (5) |
C106—C107—C110—C111 | 1.6 (5) | O31—C307—C310—C311 | 177.7 (3) |
O11—C107—C110—C111 | −177.4 (3) | C306—C307—C310—C311 | −2.8 (5) |
C106—C107—C110—C109 | 179.2 (3) | O31—C307—C310—C309 | −0.6 (4) |
O11—C107—C110—C109 | 0.2 (4) | C306—C307—C310—C309 | 178.9 (3) |
C108—C109—C110—C107 | −0.2 (4) | C308—C309—C310—C307 | 0.3 (4) |
C108—C109—C110—C111 | 176.7 (4) | C308—C309—C310—C311 | −177.4 (4) |
C105—C104—C111—C110 | −5.1 (5) | C305—C304—C311—O32 | −174.8 (3) |
C103—C104—C111—C110 | 173.3 (3) | C303—C304—C311—O32 | 9.5 (5) |
C105—C104—C111—O12 | 177.3 (3) | C305—C304—C311—C310 | 2.9 (5) |
C103—C104—C111—O12 | −4.3 (5) | C303—C304—C311—C310 | −172.9 (3) |
C107—C110—C111—C104 | 2.2 (5) | C301—O32—C311—C304 | −10.5 (4) |
C109—C110—C111—C104 | −174.5 (4) | C301—O32—C311—C310 | 171.7 (3) |
C107—C110—C111—O12 | 180.0 (3) | C307—C310—C311—C304 | 0.8 (5) |
C109—C110—C111—O12 | 3.3 (6) | C309—C310—C311—C304 | 178.4 (4) |
C101—O12—C111—C104 | −11.0 (5) | C307—C310—C311—O32 | 178.7 (3) |
C101—O12—C111—C110 | 171.3 (3) | C309—C310—C311—O32 | −3.8 (6) |
C211—O22—C201—O23 | 178.7 (3) | C411—O42—C401—O43 | −173.5 (3) |
C211—O22—C201—C202 | −2.3 (4) | C411—O42—C401—C402 | 8.4 (4) |
O23—C201—C202—C203 | −160.5 (3) | O43—C401—C402—C403 | −167.2 (3) |
O22—C201—C202—C203 | 20.5 (5) | O42—C401—C402—C403 | 10.8 (4) |
O23—C201—C202—C102 | 93.6 (4) | O43—C401—C402—C302 | −66.5 (4) |
O22—C201—C202—C102 | −85.4 (4) | O42—C401—C402—C302 | 111.5 (3) |
C101—C102—C202—C201 | 28.3 (4) | C301—C302—C402—C401 | 23.2 (4) |
C103—C102—C202—C201 | 145.5 (3) | C303—C302—C402—C401 | −100.5 (3) |
C101—C102—C202—C203 | −96.0 (3) | C301—C302—C402—C403 | 141.5 (3) |
C103—C102—C202—C203 | 21.2 (3) | C303—C302—C402—C403 | 17.7 (2) |
C201—C202—C203—C204 | −24.4 (4) | C401—C402—C403—C404 | −24.8 (4) |
C102—C202—C203—C204 | 96.6 (3) | C302—C402—C403—C404 | −140.2 (3) |
C201—C202—C203—C103 | −141.4 (3) | C401—C402—C403—C303 | 98.2 (3) |
C102—C202—C203—C103 | −20.4 (3) | C302—C402—C403—C303 | −17.2 (2) |
C104—C103—C203—C204 | 27.0 (4) | C304—C303—C403—C404 | 22.1 (4) |
C102—C103—C203—C204 | −90.6 (3) | C302—C303—C403—C404 | 134.8 (3) |
C104—C103—C203—C202 | 138.5 (3) | C304—C303—C403—C402 | −95.2 (3) |
C102—C103—C203—C202 | 21.0 (3) | C302—C303—C403—C402 | 17.5 (2) |
C202—C203—C204—C211 | 11.8 (4) | C402—C403—C404—C411 | 21.6 (4) |
C103—C203—C204—C211 | 108.9 (3) | C303—C403—C404—C411 | −81.9 (4) |
C202—C203—C204—C205 | −167.5 (3) | C402—C403—C404—C405 | −159.5 (3) |
C103—C203—C204—C205 | −70.5 (4) | C303—C403—C404—C405 | 97.1 (4) |
C212—O24—C205—C206 | 49.1 (5) | C412—O44—C405—C406 | −71.8 (4) |
C212—O24—C205—C204 | −132.1 (3) | C412—O44—C405—C404 | 111.1 (4) |
C211—C204—C205—O24 | 177.3 (3) | C411—C404—C405—O44 | 179.4 (3) |
C203—C204—C205—O24 | −3.3 (4) | C403—C404—C405—O44 | 0.4 (4) |
C211—C204—C205—C206 | −3.8 (5) | C411—C404—C405—C406 | 2.4 (5) |
C203—C204—C205—C206 | 175.6 (3) | C403—C404—C405—C406 | −176.6 (3) |
