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In both 9,10-di­methoxy-11-oxatri­cyclo­[6.2.1.02,7]­undeca-4,9-diene-3,6-diol, C12H16O5, (I), and 5,6-di­methoxy-3,7-dioxa­tetra­cyclo­[6.4.0.02,6.04,12]­dodec-9-en-11-ol, C12H16O5, (II), the hetero-oxygen-containing five-membered rings have an envelope conformation. The six-membered rings are in a boat conformation in compound (I), and in (II), one is in a half-boat and the other is in a slightly distorted boat conformation. The mol­ecules in both compounds interact through classical hydrogen bonds and C—H...O contacts.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003365/da1175sup1.cif
Contains datablocks default, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003365/da1175Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003365/da1175IIsup3.hkl
Contains datablock II

CCDC references: 164687; 164688

Comment top

Heliangolides are interesting natural products containing a polymacrocyclic structure (da Costa et al., 1993). Our investigation, aimed at the synthesis of these macrocyclic structures, started with the Diels-Alder reaction between 3,4-dimethoxyfuran and benzoquinone in benzene. The product, (III), was further reduced with sodium borohydride in the presence of ceric chloride to give (I). Due to the cage-like structure of (III), which should prevent the approach of the reagent to the concave face of the substrate, a very high stereoselectivity is expected. In fact, only one product was isolated. We noticed that compound (I) was converted into a different crystalline product, which could be (II) or (IV), within a few hours when kept in chloroform at room temperature. This unexpected result prompted us to proceed with detailed X-ray crystal structure determinations of (I) and of the other product, which was identified as (II). \sch

In order to establish possible changes in the conformations of and distances between the functional groups in the molecules, when released from interactions with surrounding molecules in the crystalline state, a series of semi-empirical (AM1 and PM3) and ab initio quantum chemistry calculations were performed. This study should help in postulating a mechanism for the transformation of (I) into (II). The calculations were carried out using the 6–31G** basis set of the MOPAC7.01 (Stewart, 1990; Csern, 2000) and GAMESS98 (Schmidt et al., 1993) packages.

The molecular structure of (I) is shown in Fig. 1. Table 3 shows the Cremer & Pople (1975) puckering parameters. As in other norbornenes (Zukerman-Schpector et al., 1999), the six-membered ring (C1, C2 and C7—C10) is in a boat conformation. The `boat' is almost symmetric, with a dihedral angle between the planes defined by C1/O1/C8 and C2/C7/C9/C10 of 86.4 (1)°, and with equal deviations of C8 and C1 from the C2/C7/C9/C10 plane of 0.794 (3) Å, the deviations of O4 and O5 from the C2/C7/C9/C10 plane being 0.598 (3) and 0.812 (3) Å, respectively. The two hetero-oxygen five-membered rings have envelope conformations, with O1 displaced 0.867 (2) Å from the C1/C2/C7/C8 plane and 0.787 (3) Å from the C1/C8/C9/C10 plane. The C2—C7 six-membered ring is also in a boat conformation, making dihedral angles of 11.1 (1)° with the C1—O1—C8 bridge and of 75.29 (8)° with the C2/C7/C9/C10 plane.

The molecular diagram of (II) is shown in Fig. 2. Table 6 shows the Cremer & Pople (1975) puckering parameters. The ring formed by atoms C1, C2, C6, C5, C4 and C12 adopts a slightly distorted boat, towards a half-boat, conformation, which is imposed by O1 bridging C2 and C4. Atoms C2 and C4 deviate from the plane defined by C1/C6/C5/C12 [planar to within 0.015 (1) Å] by 0.971 (3) and 0.712 (3) Å, respectively. The C1,C8—C12 ring is in a half-boat conformation, making dihedral angles of 18.51 (8), 88.78 (7) and 71.94 (8)° with the C2/O1/C4, C1/C6/C5/C12 and C1/C2/C6/O2/C8 planes, respectively. The three hetero-oxygen five-membered rings have envelope conformations, as shown in Table 3, with O1 displaced 0.804 (3) Å from the C1/C2/C4/C12 plane and 0.771 (3) Å from the C2/C4/C5/C6 plane, and C2 displaced 0.564 (3) Å from the C1/C8/O2/C6 plane.

