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Two of the title compounds, 1,6-anhydro-2,3-
O-(
S)-benzylidene-β-
D-mannopyranose, C
13H
14O
5, (I), and 1,6-anhydro-4-
O-benzyl-β-
D-mannopyranose, C
13H
16O
5, (II), are derived from β-
D-mannopyranose, while the third, 1,6-anhydro-3,4-
O-(
S)-benzylidene-β-
D-galactopyranose, C
13H
14O
5, (III), is derived from β-
D-galactopyranose. In the crystal packing, each hydroxyl group is involved in O—H
O hydrogen bonds, where the acceptor group is the other hydroxyl group in (II), or the endocyclic O atoms of the dioxolane [in (I)], anhydro [in (II)] or pyranose [in (III)] rings. Differences in the crystal packing arise from the contrasting O—H
O hydrogen-bonding environments.
Supporting information
CCDC references: 162573; 162574; 162575
Compounds (I), (II) and (III) were prepared according to the methods of Florent
& Monneret (1980), Reeves (1949) and Subero et al. (1980),
respectively. Crystals of (I), (II) and (III) were obtained by
recrystallization from CDCl3.
In all three compounds, the Friedel pairs were merged as no significant
information could be extracted (Flack, 1983). The enantiomers considered in
this study (Fig. 1) correspond to those known from the syntheses [Florent &
Monneret (1980), Reeves (1949) and Subero et al. (1980), respectively]
and were checked by means of the configurational angles using the torsion
angles (Cano et al., 1985). All H atoms were located on the
corresponding difference Fourier map. Nevertheless, all H atoms, except
hydroxyl-H, were generated in idealized positions and were kept fixed during
refinement (C—H = ?). Attempts to refine the secondary extinction parameters
resulted in insignificant values (Zachariasen, 1967). The weighting scheme was
established in an empirical way so as to give no trends in <wΔ2F>
versus <Fo> or <sinθ/λ>: w =
K/{[(a+b)Fo]2}[(c+d)sinθ/λ]. The parameters a, b, c and d were
adjusted to flatten the initial trends (PESOS; Martínez-Ripoll &
Cano, 1975).
For all compounds, data collection: Philips PW1100 software (Hornstra & Vossers, 1973); cell refinement: LSUCRE (Appleman, 1984); data reduction: Xtal3.6 (Hall et al., 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: CRYLSQ in Xtal3.6; molecular graphics: Xtal3.6; software used to prepare material for publication: BONDLA and CIFIO in Xtal3.6.
(I) 1,6-anhydro-2,3-
O-(
S)-benzylidene-
β-
D-mannopyranose
top
Crystal data top
C13H14O5 | F(000) = 264 |
Mr = 250.25 | Dx = 1.433 Mg m−3 |
Monoclinic, P21 | Melting point = 470–471 K |
Hall symbol: P 2y1 | Cu Kα radiation, λ = 1.54178 Å |
a = 13.0265 (7) Å | Cell parameters from 71 reflections |
b = 7.0672 (3) Å | θ = 2–45° |
c = 6.3376 (2) Å | µ = 0.93 mm−1 |
β = 96.432 (4)° | T = 293 K |
V = 579.77 (4) Å3 | Rectangular prism, colourless |
Z = 2 | 0.43 × 0.33 × 0.17 mm |
Data collection top
Philips PW1100 four-circle diffractometer | 1148 reflections with I > 0 |
Radiation source: X-ray tube | Rint = 0.016 |
Graphite monochromator | θmax = 67.5°, θmin = 3.4° |
ω/2θ scans | h = −15→15 |
Absorption correction: ψ-scan (North et al., 1968) | k = −8→8 |
Tmin = 0.776, Tmax = 0.854 | l = −7→7 |
2488 measured reflections | 2 standard reflections every 90 min |
1148 independent reflections | intensity decay: none |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.032 | w = k/[(a + b Fo)2(c + d(sinθ)/λ)] |
S = 1.00 | (Δ/σ)max = 0.001 |
1148 reflections | Δρmax = 0.18 e Å−3 |
167 parameters | Δρmin = −0.13 e Å−3 |
Crystal data top
C13H14O5 | V = 579.77 (4) Å3 |
Mr = 250.25 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 13.0265 (7) Å | µ = 0.93 mm−1 |
b = 7.0672 (3) Å | T = 293 K |
c = 6.3376 (2) Å | 0.43 × 0.33 × 0.17 mm |
β = 96.432 (4)° | |
Data collection top
Philips PW1100 four-circle diffractometer | 1148 reflections with I > 0 |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.776, Tmax = 0.854 | 2 standard reflections every 90 min |
2488 measured reflections | intensity decay: none |
1148 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.18 e Å−3 |
1148 reflections | Δρmin = −0.13 e Å−3 |
167 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.28160 (11) | 0.45000 | 0.4108 (2) | 0.0333 (7) | |
O2 | 0.35528 (11) | 0.6537 (3) | 0.7763 (2) | 0.0290 (6) | |
O3 | 0.25646 (10) | 0.4150 (3) | 0.8805 (2) | 0.0293 (6) | |
O4 | 0.42676 (13) | 0.0255 (3) | 0.8411 (3) | 0.0414 (8) | |
O5 | 0.42114 (11) | 0.2565 (3) | 0.4544 (2) | 0.0347 (7) | |
C1 | 0.38799 (15) | 0.4435 (4) | 0.4896 (3) | 0.0287 (9) | |
C2 | 0.40562 (14) | 0.4809 (4) | 0.7277 (3) | 0.0257 (8) | |
C3 | 0.35514 (15) | 0.3316 (4) | 0.8569 (3) | 0.0271 (8) | |
C4 | 0.34065 (15) | 0.1360 (4) | 0.7550 (3) | 0.0301 (9) | |
C5 | 0.33566 (16) | 0.1467 (4) | 0.5134 (3) | 0.0344 (9) | |
C6 | 0.24399 (17) | 0.2594 (5) | 0.4120 (4) | 0.0398 (11) | |
C7 | 0.27979 (15) | 0.6075 (4) | 0.9176 (3) | 0.0272 (9) | |
C8 | 0.18594 (15) | 0.7290 (4) | 0.8734 (3) | 0.0283 (9) | |
C9 | 0.15024 (18) | 0.8340 (4) | 1.0342 (3) | 0.0376 (10) | |
C10 | 0.0633 (2) | 0.9475 (5) | 0.9919 (4) | 0.0491 (13) | |
C11 | 0.0124 (2) | 0.9556 (5) | 0.7894 (4) | 0.0498 (13) | |
