Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109000225/gd3264sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109000225/gd3264Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109000225/gd3264IIsup3.hkl |
CCDC references: 724204; 724205
Racemic 2-O-benzoyl-6-O-acryloyl-myo-inositol 1,3,5-orthoformate, (1), was prepared as follows. Freshly prepared acryloyl chloride (0.182 g, 2 mmol) was added to a cooled solution of the diol [Which diol?] (0.588 g, 2 mmol) and dry triethylamine (0.405 g, 6 mmol) in dry dimethylfomamide (DMF) (12 ml) and the reaction mixture was stirred at room temperature for 12 h. The DMF was evaporated under reduced pressure, and the residue was diluted with dichloromethane and washed with water, dilute HCl, saturated sodium bicarbonate solution and brine. The organic layer was dried with anhydrous sodium sulfate and concentrated, and the product purified by column chromatography to obtain (1) (yield 0.25 g, 36%). Spectroscopic analysis: λmax (Nujol, cm-1): 1728, 1701, 3444; 1H NMR (200 MHz, CDCl3, Me4Si, δ, p.p.m.): 2.56–2.59 (1H, J = 6.1 Hz, d, OH), 4.43–4.49 (1H, m, Ins H), 4.50–4.57 (2H, m, Ins H), 4.63–4.74 (1H, m, Ins H), 5.52–5.55 (1H, J = 1.6 Hz, q, Ins H), 5.62 (1H, J = 1.3 Hz, d, Ins H), 5.66–5.71 (1H, J = 3.9 and 1.6 Hz, td, CH), 5.93–6.56 (3H, m, CH═ CH2), 7.43–7.65 (3H, m, ArH), 8.13–8.19 (2H, m, Ar H); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 63.3 (Ins C), 67.2 (Ins C), 68.1 (Ins C), 69.2 (Ins C), 71.5 (Ins C), 102.6 (O3C), 126.9 (Ar C), 128.2 (Ar C, s), 129.2 (Ar C), 129.7 (Ar C, s), 132.7 (CH2), 133.3 (═CH), 164.2 (C═ O), 166 (C═O).
Crystallization of (1) from ethyl acetate (containing only a trace of light petroleum) and from other common solvents (dichloromethane, toluene, methanol, tetrahydrofuran, chloroform and benzene) yielded exclusively plates [form (I), m.p. 421–423 K], whereas crystallization from an ethyl acetate–light petroleum mixture (1:1 v/v) produced needle-shaped crystals [form (II), m.p. 410–412 K]. Crystallization from a dichloromethane–light petroleum mixture yielded both forms concomitantly; the relative yield of crystals of form (II) was always much less than that of crystals of form (I). All the crystallization experiments were carried out under comparable conditions.
All H atoms (except hydroxyl H atoms) were placed in geometrically idealized positions for both forms. For form (I), C—H = 0.98 Å for the inositol ring H atoms and orthoformate H atom, and C—H = 0.93 Å for the aromatic and alkenyl H atoms. For form (II), C—H = 1.00 Å for the inositol ring H atoms and orthoformate H atom, and C—H = 0.95 Å for the aromatic and alkenyl H atoms. They were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The O-bound H atoms in both forms were located in difference Fourier maps and refined isotropically. The refined O—H distances were 0.95 (5) Å for form (I), and 0.82 (5) and 0.84 (6) Å for molecules 1 and 2, respectively, of form (II).
In the refinement of form (II), the data were merged using MERG4 in SHELXL97 (Sheldrick, 2008), according to the standard procedure for X-ray Mo Kα measurements of chemical compounds without heavy atoms. The E statistics and N (Z) test for form II confirmed the choice of the noncentrosymmetric space group P21.
For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Version 2.1; Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Version 6.14; Sheldrick, 2008) and PLATON (Spek, 2003).
C17H16O8 | Z = 2 |
Mr = 348.30 | F(000) = 364 |
Triclinic, P1 | Dx = 1.480 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8808 (6) Å | Cell parameters from 3975 reflections |
b = 9.5502 (6) Å | θ = 2.4–27.1° |
c = 9.7100 (6) Å | µ = 0.12 mm−1 |
α = 102.266 (1)° | T = 297 K |
β = 101.733 (1)° | Plate, colourless |
γ = 94.334 (1)° | 0.56 × 0.43 × 0.19 mm |
V = 781.83 (9) Å3 |
Bruker Smart APEX CCD area-detector diffractometer | 2755 independent reflections |
Radiation source: fine-focus sealed tube | 2374 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −10→10 |
Tmin = 0.936, Tmax = 0.978 | k = −11→11 |
9163 measured reflections | l = −11→11 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0828P)2 + 0.3438P] where P = (Fo2 + 2Fc2)/3 |
2755 reflections | (Δ/σ)max < 0.001 |
230 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C17H16O8 | γ = 94.334 (1)° |
Mr = 348.30 | V = 781.83 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8808 (6) Å | Mo Kα radiation |
b = 9.5502 (6) Å | µ = 0.12 mm−1 |
c = 9.7100 (6) Å | T = 297 K |
α = 102.266 (1)° | 0.56 × 0.43 × 0.19 mm |
β = 101.733 (1)° |
Bruker Smart APEX CCD area-detector diffractometer | 2755 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2374 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.978 | Rint = 0.014 |
9163 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.44 e Å−3 |
2755 reflections | Δρmin = −0.14 e Å−3 |
230 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 | 0.53850 (18) | 0.68286 (17) | 0.52944 (16) | 0.0564 (4) | |