In Tables 2 and 5 is shown that in (I), molecules are linked by several classical hydrogen bonds and a short C—H···O interaction, while in (II), the molecules are linked only by C—H···O short interactions. In both cases, these might be described as hydrogen-bonding interactions. However, as pointed out by Cotton et al. (1997), `the field is getting muddier and muddier as the definition of a hydrogen bond is relaxed'. Therefore, we only choose those with a C—H···O angle greater than 100° and an H···O distance of up to 2.73 Å, which corresponds to the sum of the van der Waals radii of O and H, as given by Pauling (1960), plus 5%.

The geometry optimization calculations on (I), using the three methods (AM1, PM3 and ab initio), showed three main conformational changes. Firstly, the C2—C3—O2—H2O torsion angle changes from 180 to 71°, to give an H2O···O5 distance of 2.28 Å (less than the sum of the van der Waals radii). It should be noted that in the crystal this OH moiety is involved in an intermolecular hydrogen bond (Table 2). Secondly, the C13—O5—C10—C1 torsion angle changes from 39.9 (3) to 71.1°, to leave space for atom H2O. Thirdly, the H3O—O3—C6—C7 torsion angle changes from 67 to -69°, to give a final H3···O4 distance of 2.33 Å. Recall that in (I) the O3—H3O hydroxyl group is involved in an intermolecular hydrogen bond and in (II) it forms an intramolecular hydrogen bond (Table 5). These results strongly suggest that the transformation of (I) into (II) is by the mechanism shown in Scheme 2.

Related literature top

For related literature, see: Costa et al. (1993); Cotton et al. (1997); Cremer & Pople (1975); Csern (2000); Pauling (1960); Schmidt et al. (1993); Stewart (1990); Zukerman-Schpector, Gruber & Camilo (1999).

Experimental top

Brief details of the preparation of (I) and (II) are given in the Comment. In order to prevent transformation into (II), (I) was kept in and crystallized from ethyl acetate. Suitable crystals of (II) were obtained by slow evaporation from an ethanolic solution.

Refinement top

In spite of the rather poor diffraction quality of (I), which made collecting Friedel-related reflections useless, the main aim of the work was achieved, which was to obtain the relevant structural information. H atoms were located on stereochemical grounds, except those of the hydroxyl groups, and refined as riding, with an isotropic displacement parameter amounting to 1.5 (for methyl H atoms) or 1.2 (for the other H atoms) times the value of the equivalent isotropic displacement parameter of the parent atom.