C12 | 0.0479 (2) | 0.8523 (5) | 0.6276 (4) | 0.0466 (12) | |
C13 | 0.13419 (17) | 0.7393 (5) | 0.6687 (3) | 0.0380 (10) | |
H41 | 0.409 (3) | −0.102 (7) | 0.802 (6) | 0.044 (10)* | |
H1 | 0.43031 | 0.53923 | 0.40958 | 0.04300* | |
H2 | 0.48478 | 0.48122 | 0.77457 | 0.03100* | |
H3 | 0.40065 | 0.31617 | 1.00138 | 0.02900* | |
H4 | 0.27254 | 0.07696 | 0.79551 | 0.03200* | |
H5 | 0.33933 | 0.01083 | 0.45219 | 0.03700* | |
H6a | 0.22163 | 0.21199 | 0.25868 | 0.04200* | |
H6b | 0.18209 | 0.24890 | 0.50175 | 0.04200* | |
H7 | 0.31007 | 0.62870 | 1.07459 | 0.03000* | |
H9 | 0.18870 | 0.82888 | 1.18678 | 0.04100* | |
H10 | 0.03632 | 1.02635 | 1.11253 | 0.05300* | |
H11 | −0.05259 | 1.04032 | 0.75833 | 0.05200* | |
H12 | 0.00945 | 0.85921 | 0.47472 | 0.04900* | |
H13 | 0.16092 | 0.66127 | 0.54725 | 0.04100* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0325 (7) | 0.0404 (8) | 0.0255 (6) | 0.0027 (6) | −0.0035 (5) | 0.0015 (6) |
O2 | 0.0302 (7) | 0.0245 (7) | 0.0329 (7) | −0.0022 (6) | 0.0068 (5) | −0.0001 (6) |
O3 | 0.0324 (7) | 0.0263 (7) | 0.0307 (6) | −0.0012 (6) | 0.0104 (5) | 0.0027 (6) |
O4 | 0.0419 (8) | 0.0281 (8) | 0.0506 (9) | 0.0050 (7) | −0.0107 (7) | 0.0021 (7) |
O5 | 0.0326 (7) | 0.0377 (8) | 0.0349 (7) | 0.0034 (7) | 0.0093 (5) | −0.0048 (6) |
C1 | 0.0289 (9) | 0.0318 (10) | 0.0258 (8) | 0.0001 (9) | 0.0052 (7) | 0.0013 (8) |
C2 | 0.0226 (8) | 0.0243 (9) | 0.0295 (9) | −0.0008 (7) | 0.0006 (6) | −0.0008 (8) |
C3 | 0.0294 (9) | 0.0272 (10) | 0.0243 (8) | −0.0005 (8) | 0.0014 (7) | 0.0021 (8) |
C4 | 0.0281 (9) | 0.0264 (10) | 0.0352 (10) | −0.0009 (8) | 0.0010 (8) | 0.0019 (9) |
C5 | 0.0325 (9) | 0.0344 (11) | 0.0353 (10) | −0.0021 (9) | −0.0008 (8) | −0.0073 (10) |
C6 | 0.0371 (11) | 0.0441 (13) | 0.0354 (11) | −0.0045 (10) | −0.0086 (8) | −0.0040 (10) |
C7 | 0.0353 (10) | 0.0263 (10) | 0.0207 (8) | −0.0020 (8) | 0.0055 (7) | −0.0007 (7) |
C8 | 0.0309 (9) | 0.0279 (10) | 0.0271 (9) | −0.0018 (8) | 0.0073 (7) | 0.0009 (8) |
C9 | 0.0447 (11) | 0.0383 (12) | 0.0313 (9) | −0.0016 (10) | 0.0103 (8) | −0.0048 (9) |
C10 | 0.0516 (13) | 0.0473 (14) | 0.0512 (13) | 0.0104 (12) | 0.0182 (10) | −0.0099 (12) |
C11 | 0.0434 (12) | 0.0480 (14) | 0.0584 (14) | 0.0132 (12) | 0.0070 (10) | −0.0007 (13) |
C12 | 0.0420 (11) | 0.0564 (16) | 0.0406 (11) | 0.0105 (12) | 0.0015 (9) | 0.0006 (12) |
C13 | 0.0376 (10) | 0.0465 (13) | 0.0300 (9) | 0.0056 (11) | 0.0037 (8) | −0.0029 (10) |
Geometric parameters (Å, º) top
O1—C1 | 1.420 (2) | C5—H5 | 1.039 |
O1—C6 | 1.433 (3) | C5—C6 | 1.517 (3) |
O2—C2 | 1.436 (3) | C6—H6a | 1.038 |
O2—C7 | 1.440 (3) | C6—H6b | 1.040 |
O3—C7 | 1.408 (3) | C7—H7 | 1.039 |
O3—C3 | 1.437 (3) | C7—C8 | 1.495 (3) |
O4—H41 | 0.96 (5) | C8—C9 | 1.383 (3) |
O4—C4 | 1.424 (3) | C8—C13 | 1.395 (3) |
O5—C1 | 1.416 (4) | C9—H9 | 1.039 |
O5—C5 | 1.441 (3) | C9—C10 | 1.389 (4) |
C1—H1 | 1.040 | C10—H10 | 1.039 |
C1—C2 | 1.524 (3) | C10—C11 | 1.379 (4) |
C2—H2 | 1.041 | C11—H11 | 1.038 |
C2—C3 | 1.528 (3) | C11—C12 | 1.379 (4) |
C3—H3 | 1.039 | C12—H12 | 1.041 |
C3—C4 | 1.529 (4) | C12—C13 | 1.380 (4) |
C4—H4 | 1.038 | C13—H13 | 1.038 |
C4—C5 | 1.527 (3) | | |
| | | |
H6a···H6b | 1.698 | C9···H4i | 2.883 |
O2···H41i | 1.86 (5) | O5···H3iii | 2.884 |
C4···H41 | 1.91 (5) | O3···H13 | 2.907 |
O3···H7 | 2.022 | H41···H2v | 2.94 (4) |
O5···H1 | 2.023 | O4···O5 | 2.939 (3) |
O4···H4 | 2.030 | H6b···H13 | 2.945 |
O5···H5 | 2.037 | O2···C13 | 2.947 (3) |
O1···H1 | 2.038 | H41···H7xi | 2.96 (5) |
O1···H6b | 2.049 | C1···H6a | 2.967 |
O1···H6a | 2.050 | C2···H41i | 2.98 (5) |
O2···H7 | 2.050 | O1···C3 | 3.001 (2) |
O3···H3 | 2.069 | C1···H7iii | 3.011 |
C8···H7 | 2.069 | H1···H3iii | 3.017 |
O2···H2 | 2.082 | O3···C13 | 3.019 (3) |
C2···H3 | 2.096 | C1···H6b | 3.023 |
C4···H3 | 2.097 | H6b···H11vii | 3.030 |
C11···H10 | 2.097 | H1···H5x | 3.037 |
C10···H11 | 2.098 | O1···O3 | 3.041 (2) |
C12···H11 | 2.099 | C13···H4i | 3.043 |
C1···H2 | 2.100 | C7···H2 | 3.048 |
C12···H13 | 2.102 | O5···H41x | 3.06 (4) |
C13···H12 | 2.103 | C3···H6b | 3.058 |
C11···H12 | 2.104 | H2···H3xii | 3.061 |
C8···H9 | 2.104 | C3···C6 | 3.065 (3) |
C3···H2 | 2.107 | H12···H13ii | 3.071 |
C10···H9 | 2.108 | C4···H2 | 3.073 |
C5···H4 | 2.108 | H3···H6avi | 3.081 |
C3···H4 | 2.111 | C12···H10viii | 3.103 |
C8···H13 | 2.111 | C12···H6bii | 3.103 |
C4···H5 | 2.111 | H41···H2xi | 3.12 (5) |
C9···H10 | 2.112 | C9···H6axiii | 3.119 |
C2···H1 | 2.117 | O1···H11vii | 3.121 |
C5···H6a | 2.119 | C5···H1iv | 3.127 |
C5···H6b | 2.120 | C1···H5 | 3.127 |
C6···H5 | 2.150 | H9···H12vi | 3.128 |
H41···H4 | 2.18 (4) | C13···H11vii | 3.129 |
C1···C5 | 2.216 (4) | C6···H1 | 3.132 |
H2···H3 | 2.232 | C13···H10viii | 3.132 |
C3···C7 | 2.236 (4) | C10···H6axiii | 3.134 |
O2···O3 | 2.265 (3) | C5···H1 | 3.135 |
O1···O5 | 2.267 (2) | O1···C4 | 3.146 (3) |
C1···C6 | 2.291 (3) | C2···C6 | 3.153 (3) |
H7···H9 | 2.293 | O3···C6 | 3.153 (3) |
O5···C6 | 2.293 (3) | O3···H2 | 3.157 |
O3···C2 | 2.313 (2) | O5···H6b | 3.162 |
C2···C7 | 2.319 (3) | O3···C1 | 3.172 (2) |
O1···C5 | 2.326 (3) | C3···H41 | 3.17 (5) |
O2···C3 | 2.333 (4) | C11···H10viii | 3.175 |
O4···H3 | 2.333 | O2···H4i | 3.186 |
H5···H6a | 2.336 | C6···H13 | 3.190 |