O2 | 0.37202 (16) | 0.58168 (15) | 0.72371 (17) | 0.0496 (4) | |
O3 | 0.40799 (17) | 0.85290 (18) | 0.64395 (19) | 0.0589 (5) | |
O4 | 0.6867 (2) | 0.9262 (2) | 0.98833 (18) | 0.0657 (5) | |
O5 | 0.64770 (19) | 0.92263 (18) | 0.60408 (18) | 0.0593 (5) | |
O6 | 0.84623 (16) | 0.70840 (17) | 0.84356 (18) | 0.0538 (4) | |
O7 | 0.48886 (19) | 0.41461 (19) | 0.8209 (2) | 0.0701 (6) | |
O8 | 1.0670 (2) | 0.8405 (2) | 0.8506 (2) | 0.0772 (6) | |
C1 | 0.6147 (2) | 0.6506 (2) | 0.6613 (2) | 0.0469 (5) | |
H1 | 0.6348 | 0.5495 | 0.6433 | 0.056* | |
C2 | 0.5157 (2) | 0.6779 (2) | 0.7715 (2) | 0.0455 (5) | |
H2 | 0.5725 | 0.6658 | 0.8650 | 0.055* | |
C3 | 0.4744 (3) | 0.8323 (2) | 0.7859 (3) | 0.0527 (6) | |
H3 | 0.4011 | 0.8502 | 0.8488 | 0.063* | |
C4 | 0.6215 (3) | 0.9389 (2) | 0.8467 (3) | 0.0530 (6) | |
H4 | 0.5948 | 1.0372 | 0.8507 | 0.064* | |
C5 | 0.7288 (2) | 0.9064 (2) | 0.7444 (2) | 0.0462 (5) | |
H5 | 0.8243 | 0.9742 | 0.7794 | 0.055* | |
C6 | 0.7679 (2) | 0.7503 (2) | 0.7159 (2) | 0.0478 (5) | |
H6 | 0.8300 | 0.7355 | 0.6425 | 0.057* | |
C7 | 0.5085 (3) | 0.8270 (3) | 0.5527 (3) | 0.0588 (6) | |
H7 | 0.4575 | 0.8437 | 0.4591 | 0.071* | |
C8 | 0.3743 (2) | 0.4521 (2) | 0.7575 (2) | 0.0456 (5) | |
C9 | 0.2212 (2) | 0.3629 (2) | 0.7063 (2) | 0.0437 (5) | |
C10 | 0.2135 (3) | 0.2196 (2) | 0.7166 (3) | 0.0527 (6) | |
H10 | 0.3019 | 0.1836 | 0.7577 | 0.063* | |
C11 | 0.0740 (3) | 0.1307 (3) | 0.6654 (3) | 0.0620 (6) | |
H11 | 0.0686 | 0.0348 | 0.6718 | 0.074* | |
C12 | −0.0563 (3) | 0.1837 (3) | 0.6052 (3) | 0.0632 (7) | |
H12 | −0.1494 | 0.1232 | 0.5698 | 0.076* | |
C13 | −0.0501 (3) | 0.3265 (3) | 0.5968 (3) | 0.0617 (7) | |
H13 | −0.1394 | 0.3620 | 0.5568 | 0.074* | |
C14 | 0.0881 (2) | 0.4167 (3) | 0.6475 (2) | 0.0511 (5) | |
H14 | 0.0921 | 0.5130 | 0.6423 | 0.061* | |
C15 | 0.9953 (3) | 0.7570 (2) | 0.8983 (3) | 0.0518 (5) | |
C16 | 1.0577 (3) | 0.6937 (3) | 1.0190 (3) | 0.0603 (6) | |
H16 | 0.9902 | 0.6599 | 1.0697 | 0.072* | |
C17 | 1.2035 (3) | 0.6832 (3) | 1.0575 (4) | 0.0777 (8) | |
H17A | 1.2725 | 0.7166 | 1.0079 | 0.093* | |
H17B | 1.2396 | 0.6424 | 1.1349 | 0.093* | |
H18 | 0.771 (5) | 1.000 (5) | 1.036 (5) | 0.136 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0539 (9) | 0.0553 (10) | 0.0513 (9) | −0.0043 (7) | 0.0015 (7) | 0.0073 (7) |
O2 | 0.0349 (8) | 0.0459 (8) | 0.0645 (9) | −0.0086 (6) | 0.0013 (7) | 0.0197 (7) |
O3 | 0.0413 (8) | 0.0559 (10) | 0.0768 (11) | 0.0037 (7) | 0.0009 (8) | 0.0222 (8) |
O4 | 0.0733 (12) | 0.0609 (11) | 0.0522 (10) | −0.0086 (9) | 0.0065 (8) | 0.0030 (8) |
O5 | 0.0542 (9) | 0.0577 (10) | 0.0627 (10) | −0.0097 (7) | −0.0001 (7) | 0.0253 (8) |
O6 | 0.0359 (8) | 0.0527 (9) | 0.0698 (10) | −0.0028 (6) | 0.0006 (7) | 0.0217 (7) |
O7 | 0.0442 (9) | 0.0663 (11) | 0.0942 (13) | −0.0069 (8) | −0.0115 (9) | 0.0371 (10) |
O8 | 0.0453 (10) | 0.0868 (14) | 0.0962 (14) | −0.0141 (9) | −0.0026 (9) | 0.0397 (11) |
C1 | 0.0417 (11) | 0.0398 (11) | 0.0522 (12) | −0.0026 (9) | 0.0033 (9) | 0.0049 (9) |
C2 | 0.0344 (10) | 0.0439 (11) | 0.0528 (12) | −0.0084 (8) | 0.0006 (9) | 0.0130 (9) |
C3 | 0.0418 (12) | 0.0464 (12) | 0.0651 (14) | −0.0013 (9) | 0.0094 (10) | 0.0073 (10) |
C4 | 0.0512 (13) | 0.0395 (11) | 0.0608 (14) | −0.0028 (9) | 0.0060 (10) | 0.0046 (10) |
C5 | 0.0396 (11) | 0.0404 (11) | 0.0531 (12) | −0.0082 (8) | 0.0004 (9) | 0.0134 (9) |
C6 | 0.0390 (11) | 0.0481 (12) | 0.0527 (12) | −0.0031 (9) | 0.0062 (9) | 0.0111 (9) |
C7 | 0.0530 (13) | 0.0568 (14) | 0.0589 (14) | −0.0066 (11) | −0.0064 (11) | 0.0196 (11) |
C8 | 0.0390 (11) | 0.0475 (12) | 0.0485 (11) | −0.0024 (9) | 0.0044 (9) | 0.0156 (9) |
C9 | 0.0397 (11) | 0.0475 (12) | 0.0426 (11) | −0.0049 (9) | 0.0070 (8) | 0.0138 (9) |
C10 | 0.0488 (13) | 0.0517 (13) | 0.0594 (13) | −0.0013 (10) | 0.0095 (10) | 0.0216 (10) |
C11 | 0.0649 (16) | 0.0475 (13) | 0.0707 (15) | −0.0145 (11) | 0.0134 (12) | 0.0167 (11) |
C12 | 0.0487 (13) | 0.0689 (16) | 0.0648 (15) | −0.0219 (11) | 0.0051 (11) | 0.0177 (12) |
C13 | 0.0394 (12) | 0.0769 (17) | 0.0672 (15) | −0.0069 (11) | 0.0014 (11) | 0.0282 (13) |
C14 | 0.0427 (12) | 0.0519 (12) | 0.0597 (13) | −0.0029 (9) | 0.0066 (10) | 0.0226 (10) |
C15 | 0.0396 (11) | 0.0446 (12) | 0.0662 (14) | −0.0018 (9) | 0.0059 (10) | 0.0104 (10) |
C16 | 0.0461 (13) | 0.0619 (15) | 0.0682 (15) | 0.0020 (11) | 0.0023 (11) | 0.0165 (12) |
C17 | 0.0562 (16) | 0.0781 (19) | 0.094 (2) | 0.0108 (13) | −0.0010 (14) | 0.0262 (16) |
O1—C7 | 1.402 (3) | C4—H4 | 0.9800 |
O1—C1 | 1.428 (3) | C5—C6 | 1.537 (3) |
O2—C8 | 1.346 (2) | C5—H5 | 0.9800 |
O2—C2 | 1.445 (2) | C6—H6 | 0.9800 |
O3—C7 | 1.380 (3) | C7—H7 | 0.9800 |
O3—C3 | 1.445 (3) | C8—C9 | 1.481 (3) |
O4—C4 | 1.414 (3) | C9—C14 | 1.389 (3) |
O4—H18 | 0.95 (5) | C9—C10 | 1.390 (3) |
O5—C7 | 1.413 (3) | C10—C11 | 1.384 (3) |
O5—C5 | 1.451 (3) | C10—H10 | 0.9300 |
O6—C15 | 1.329 (3) | C11—C12 | 1.369 (4) |
O6—C6 | 1.443 (3) | C11—H11 | 0.9300 |
O7—C8 | 1.199 (3) | C12—C13 | 1.381 (4) |
O8—C15 | 1.207 (3) | C12—H12 | 0.9300 |