Computing details top

For both compounds, data collection: CAD-4 Software (Enraf-Nonius,1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1985) for (I); SIR92 (Altomare et al., 1993) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995). Software used to prepare material for publication: PARST95 (Nardelli, 1995), PLATON (Spek, 1998) and WinGX (Farrugia, 1999) for (I); PARST95 (Nardelli, 1995), PLATON (Spek, 1998), WinGX (Farrugia, 1999) for (II).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The molecular structure of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
(I) 9,10-dimethoxy-11-oxatricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-diol top
Crystal data top
C12H16O5Dx = 1.408 Mg m3
Mr = 240.25Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 25 reflections
a = 8.0796 (4) Åθ = 10.0–18.4°
b = 10.1970 (7) ŵ = 0.11 mm1
c = 13.7534 (9) ÅT = 293 K
V = 1133.11 (12) Å3Irregular, colourless
Z = 40.20 × 0.10 × 0.05 mm
F(000) = 512
Data collection top
Enraf-Nonius CAD-4
diffractometer
θmax = 25.5°
Radiation source: fine-focus sealed tubeh = 90
Graphite monochromatork = 120
ω/2θ scansl = 016
1235 measured reflections3 standard reflections every 30 min
1235 independent reflections intensity decay: 1.0%
1131 reflections with F2 > 2σF2
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0386P)2 + 0.2105P]
where P = (Fo2 + 2Fc2)/3
1235 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.12 e Å3
Crystal data top
C12H16O5V = 1133.11 (12) Å3
Mr = 240.25Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.0796 (4) ŵ = 0.11 mm1
b = 10.1970 (7) ÅT = 293 K
c = 13.7534 (9) Å0.20 × 0.10 × 0.05 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
1131 reflections with F2 > 2σF2
1235 measured reflections3 standard reflections every 30 min
1235 independent reflections intensity decay: 1.0%
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 1.05Δρmax = 0.13 e Å3
1235 reflectionsΔρmin = 0.12 e Å3
156 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 on F2 for ALL reflections. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor-obs 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
xyzUiso*/Ueq
O10.3506 (2)0.67628 (13)0.90520 (10)0.0405 (4)
O20.2964 (2)0.84561 (16)0.63248 (10)0.0475 (4)
H2O0.29200.90690.58020.057*
O30.04948 (19)0.99741 (16)0.99053 (11)0.0466 (4)
H3O0.02390.94141.02170.056*
O40.42929 (19)0.99291 (15)0.99572 (10)0.0437 (4)
O50.57015 (19)0.94012 (14)0.78760 (11)0.0417 (4)
C10.3791 (3)0.74063 (19)0.81226 (14)0.0353 (5)
H10.43770.68690.76420.042*
C20.1975 (3)0.77429 (19)0.78484 (14)0.0335 (5)
H20.14280.69370.76310.040*
C30.1784 (3)0.8779 (2)0.70497 (13)0.0364 (5)
H30.06780.86870.67660.044*
C40.1948 (3)1.0150 (2)0.74374 (15)0.0407 (5)
H40.24811.07830.70640.049*
C50.1349 (3)1.0474 (2)0.82980 (15)0.0421 (5)
H50.14671.13320.85170.051*
C60.0491 (3)0.9499 (2)0.89263 (15)0.0381 (5)
H60.06620.94400.87100.046*
C70.1255 (3)0.8125 (2)0.88593 (14)0.0345 (5)
H70.04070.74810.90380.041*