O4···C3 | 2.363 (4) | H6a···H11vii | 3.192 |
O5···C2 | 2.374 (3) | O1···H5 | 3.197 |
H1···H2 | 2.378 | O1···H9iii | 3.204 |
C11···C13 | 2.389 (4) | C8···H41i | 3.22 (4) |
C10···C12 | 2.391 (4) | H41···H3 | 3.22 (5) |
C9···C11 | 2.397 (3) | H4···H6avi | 3.225 |
C9···C13 | 2.397 (3) | C8···H10viii | 3.241 |
O1···H13 | 2.400 | C1···H3iii | 3.245 |
O3···C8 | 2.401 (3) | O2···H5i | 3.246 |
C8···C10 | 2.402 (4) | C10···H4i | 3.252 |
C8···C12 | 2.407 (3) | O3···C5 | 3.257 (3) |
H10···H11 | 2.410 | C11···H13ii | 3.268 |
O2···C8 | 2.415 (3) | C6···H11vii | 3.274 |
H4···H6b | 2.416 | C13···H9iii | 3.274 |
H11···H12 | 2.418 | C10···H12vi | 3.275 |
H12···H13 | 2.420 | C10···H10viii | 3.284 |
H11···H13ii | 2.421 | O5···C2iv | 3.287 (3) |
O2···C1 | 2.421 (3) | H2···H7 | 3.294 |
H9···H10 | 2.429 | C10···H11viii | 3.294 |
O4···C5 | 2.429 (3) | C12···H11vii | 3.299 |
O5···C4 | 2.430 (3) | O4···C2 | 3.302 (4) |
O3···C4 | 2.433 (3) | C11···H6bii | 3.303 |
H41···H5 | 2.44 (4) | C11···H12ii | 3.303 |
O1···C2 | 2.442 (2) | O1···H3iii | 3.307 |
O3···H4 | 2.463 | O5···H4 | 3.312 |
H4···H5 | 2.477 | C9···H10viii | 3.315 |
C7···C9 | 2.497 (4) | O1···C7iii | 3.315 (2) |
C7···C13 | 2.507 (3) | O4···C2v | 3.317 (2) |
C9···H7 | 2.527 | O1···H2 | 3.317 |
C3···C5 | 2.527 (3) | O5···C1iv | 3.317 (3) |
C1···C3 | 2.540 (3) | H4···H9xi | 3.320 |
O1···H7iii | 2.540 | C13···H11 | 3.328 |
C4···C6 | 2.542 (3) | C12···H10 | 3.329 |
O5···H1iv | 2.544 | C11···H13 | 3.330 |
H3···H7 | 2.571 | C10···H12 | 3.333 |
H1···H7iii | 2.572 | H6b···H10ix | 3.334 |
O4···H1iv | 2.581 | C11···H9 | 3.335 |
C2···C4 | 2.593 (4) | C5···H2iv | 3.336 |
O4···H2v | 2.594 | C5···H3 | 3.336 |
C4···H6b | 2.596 | C9···H11 | 3.336 |
O4···H5 | 2.599 | C9···H13 | 3.336 |
C7···H3 | 2.610 | C8···H11viii | 3.340 |
C3···H7 | 2.615 | C4···H1iv | 3.340 |
H3···H4 | 2.619 | C13···H7 | 3.340 |
H9···H13vi | 2.634 | C13···H9 | 3.341 |
H6b···H12vii | 2.634 | C13···H12vii | 3.341 |
O5···H2 | 2.636 | C8···H10 | 3.343 |
H10···H12vi | 2.639 | O4···H2 | 3.345 |
C5···H41 | 2.64 (4) | C8···H12 | 3.349 |
C7···H9 | 2.687 | C3···H6avi | 3.349 |
C7···H13 | 2.690 | O1···O3iii | 3.349 (2) |
H5···H6b | 2.696 | C1···H3 | 3.352 |
H41···H3v | 2.71 (4) | O1···C13 | 3.353 (3) |
C6···H4 | 2.740 | C5···H2 | 3.374 |
O2···H1 | 2.742 | O5···H41 | 3.38 (5) |
O3···H6b | 2.749 | C1···H13 | 3.390 |
H9···H11viii | 2.750 | C4···H6a | 3.390 |
H5···H9ix | 2.756 | C2···H4 | 3.392 |
C10···C13 | 2.763 (4) | C12···H4i | 3.394 |
C9···C12 | 2.768 (3) | C1···C7 | 3.398 (3) |
O5···H6a | 2.769 | O1···C7 | 3.402 (2) |
H6a···H9ix | 2.771 | C6···H9ix | 3.403 |
C8···H4i | 2.772 | C7···H4i | 3.406 |
C8···C11 | 2.773 (4) | C1···H41x | 3.41 (4) |
O2···H13 | 2.774 | C3···H5 | 3.412 |
O4···H3v | 2.782 | H6a···H7iii | 3.415 |
H11···H12ii | 2.786 | O2···C4i | 3.415 (4) |
O5···H2iv | 2.791 | O4···C1iv | 3.418 (3) |
H41···H1iv | 2.80 (4) | C3···H1 | 3.431 |
C7···H41i | 2.80 (5) | C12···H6bi | 3.444 |
O2···O4i | 2.803 (3) | O4···O5iv | 3.446 (3) |
O1···O2 | 2.804 (2) | O3···C9 | 3.455 (4) |
O2···H3 | 2.808 | C9···H13vi | 3.462 |
H6a···H10ix | 2.811 | C12···H10iii | 3.476 |
C2···C5 | 2.824 (4) | O2···O5x | 3.479 (2) |
O5···C3 | 2.832 (3) | C5···H9ix | 3.480 |
C9···H11viii | 2.834 | C11···H6aii | 3.485 |
C2···H7 | 2.844 | O4···H7v | 3.487 |
H2···H5x | 2.845 | H5···H13xi | 3.490 |
C1···C4 | 2.858 (4) | C11···H4i | 3.491 |
O3···H6avi | 2.873 | | |
| | | |
C1—O1—C6 | 106.78 (16) | O5—C5—C4 | 109.87 (17) |
C2—O2—C7 | 107.5 (2) | C6—C5—C4 | 113.2 (2) |
C7—O3—C3 | 103.57 (17) | H6a—C6—H6b | 109.6 |
H41—O4—C4 | 105 (2) | H6a—C6—O1 | 111.0 |
C1—O5—C5 | 101.75 (17) | H6a—C6—C5 | 110.6 |
H1—C1—O5 | 110.0 | H6b—C6—O1 | 110.9 |
H1—C1—O1 | 110.9 | H6b—C6—C5 | 110.6 |
H1—C1—C2 | 110.0 | O1—C6—C5 | 104.02 (18) |
O5—C1—O1 | 106.10 (17) | H7—C7—O3 | 110.5 |
O5—C1—C2 | 107.65 (18) | H7—C7—O2 | 110.5 |
O1—C1—C2 | 112.07 (16) | H7—C7—C8 | 108.2 |
H2—C2—O2 | 113.5 | O3—C7—O2 | 105.35 (17) |
H2—C2—C1 | 108.5 | O3—C7—C8 | 111.54 (17) |
H2—C2—C3 | 108.7 | O2—C7—C8 | 110.74 (18) |
O2—C2—C1 | 109.74 (17) | C9—C8—C13 | 119.3 (2) |
O2—C2—C3 | 103.8 (2) | C9—C8—C7 | 120.37 (17) |
C1—C2—C3 | 112.63 (19) | C13—C8—C7 | 120.3 (2) |
H3—C3—O3 | 112.3 | H9—C9—C8 | 120.0 |
H3—C3—C2 | 107.9 | H9—C9—C10 | 119.8 |
H3—C3—C4 | 107.9 | C8—C9—C10 | 120.1 (2) |
O3—C3—C2 | 102.5 (2) | H10—C10—C11 | 119.7 |
O3—C3—C4 | 110.2 (2) | H10—C10—C9 | 120.3 |
C2—C3—C4 | 115.98 (17) | C11—C10—C9 | 120.0 (3) |
H4—C4—O4 | 110.1 | H11—C11—C10 | 119.8 |
H4—C4—C5 | 109.0 | H11—C11—C12 | 119.9 |
H4—C4—C3 | 109.1 | C10—C11—C12 | 120.3 (3) |
O4—C4—C5 | 110.8 (2) | H12—C12—C11 | 120.1 |
O4—C4—C3 | 106.2 (2) | H12—C12—C13 | 120.0 |
C5—C4—C3 | 111.6 (2) | C11—C12—C13 | 120.0 (2) |
H5—C5—O5 | 109.4 | H13—C13—C12 | 120.1 |
H5—C5—C6 | 113.2 | H13—C13—C8 | 119.6 |
H5—C5—C4 | 109.3 | C12—C13—C8 | 120.3 (2) |
O5—C5—C6 | 101.6 (2) | | |
| | | |
C6—O1—C1—O5 | 23.2 (2) | H3—C3—C4—O4 | −24.9 |
C6—O1—C1—C2 | −94.1 (2) | H3—C3—C4—C5 | −145.8 |
C6—O1—C1—H1 | 142.6 | H3—C3—C4—H4 | 93.7 |
C1—O1—C6—C5 | 4.1 (2) | O4—C4—C5—O5 | −68.4 (3) |
C1—O1—C6—H6a | −114.9 | O4—C4—C5—C6 | 178.8 (2) |
C1—O1—C6—H6b | 123.1 | O4—C4—C5—H5 | 51.6 |