C1—C2 | 1.512 (3) | C13—C14 | 1.380 (3) |
C1—C6 | 1.528 (3) | C13—H13 | 0.9300 |
C1—H1 | 0.9800 | C14—H14 | 0.9300 |
C2—C3 | 1.531 (3) | C15—C16 | 1.461 (3) |
C2—H2 | 0.9800 | C16—C17 | 1.290 (4) |
C3—C4 | 1.524 (3) | C16—H16 | 0.9300 |
C3—H3 | 0.9800 | C17—H17A | 0.9300 |
C4—C5 | 1.513 (3) | C17—H17B | 0.9300 |
C7—O1—C1 | 110.89 (16) | O6—C6—H6 | 109.9 |
C8—O2—C2 | 116.56 (15) | C1—C6—H6 | 109.9 |
C7—O3—C3 | 111.51 (17) | C5—C6—H6 | 109.9 |
C4—O4—H18 | 112 (3) | O3—C7—O1 | 111.01 (19) |
C7—O5—C5 | 110.88 (16) | O3—C7—O5 | 111.9 (2) |
C15—O6—C6 | 118.78 (17) | O1—C7—O5 | 111.02 (19) |
O1—C1—C2 | 110.08 (17) | O3—C7—H7 | 107.6 |
O1—C1—C6 | 107.00 (17) | O1—C7—H7 | 107.6 |
C2—C1—C6 | 110.04 (17) | O5—C7—H7 | 107.6 |
O1—C1—H1 | 109.9 | O7—C8—O2 | 122.97 (19) |
C2—C1—H1 | 109.9 | O7—C8—C9 | 124.61 (19) |
C6—C1—H1 | 109.9 | O2—C8—C9 | 112.41 (17) |
O2—C2—C1 | 110.92 (17) | C14—C9—C10 | 119.83 (19) |
O2—C2—C3 | 107.37 (16) | C14—C9—C8 | 122.42 (19) |
C1—C2—C3 | 108.23 (18) | C10—C9—C8 | 117.74 (19) |
O2—C2—H2 | 110.1 | C11—C10—C9 | 119.8 (2) |
C1—C2—H2 | 110.1 | C11—C10—H10 | 120.1 |
C3—C2—H2 | 110.1 | C9—C10—H10 | 120.1 |
O3—C3—C4 | 107.09 (18) | C12—C11—C10 | 120.1 (2) |
O3—C3—C2 | 109.12 (18) | C12—C11—H11 | 119.9 |
C4—C3—C2 | 109.51 (18) | C10—C11—H11 | 119.9 |
O3—C3—H3 | 110.4 | C11—C12—C13 | 120.4 (2) |
C4—C3—H3 | 110.4 | C11—C12—H12 | 119.8 |
C2—C3—H3 | 110.4 | C13—C12—H12 | 119.8 |
O4—C4—C5 | 113.09 (19) | C14—C13—C12 | 120.2 (2) |
O4—C4—C3 | 108.84 (19) | C14—C13—H13 | 119.9 |
C5—C4—C3 | 107.77 (18) | C12—C13—H13 | 119.9 |
O4—C4—H4 | 109.0 | C13—C14—C9 | 119.7 (2) |
C5—C4—H4 | 109.0 | C13—C14—H14 | 120.2 |
C3—C4—H4 | 109.0 | C9—C14—H14 | 120.2 |
O5—C5—C4 | 107.28 (17) | O8—C15—O6 | 123.1 (2) |
O5—C5—C6 | 104.45 (17) | O8—C15—C16 | 125.9 (2) |
C4—C5—C6 | 114.75 (17) | O6—C15—C16 | 110.95 (19) |
O5—C5—H5 | 110.0 | C17—C16—C15 | 122.1 (3) |
C4—C5—H5 | 110.0 | C17—C16—H16 | 119.0 |
C6—C5—H5 | 110.0 | C15—C16—H16 | 119.0 |
O6—C6—C1 | 105.53 (16) | C16—C17—H17A | 120.0 |
O6—C6—C5 | 114.10 (17) | C16—C17—H17B | 120.0 |
C1—C6—C5 | 107.40 (17) | H17A—C17—H17B | 120.0 |
C7—O1—C1—C2 | 58.8 (2) | O5—C5—C6—O6 | −178.26 (15) |
C7—O1—C1—C6 | −60.8 (2) | C4—C5—C6—O6 | −61.1 (2) |
C8—O2—C2—C1 | 87.3 (2) | O5—C5—C6—C1 | −61.7 (2) |
C8—O2—C2—C3 | −154.63 (19) | C4—C5—C6—C1 | 55.5 (2) |
O1—C1—C2—O2 | 64.0 (2) | C3—O3—C7—O1 | 63.1 (2) |
C6—C1—C2—O2 | −178.33 (16) | C3—O3—C7—O5 | −61.5 (2) |
O1—C1—C2—C3 | −53.6 (2) | C1—O1—C7—O3 | −63.2 (2) |
C6—C1—C2—C3 | 64.1 (2) | C1—O1—C7—O5 | 61.9 (2) |
C7—O3—C3—C4 | 60.4 (2) | C5—O5—C7—O3 | 60.9 (2) |
C7—O3—C3—C2 | −58.1 (2) | C5—O5—C7—O1 | −63.7 (2) |
O2—C2—C3—O3 | −67.2 (2) | C2—O2—C8—O7 | −1.6 (3) |
C1—C2—C3—O3 | 52.6 (2) | C2—O2—C8—C9 | 178.90 (17) |
O2—C2—C3—C4 | 175.88 (17) | O7—C8—C9—C14 | 172.7 (2) |
C1—C2—C3—C4 | −64.3 (2) | O2—C8—C9—C14 | −7.8 (3) |
O3—C3—C4—O4 | 177.61 (17) | O7—C8—C9—C10 | −8.3 (3) |
C2—C3—C4—O4 | −64.2 (2) | O2—C8—C9—C10 | 171.18 (19) |
O3—C3—C4—C5 | −59.4 (2) | C14—C9—C10—C11 | 1.3 (3) |
C2—C3—C4—C5 | 58.8 (2) | C8—C9—C10—C11 | −177.7 (2) |
C7—O5—C5—C4 | −59.5 (2) | C9—C10—C11—C12 | −0.2 (4) |
C7—O5—C5—C6 | 62.7 (2) | C10—C11—C12—C13 | −0.8 (4) |
O4—C4—C5—O5 | 179.72 (16) | C11—C12—C13—C14 | 0.8 (4) |
C3—C4—C5—O5 | 59.4 (2) | C12—C13—C14—C9 | 0.3 (4) |
O4—C4—C5—C6 | 64.2 (2) | C10—C9—C14—C13 | −1.4 (3) |
C3—C4—C5—C6 | −56.2 (2) | C8—C9—C14—C13 | 177.6 (2) |
C15—O6—C6—C1 | 166.90 (18) | C6—O6—C15—O8 | 3.8 (3) |
C15—O6—C6—C5 | −75.4 (2) | C6—O6—C15—C16 | −175.12 (19) |
O1—C1—C6—O6 | −176.31 (16) | O8—C15—C16—C17 | −22.9 (4) |
C2—C1—C6—O6 | 64.1 (2) | O6—C15—C16—C17 | 156.0 (3) |
O1—C1—C6—C5 | 61.6 (2) | C3—C4—O4—H18 | −172 (3) |
C2—C1—C6—C5 | −58.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H18···O8i | 0.95 (5) | 1.98 (5) | 2.930 (3) | 174 (4) |
Symmetry code: (i) −x+2, −y+2, −z+2. |
C17H16O8 | F(000) = 728 |
Mr = 348.30 | Dx = 1.463 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3573 reflections |
a = 13.813 (4) Å | θ = 2.6–27.9° |
b = 19.279 (5) Å | µ = 0.12 mm−1 |
c = 5.9801 (15) Å | T = 133 K |
β = 96.665 (4)° | Needle, colourless |
V = 1581.8 (7) Å3 | 0.19 × 0.12 × 0.05 mm |
Z = 4 |
Bruker Smart APEX CCD area-detector diffractometer | 2870 independent reflections |
Radiation source: fine-focus sealed tube | 2669 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −16→16 |
Tmin = 0.978, Tmax = 0.994 | k = −22→22 |
15127 measured reflections | l = −7→7 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0542P)2 + 0.5516P] where P = (Fo2 + 2Fc2)/3 |
2870 reflections | (Δ/σ)max < 0.001 |
459 parameters | Δρmax = 0.29 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
C17H16O8 | V = 1581.8 (7) Å3 |
Mr = 348.30 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 13.813 (4) Å | µ = 0.12 mm−1 |
b = 19.279 (5) Å | T = 133 K |
c = 5.9801 (15) Å | 0.19 × 0.12 × 0.05 mm |
β = 96.665 (4)° |
Bruker Smart APEX CCD area-detector diffractometer | 2870 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2669 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 0.994 | Rint = 0.075 |