C213—O25—C206—C207 | −94.7 (5) | C413—O45—C406—C407 | 105.4 (5) |
C213—O25—C206—C205 | 85.2 (5) | C413—O45—C406—C405 | −76.6 (6) |
O24—C205—C206—O25 | 1.4 (5) | O44—C405—C406—O45 | 3.5 (5) |
C204—C205—C206—O25 | −177.3 (3) | C404—C405—C406—O45 | −179.6 (3) |
O24—C205—C206—C207 | −178.7 (3) | O44—C405—C406—C407 | −178.4 (3) |
C204—C205—C206—C207 | 2.6 (5) | C404—C405—C406—C407 | −1.5 (5) |
C208—O21—C207—C210 | 0.6 (4) | C408—O41—C407—C410 | −1.5 (5) |
C208—O21—C207—C206 | −178.9 (3) | C408—O41—C407—C406 | 178.3 (4) |
O25—C206—C207—C210 | −179.4 (3) | O45—C406—C407—O41 | −1.7 (6) |
C205—C206—C207—C210 | 0.7 (5) | C405—C406—C407—O41 | −179.8 (3) |
O25—C206—C207—O21 | 0.0 (6) | O45—C406—C407—C410 | 178.1 (3) |
C205—C206—C207—O21 | −179.9 (3) | C405—C406—C407—C410 | 0.0 (6) |
C207—O21—C208—C209 | −0.3 (4) | C407—O41—C408—C409 | 1.8 (6) |
O21—C208—C209—C210 | −0.1 (4) | O41—C408—C409—C410 | −1.3 (6) |
O21—C207—C210—C211 | 178.0 (3) | O41—C407—C410—C411 | −179.6 (3) |
C206—C207—C210—C211 | −2.6 (5) | C406—C407—C410—C411 | 0.6 (6) |
O21—C207—C210—C209 | −0.6 (4) | O41—C407—C410—C409 | 0.7 (4) |
C206—C207—C210—C209 | 178.8 (3) | C406—C407—C410—C409 | −179.1 (4) |
C208—C209—C210—C207 | 0.4 (4) | C408—C409—C410—C407 | 0.3 (5) |
C208—C209—C210—C211 | −177.9 (4) | C408—C409—C410—C411 | −179.3 (4) |
C207—C210—C211—C204 | 1.1 (5) | C405—C404—C411—O42 | 177.7 (3) |
C209—C210—C211—C204 | 179.3 (3) | C403—C404—C411—O42 | −3.4 (4) |
C207—C210—C211—O22 | 178.9 (3) | C405—C404—C411—C410 | −1.7 (5) |
C209—C210—C211—O22 | −2.9 (5) | C403—C404—C411—C410 | 177.3 (3) |
C205—C204—C211—C210 | 1.9 (4) | C401—O42—C411—C404 | −13.0 (4) |
C203—C204—C211—C210 | −177.5 (3) | C401—O42—C411—C410 | 166.4 (3) |
C205—C204—C211—O22 | −175.7 (3) | C407—C410—C411—C404 | 0.3 (5) |
C203—C204—C211—O22 | 4.9 (5) | C409—C410—C411—C404 | 179.9 (4) |
C201—O22—C211—C210 | 171.4 (3) | C407—C410—C411—O42 | −179.1 (3) |
C201—O22—C211—C204 | −10.8 (4) | C409—C410—C411—O42 | 0.5 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C103—H103···O33i | 0.98 | 2.55 | 3.320 (4) | 135 |
C202—H202···O33i | 0.98 | 2.59 | 3.353 (5) | 135 |
C212—H12E···O31ii | 0.96 | 2.54 | 3.477 (5) | 166 |
C209—H209···O23iii | 0.93 | 2.60 | 3.378 (4) | 142 |
C209—H209···O33iv | 0.93 | 2.57 | 3.297 (4) | 136 |
C309—H309···O23i | 0.93 | 2.35 | 3.244 (5) | 161 |
C302—H302···O13iv | 0.98 | 2.57 | 3.272 (4) | 129 |
C312—H12H···O21v | 0.96 | 2.56 | 3.499 (5) | 165 |
C402—H402···O13iv | 0.98 | 2.46 | 3.196 (4) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x−1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C13H10O5 | C26H20O10 |
Mr | 246.21 | 492.44 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 3.9069 (1), 13.4984 (5), 20.9360 (9) | 9.205 (2), 14.285 (4), 17.978 (5) |
α, β, γ (°) | 90, 91.733 (2), 90 | 84.00 (1), 83.28 (1), 77.66 (1) |
V (Å3) | 1103.59 (7) | 2285.8 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.11 |