C7—O2—C2—C1 | 119.18 (17) | C3—C4—C5—O5 | 49.8 (2) |
C7—O2—C2—C3 | −1.4 (2) | C3—C4—C5—C6 | −63.1 (3) |
C7—O2—C2—H2 | −119.2 | C3—C4—C5—H5 | 169.8 |
C2—O2—C7—O3 | −23.7 (2) | H4—C4—C5—O5 | 170.3 |
C2—O2—C7—C8 | −144.45 (17) | H4—C4—C5—C6 | 57.5 |
C2—O2—C7—H7 | 95.7 | H4—C4—C5—H5 | −69.7 |
C7—O3—C3—C2 | −40.1 (2) | O5—C5—C6—O1 | −29.0 (2) |
C7—O3—C3—C4 | −164.14 (16) | O5—C5—C6—H6a | 90.2 |
C7—O3—C3—H3 | 75.4 | O5—C5—C6—H6b | −148.1 |
C3—O3—C7—O2 | 40.3 (2) | C4—C5—C6—O1 | 88.7 (2) |
C3—O3—C7—C8 | 160.49 (15) | C4—C5—C6—H6a | −152.0 |
C3—O3—C7—H7 | −79.1 | C4—C5—C6—H6b | −30.4 |
H41—O4—C4—C3 | 167 (3) | H5—C5—C6—O1 | −146.2 |
H41—O4—C4—C5 | −72 (3) | H5—C5—C6—H6a | −26.9 |
H41—O4—C4—H4 | 49 (3) | H5—C5—C6—H6b | 94.7 ( |
C5—O5—C1—O1 | −41.93 (18) | O2—C7—C8—C9 | −125.4 (2) |
C5—O5—C1—C2 | 78.22 (18) | O2—C7—C8—C13 | 53.9 (3) |
C5—O5—C1—H1 | −162.0 | O3—C7—C8—C9 | 117.6 (2) |
C1—O5—C5—C4 | −77.4 (2) | O3—C7—C8—C13 | −63.1 (3) |
C1—O5—C5—C6 | 42.8 (2) | H7—C7—C8—C9 | −4.2 |
C1—O5—C5—H5 | 162.7 | H7—C7—C8—C13 | 175.1 |
O1—C1—C2—O2 | −52.6 (2) | C7—C8—C9—C10 | 179.7 (3) |
O1—C1—C2—C3 | 62.5 (3) | C7—C8—C9—H9 | 0.1 |
O1—C1—C2—H2 | −177.1 | C13—C8—C9—C10 | 0.4 (4) |
O5—C1—C2—O2 | −168.89 (16) | C13—C8—C9—H9 | −179.2 |
O5—C1—C2—C3 | −53.8 (2) | C7—C8—C13—C12 | −179.7 (3) |
O5—C1—C2—H2 | 66.6 | C7—C8—C13—H13 | 0.4 |
H1—C1—C2—O2 | 71.3 | C9—C8—C13—C12 | −0.4 (4) |
H1—C1—C2—C3 | −173.7 | C9—C8—C13—H13 | 179.7 |
H1—C1—C2—H2 | −53.3 | C8—C9—C10—C11 | −0.0 (4) |
O2—C2—C3—O3 | 25.2 (2) | C8—C9—C10—H10 | 179.9 |
O2—C2—C3—C4 | 145.31 (16) | H9—C9—C10—C11 | 179.6 (3) |
O2—C2—C3—H3 | −93.5 | H9—C9—C10—H10 | −0.4 |
C1—C2—C3—O3 | −93.4 (2) | C9—C10—C11—C12 | −0.4 (5) |
C1—C2—C3—C4 | 26.7 (2) | C9—C10—C11—H11 | 179.9 |
C1—C2—C3—H3 | 147.9 | H10—C10—C11—C12 | 179.6 |
H2—C2—C3—O3 | 146.3 | H10—C10—C11—H11 | −0.0 |
H2—C2—C3—C4 | −93.6 | C10—C11—C12—C13 | 0.4 (5) |
H2—C2—C3—H3 | 27.6 | C10—C11—C12—H12 | −179.7 |
O3—C3—C4—O4 | −147.96 (17) | H11—C11—C12—C13 | −179.9 |
O3—C3—C4—C5 | 91.2 (2) | H11—C11—C12—H12 | −0.1 |
O3—C3—C4—H4 | −29.3 | C11—C12—C13—C8 | −0.0 (5) |
C2—C3—C4—O4 | 96.2 (2) | C11—C12—C13—H13 | 179.9 |
C2—C3—C4—C5 | −24.6 (2) | H12—C12—C13—C8 | −179.9 |
C2—C3—C4—H4 | −145.2 | H12—C12—C13—H13 | 0.1 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z+1; (iii) x, y, z−1; (iv) −x+1, y−1/2, −z+1; (v) −x+1, y−1/2, −z+2; (vi) x, y, z+1; (vii) −x, y−1/2, −z+1; (viii) −x, y−1/2, −z+2; (ix) x, y−1, z−1; (x) −x+1, y+1/2, −z+1; (xi) x, y−1, z; (xii) −x+1, y+1/2, −z+2; (xiii) x, y+1, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H41···O2xi | 0.96 (5) | 1.86 (5) | 2.803 (3) | 167 (4) |
C2—H2···O4xii | 1.04 | 2.59 | 3.317 (2) | 126 |
C7—H7···O1vi | 1.04 | 2.54 | 3.316 (2) | 131 |
C13—H13···O1 | 1.04 | 2.40 | 3.353 (3) | 152 |
C1—H1···O5x | 1.04 | 2.54 | 3.317 (3) | 131 |
C4—H4···Cgxi | 1.04 | 2.83 | 3.843 (3) | 165 |
C10—H10···Cgxiv | 1.04 | 2.90 | 3.752 (4) | 140 |
Symmetry codes: (vi) x, y, z+1; (x) −x+1, y+1/2, −z+1; (xi) x, y−1, z; (xii) −x+1, y+1/2, −z+2; (xiv) −x, y+1/2, −z+2. |
(II) 1,6-anhydro-4-
O-benzyl-
β-
D-mannopyranose
top
Crystal data top
C13H16O5 | F(000) = 536 |
Mr = 252.27 | Dx = 1.369 Mg m−3 |
Monoclinic, C2 | Melting point = 395–396 K |
Hall symbol: C 2y | Cu Kα radiation, λ = 1.54178 Å |
a = 11.9752 (5) Å | Cell parameters from 48 reflections |
b = 5.7487 (2) Å | θ = 2–45° |
c = 18.0759 (14) Å | µ = 0.88 mm−1 |
β = 100.295 (6)° | T = 293 K |
V = 1224.34 (12) Å3 | Rectangular plate, colourless |
Z = 4 | 0.43 × 0.33 × 0.05 mm |
Data collection top
Philips PW1100 four-circle diffractometer | 1208 reflections with I > 0 |
Radiation source: X-ray tube | Rint = 0.033 |
Graphite monochromator | θmax = 67.4°, θmin = 2.5° |
ω/2θ scans | h = −14→14 |
Absorption correction: ψ-scan (North et al., 1968) | k = −6→6 |
Tmin = 0.794, Tmax = 0.957 | l = −21→21 |
2496 measured reflections | 2 standard reflections every 90 min |
1208 independent reflections | intensity decay: none |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.040 | w = k/[(a + b Fo)2(c + d(sinθ)/λ)] |
S = 1.08 | (Δ/σ)max < 0.001 |
1208 reflections | Δρmax = 0.13 e Å−3 |
171 parameters | Δρmin = −0.13 e Å−3 |
Crystal data top
C13H16O5 | V = 1224.34 (12) Å3 |
Mr = 252.27 | Z = 4 |
Monoclinic, C2 | Cu Kα radiation |
a = 11.9752 (5) Å | µ = 0.88 mm−1 |
b = 5.7487 (2) Å | T = 293 K |
c = 18.0759 (14) Å | 0.43 × 0.33 × 0.05 mm |
β = 100.295 (6)° | |
Data collection top
Philips PW1100 four-circle diffractometer | 1208 reflections with I > 0 |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.033 |
Tmin = 0.794, Tmax = 0.957 | 2 standard reflections every 90 min |
2496 measured reflections | intensity decay: none |
1208 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.13 e Å−3 |
1208 reflections | Δρmin = −0.13 e Å−3 |
171 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.05617 (13) | 0.45000 | 0.40193 (9) | 0.05042 | |
O2 | 0.17482 (14) | 0.5584 (5) | 0.48498 (9) | 0.05069 | |
O3 | 0.14253 (16) | 0.1487 (5) | 0.40399 (11) | 0.05179 | |
O4 | 0.15252 (13) | 0.4803 (5) | 0.23568 (9) | 0.04512 | |
O5 | −0.01289 (14) | 0.6683 (5) | 0.30754 (9) | 0.04462 | |