15127 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 1 restraint |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.29 e Å−3 |
2870 reflections | Δρmin = −0.20 e Å−3 |
459 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 | 0.8125 (2) | 0.47512 (15) | 0.9305 (5) | 0.0214 (7) | |
O2 | 0.6847 (2) | 0.37656 (16) | 0.6627 (5) | 0.0228 (7) | |
O3 | 0.7345 (2) | 0.39965 (15) | 1.1492 (5) | 0.0204 (6) | |
O4 | 0.8928 (2) | 0.25283 (15) | 1.0481 (5) | 0.0219 (7) | |
O5 | 0.8950 (2) | 0.43014 (15) | 1.2587 (5) | 0.0201 (7) | |
O6 | 0.9859 (2) | 0.34782 (15) | 0.7662 (5) | 0.0199 (6) | |
O7 | 0.6789 (2) | 0.27059 (16) | 0.5052 (5) | 0.0292 (8) | |
O8 | 1.1357 (2) | 0.37660 (18) | 0.9296 (5) | 0.0298 (8) | |
C1 | 0.8457 (3) | 0.4201 (2) | 0.7955 (7) | 0.0194 (9) | |
H1 | 0.8508 | 0.4372 | 0.6394 | 0.023* | |
C2 | 0.7763 (3) | 0.3585 (2) | 0.7881 (7) | 0.0191 (9) | |
H2 | 0.8055 | 0.3183 | 0.7140 | 0.023* | |
C3 | 0.7632 (3) | 0.3394 (2) | 1.0299 (7) | 0.0216 (9) | |
H3 | 0.7125 | 0.3024 | 1.0309 | 0.026* | |
C4 | 0.8602 (3) | 0.3134 (2) | 1.1506 (7) | 0.0190 (9) | |
H4 | 0.8517 | 0.3028 | 1.3108 | 0.023* | |
C5 | 0.9345 (3) | 0.3721 (2) | 1.1456 (7) | 0.0185 (9) | |
H5 | 0.9990 | 0.3580 | 1.2256 | 0.022* | |
C6 | 0.9459 (3) | 0.3982 (2) | 0.9075 (7) | 0.0179 (9) | |
H6 | 0.9894 | 0.4398 | 0.9201 | 0.021* | |
C7 | 0.8047 (3) | 0.4522 (2) | 1.1506 (7) | 0.0207 (10) | |
H7 | 0.7823 | 0.4923 | 1.2376 | 0.025* | |
C8 | 0.6432 (3) | 0.3273 (2) | 0.5226 (7) | 0.0228 (10) | |
C9 | 0.5519 (3) | 0.3507 (3) | 0.3920 (7) | 0.0257 (10) | |
C10 | 0.5079 (4) | 0.3076 (3) | 0.2251 (9) | 0.0391 (13) | |
H10 | 0.5350 | 0.2633 | 0.2023 | 0.047* | |
C11 | 0.4248 (4) | 0.3287 (4) | 0.0914 (10) | 0.0564 (18) | |
H11 | 0.3948 | 0.2988 | −0.0224 | 0.068* | |
C12 | 0.3855 (4) | 0.3927 (4) | 0.1226 (10) | 0.0558 (17) | |
H12 | 0.3288 | 0.4072 | 0.0289 | 0.067* | |
C13 | 0.4275 (4) | 0.4359 (4) | 0.2886 (11) | 0.0524 (16) | |
H13 | 0.3990 | 0.4799 | 0.3113 | 0.063* | |
C14 | 0.5111 (4) | 0.4158 (3) | 0.4231 (9) | 0.0381 (13) | |
H14 | 0.5407 | 0.4462 | 0.5362 | 0.046* | |
C15 | 1.0850 (3) | 0.3449 (2) | 0.7887 (7) | 0.0191 (9) | |
C16 | 1.1199 (3) | 0.2986 (2) | 0.6175 (7) | 0.0236 (10) | |
H16 | 1.0773 | 0.2651 | 0.5427 | 0.028* | |
C17 | 1.2100 (4) | 0.3040 (3) | 0.5695 (9) | 0.0363 (12) | |
H17A | 1.2525 | 0.3375 | 0.6445 | 0.044* | |
H17B | 1.2327 | 0.2743 | 0.4598 | 0.044* | |
H18 | 0.847 (3) | 0.226 (3) | 1.058 (7) | 0.018 (12)* | |
O1' | 0.8180 (2) | −0.02353 (15) | 0.4633 (5) | 0.0214 (7) | |
O2' | 0.7004 (2) | 0.08949 (16) | 0.2611 (5) | 0.0239 (7) | |
O3' | 0.7615 (2) | 0.05067 (15) | 0.7235 (5) | 0.0194 (6) | |
O4' | 0.9392 (2) | 0.18745 (16) | 0.6450 (5) | 0.0224 (7) | |
O5' | 0.9168 (2) | 0.00484 (15) | 0.7903 (5) | 0.0197 (7) | |
O6' | 0.9993 (2) | 0.09656 (15) | 0.3030 (5) | 0.0198 (6) | |
O7' | 0.7191 (2) | 0.17852 (15) | 0.0286 (5) | 0.0208 (7) | |
O8' | 1.1516 (2) | 0.07692 (17) | 0.4663 (5) | 0.0262 (7) | |
C1' | 0.8559 (3) | 0.0326 (2) | 0.3410 (7) | 0.0208 (10) | |
H1' | 0.8528 | 0.0203 | 0.1779 | 0.025* | |
C2' | 0.7984 (3) | 0.0984 (2) | 0.3686 (7) | 0.0192 (9) | |
H2' | 0.8300 | 0.1382 | 0.2981 | 0.023* | |
C3' | 0.7961 (3) | 0.1123 (2) | 0.6172 (7) | 0.0189 (9) | |
H3' | 0.7529 | 0.1528 | 0.6393 | 0.023* | |
C4' | 0.8995 (3) | 0.1260 (2) | 0.7286 (7) | 0.0184 (9) | |
H4' | 0.8976 | 0.1314 | 0.8943 | 0.022* | |
C5' | 0.9617 (3) | 0.0630 (2) | 0.6888 (7) | 0.0185 (9) | |
H5' | 1.0300 | 0.0698 | 0.7613 | 0.022* | |
C6' | 0.9616 (3) | 0.0434 (2) | 0.4398 (7) | 0.0200 (9) | |
H6' | 0.9991 | −0.0006 | 0.4276 | 0.024* | |
C7' | 0.8209 (3) | −0.0061 (2) | 0.6930 (7) | 0.0194 (9) | |
H7' | 0.7946 | −0.0465 | 0.7715 | 0.023* | |
C8' | 0.6696 (3) | 0.1330 (2) | 0.0917 (7) | 0.0193 (9) | |
C9' | 0.5686 (3) | 0.1186 (2) | −0.0084 (7) | 0.0239 (10) | |
C10' | 0.5339 (3) | 0.1548 (2) | −0.2026 (8) | 0.0292 (11) | |
H10' | 0.5745 | 0.1879 | −0.2640 | 0.035* | |
C11' | 0.4413 (4) | 0.1430 (3) | −0.3055 (9) | 0.0422 (14) | |
H11' | 0.4180 | 0.1674 | −0.4390 | 0.051* | |
C12' | 0.3824 (4) | 0.0957 (3) | −0.2142 (11) | 0.0535 (17) | |
H12' | 0.3183 | 0.0874 | −0.2851 | 0.064* | |
C13' | 0.4161 (4) | 0.0602 (4) | −0.0204 (11) | 0.0571 (18) | |
H13' | 0.3746 | 0.0282 | 0.0428 | 0.069* | |
C14' | 0.5098 (4) | 0.0708 (3) | 0.0825 (9) | 0.0410 (13) | |
H14' | 0.5334 | 0.0456 | 0.2142 | 0.049* | |
C15' | 1.0961 (3) | 0.1069 (2) | 0.3299 (7) | 0.0202 (9) | |
C16' | 1.1229 (3) | 0.1595 (2) | 0.1670 (8) | 0.0255 (10) | |
H16' | 1.0734 | 0.1869 | 0.0868 | 0.031* | |
C17' | 1.2132 (4) | 0.1687 (3) | 0.1320 (10) | 0.0447 (14) | |
H17C | 1.2632 | 0.1414 | 0.2114 | 0.054* | |
H17D | 1.2291 | 0.2026 | 0.0270 | 0.054* | |
H18' | 0.926 (4) | 0.219 (3) | 0.733 (9) | 0.031 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0274 (16) | 0.0169 (16) | 0.0199 (15) | 0.0032 (13) | 0.0030 (13) | 0.0013 (12) |
O2 | 0.0198 (15) | 0.0247 (16) | 0.0231 (16) | 0.0015 (13) | −0.0010 (12) | −0.0067 (13) |