C80.2795 (3)0.7905 (2)0.95180 (13)0.0357 (5)
H80.25350.77821.02080.043*
C90.4108 (3)0.89169 (19)0.93237 (14)0.0334 (4)
C100.4725 (2)0.86280 (19)0.84497 (13)0.0322 (4)
C110.5495 (4)1.0897 (3)0.97103 (18)0.0638 (8)
H11A0.54681.15901.01820.096*
H11B0.52521.12470.90780.096*
H11C0.65751.05050.97040.096*
C120.6722 (3)0.8738 (2)0.71896 (16)0.0475 (6)
H12A0.60380.83040.67180.071*
H12B0.73920.81010.75210.071*
H12C0.74230.93610.68670.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0568 (9)0.0323 (7)0.0325 (7)0.0042 (7)0.0020 (7)0.0081 (6)
O20.0607 (10)0.0526 (9)0.0294 (7)0.0118 (9)0.0070 (7)0.0078 (6)
O30.0514 (9)0.0510 (10)0.0374 (8)0.0111 (8)0.0095 (7)0.0091 (8)
O40.0484 (8)0.0499 (10)0.0329 (7)0.0113 (8)0.0031 (7)0.0096 (8)
O50.0456 (8)0.0376 (7)0.0419 (8)0.0002 (7)0.0139 (7)0.0015 (7)
C10.0468 (13)0.0318 (10)0.0273 (9)0.0029 (10)0.0006 (9)0.0035 (8)
C20.0392 (11)0.0323 (9)0.0290 (9)0.0058 (9)0.0013 (9)0.0000 (8)
C30.0358 (10)0.0464 (12)0.0270 (9)0.0045 (10)0.0031 (9)0.0044 (9)
C40.0473 (12)0.0380 (10)0.0367 (10)0.0078 (10)0.0033 (10)0.0131 (9)
C50.0468 (13)0.0359 (10)0.0437 (11)0.0073 (10)0.0015 (10)0.0039 (9)
C60.0344 (11)0.0458 (11)0.0340 (10)0.0002 (10)0.0028 (9)0.0030 (9)
C70.0367 (11)0.0374 (10)0.0294 (9)0.0098 (9)0.0017 (9)0.0029 (8)
C80.0453 (12)0.0374 (10)0.0245 (8)0.0003 (10)0.0014 (8)0.0058 (8)
C90.0349 (10)0.0369 (10)0.0283 (9)0.0015 (9)0.0052 (8)0.0006 (8)
C100.0326 (10)0.0330 (9)0.0309 (9)0.0020 (9)0.0012 (8)0.0028 (9)
C110.080 (2)0.0637 (16)0.0481 (13)0.0316 (16)0.0129 (14)0.0151 (12)
C120.0440 (12)0.0519 (13)0.0465 (12)0.0005 (11)0.0117 (11)0.0062 (11)
Geometric parameters (Å, º) top
O1—C81.448 (2)C2—C31.532 (3)
O1—C11.455 (2)C2—C71.557 (3)
O2—C31.418 (2)C3—C41.502 (3)
O3—C61.431 (2)C4—C51.321 (3)
O4—C91.359 (2)C5—C61.488 (3)
O4—C111.426 (3)C6—C71.534 (3)
O5—C101.366 (2)C7—C81.556 (3)
O5—C121.424 (3)C8—C91.504 (3)
C1—C101.524 (3)C9—C101.334 (3)
C1—C21.554 (3)
C8—O1—C195.09 (13)O3—C6—C7111.40 (17)
C9—O4—C11116.61 (16)C5—C6—C7112.82 (17)
C10—O5—C12116.29 (16)C6—C7—C8114.74 (16)
O1—C1—C10100.82 (14)C6—C7—C2115.63 (16)
O1—C1—C299.41 (15)C8—C7—C2100.66 (16)
C10—C1—C2111.03 (16)O1—C8—C9101.15 (15)
C3—C2—C1114.91 (17)O1—C8—C7100.12 (15)
C3—C2—C7115.49 (16)C9—C8—C7111.22 (16)
C1—C2—C7101.04 (15)C10—C9—O4134.8 (2)
O2—C3—C4113.99 (19)C10—C9—C8105.80 (17)
O2—C3—C2106.04 (16)O4—C9—C8119.00 (17)
C4—C3—C2112.25 (16)C9—C10—O5127.49 (19)
C5—C4—C3121.2 (2)C9—C10—C1105.14 (17)
C4—C5—C6121.6 (2)O5—C10—C1125.95 (16)
O3—C6—C5108.64 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O20.962.553.273 (3)133
O2—H2O···O3i0.952.032.815 (2)139
O2—H2O···O4i0.952.363.094 (2)133
O3—H3O···O1ii0.931.872.788 (2)173
C1—H1···O5iii0.982.623.383 (2)135
Symmetry codes: (i) x+1/2, y+2, z1/2; (ii) x1/2, y+3/2, z+2; (iii) x+1, y1/2, z+3/2.
(II) 5,6-dimethoxy-3,7-dioxatetracyclo[6.4.0.02,604,12]dodec-9-en-11-ol top
Crystal data top
C12H16O5F(000) = 1024.0
Mr = 240.25Dx = 1.444 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 7.545 (1) ÅCell parameters from 25 reflections