C1 | 0.0149 (2) | 0.6359 (6) | 0.38552 (13) | 0.04332 | |
C2 | 0.14017 (19) | 0.5739 (6) | 0.40580 (12) | 0.03751 | |
C3 | 0.16910 (17) | 0.3513 (6) | 0.36660 (12) | 0.03725 | |
C4 | 0.10141 (18) | 0.3392 (6) | 0.28520 (11) | 0.03846 | |
C5 | −0.01856 (18) | 0.4330 (6) | 0.28036 (12) | 0.04094 | |
C6 | −0.08476 (19) | 0.3149 (7) | 0.33444 (13) | 0.04869 | |
C7 | 0.2379 (2) | 0.3640 (7) | 0.20513 (15) | 0.05073 | |
C8 | 0.28658 (18) | 0.5257 (6) | 0.15410 (12) | 0.04184 | |
C9 | 0.3955 (2) | 0.4879 (7) | 0.13973 (14) | 0.05165 | |
C10 | 0.4411 (2) | 0.6339 (8) | 0.09248 (15) | 0.05999 | |
C11 | 0.3808 (3) | 0.8221 (7) | 0.05976 (15) | 0.06002 | |
C12 | 0.2728 (3) | 0.8619 (8) | 0.07337 (16) | 0.06217 | |
C13 | 0.2266 (2) | 0.7155 (7) | 0.12012 (15) | 0.05387 | |
H21 | 0.124 (3) | 0.458 (7) | 0.5031 (17) | 0.05200* | |
H31 | 0.191 (3) | 0.124 (8) | 0.449 (2) | 0.04327* | |
H1 | −0.00104 | 0.78835 | 0.41279 | 0.04500* | |
H2 | 0.18807 | 0.71074 | 0.39033 | 0.03900* | |
H3 | 0.25553 | 0.35077 | 0.36482 | 0.03900* | |
H4 | 0.09727 | 0.16747 | 0.26747 | 0.04000* | |
H5 | −0.06030 | 0.42915 | 0.22483 | 0.04200* | |
H6a | −0.05989 | 0.14350 | 0.34368 | 0.05000* | |
H6b | −0.17162 | 0.32262 | 0.31379 | 0.05000* | |
H7a | 0.20315 | 0.22027 | 0.17485 | 0.05400* | |
H7b | 0.30189 | 0.31111 | 0.24859 | 0.05400* | |
H9 | 0.44244 | 0.34797 | 0.16471 | 0.05400* | |
H10 | 0.52244 | 0.60283 | 0.08167 | 0.06300* | |
H11 | 0.41584 | 0.93377 | 0.02487 | 0.06400* | |
H12 | 0.22663 | 1.00363 | 0.04864 | 0.06500* | |
H13 | 0.14514 | 0.74802 | 0.13021 | 0.05700* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.04494 | 0.06662 | 0.04933 | −0.00574 | 0.01609 | 0.00191 |
O2 | 0.05315 | 0.06256 | 0.04005 | −0.01965 | 0.00321 | −0.00167 |
O3 | 0.05727 | 0.03655 | 0.05970 | −0.00586 | −0.01076 | 0.01239 |
O4 | 0.04914 | 0.04473 | 0.05110 | 0.00684 | 0.01962 | 0.00275 |
O5 | 0.04728 | 0.04319 | 0.04854 | 0.00937 | 0.00615 | 0.00690 |
C1 | 0.04707 | 0.04286 | 0.04552 | 0.00344 | 0.01190 | −0.00154 |
C2 | 0.04130 | 0.03647 | 0.03946 | −0.00667 | 0.00649 | 0.00096 |
C3 | 0.03429 | 0.03569 | 0.04618 | 0.00005 | 0.00288 | 0.00207 |
C4 | 0.04225 | 0.03910 | 0.04032 | −0.00028 | 0.00698 | −0.00161 |
C5 | 0.03887 | 0.04738 | 0.03946 | −0.00058 | 0.00282 | 0.00103 |
C6 | 0.03810 | 0.06119 | 0.05137 | −0.00748 | 0.00683 | 0.00270 |
C7 | 0.04770 | 0.05025 | 0.06327 | 0.00938 | 0.02338 | 0.00118 |
C8 | 0.04262 | 0.04726 | 0.04196 | 0.00279 | 0.00850 | −0.00635 |
C9 | 0.04469 | 0.06305 | 0.05344 | 0.00781 | 0.01202 | 0.00117 |
C10 | 0.05022 | 0.08175 | 0.05690 | 0.00388 | 0.01980 | 0.00495 |
C11 | 0.07015 | 0.06875 | 0.05214 | −0.00127 | 0.02242 | 0.00404 |
C12 | 0.07449 | 0.06169 | 0.05994 | 0.01374 | 0.02003 | 0.00901 |
C13 | 0.05217 | 0.05875 | 0.05901 | 0.01383 | 0.01848 | 0.00355 |
O1 | 0.0440 (8) | 0.0626 (11) | 0.0473 (8) | −0.0053 (9) | 0.0153 (6) | 0.0014 (9) |
O2 | 0.0524 (9) | 0.0603 (11) | 0.0371 (8) | −0.0193 (9) | 0.0019 (6) | −0.0019 (8) |
O3 | 0.0552 (10) | 0.0336 (9) | 0.0583 (10) | −0.0057 (8) | −0.0122 (8) | 0.0126 (8) |
O4 | 0.0486 (8) | 0.0414 (9) | 0.0491 (8) | 0.0066 (8) | 0.0189 (7) | 0.0027 (8) |
O5 | 0.0459 (8) | 0.0410 (9) | 0.0457 (9) | 0.0098 (8) | 0.0047 (6) | 0.0068 (8) |
C1 | 0.0466 (11) | 0.0405 (12) | 0.0441 (11) | 0.0037 (11) | 0.0116 (9) | −0.0017 (11) |
C2 | 0.0403 (11) | 0.0349 (12) | 0.0368 (11) | −0.0076 (10) | 0.0053 (9) | 0.0008 (9) |
C3 | 0.0329 (9) | 0.0331 (10) | 0.0439 (11) | −0.0007 (9) | 0.0020 (8) | 0.0021 (10) |
C4 | 0.0399 (10) | 0.0366 (11) | 0.0385 (10) | −0.0009 (10) | 0.0061 (8) | −0.0014 (10) |
C5 | 0.0382 (10) | 0.0448 (13) | 0.0380 (11) | −0.0012 (10) | 0.0018 (8) | 0.0012 (10) |
C6 | 0.0374 (10) | 0.0591 (17) | 0.0490 (12) | −0.0070 (12) | 0.0061 (9) | 0.0021 (12) |
C7 | 0.0477 (12) | 0.0494 (15) | 0.0599 (13) | 0.0100 (12) | 0.0223 (10) | 0.0013 (13) |
C8 | 0.0416 (11) | 0.0434 (13) | 0.0405 (10) | 0.0033 (11) | 0.0072 (9) | −0.0061 (10) |
C9 | 0.0433 (11) | 0.0614 (17) | 0.0513 (12) | 0.0076 (13) | 0.0113 (9) | 0.0014 (13) |
C10 | 0.0501 (13) | 0.079 (2) | 0.0542 (14) | 0.0043 (15) | 0.0183 (11) | 0.0043 (16) |
C11 | 0.0695 (16) | 0.064 (2) | 0.0502 (13) | −0.0022 (16) | 0.0216 (12) | 0.0041 (14) |
C12 | 0.0731 (17) | 0.0591 (17) | 0.0572 (14) | 0.0133 (16) | 0.0192 (13) | 0.0094 (15) |
C13 | 0.0514 (13) | 0.0562 (17) | 0.0570 (14) | 0.0143 (13) | 0.0177 (11) | 0.0036 (13) |
Geometric parameters (Å, º) top
O1—C1 | 1.430 (3) | C5—H5 | 1.039 |
O1—C6 | 1.435 (3) | C5—C6 | 1.524 (4) |
O2—H21 | 0.94 (4) | C6—H6a | 1.034 |
O2—C2 | 1.420 (3) | C6—H6b | 1.041 |
O3—H31 | 0.93 (3) | C7—H7a | 1.036 |
O3—C3 | 1.412 (4) | C7—H7b | 1.040 |
O4—C7 | 1.414 (4) | C7—C8 | 1.499 (4) |
O4—C4 | 1.425 (3) | C8—C13 | 1.388 (4) |
O5—C1 | 1.402 (3) | C8—C9 | 1.391 (3) |
O5—C5 | 1.437 (4) | C9—H9 | 1.038 |
C1—H1 | 1.040 | C9—C10 | 1.378 (5) |
C1—C2 | 1.522 (3) | C10—H10 | 1.042 |
C2—H2 | 1.041 | C10—C11 | 1.374 (5) |
C2—C3 | 1.532 (4) | C11—H11 | 1.039 |
C3—H3 | 1.041 | C11—C12 | 1.379 (5) |
C3—C4 | 1.549 (3) | C12—H12 | 1.040 |
C4—H4 | 1.037 | C12—C13 | 1.376 (5) |
C4—C5 | 1.522 (3) | C13—H13 | 1.041 |
| | | |
H6a···H6b | 1.698 | O4···C13 | 2.764 (4) |