O3 | 0.0213 (15) | 0.0199 (15) | 0.0210 (15) | −0.0006 (12) | 0.0072 (12) | −0.0009 (13) |
O4 | 0.0256 (17) | 0.0132 (15) | 0.0277 (17) | −0.0049 (13) | 0.0076 (13) | 0.0011 (12) |
O5 | 0.0241 (16) | 0.0194 (15) | 0.0170 (14) | 0.0003 (13) | 0.0038 (12) | −0.0054 (12) |
O6 | 0.0234 (16) | 0.0213 (16) | 0.0157 (14) | −0.0036 (13) | 0.0050 (12) | −0.0034 (12) |
O7 | 0.0347 (19) | 0.0178 (17) | 0.0334 (18) | −0.0020 (14) | −0.0036 (15) | 0.0007 (14) |
O8 | 0.0217 (16) | 0.0364 (19) | 0.0309 (18) | −0.0009 (15) | 0.0009 (14) | −0.0088 (15) |
C1 | 0.025 (2) | 0.020 (2) | 0.015 (2) | 0.0001 (19) | 0.0074 (17) | 0.0010 (17) |
C2 | 0.015 (2) | 0.021 (2) | 0.022 (2) | −0.0017 (17) | 0.0024 (16) | −0.0034 (18) |
C3 | 0.025 (2) | 0.018 (2) | 0.023 (2) | −0.0031 (18) | 0.0091 (18) | 0.0004 (18) |
C4 | 0.025 (2) | 0.018 (2) | 0.016 (2) | 0.0015 (18) | 0.0081 (17) | −0.0007 (17) |
C5 | 0.016 (2) | 0.020 (2) | 0.020 (2) | 0.0014 (18) | 0.0039 (16) | −0.0018 (17) |
C6 | 0.019 (2) | 0.017 (2) | 0.018 (2) | −0.0067 (17) | 0.0026 (16) | −0.0016 (17) |
C7 | 0.024 (2) | 0.020 (2) | 0.017 (2) | −0.0003 (18) | 0.0007 (17) | −0.0042 (17) |
C8 | 0.023 (2) | 0.026 (3) | 0.020 (2) | −0.010 (2) | 0.0069 (18) | 0.0011 (19) |
C9 | 0.020 (2) | 0.033 (3) | 0.025 (2) | −0.0062 (19) | 0.0069 (18) | −0.002 (2) |
C10 | 0.025 (3) | 0.051 (3) | 0.039 (3) | −0.004 (2) | −0.004 (2) | −0.014 (3) |
C11 | 0.034 (3) | 0.082 (5) | 0.048 (4) | 0.003 (3) | −0.014 (3) | −0.033 (3) |
C12 | 0.028 (3) | 0.085 (5) | 0.051 (4) | 0.018 (3) | −0.012 (3) | −0.015 (3) |
C13 | 0.032 (3) | 0.061 (4) | 0.062 (4) | 0.018 (3) | −0.008 (3) | −0.017 (3) |
C14 | 0.028 (3) | 0.043 (3) | 0.041 (3) | 0.008 (2) | −0.006 (2) | −0.013 (2) |
C15 | 0.020 (2) | 0.018 (2) | 0.020 (2) | −0.0029 (18) | 0.0032 (18) | 0.0037 (18) |
C16 | 0.024 (2) | 0.021 (2) | 0.025 (2) | −0.0011 (19) | 0.0009 (18) | −0.0024 (19) |
C17 | 0.032 (3) | 0.036 (3) | 0.041 (3) | 0.000 (2) | 0.009 (2) | −0.013 (2) |
O1' | 0.0284 (17) | 0.0197 (16) | 0.0161 (15) | −0.0060 (13) | 0.0019 (13) | −0.0015 (12) |
O2' | 0.0193 (15) | 0.0269 (17) | 0.0248 (16) | −0.0027 (13) | −0.0007 (12) | 0.0103 (13) |
O3' | 0.0209 (15) | 0.0187 (15) | 0.0191 (15) | 0.0006 (12) | 0.0038 (12) | 0.0034 (12) |
O4' | 0.0280 (17) | 0.0155 (16) | 0.0242 (17) | −0.0036 (13) | 0.0052 (13) | −0.0007 (13) |
O5' | 0.0219 (16) | 0.0168 (15) | 0.0204 (15) | −0.0008 (12) | 0.0027 (12) | 0.0052 (12) |
O6' | 0.0185 (15) | 0.0246 (16) | 0.0159 (14) | −0.0014 (13) | 0.0007 (11) | 0.0026 (13) |
O7' | 0.0212 (15) | 0.0159 (15) | 0.0248 (16) | −0.0036 (13) | 0.0000 (12) | 0.0052 (12) |
O8' | 0.0216 (16) | 0.0293 (18) | 0.0274 (16) | 0.0002 (14) | 0.0019 (13) | 0.0038 (14) |
C1' | 0.029 (2) | 0.017 (2) | 0.016 (2) | −0.0056 (18) | 0.0021 (18) | 0.0024 (17) |
C2' | 0.020 (2) | 0.018 (2) | 0.018 (2) | −0.0044 (18) | −0.0015 (17) | 0.0068 (17) |
C3' | 0.022 (2) | 0.013 (2) | 0.022 (2) | 0.0019 (17) | 0.0055 (17) | 0.0016 (17) |
C4' | 0.024 (2) | 0.016 (2) | 0.015 (2) | −0.0013 (18) | 0.0044 (17) | −0.0018 (17) |
C5' | 0.018 (2) | 0.018 (2) | 0.019 (2) | −0.0009 (17) | 0.0011 (17) | 0.0039 (17) |
C6' | 0.026 (2) | 0.016 (2) | 0.018 (2) | 0.0005 (18) | 0.0055 (17) | 0.0012 (17) |
C7' | 0.023 (2) | 0.017 (2) | 0.018 (2) | −0.0028 (18) | 0.0034 (18) | 0.0015 (17) |
C8' | 0.025 (2) | 0.015 (2) | 0.019 (2) | −0.0008 (18) | 0.0093 (18) | −0.0008 (18) |
C9' | 0.024 (2) | 0.023 (2) | 0.024 (2) | 0.0040 (18) | −0.0004 (18) | −0.0032 (19) |
C10' | 0.025 (3) | 0.028 (3) | 0.033 (3) | −0.001 (2) | −0.003 (2) | 0.008 (2) |
C11' | 0.035 (3) | 0.047 (3) | 0.040 (3) | −0.006 (3) | −0.011 (2) | 0.015 (3) |
C12' | 0.028 (3) | 0.063 (4) | 0.064 (4) | −0.016 (3) | −0.017 (3) | 0.010 (3) |
C13' | 0.034 (3) | 0.065 (4) | 0.069 (4) | −0.023 (3) | −0.011 (3) | 0.030 (4) |
C14' | 0.028 (3) | 0.046 (3) | 0.046 (3) | −0.011 (2) | −0.005 (2) | 0.018 (3) |
C15' | 0.020 (2) | 0.023 (2) | 0.017 (2) | 0.0041 (19) | 0.0019 (18) | −0.0032 (18) |
C16' | 0.025 (2) | 0.027 (3) | 0.023 (2) | −0.0031 (19) | −0.0026 (19) | −0.0006 (19) |
C17' | 0.038 (3) | 0.056 (4) | 0.041 (3) | −0.003 (3) | 0.008 (2) | 0.014 (3) |
C1—O1 | 1.440 (5) | C1'—O1' | 1.438 (5) |
C1—C2 | 1.524 (6) | C1'—C2' | 1.516 (6) |
C1—C6 | 1.525 (6) | C1'—C6' | 1.524 (6) |
C1—H1 | 1.0000 | C1'—H1' | 1.0000 |
C2—O2 | 1.437 (5) | C2'—O2' | 1.440 (5) |
C2—C3 | 1.523 (6) | C2'—C3' | 1.515 (6) |
C2—H2 | 1.0000 | C2'—H2' | 1.0000 |
C3—O3 | 1.442 (5) | C3'—O3' | 1.454 (5) |
C3—C4 | 1.531 (6) | C3'—C4' | 1.528 (6) |
C3—H3 | 1.0000 | C3'—H3' | 1.0000 |
C4—O4 | 1.416 (5) | C4'—O4' | 1.420 (5) |
C4—C5 | 1.530 (6) | C4'—C5' | 1.523 (6) |
C4—H4 | 1.0000 | C4'—H4' | 1.0000 |
C5—O5 | 1.446 (5) | C5'—O5' | 1.448 (5) |
C5—C6 | 1.536 (6) | C5'—C6' | 1.536 (6) |
C5—H5 | 1.0000 | C5'—H5' | 1.0000 |
C6—O6 | 1.439 (5) | C6'—O6' | 1.446 (5) |
C6—H6 | 1.0000 | C6'—H6' | 1.0000 |
C7—O3 | 1.401 (5) | C7'—O3' | 1.392 (5) |
C7—O5 | 1.403 (5) | C7'—O5' | 1.400 (5) |
C7—O1 | 1.405 (5) | C7'—O1' | 1.410 (5) |