b = 10.750 (1) Åθ = 9.9–18.2°
c = 27.336 (3) ŵ = 0.11 mm1
β = 94.69 (2)°T = 293 K
V = 2209.8 (4) Å3Irregular, colourless
Z = 80.25 × 0.20 × 0.16 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.026
Radiation source: fine-focus sealed tubeθmax = 25.5°
Graphite monochromatorh = 79
ω/2θ scansk = 712
4326 measured reflectionsl = 3333
2038 independent reflections3 standard reflections every 30 min
1513 reflections with F2 > 2σF2 intensity decay: 1.1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: mixed
wR(F2) = 0.100H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0465P)2 + 1.8597P]
where P = (Fo2 + 2Fc2)/3
2038 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C12H16O5V = 2209.8 (4) Å3
Mr = 240.25Z = 8
Monoclinic, C2/cMo Kα radiation
a = 7.545 (1) ŵ = 0.11 mm1
b = 10.750 (1) ÅT = 293 K
c = 27.336 (3) Å0.25 × 0.20 × 0.16 mm
β = 94.69 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.026
4326 measured reflections3 standard reflections every 30 min
2038 independent reflections intensity decay: 1.1%
1513 reflections with F2 > 2σF2
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.06Δρmax = 0.19 e Å3
2038 reflectionsΔρmin = 0.21 e Å3
156 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 on F2 for ALL reflections. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor-obs 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
xyzUiso*/Ueq
O10.5145 (2)0.37746 (15)0.12294 (6)0.0487 (4)
O20.40985 (17)0.06233 (14)0.11975 (5)0.0384 (4)
O30.96747 (18)0.16362 (17)0.17533 (6)0.0534 (5)
H3O0.93720.11780.14110.064*
O40.32909 (16)0.17881 (16)0.05138 (5)0.0432 (4)
O50.74248 (17)0.10451 (15)0.08970 (5)0.0416 (4)
C10.4723 (2)0.2171 (2)0.18084 (7)0.0382 (5)
H10.41880.24880.20980.046*
C20.3940 (3)0.2797 (2)0.13359 (7)0.0409 (5)
H20.26920.30490.13370.049*
C40.6745 (3)0.3031 (2)0.12733 (8)0.0426 (5)
H40.78190.35060.12190.051*
C50.6264 (2)0.2071 (2)0.08736 (7)0.0375 (5)
H50.62940.24710.05520.045*
C60.4300 (2)0.1778 (2)0.09652 (7)0.0354 (5)
C80.4345 (3)0.0799 (2)0.17260 (7)0.0379 (5)
H80.32370.05850.18700.046*
C90.5782 (3)0.0054 (2)0.19291 (7)0.0420 (5)
H90.55060.08870.19740.050*
C100.7427 (3)0.0320 (2)0.20482 (7)0.0441 (5)
H100.82410.02810.21660.053*
C110.8095 (3)0.1612 (2)0.20115 (7)0.0427 (5)
H110.84530.18780.23480.051*
C120.6707 (3)0.2561 (2)0.18038 (7)0.0400 (5)
H120.68570.32970.20140.048*
C130.7111 (3)0.0236 (3)0.04885 (8)0.0539 (6)
H13A0.79970.04070.05050.081*
H13B0.71690.07000.01900.081*
H13C0.59530.01320.04940.081*
C140.1424 (3)0.1584 (3)0.05426 (8)0.0519 (6)
H14A0.08310.15980.02180.078*
H14B0.09490.22280.07370.078*
H14C0.12440.07910.06920.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0493 (9)0.0391 (9)0.0568 (9)0.0008 (7)0.0013 (7)0.0039 (7)
O20.0425 (8)0.0446 (9)0.0275 (7)0.0091 (7)0.0008 (5)0.0011 (6)
O30.0306 (7)0.0782 (13)0.0509 (9)0.0031 (8)0.0001 (6)0.0055 (8)
O40.0293 (7)0.0698 (11)0.0298 (7)0.0035 (7)0.0028 (5)0.0050 (7)