H7a···H7b | 1.698 | O5···H6b | 2.766 |
O2···H31i | 1.85 (3) | O4···O5 | 2.775 (3) |
C2···H21 | 1.92 (3) | C8···C11 | 2.788 (4) |
O2···H2 | 1.953 | O2···H3 | 2.798 |
C3···H31 | 1.97 (4) | C2···C5 | 2.805 (3) |
O5···H1 | 2.005 | C6···H4 | 2.807 |
O3···H3 | 2.006 | C1···C4 | 2.818 (4) |
O4···H7a | 2.012 | C11···H12x | 2.819 |
O4···H7b | 2.013 | H5···H7biv | 2.825 |
O1···H21ii | 2.03 (3) | C7···H3 | 2.857 |
O4···H4 | 2.034 | H3···H6avi | 2.858 |
O5···H5 | 2.036 | H7a···H13ix | 2.882 |
O1···H6a | 2.049 | H6a···H7bviii | 2.886 |
O1···H6b | 2.049 | O5···H6av | 2.887 |
O1···H1 | 2.052 | C3···H7b | 2.889 |
C8···H7a | 2.087 | O5···C3 | 2.895 (3) |
C8···H7b | 2.088 | H10···H11iii | 2.895 |
C12···H13 | 2.093 | H10···H10iii | 2.905 |
C11···H10 | 2.093 | H1···H3iv | 2.911 |
C10···H9 | 2.097 | C4···H2 | 2.923 |
C11···H12 | 2.099 | C9···H7a | 2.932 |
C12···H11 | 2.100 | C10···H5vi | 2.936 |
C13···H12 | 2.101 | O1···C3 | 2.936 (3) |
C9···H10 | 2.103 | O1···O3 | 2.938 (3) |
C5···H4 | 2.103 | O3···C6 | 2.946 (3) |
C10···H11 | 2.104 | C3···H6a | 2.952 |
C8···H13 | 2.104 | H21···H21ii | 2.95 (4) |
C1···H2 | 2.105 | C9···H5vi | 2.965 |
C8···H9 | 2.106 | O1···O2 | 2.968 (2) |
C4···H5 | 2.110 | C12···H7av | 2.975 |
C2···H3 | 2.114 | C1···H6b | 2.979 |
C3···H2 | 2.114 | H21···H1ii | 2.98 (4) |
C2···H1 | 2.115 | H31···H1ix | 2.99 (4) |
C3···H4 | 2.125 | H7a···H9 | 2.995 |
C5···H6b | 2.127 | C3···C6 | 2.999 (3) |
C5···H6a | 2.128 | C11···H5vi | 3.004 |
C4···H3 | 2.129 | H4···H9viii | 3.005 |
C6···H5 | 2.156 | C1···H21ii | 3.01 (3) |
C1···C5 | 2.205 (4) | C12···H12x | 3.018 |
H31···H3 | 2.24 (4) | C2···H31i | 3.02 (3) |
O1···O5 | 2.252 (3) | C1···H6a | 3.024 |
H3···H7b | 2.278 | C5···H7biv | 3.039 |
O5···C6 | 2.292 (4) | O4···H6bvi | 3.039 |
H4···H7a | 2.294 | H6b···H7biv | 3.040 |
H2···H3 | 2.298 | H31···H2xi | 3.04 (3) |
C1···C6 | 2.300 (5) | H21···H2xi | 3.04 (3) |
O1···C5 | 2.323 (3) | H3···H6bvi | 3.043 |
H5···H6b | 2.346 | C13···H7a | 3.044 |
O4···C5 | 2.348 (3) | C10···H12x | 3.045 |
H11···H11iii | 2.349 | O4···H2 | 3.054 |
H21···H31 | 2.36 (6) | C8···H5vi | 3.088 |
C4···C7 | 2.373 (4) | C13···H7av | 3.095 |
O5···C2 | 2.376 (3) | C1···H6av | 3.106 |
C10···C12 | 2.378 (5) | C12···H5vi | 3.112 |
O4···C8 | 2.380 (3) | C1···H5 | 3.118 |
C9···C13 | 2.381 (4) | C6···H2viii | 3.124 |
O3···C4 | 2.382 (3) | C5···H1 | 3.125 |
C11···C13 | 2.387 (4) | O1···C4 | 3.137 (3) |
C9···C11 | 2.392 (5) | O3···C5 | 3.138 (3) |
C8···C10 | 2.406 (4) | C13···H5vi | 3.143 |
H12···H13 | 2.408 | C2···C6 | 3.146 (4) |
C8···C12 | 2.409 (5) | C6···H1 | 3.148 |
O5···C4 | 2.411 (4) | H1···H1ii | 3.148 |
H1···H2 | 2.413 | O4···C2 | 3.151 (3) |
H11···H12 | 2.414 | C5···H9iv | 3.151 |
H9···H10 | 2.415 | O5···H6a | 3.159 |
H10···H11 | 2.416 | H11···H12x | 3.159 |
H21···H31i | 2.42 (5) | H6b···H7bviii | 3.163 |
O2···C1 | 2.422 (3) | C11···H11iii | 3.164 |
O5···H7biv | 2.426 | C6···H21ii | 3.17 (3) |
H4···H5 | 2.429 | C3···C7 | 3.172 (4) |
H1···H6av | 2.431 | O2···H3i | 3.175 |
O3···H4 | 2.433 | O3···C1 | 3.180 (4) |
O2···C3 | 2.439 (3) | H7a···H13 | 3.184 |
O4···H13 | 2.439 | O3···H21xi | 3.19 (3) |
O3···C2 | 2.445 (4) | O1···H5 | 3.195 |
O1···C2 | 2.446 (3) | C9···H4vi | 3.201 |
H2···H6bvi | 2.446 | O1···H3iv | 3.210 |
O4···C3 | 2.454 (3) | C4···H31 | 3.22 (4) |
C7···H4 | 2.462 | O2···H2xi | 3.232 |
H7b···H9 | 2.468 | H21···H3 | 3.24 (3) |
O3···H6a | 2.474 | C11···H10iii | 3.244 |
C7···C9 | 2.502 (4) | C10···H10iii | 3.259 |
C1···H21 | 2.51 (3) | C10···H7avi | 3.262 |
H4···H6a | 2.527 | H31···H6a | 3.26 (3) |
C7···C13 | 2.528 (5) | H5···H7aiv | 3.275 |
C2···C4 | 2.535 (3) | C10···H13vii | 3.280 |
C1···C3 | 2.535 (4) | C13···H11x | 3.287 |
O4···H5 | 2.538 | H31···H4 | 3.29 (3) |
C3···C5 | 2.539 (3) | C13···H10iv | 3.288 |
C4···C6 | 2.548 (3) | C2···H31v | 3.29 (4) |
O4···H3 | 2.549 | O5···H4v | 3.293 |
O3···H21 | 2.56 (4) | O3···H2 | 3.294 |
O1···H21 | 2.57 (3) | C13···H7b | 3.296 |
H3···H4 | 2.570 | C5···H2 | 3.296 |
H10···H13vii | 2.575 | O2···H1ii | 3.297 |
H7a···H10viii | 2.583 | H2···H6avi | 3.298 |
O2···H31 | 2.60 (4) | O5···H3iv | 3.300 |
O3···H2ix | 2.597 | O5···H4 | 3.301 |
H31···H2ix | 2.60 (4) | C1···H3iv | 3.301 |
C4···H7b | 2.607 | O3···C2ix | 3.305 (4) |
C4···H7a | 2.608 | H11···H13xii | 3.305 |
O5···H2 | 2.608 | O2···H21i | 3.31 (4) |
C4···H6a | 2.616 | O3···C1ix | 3.310 (4) |
O2···H1 | 2.627 | C8···H6bvi | 3.313 |
C9···H7b | 2.636 | C10···H12 | 3.319 |
H5···H9iv | 2.644 | C12···H10 | 3.320 |
H7a···H12ix | 2.658 | C13···H9 | 3.324 |
H4···H7b | 2.665 | C11···H13 | 3.325 |
H9···H13vii | 2.674 | C9···H13vii | 3.325 |
C7···H9 | 2.680 | O1···H2 | 3.326 |
H10···H12vii | 2.680 | C9···H13 | 3.327 |
C3···H21 | 2.69 (3) | C13···H11 | 3.327 |
H5···H6a | 2.703 | O2···H31v | 3.33 (4) |
O3···H1ix | 2.715 | C11···H9 | 3.327 |
C7···H13 | 2.721 | O1···H2viii | 3.330 |
H21···H2 | 2.72 (4) | C12···H10iv | 3.330 |
C2···H31 | 2.74 (4) | H3···H6bvii | 3.334 |
O2···O3i | 2.741 (2) | C9···H11 | 3.335 |
O5···H9iv | 2.743 | H4···H10viii | 3.338 |
C10···C13 | 2.744 (4) | C8···H12 | 3.348 |
C9···C12 | 2.755 (5) | C8···H10 | 3.348 |
O1···O2ii | 2.761 (3) | H21···H6bii | 3.35 (3) |
H21···H1 | 2.76 (3) | C7···H6bvi | 3.350 |