C7—H7 | 1.0000 | C7'—H7' | 1.0000 |
C8—O7 | 1.209 (6) | C8'—O7' | 1.199 (5) |
C8—O2 | 1.349 (5) | C8'—O2' | 1.346 (5) |
C8—C9 | 1.475 (6) | C8'—C9' | 1.480 (6) |
C9—C10 | 1.383 (7) | C9'—C14' | 1.380 (7) |
C9—C14 | 1.398 (7) | C9'—C10' | 1.392 (6) |
C10—C11 | 1.382 (7) | C10'—C11' | 1.372 (7) |
C10—H10 | 0.9500 | C10'—H10' | 0.9500 |
C11—C12 | 1.369 (9) | C11'—C12' | 1.377 (8) |
C11—H11 | 0.9500 | C11'—H11' | 0.9500 |
C12—C13 | 1.373 (8) | C12'—C13' | 1.379 (8) |
C12—H12 | 0.9500 | C12'—H12' | 0.9500 |
C13—C14 | 1.384 (7) | C13'—C14' | 1.383 (7) |
C13—H13 | 0.9500 | C13'—H13' | 0.9500 |
C14—H14 | 0.9500 | C14'—H14' | 0.9500 |
C15—O8 | 1.198 (5) | C15'—O8' | 1.201 (5) |
C15—O6 | 1.360 (5) | C15'—O6' | 1.343 (5) |
C15—C16 | 1.481 (6) | C15'—C16' | 1.483 (6) |
C16—C17 | 1.313 (7) | C16'—C17' | 1.300 (7) |
C16—H16 | 0.9500 | C16'—H16' | 0.9500 |
C17—H17A | 0.9500 | C17'—H17C | 0.9500 |
C17—H17B | 0.9500 | C17'—H17D | 0.9500 |
O4—H18 | 0.82 (5) | O4'—H18' | 0.84 (6) |
O1—C1—C2 | 110.5 (3) | O2'—C2'—C3' | 109.4 (3) |
O1—C1—C6 | 106.8 (3) | O2'—C2'—C1' | 109.2 (3) |
C2—C1—C6 | 109.4 (3) | C3'—C2'—C1' | 109.1 (3) |
O1—C1—H1 | 110.0 | O2'—C2'—H2' | 109.7 |
C2—C1—H1 | 110.0 | C3'—C2'—H2' | 109.7 |
C6—C1—H1 | 110.0 | C1'—C2'—H2' | 109.7 |
O2—C2—C3 | 111.1 (3) | O3'—C3'—C2' | 109.2 (3) |
O2—C2—C1 | 109.8 (3) | O3'—C3'—C4' | 106.7 (3) |
C3—C2—C1 | 107.7 (3) | C2'—C3'—C4' | 109.4 (3) |
O2—C2—H2 | 109.4 | O3'—C3'—H3' | 110.5 |
C3—C2—H2 | 109.4 | C2'—C3'—H3' | 110.5 |
C1—C2—H2 | 109.4 | C4'—C3'—H3' | 110.5 |
O3—C3—C2 | 110.2 (3) | O4'—C4'—C5' | 111.3 (3) |
O3—C3—C4 | 107.8 (3) | O4'—C4'—C3' | 111.7 (3) |
C2—C3—C4 | 109.4 (3) | C5'—C4'—C3' | 108.1 (3) |
O3—C3—H3 | 109.8 | O4'—C4'—H4' | 108.6 |
C2—C3—H3 | 109.8 | C5'—C4'—H4' | 108.6 |
C4—C3—H3 | 109.8 | C3'—C4'—H4' | 108.6 |
O4—C4—C5 | 110.7 (3) | O5'—C5'—C4' | 106.0 (3) |
O4—C4—C3 | 111.8 (3) | O5'—C5'—C6' | 105.3 (3) |
C5—C4—C3 | 107.5 (3) | C4'—C5'—C6' | 114.3 (3) |
O4—C4—H4 | 108.9 | O5'—C5'—H5' | 110.4 |
C5—C4—H4 | 108.9 | C4'—C5'—H5' | 110.4 |
C3—C4—H4 | 108.9 | C6'—C5'—H5' | 110.4 |
O5—C5—C4 | 105.9 (3) | O6'—C6'—C1' | 105.6 (3) |
O5—C5—C6 | 105.4 (3) | O6'—C6'—C5' | 114.5 (3) |
C4—C5—C6 | 113.7 (3) | C1'—C6'—C5' | 107.6 (3) |
O5—C5—H5 | 110.6 | O6'—C6'—H6' | 109.7 |
C4—C5—H5 | 110.6 | C1'—C6'—H6' | 109.7 |
C6—C5—H5 | 110.6 | C5'—C6'—H6' | 109.7 |
O6—C6—C1 | 108.7 (3) | O3'—C7'—O5' | 111.8 (3) |
O6—C6—C5 | 114.3 (3) | O3'—C7'—O1' | 111.4 (3) |
C1—C6—C5 | 108.2 (3) | O5'—C7'—O1' | 111.1 (3) |
O6—C6—H6 | 108.5 | O3'—C7'—H7' | 107.5 |
C1—C6—H6 | 108.5 | O5'—C7'—H7' | 107.5 |
C5—C6—H6 | 108.5 | O1'—C7'—H7' | 107.5 |
O3—C7—O5 | 111.2 (3) | O7'—C8'—O2' | 123.4 (4) |
O3—C7—O1 | 110.5 (3) | O7'—C8'—C9' | 123.8 (4) |
O5—C7—O1 | 111.5 (3) | O2'—C8'—C9' | 112.8 (4) |
O3—C7—H7 | 107.8 | C14'—C9'—C10' | 120.1 (4) |
O5—C7—H7 | 107.8 | C14'—C9'—C8' | 122.5 (4) |
O1—C7—H7 | 107.8 | C10'—C9'—C8' | 117.4 (4) |
O7—C8—O2 | 122.8 (4) | C11'—C10'—C9' | 120.2 (5) |
O7—C8—C9 | 124.2 (4) | C11'—C10'—H10' | 119.9 |
O2—C8—C9 | 112.9 (4) | C9'—C10'—H10' | 119.9 |
C10—C9—C14 | 119.0 (5) | C10'—C11'—C12' | 119.7 (5) |
C10—C9—C8 | 118.4 (4) | C10'—C11'—H11' | 120.2 |
C14—C9—C8 | 122.5 (4) | C12'—C11'—H11' | 120.2 |
C11—C10—C9 | 120.5 (5) | C11'—C12'—C13' | 120.3 (5) |
C11—C10—H10 | 119.8 | C11'—C12'—H12' | 119.8 |
C9—C10—H10 | 119.8 | C13'—C12'—H12' | 119.8 |
C12—C11—C10 | 120.1 (5) | C12'—C13'—C14' | 120.5 (5) |
C12—C11—H11 | 119.9 | C12'—C13'—H13' | 119.8 |
C10—C11—H11 | 119.9 | C14'—C13'—H13' | 119.8 |
C11—C12—C13 | 120.3 (5) | C9'—C14'—C13' | 119.1 (5) |
C11—C12—H12 | 119.8 | C9'—C14'—H14' | 120.4 |
C13—C12—H12 | 119.8 | C13'—C14'—H14' | 120.4 |
C12—C13—C14 | 120.3 (6) | O8'—C15'—O6' | 123.9 (4) |
C12—C13—H13 | 119.9 | O8'—C15'—C16' | 125.9 (4) |
C14—C13—H13 | 119.9 | O6'—C15'—C16' | 110.1 (3) |
C13—C14—C9 | 119.8 (5) | C17'—C16'—C15' | 121.1 (5) |
C13—C14—H14 | 120.1 | C17'—C16'—H16' | 119.5 |
C9—C14—H14 | 120.1 | C15'—C16'—H16' | 119.5 |
O8—C15—O6 | 123.2 (4) | C16'—C17'—H17C | 120.0 |
O8—C15—C16 | 125.6 (4) | C16'—C17'—H17D | 120.0 |
O6—C15—C16 | 111.2 (3) | H17C—C17'—H17D | 120.0 |
C17—C16—C15 | 119.8 (4) | C7—O1—C1 | 111.0 (3) |
C17—C16—H16 | 120.1 | C8—O2—C2 | 116.0 (3) |
C15—C16—H16 | 120.1 | C7—O3—C3 | 110.8 (3) |
C16—C17—H17A | 120.0 | C4—O4—H18 | 102 (3) |
C16—C17—H17B | 120.0 | C7—O5—C5 | 112.5 (3) |
H17A—C17—H17B | 120.0 | C15—O6—C6 | 114.8 (3) |
O1'—C1'—C2' | 110.4 (3) | C7'—O1'—C1' | 110.2 (3) |
O1'—C1'—C6' | 107.1 (3) | C8'—O2'—C2' | 117.4 (3) |
C2'—C1'—C6' | 109.5 (3) | C7'—O3'—C3' | 110.9 (3) |
O1'—C1'—H1' | 109.9 | C4'—O4'—H18' | 106 (4) |
C2'—C1'—H1' | 109.9 | C7'—O5'—C5' | 111.9 (3) |
C6'—C1'—H1' | 109.9 | C15'—O6'—C6' | 117.2 (3) |
O1—C1—C2—O2 | 68.4 (4) | C4'—C5'—C6'—O6' | 61.1 (5) |
C6—C1—C2—O2 | −174.2 (3) | O5'—C5'—C6'—C1' | 59.9 (4) |
O1—C1—C2—C3 | −52.6 (4) | C4'—C5'—C6'—C1' | −56.0 (4) |
C6—C1—C2—C3 | 64.8 (4) | O7'—C8'—C9'—C14' | −172.9 (5) |
O2—C2—C3—O3 | −67.3 (4) | O2'—C8'—C9'—C14' | 7.3 (6) |
C1—C2—C3—O3 | 52.9 (4) | O7'—C8'—C9'—C10' | 7.6 (7) |