Crystal size (mm) | 0.30 × 0.23 × 0.20 | 0.30 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4519, 2491, 1609 | 15850, 10555, 4472 |
Rint | 0.029 | 0.050 |
(sin θ/λ)max (Å−1) | 0.650 | 0.651 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.153, 1.03 | 0.076, 0.183, 1.01 |
No. of reflections | 2491 | 10375 |
No. of parameters | 163 | 650 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 | 0.19, −0.18 |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C103—H103···O33i | 0.98 | 2.55 | 3.320 (4) | 135 |
C202—H202···O33i | 0.98 | 2.59 | 3.353 (5) | 135 |
C212—H12E···O31ii | 0.96 | 2.54 | 3.477 (5) | 166 |
C209—H209···O23iii | 0.93 | 2.60 | 3.378 (4) | 142 |
C209—H209···O33iv | 0.93 | 2.57 | 3.297 (4) | 136 |
C309—H309···O23i | 0.93 | 2.35 | 3.244 (5) | 161 |
C302—H302···O13iv | 0.98 | 2.57 | 3.272 (4) | 129 |
C312—H12H···O21v | 0.96 | 2.56 | 3.499 (5) | 165 |
C402—H402···O13iv | 0.98 | 2.46 | 3.196 (4) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x−1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) x+1, y, z. |
Cremer & Pople's puckering parameters topRing | | | q2 | q3 | ϕ2 | θ2 | Q |
C101-O12-C111-C104-C103-C102 | | | 2.321 (3) | 0.034 (3) | 151.41 (8) | 89.16 (8) | 2.322 (3) |
C201-O22-C211-C204-C203-C202 | | | 1.445 (3) | 0.053 (3) | 155.6 (1) | 87.9 (1) | 1.445 (3) |
Furanocoumarins have received much attention on account of their ability to perform cycloaddition reactions with DNA during irradiation with UV light (Zarbska, 1994; Moor, 1996; Brown, 2001), a property that has given rise to wide-ranging photochemotherapeutic applications (Miolo et al., 1989). The furanocoumarins can also undergo cyclodimerization reactions, leading to the possibility of formation of different configurational isomers that may be of the head-to-head or head-to-tail type (Krauch et al., 1966; Zdero et al., 1990; Rojas-Lima et al., 1999). A mixture of the monomer and the dimer (1:2) of the furanocoumarin pimpinellin was isolated, and the individual components were identified on the basis of their spectral data. The main indications of the presence of the dimeric molecule were the absence of the H and C atoms associated with the coumarin double bond present in the monomer [δH: 6.38 and 8.09 (d, J = 9.7 Hz); δC: 114.13 and 140.33], and the presence of signals for a carbonyl group (δC: 165.05), two saturated C atoms (δC: 40.21 and 38.64) and two methoxy groups (δC: 61.17 and 61.15). A combination of two-dimensional NMR experiments (1H–1H COSY, HMQC and HMBC) and comparison with data of models in the literature (Zdero et al., 1990; Rojas-Lima et al., 1999) supported all assignments of the 1H and 13C chemical shifts. The stereochemistry of the pimpinellin dimer, however, could not be deduced directly from the NMR data, and X-ray diffraction analysis was employed to establish its cis–syn conformation.