O50.0311 (7)0.0576 (10)0.0353 (7)0.0040 (7)0.0015 (5)0.0042 (7)
C10.0343 (10)0.0497 (13)0.0304 (10)0.0031 (9)0.0023 (8)0.0057 (9)
C20.0339 (10)0.0476 (14)0.0410 (11)0.0034 (9)0.0021 (8)0.0002 (10)
C40.0347 (10)0.0444 (13)0.0477 (12)0.0075 (9)0.0022 (8)0.0029 (10)
C50.0311 (10)0.0489 (13)0.0323 (10)0.0024 (9)0.0016 (7)0.0064 (9)
C60.0294 (9)0.0469 (13)0.0292 (9)0.0019 (9)0.0019 (7)0.0055 (9)
C80.0345 (10)0.0521 (14)0.0273 (9)0.0042 (9)0.0031 (7)0.0017 (9)
C90.0474 (12)0.0442 (13)0.0344 (10)0.0013 (10)0.0029 (8)0.0078 (9)
C100.0449 (12)0.0539 (15)0.0326 (10)0.0095 (10)0.0029 (8)0.0041 (10)
C110.0350 (10)0.0599 (15)0.0319 (10)0.0020 (10)0.0046 (8)0.0071 (10)
C120.0384 (10)0.0423 (13)0.0384 (11)0.0029 (9)0.0025 (8)0.0101 (9)
C130.0531 (13)0.0686 (18)0.0393 (12)0.0112 (12)0.0012 (9)0.0111 (12)
C140.0316 (10)0.0800 (19)0.0427 (12)0.0059 (11)0.0053 (9)0.0036 (12)
Geometric parameters (Å, º) top
O1—C21.435 (3)C1—C21.531 (3)
O1—C41.444 (3)C1—C121.555 (3)
O2—C61.408 (2)C2—C61.532 (3)
O2—C81.454 (2)C4—C51.525 (3)
O3—C111.434 (2)C4—C121.538 (3)
O4—C61.396 (2)C5—C61.555 (2)
O4—C141.434 (2)C8—C91.492 (3)
O5—C51.406 (3)C9—C101.319 (3)
O5—C131.420 (3)C10—C111.483 (3)
C1—C81.516 (3)C11—C121.537 (3)
C2—O1—C496.72 (15)O4—C6—C2117.74 (17)
C6—O2—C8108.91 (15)O2—C6—C2107.49 (15)
C6—O4—C14114.67 (15)O4—C6—C5108.31 (15)
C5—O5—C13112.42 (15)O2—C6—C5113.01 (16)
C8—C1—C2104.31 (16)C2—C6—C5100.63 (16)
C8—C1—C12115.46 (17)O2—C8—C9108.69 (16)
C2—C1—C12100.39 (16)O2—C8—C1106.33 (16)
O1—C2—C1106.58 (16)C9—C8—C1114.86 (16)
O1—C2—C6103.88 (16)C10—C9—C8123.0 (2)
C1—C2—C699.60 (17)C9—C10—C11125.9 (2)
O1—C4—C599.60 (15)O3—C11—C10110.56 (18)
O1—C4—C12100.40 (16)O3—C11—C12111.99 (18)
C5—C4—C12115.55 (18)C10—C11—C12114.92 (17)
O5—C5—C4112.80 (15)C11—C12—C4120.12 (17)
O5—C5—C6115.55 (17)C11—C12—C1116.46 (18)
C4—C5—C6101.29 (16)C4—C12—C1100.85 (15)
O4—C6—O2109.54 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O51.061.952.849 (2)140
C13—H13C···O20.962.603.133 (3)115
C13—H13A···O1i0.962.613.325 (3)132
C4—H4···O2ii0.982.473.320 (3)144
C11—H11···O3iii0.982.743.648 (3)154
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x+1/2, y+1/2, z; (iii) x+2, y, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC12H16O5C12H16O5
Mr240.25240.25
Crystal system, space groupOrthorhombic, P212121Monoclinic, C2/c
Temperature (K)293293
a, b, c (Å)8.0796 (4), 10.1970 (7), 13.7534 (9)7.545 (1), 10.750 (1), 27.336 (3)
α, β, γ (°)90, 90, 9090, 94.69 (2), 90
V3)1133.11 (12)2209.8 (4)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.110.11
Crystal size (mm)0.20 × 0.10 × 0.050.25 × 0.20 × 0.16
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Enraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed (F2 > 2σF2) reflections
1235, 1235, 1131 4326, 2038, 1513
Rint?0.026
(sin θ/λ)max1)0.6050.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.071, 1.05 0.040, 0.100, 1.06
No. of reflections12352038
No. of parameters156156
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.13, 0.120.19, 0.21