O2—C2—C3—C4 | 174.2 (3) | O2'—C8'—C9'—C10' | −172.2 (4) |
C1—C2—C3—C4 | −65.5 (4) | C14'—C9'—C10'—C11' | −0.5 (7) |
O3—C3—C4—O4 | 178.4 (3) | C8'—C9'—C10'—C11' | 179.1 (5) |
C2—C3—C4—O4 | −61.8 (4) | C9'—C10'—C11'—C12' | 0.8 (9) |
O3—C3—C4—C5 | −60.0 (4) | C10'—C11'—C12'—C13' | 0.0 (10) |
C2—C3—C4—C5 | 59.9 (4) | C11'—C12'—C13'—C14' | −1.1 (11) |
O4—C4—C5—O5 | −178.6 (3) | C10'—C9'—C14'—C13' | −0.6 (8) |
C3—C4—C5—O5 | 59.1 (4) | C8'—C9'—C14'—C13' | 179.9 (5) |
O4—C4—C5—C6 | 66.2 (4) | C12'—C13'—C14'—C9' | 1.4 (10) |
C3—C4—C5—C6 | −56.1 (4) | O8'—C15'—C16'—C17' | 12.5 (7) |
O1—C1—C6—O6 | −174.6 (3) | O6'—C15'—C16'—C17' | −167.0 (5) |
C2—C1—C6—O6 | 65.8 (4) | O3—C7—O1—C1 | −63.1 (4) |
O1—C1—C6—C5 | 60.9 (4) | O5—C7—O1—C1 | 61.1 (4) |
C2—C1—C6—C5 | −58.8 (4) | C2—C1—O1—C7 | 58.3 (4) |
O5—C5—C6—O6 | 179.2 (3) | C6—C1—O1—C7 | −60.7 (4) |
C4—C5—C6—O6 | −65.3 (4) | O7—C8—O2—C2 | 1.6 (6) |
O5—C5—C6—C1 | −59.6 (4) | C9—C8—O2—C2 | −177.3 (3) |
C4—C5—C6—C1 | 55.9 (4) | C3—C2—O2—C8 | −102.0 (4) |
O7—C8—C9—C10 | −5.7 (7) | C1—C2—O2—C8 | 139.0 (4) |
O2—C8—C9—C10 | 173.2 (4) | O5—C7—O3—C3 | −60.8 (4) |
O7—C8—C9—C14 | 177.5 (5) | O1—C7—O3—C3 | 63.6 (4) |
O2—C8—C9—C14 | −3.6 (6) | C2—C3—O3—C7 | −59.2 (4) |
C14—C9—C10—C11 | 0.0 (8) | C4—C3—O3—C7 | 60.2 (4) |
C8—C9—C10—C11 | −177.0 (5) | O3—C7—O5—C5 | 62.1 (4) |
C9—C10—C11—C12 | 0.3 (10) | O1—C7—O5—C5 | −61.6 (4) |
C10—C11—C12—C13 | −0.9 (11) | C4—C5—O5—C7 | −60.8 (4) |
C11—C12—C13—C14 | 1.3 (10) | C6—C5—O5—C7 | 60.0 (4) |
C12—C13—C14—C9 | −1.1 (9) | O8—C15—O6—C6 | 7.0 (6) |
C10—C9—C14—C13 | 0.4 (8) | C16—C15—O6—C6 | −172.6 (3) |
C8—C9—C14—C13 | 177.3 (5) | C1—C6—O6—C15 | 153.8 (3) |
O8—C15—C16—C17 | −19.0 (7) | C5—C6—O6—C15 | −85.3 (4) |
O6—C15—C16—C17 | 160.6 (4) | O3'—C7'—O1'—C1' | 63.1 (4) |
O1'—C1'—C2'—O2' | −66.3 (4) | O5'—C7'—O1'—C1' | −62.2 (4) |
C6'—C1'—C2'—O2' | 176.0 (3) | C2'—C1'—O1'—C7' | −57.7 (4) |
O1'—C1'—C2'—C3' | 53.3 (4) | C6'—C1'—O1'—C7' | 61.4 (4) |
C6'—C1'—C2'—C3' | −64.4 (4) | O7'—C8'—O2'—C2' | −0.6 (6) |
O2'—C2'—C3'—O3' | 66.8 (4) | C9'—C8'—O2'—C2' | 179.1 (3) |
C1'—C2'—C3'—O3' | −52.6 (4) | C3'—C2'—O2'—C8' | 121.2 (4) |
O2'—C2'—C3'—C4' | −176.7 (3) | C1'—C2'—O2'—C8' | −119.5 (4) |
C1'—C2'—C3'—C4' | 63.9 (4) | O5'—C7'—O3'—C3' | 61.3 (4) |
O3'—C3'—C4'—O4' | −177.1 (3) | O1'—C7'—O3'—C3' | −63.6 (4) |
C2'—C3'—C4'—O4' | 64.8 (4) | C2'—C3'—O3'—C7' | 58.1 (4) |
O3'—C3'—C4'—C5' | 60.1 (4) | C4'—C3'—O3'—C7' | −60.1 (4) |
C2'—C3'—C4'—C5' | −58.0 (4) | O3'—C7'—O5'—C5' | −62.0 (4) |
O4'—C4'—C5'—O5' | 177.3 (3) | O1'—C7'—O5'—C5' | 63.0 (4) |
C3'—C4'—C5'—O5' | −59.7 (4) | C4'—C5'—O5'—C7' | 60.3 (4) |
O4'—C4'—C5'—C6' | −67.3 (4) | C6'—C5'—O5'—C7' | −61.1 (4) |
C3'—C4'—C5'—C6' | 55.7 (4) | O8'—C15'—O6'—C6' | −3.3 (6) |
O1'—C1'—C6'—O6' | 176.1 (3) | C16'—C15'—O6'—C6' | 176.2 (3) |
C2'—C1'—C6'—O6' | −64.3 (4) | C1'—C6'—O6'—C15' | −168.4 (3) |
O1'—C1'—C6'—C5' | −61.3 (4) | C5'—C6'—O6'—C15' | 73.5 (4) |
C2'—C1'—C6'—C5' | 58.4 (4) | C3—C4—O4—H18 | −59 (3) |
O5'—C5'—C6'—O6' | 177.0 (3) | C3'—C4'—O4'—H18' | 93 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4′—H18′···O4 | 0.84 (6) | 2.09 (6) | 2.858 (5) | 151 (5) |
O4—H18···O7′i | 0.82 (5) | 1.98 (5) | 2.785 (4) | 165 (4) |
C1—H1···O5ii | 1.00 | 2.43 | 3.364 (5) | 155 |
C1′—H1′···O5′ii | 1.00 | 2.59 | 3.533 (5) | 157 |
C3—H3···O7′i | 1.00 | 2.39 | 3.161 (5) | 133 |
C3′—H3′···O7 | 1.00 | 2.58 | 3.482 (5) | 150 |
C16—H16···O4′ | 0.95 | 2.55 | 3.308 (5) | 136 |
C7—H7···O8′iii | 1.00 | 2.50 | 3.328 (5) | 140 |
C6—H6···O5′iii | 1.00 | 2.39 | 3.208 (5) | 138 |
C7′—H7′···O8iv | 1.00 | 2.43 | 3.202 (5) | 133 |
C12′—H12′···O8′v | 0.95 | 2.60 | 3.540 (6) | 171 |
C13—H13···O3′vi | 0.95 | 2.59 | 3.416 (6) | 145 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1; (iii) −x+2, y+1/2, −z+2; (iv) −x+2, y−1/2, −z+2; (v) x−1, y, z−1; (vi) −x+1, y+1/2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C17H16O8 | C17H16O8 |
Mr | 348.30 | 348.30 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 297 | 133 |
a, b, c (Å) | 8.8808 (6), 9.5502 (6), 9.7100 (6) | 13.813 (4), 19.279 (5), 5.9801 (15) |
α, β, γ (°) | 102.266 (1), 101.733 (1), 94.334 (1) | 90, 96.665 (4), 90 |
V (Å3) | 781.83 (9) | 1581.8 (7) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.12 |
Crystal size (mm) | 0.56 × 0.43 × 0.19 | 0.19 × 0.12 × 0.05 |
Data collection | ||
Diffractometer | Bruker Smart APEX CCD area-detector diffractometer | Bruker Smart APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.936, 0.978 | 0.978, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9163, 2755, 2374 | 15127, 2870, 2669 |
Rint | 0.014 | 0.075 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.152, 1.04 | 0.048, 0.114, 1.14 |
No. of reflections | 2755 | 2870 |
No. of parameters | 230 | 459 |
No. of restraints | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.14 | 0.29, −0.20 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Version 2.1; Macrae et al., 2006), SHELXTL (Version 6.14; Sheldrick, 2008) and PLATON (Spek, 2003).