The structure of the monomer, (I), of pimpinellin is shown in Fig. 1. The atoms of the three rings of the molecule are nearly coplanar; the largest deviation [0.044 (2) Å] from the least-squares plane is exhibited by atom C1. An interesting feature of the packing of the structure is that the two methoxy groups, C12/O4 and C13/O5, exhibit a syn conformation, even though MM2 and AM1 calculations indicate that this conformer should be around 1.4 kcal less stable than the anti conformer. It is suggested that the monomer of pimpinellin crystallizes as the syn conformer in order to facilitate the formation of two non-classic hydrogen bonds, C12—H12C···O4i and C13—H13C···O3ii [symmetry codes: (i) 1 + x, y, z; (ii) −1/2 + x, 1/2 − y, −1/2 + z], as shown in Fig. 2.
The asymmetric unit of the pimpinellin dimer, (II), consists of two independent molecules that are not related by symmetry (Fig. 3). No significant conformational differences were observed between these independent molecules, however, and the bond lengths and angles are in good agreement (within experimental error) with literature values. For the purposes of simplification, therefore, only one independent molecule is considered in the following discussion. The atoms of the furan and aromatic rings on each side of the dimer are coplanar; the mean deviations with respect to the reference plane of the ring atoms are 0.023 and 0.014 Å. Atoms O14, O15, O24 and O25 of the methoxy groups also lie in the mean plane of the ring atoms, at distances of 0.035 (3), 0.054 (3), 0.002 (3) and 0.065 (2) Å, respectively, from that plane. However, atoms C112, C113, C212 and C213 of the methoxy groups of (II) are located on opposite sides of the reference plane of the rings, in accordance with the angular furanocoumarin nucleus. For these groups, the C104—C105—O14—C112, C105—C106—O15—C113, C207—C206—O25—C213 and C206—C205—O24—C212 torsion angles are 102.16, −70.65, −94.76 and 49.09°. In the dimeric form of pimpinellin, the heterocyclic rings are in a twisted-boat conformation, as indicated by the Cremer and Pople (1975) puckering parameters (shown in Table 2 for both rings of the dimer). The distances of atoms O12, C101, C102 and C103 from the mean plane of the aromatic ring atoms are 0.034 (2), 0.198 (3), 0.277 (3) and 0.218 (3) Å, respectively. Atoms C102, C103, C202 and C203, which bind the monomer units to form the dimer, are in a twisted- square conformation, with a mean bond length of 1.562 Å. The four H atoms associated with these atoms are in cis positions, such that the pimpinellin dimer exhibits a cis–syn conformation. The dihedral angle between the least-square planes passing through the furan and aromatic rings of each monomer of the molecule is 38.3°. The molecules are held together by many weak secondary C—H···O interactions, as shown in Table 1. Fig. 4 depicts the molecular packing along the a axis. The syn stereochemistry of the four H atoms in the cyclobutane ring of the dimer of pimpinellin, a conformation also observed in the excited singlet state of coumarin (Hoffman et al., 1971), suggests that (II) was formed when the pimpinellin monomer was photo-irradiated during the process of isolation. In the singlet-state photodimerization reaction of olefins, the set of orbitals involved in the reaction have identical energies. The very strong bonding interactions should lead to the formation of the endo-head-to-head adduct, which is preferred over the exo-head-to-head adduct by virtue of the secondary orbital interactions. The crystallographic study of the dimer of pimpinellin revealed that both carbonyl groups, O13 and O23, of the monomers are positioned on the same side of the molecule, characterizing the conformation as head-to-head. This finding is particularly significant in providing information concerning the mode of cyclodimerization of the pimpinellin monomers.