Computer programs: CAD-4 Software (Enraf-Nonius,1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 1985), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1995), PARST95 (Nardelli, 1995), PLATON (Spek, 1998) and WinGX (Farrugia, 1999), PARST95 (Nardelli, 1995), PLATON (Spek, 1998), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) for (I) top
O1—C81.448 (2)O3—C61.431 (2)
O1—C11.455 (2)C4—C51.321 (3)
O2—C31.418 (2)C9—C101.334 (3)
C8—O1—C195.09 (13)C5—C4—C3121.2 (2)
C9—O4—C11116.61 (16)C4—C5—C6121.6 (2)
C10—O5—C12116.29 (16)O1—C8—C9101.15 (15)
O1—C1—C10100.82 (14)O1—C8—C7100.12 (15)
O1—C1—C299.41 (15)C9—C8—C7111.22 (16)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O20.962.553.273 (3)133
O2—H2O···O3i0.952.032.815 (2)139
O2—H2O···O4i0.952.363.094 (2)133
O3—H3O···O1ii0.931.872.788 (2)173
C1—H1···O5iii0.982.623.383 (2)135
Symmetry codes: (i) x+1/2, y+2, z1/2; (ii) x1/2, y+3/2, z+2; (iii) x+1, y1/2, z+3/2.
Cremer &amp; Pople (1975) puckering parameters top
Ringq2Åq3Åϕ2°θ2°
O1-C1-C2-C7-C80.614 (2)1.0 (2)
O1-C1-C10-C9-C80.533 (3)179.2 (2)
C1-C2-C7-C8-C9-C100.917 (2)0.002 (2)-1.3 (1)89.9 (1)0.917 (2)
C2-C3-C4-C5-C6-C70.496 (2)-0.010 (2)-120.7 (2)91.1 (3)0.497 (2)
Selected geometric parameters (Å, º) for (II) top
O1—C21.435 (3)O2—C81.454 (2)
O1—C41.444 (3)C9—C101.319 (3)
O2—C61.408 (2)
C2—O1—C496.72 (15)C1—C2—C699.60 (17)
C6—O2—C8108.91 (15)O1—C4—C599.60 (15)
C6—O4—C14114.67 (15)O1—C4—C12100.40 (16)
C5—O5—C13112.42 (15)C5—C4—C12115.55 (18)
O1—C2—C1106.58 (16)C10—C9—C8123.0 (2)
O1—C2—C6103.88 (16)C9—C10—C11125.9 (2)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O51.061.952.849 (2)140
C13—H13C···O20.962.603.133 (3)115
C13—H13A···O1i0.962.613.325 (3)132
C4—H4···O2ii0.982.473.320 (3)144
C11—H11···O3iii0.982.743.648 (3)154
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x+1/2, y+1/2, z; (iii) x+2, y, z+1/2.
Cremer &amp; Pople (1975) puckering parameters top
Ringq2Åq3Åϕ2°θ2°
O1-C2-C1-C12-C40.549 (2)164.4 (2)
O1-C2-C6-C5-C40.568 (2)-10.4 (2)
C1-C2-C6-O2-C80.357 (2)34.7 (3)
C1-C2-C6-C5-C4-C120.978 (2)-0.133 (2)-121.7 (1)97.8 (1)0.987 (2)
C1-C8-C9-C10-C11-C120.225 (2)-0.179 (2)-179.0 (5)128.6 (4)0.288 (2)
 

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