C8—O2—C2—C1 | 87.3 (2) | C3—C4—O4—H18 | −172 (3) |
C15—O6—C6—C1 | 166.90 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H18···O8i | 0.95 (5) | 1.98 (5) | 2.930 (3) | 174 (4) |
Symmetry code: (i) −x+2, −y+2, −z+2. |
C1—C2—O2—C8 | 139.0 (4) | C1'—C6'—O6'—C15' | −168.4 (3) |
C1—C6—O6—C15 | 153.8 (3) | C3—C4—O4—H18 | −59 (3) |
C1'—C2'—O2'—C8' | −119.5 (4) | C3'—C4'—O4'—H18' | 93 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4'—H18'···O4 | 0.84 (6) | 2.09 (6) | 2.858 (5) | 151 (5) |
O4—H18···O7'i | 0.82 (5) | 1.98 (5) | 2.785 (4) | 165 (4) |
C1—H1···O5ii | 1.00 | 2.43 | 3.364 (5) | 155.4 |
C1'—H1'···O5'ii | 1.00 | 2.59 | 3.533 (5) | 156.8 |
C3—H3···O7'i | 1.00 | 2.39 | 3.161 (5) | 133.3 |
C3'—H3'···O7 | 1.00 | 2.58 | 3.482 (5) | 150.1 |
C16—H16···O4' | 0.95 | 2.55 | 3.308 (5) | 136.4 |
C7—H7···O8'iii | 1.00 | 2.50 | 3.328 (5) | 139.7 |
C6—H6···O5'iii | 1.00 | 2.39 | 3.208 (5) | 138.2 |
C7'—H7'···O8iv | 1.00 | 2.43 | 3.202 (5) | 133.3 |
C12'—H12'···O8'v | 0.95 | 2.60 | 3.540 (6) | 170.5 |
C13—H13···O3'vi | 0.95 | 2.59 | 3.416 (6) | 145.3 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1; (iii) −x+2, y+1/2, −z+2; (iv) −x+2, y−1/2, −z+2; (v) x−1, y, z−1; (vi) −x+1, y+1/2, −z+1. |
myo-Inositol 1,3,5-orthoester derivatives serve as key intermediates (Sureshan et al., 2003) for the preparation of biologically relevant myo-inositol phosphates, which play a significant role in cellular signal transduction pathways (Potter & Lampe, 1995). The title compound, (1), was synthesized to examine the acyl transfer reactivities in crystals of myo-inositol orthoester derivatives carrying different ester groups (Praveen et al.,1998; Sarmah et al., 2005; Murali et al., 2007). Here, we report the structures of dimorphs of (1), namely form (I) (plates) and form (II) (needles). The two sets of atom numbers for the C atoms of the inositol ring in the scheme below refer to the two enantiomers: anticlockwise numbering for the D configuration and clockwise numbering for the L configuration (Parthasarathy & Eisenberg, 1986).
Single-crystal X-ray intensity measurements for crystals of form (I) were recorded at ambient temperature (297 K), while data for crystals of form (II) were measured at 133 K to minimize the large thermal anisotropies observed for the phenyl ring atoms at room temperature. Crystals of form (I) are triclinic, space group P1 (Fig. 1), while form (II) crystallises in the noncentrosymmetric space group P21 with two independent molecules in the asymmetric unit having different chirality (Fig. 2). The two molecules in the crystal structure of form (II) show significant differences in the torsion angles associated with the three functional groups, namely C1—C2—O2—C8 (the benzoyl group), C1—C6—O6—C15 (the acryloyl group) and C3—C4—O4—H18 (the hydroxyl group). The torsion-angle difference for the benzoyl group is 20°, for the acryloyl group 15° and for the hydroxyl group 34° (Table 1). The molecular overlap of form (I) and molecule 1 of form (II) reveals major conformational changes in the hydroxyl groups and in the benzoyl groups (Fig. 3). The orientations of the hydroxyl groups are almost reversed (113°), whereas the benzoyl groups show a difference of ~52° in their torsion angles. The difference in the torsion angles of the acryloyl group (C1—C6—O6—C15) is 13°. These conformational changes in the three functional groups have a profound influence on the molecular association in the dimorphs.
The hydroxyl group forms different intermolecular O—H···O hydrogen bonds in the crystal structures of forms (I) and (II). In form (I), adjacent molecules form centrosymmetric dimers via O—H···O hydrogen bonds involving the OH group (O4—H18) and carbonyl atom O8 of the acryloyl group (Fig. 4). In form (II), the –OH groups of the two symmetry-independent molecules are involved in a hydrogen-bonding interaction (O4'—H18'···O4). The acceptor atom O4 also acts as a donor in a hydroxyl···carbonyl interaction (O4—H18···O7'), resulting in a catemeric arrangement along the c axis (Fig. 5). Additionally, five supporting C—H···O interactions (C1—H1···O5, C1'—H1'···O5', C3—H3···O7', C3'—H3'···O7 and C16—H16···O4') hold the molecules within the chain.
The hydrogen-bonded units thus formed make different three-dimensional patterns of molecular organization in the polymorphs. In form (I), O—H···O-linked centrosymmetric dimers form a planar structure. In form (II), each molecule in the asymmetric unit forms a dimer by aggregating sideways, bringing orthoformate groups closer via noncentrosymmetric C—H···O interactions (C7—H7···O8', C6—H6···O5' and C7'-H7'···O8) of comparable strength (Table 2). These dimeric units are are further joined via O4'—H18'···O4, C3'—H3'···O7 and C16—H16···O4' hydrogen-bonding interactions, thus forming a chain extending along the b axis. Neighbouring chains are weakly associated along the a axis via C12'—H12'···O8' and C13—H13···O3' contacts, thus forming a layered arrangement (Fig. 6).
A differential scanning calorimetry study of crystals of form (I) shows only a single endotherm at 426 K, while crystals of form (II) show two endothermic peaks. The first of these, at 411 K, was established by hot-stage microscopy to be the structural phase transition to form (I) via a molten phase. The second endotherm at 425 K corresponds to the melting of the crystals of form (I). While single-crystal to single-crystal thermal phase transitions have been reported earlier in myo-inositol derivatives (Steiner et al., 1993; Gonnade et al., 2005, 2008), in this instance the conversion of form (II) to form (I) occurs via melt crystallization, often observed amongst polymorphs of pharmaceutical crystals (Cosgrove et al., 2005; Wishkerman & Bernstein, 2006; Vega et al., 2006; Roy et al., 2007; Grooff et al., 2007). Thus, form (II) upon heating transforms irreversibly to form (I).
In conclusion, orientational changes in a small functional group like –OH (Ibberson et al., 2008) and the benzoyl group induce diverse hydrogen-bonding patterns in molecular associations and result in polymorphic modifications. The significantly higher yield of form (I) over form (II), and the irreversible transformation of form (II) to form (I), suggest a preference for a dimeric O—H···O hydrogen bond over a catemeric O—H···O hydrogen bond (Das & Desiraju, 2006) in nucleation and crystal growth.