O2···O3 | 2.764 (4) | | |
| | | |
C1—O1—C6 | 106.8 (2) | O5—C5—C6 | 101.4 (2) |
H21—O2—C2 | 107 (2) | C4—C5—C6 | 113.5 (2) |
H31—O3—C3 | 113 (3) | H6a—C6—H6b | 109.8 |
C7—O4—C4 | 113.5 (3) | H6a—C6—O1 | 111.1 |
C1—O5—C5 | 101.9 (2) | H6a—C6—C5 | 111.1 |
H1—C1—O5 | 109.5 | H6b—C6—O1 | 110.7 |
H1—C1—O1 | 111.4 | H6b—C6—C5 | 110.6 |
H1—C1—C2 | 109.9 | O1—C6—C5 | 103.4 (2) |
O5—C1—O1 | 105.4 (2) | H7a—C7—H7b | 109.7 |
O5—C1—C2 | 108.7 (2) | H7a—C7—O4 | 109.5 |
O1—C1—C2 | 111.9 (2) | H7a—C7—C8 | 109.5 |
H2—C2—O2 | 104.0 | H7b—C7—O4 | 109.3 |
H2—C2—C1 | 109.0 | H7b—C7—C8 | 109.3 |
H2—C2—C3 | 109.0 | O4—C7—C8 | 109.6 (3) |
O2—C2—C1 | 110.8 (2) | C13—C8—C9 | 117.9 (3) |
O2—C2—C3 | 111.4 (2) | C13—C8—C7 | 122.2 (2) |
C1—C2—C3 | 112.3 (2) | C9—C8—C7 | 119.9 (3) |
H3—C3—O3 | 108.8 | H9—C9—C10 | 119.8 |
H3—C3—C2 | 109.0 | H9—C9—C8 | 119.6 |
H3—C3—C4 | 109.0 | C10—C9—C8 | 120.6 (3) |
O3—C3—C2 | 112.3 (2) | H10—C10—C11 | 119.4 |
O3—C3—C4 | 107.1 (2) | H10—C10—C9 | 120.0 |
C2—C3—C4 | 110.7 (2) | C11—C10—C9 | 120.7 (3) |
H4—C4—O4 | 110.5 | H11—C11—C10 | 120.6 |
H4—C4—C5 | 109.1 | H11—C11—C12 | 119.9 |
H4—C4—C3 | 108.9 | C10—C11—C12 | 119.4 (3) |
O4—C4—C5 | 105.6 (2) | H12—C12—C13 | 120.2 |
O4—C4—C3 | 111.1 (2) | H12—C12—C11 | 119.8 |
C5—C4—C3 | 111.5 (2) | C13—C12—C11 | 120.1 (3) |
H5—C5—O5 | 109.6 | H13—C13—C12 | 119.3 |
H5—C5—C4 | 109.5 | H13—C13—C8 | 119.4 |
H5—C5—C6 | 113.3 | C12—C13—C8 | 121.3 (3) |
O5—C5—C4 | 109.1 (2) | | |
| | | |
C6—O1—C1—O5 | 25.0 (3) | H3—C3—C4—H4 | 82.0 |
C6—O1—C1—C2 | −92.9 (2) | O4—C4—C5—O5 | −63.3 (2) |
C6—O1—C1—H1 | 143.6 | O4—C4—C5—C6 | −175.6 (2) |
C1—O1—C6—C5 | 3.0 (2) | O4—C4—C5—H5 | 56.7 |
C1—O1—C6—H6a | 122.2 | C3—C4—C5—O5 | 57.5 (3) |
C1—O1—C6—H6b | −115.5 | C3—C4—C5—C6 | −54.8 (3) |
H21—O2—C2—C1 | 52 (2) | C3—C4—C5—H5 | 177.5 |
H21—O2—C2—C3 | −74 (2) | H4—C4—C5—O5 | 177.9 |
H21—O2—C2—H2 | 169 (2) | H4—C4—C5—C6 | 65.6 |
H31—O3—C3—C2 | −72 (3) | H4—C4—C5—H5 | −62.1 |
H31—O3—C3—C4 | 167 (3) | O5—C5—C6—O1 | −28.8 (2) |
H31—O3—C3—H3 | 49 (3) | O5—C5—C6—H6a | −148.0 |
C7—O4—C4—C3 | 87.1 (3) | O5—C5—C6—H6b | 89.7 |
C7—O4—C4—C5 | −151.8 (2) | C4—C5—C6—O1 | 88.1 (3) |
C7—O4—C4—H4 | −34.0 | C4—C5—C6—H6a | −31.1 |
C4—O4—C7—C8 | −179.9 (2) | C4—C5—C6—H6b | −153.4 |
C4—O4—C7—H7a | 60.1 | H5—C5—C6—O1 | −146.1 |
C4—O4—C7—H7b | −60.1 | H5—C5—C6—H6a | 94.6 |
C5—O5—C1—O1 | −43.8 (2) | H5—C5—C6—H6b | −27.7 |
C5—O5—C1—C2 | 76.3 (3) | O4—C7—C8—C9 | 156.1 (2) |
C5—O5—C1—H1 | −163.7 | O4—C7—C8—C13 | −23.7 (3) |
C1—O5—C5—C4 | −75.9 (2) | H7a—C7—C8—C9 | −83.8 |
C1—O5—C5—C6 | 44.1 (2) | H7a—C7—C8—C13 | 96.4 |
C1—O5—C5—H5 | 164.1 | H7b—C7—C8—C9 | 36.4 |
O1—C1—C2—O2 | −69.0 (3) | H7b—C7—C8—C13 | −143.4 |
O1—C1—C2—C3 | 56.2 (3) | C7—C8—C9—C10 | 179.5 (3) |
O1—C1—C2—H2 | 177.1 | C7—C8—C9—H9 | −0.3 |
O5—C1—C2—O2 | 175.1 (3) | C13—C8—C9—C10 | −0.7 (4) |
O5—C1—C2—C3 | −59.7 (3) | C13—C8—C9—H9 | 179.6 |
O5—C1—C2—H2 | 61.2 | C7—C8—C13—C12 | −179.9 (3) |
H1—C1—C2—O2 | 55.3 | C7—C8—C13—H13 | 0.1 |
H1—C1—C2—C3 | −179.5 | C9—C8—C13—C12 | 0.2 (4) |
H1—C1—C2—H2 | −58.6 | C9—C8—C13—H13 | −179.7 |
O2—C2—C3—O3 | 43.8 (2) | C8—C9—C10—C11 | 1.2 (5) |
O2—C2—C3—C4 | 163.4 (2) | C8—C9—C10—H10 | −179.3 |
O2—C2—C3—H3 | −76.8 | H9—C9—C10—C11 | −179.0 |
C1—C2—C3—O3 | −81.1 (2) | H9—C9—C10—H10 | 0.4 |
C1—C2—C3—C4 | 38.4 (3) | C9—C10—C11—C12 | −1.3 (5) |
C1—C2—C3—H3 | 158.2 | C9—C10—C11—H11 | 178.9 |
H2—C2—C3—O3 | 158.0 | H10—C10—C11—C12 | 179.3 |
H2—C2—C3—C4 | −82.4 | H10—C10—C11—H11 | −0.5 |
H2—C2—C3—H3 | 37.4 | C10—C11—C12—C13 | 0.8 (5) |
O3—C3—C4—O4 | −157.5 (2) | C10—C11—C12—H12 | −179.8 |
O3—C3—C4—C5 | 84.9 (3) | H11—C11—C12—C13 | −179.4 |
O3—C3—C4—H4 | −35.6 | H11—C11—C12—H12 | 0.0 |
C2—C3—C4—O4 | 79.8 (3) | C11—C12—C13—C8 | −0.3 (5) |
C2—C3—C4—C5 | −37.8 (3) | C11—C12—C13—H13 | 179.6 |
C2—C3—C4—H4 | −158.2 | H12—C12—C13—C8 | −179.7 |
H3—C3—C4—O4 | −40.0 | H12—C12—C13—H13 | 0.2 |
H3—C3—C4—C5 | −157.6 | | |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) −x, y, −z+1; (iii) −x+1, y, −z; (iv) x−1/2, y+1/2, z; (v) x, y+1, z; (vi) x+1/2, y+1/2, z; (vii) x+1/2, y−1/2, z; (viii) x−1/2, y−1/2, z; (ix) x, y−1, z; (x) −x+1/2, y−1/2, −z; (xi) −x+1/2, y−1/2, −z+1; (xii) −x+1/2, y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O1ii | 0.94 (4) | 2.03 (2) | 2.761 (3) | 134 (3) |
O2—H21···O3 | 0.94 (4) | 2.56 (4) | 2.764 (3) | 92 (2) |
O3—H31···O2xi | 0.93 (3) | 1.85 (3) | 2.741 (2) | 159 (4) |
C2—H2···O3v | 1.04 | 2.60 | 3.305 (4) | 125 |
C7—H7b···O5vii | 1.04 | 2.43 | 3.409 (3) | 157 |
C5—H5···Cgviii | 1.04 | 2.71 | 3.635 (3) | 148 |
Symmetry codes: (ii) −x, y, −z+1; (v) x, y+1, z; (vii) x+1/2, y−1/2, z; (viii) x−1/2, y−1/2, z; (xi) −x+1/2, y−1/2, −z+1. |
(III) 1,6-anhydro-3,4-
O-(
S)-benzylidene-
β-
D-galactopyranose
top
Crystal data top
C13H14O5 | F(000) = 264 |
Mr = 250.25 | Dx = 1.45 Mg m−3 |
Monoclinic, P21 | Melting point = 459–462 K |
Hall symbol: P 2y1 | Cu Kα radiation, λ = 1.54178 Å |
a = 9.0956 (3) Å | Cell parameters from 76 reflections |
b = 5.8461 (2) Å | θ = 2–45° |
c = 11.0603 (5) Å | µ = 0.94 mm−1 |
β = 102.871 (4)° | T = 293 K |
V = 573.34 (4) Å3 | Rectangular prism, colourless |
Z = 2 | 0.43 × 0.30 × 0.17 mm |
Data collection top
Philips PW1100 four-circle diffractometer | 1127 reflections with I > 0 |
Radiation source: X-ray tube | Rint = 0.049 |
Graphite monochromator | θmax = 67.5°, θmin = 4.1° |
ω/2θ scans | h = −10→10 |
Absorption correction: ψ-scan (North et al., 1968) | k = −7→7 |
Tmin = 0.760, Tmax = 0.850 | l = −13→13 |
2368 measured reflections | 2 standard reflections every 90 min |
1127 independent reflections | intensity decay: none |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.043 | w = k/[(a + b Fo)2(c + d(sinθ)/λ)] |
S = 1.05 | (Δ/σ)max < 0.001 |
1127 reflections | Δρmax = 0.15 e Å−3 |
167 parameters | Δρmin = −0.12 e Å−3 |
Crystal data top
C13H14O5 | V = 573.34 (4) Å3 |
Mr = 250.25 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 9.0956 (3) Å | µ = 0.94 mm−1 |
b = 5.8461 (2) Å | T = 293 K |
c = 11.0603 (5) Å | 0.43 × 0.30 × 0.17 mm |
β = 102.871 (4)° | |
Data collection top
Philips PW1100 four-circle diffractometer | 1127 reflections with I > 0 |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.049 |
Tmin = 0.760, Tmax = 0.850 | 2 standard reflections every 90 min |
2368 measured reflections | intensity decay: none |
1127 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.15 e Å−3 |
1127 reflections | Δρmin = −0.12 e Å−3 |
167 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.1739 (2) | 0.45000 | 0.5794 (2) | 0.0610 (11) | |
O2 | 0.5544 (3) | 0.2745 (6) | 0.5685 (2) | 0.0632 (12) | |
O3 | 0.40298 (17) | 0.3488 (5) | 0.83675 (14) | 0.0406 (8) | |
O4 | 0.2845 (2) | 0.0107 (5) | 0.84334 (16) | 0.0489 (9) | |
O5 | 0.2455 (3) | 0.1091 (6) | 0.51352 (18) | 0.0588 (11) | |
C1 | 0.2890 (3) | 0.3421 (7) | 0.5331 (2) | 0.0506 (13) | |
C2 | 0.4393 (3) | 0.3576 (6) | 0.6253 (2) | 0.0427 (11) | |
C3 | 0.4423 (3) | 0.2134 (7) | 0.7409 (2) | 0.0417 (11) | |
C4 | 0.3271 (3) | 0.0171 (6) | 0.7268 (2) | 0.0445 (12) | |
C5 | 0.1901 (3) | 0.0595 (7) | 0.6228 (2) | 0.0509 (14) | |
C6 | 0.1029 (3) | 0.2754 (8) | 0.6378 (3) | 0.0559 (14) | |
C7 | 0.3703 (3) | 0.1849 (6) | 0.9202 (2) | 0.0414 (11) | |
C8 | 0.2819 (2) | 0.2800 (6) | 1.0074 (2) | 0.0371 (10) | |
C9 | 0.2712 (3) | 0.1490 (7) | 1.1094 (2) | 0.0470 (12) | |
C10 | 0.1879 (3) | 0.2222 (8) | 1.1920 (3) | 0.0594 (16) | |
C11 | 0.1161 (4) | 0.4318 (8) | 1.1733 (3) | 0.0618 (17) | |
C12 | 0.1260 (3) | 0.5651 (7) | 1.0728 (3) | 0.0560 (14) | |
C13 | 0.2101 (3) | 0.4903 (7) | 0.9895 (2) | 0.0447 (12) | |
H21 | 0.597 (5) | 0.387 (10) | 0.529 (4) | 0.056 (12)* | |
H1 | 0.29880 | 0.41594 | 0.44975 | 0.06500* | |
H2 | 0.46026 | 0.52732 | 0.65188 | 0.05400* | |
H3 | 0.54953 | 0.14214 | 0.76819 | 0.05200* | |
H4 | 0.37932 | −0.13346 | 0.70852 | 0.05700* | |
H5 | 0.12224 | −0.08572 | 0.60895 | 0.06400* | |
H6a | −0.01030 | 0.25796 | 0.59385 | 0.05500* | |
H6b | 0.11135 | 0.31293 | 0.73112 | 0.05500* | |
H7 | 0.46905 | 0.11657 | 0.97369 | 0.05000* | |
H9 | 0.32553 | −0.00879 | 1.12346 | 0.04700* | |
H10 | 0.18014 | 0.12221 | 1.26808 | 0.06000* | |
H11 | 0.05310 | 0.48793 | 1.23521 | 0.06300* | |
H12 | 0.07204 | 0.72141 | 1.05990 | 0.05500* | |
H13 | 0.21812 | 0.59214 | 0.91412 | 0.04300* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0514 (11) | 0.0568 (13) | 0.0718 (13) | 0.0027 (10) | 0.0072 (10) | 0.0168 (11) |
O2 | 0.0709 (12) | 0.0567 (14) | 0.0759 (13) | 0.0031 (11) | 0.0456 (11) | 0.0015 (11) |
O3 | 0.0379 (8) | 0.0444 (10) | 0.0400 (8) | −0.0074 (8) | 0.0098 (6) | −0.0063 (8) |
O4 | 0.0692 (11) | 0.0357 (9) | 0.0449 (9) | −0.0066 (9) | 0.0196 (8) | −0.0007 (8) |
O5 | 0.0758 (13) | 0.0594 (13) | 0.0410 (9) | −0.0193 (11) | 0.0124 (9) | −0.0093 (9) |
C1 | 0.0622 (16) | 0.0476 (16) | 0.0417 (12) | −0.0058 (14) | 0.0110 (11) | 0.0051 (13) |
C2 | 0.0472 (12) | 0.0362 (13) | 0.0481 (12) | −0.0025 (11) | 0.0177 (10) | −0.0022 (11) |
C3 | 0.0406 (11) | 0.0429 (15) | 0.0427 (11) | 0.0025 (11) | 0.0118 (9) | −0.0019 (12) |
C4 | 0.0586 (14) | 0.0322 (12) | 0.0459 (12) | −0.0005 (11) | 0.0182 (10) | −0.0019 (11) |
C5 | 0.0618 (16) | 0.0466 (17) | 0.0441 (13) | −0.0164 (14) | 0.0117 (11) | −0.0075 (12) |
C6 | 0.0428 (12) | 0.068 (2) | 0.0525 (14) | −0.0035 (14) | 0.0007 (10) | 0.0064 (14) |
C7 | 0.0382 (10) | 0.0456 (14) | 0.0383 (11) | 0.0053 (10) | 0.0040 (9) | 0.0023 (11) |
C8 | 0.0278 (9) | 0.0424 (14) | 0.0379 (11) | −0.0003 (10) | 0.0005 (7) | −0.0035 (10) |
C9 | 0.0430 (12) | 0.0543 (17) | 0.0413 (12) | 0.0055 (12) | 0.0042 (9) | 0.0043 (12) |
C10 | 0.0585 (16) | 0.076 (2) | 0.0446 (13) | 0.0011 (17) | 0.0133 (11) | 0.0035 (15) |
C11 | 0.0561 (16) | 0.075 (2) | 0.0569 (16) | 0.0052 (16) | 0.0177 (13) | −0.0147 (16) |
C12 | 0.0419 (13) | 0.0547 (18) | 0.0690 (17) | 0.0086 (13) | 0.0070 (11) | −0.0128 (15) |
C13 | 0.0392 (11) | 0.0413 (15) | 0.0501 (13) | 0.0015 (11) | 0.0024 (9) | −0.0009 (12) |
Geometric parameters (Å, º) top
O1—C1 | 1.412 (4) | C5—H5 | 1.041 |
O1—C6 | 1.436 (4) | C5—C6 | 1.519 (5) |
O2—H21 | 0.92 (5) | C6—H6b | 1.041 |
O2—C2 | 1.421 (4) | C6—H6a | 1.042 |
O3—C7 | 1.407 (4) | C7—H7 | 1.039 |
O3—C3 | 1.431 (4) | C7—C8 | 1.494 (4) |
O4—C4 | 1.426 (3) | C8—C9 | 1.384 (4) |
O4—C7 | 1.440 (4) | C8—C13 | 1.386 (5) |
O5—C1 | 1.422 (5) | C9—H9 | 1.042 |
O5—C5 | 1.439 (4) | C9—C10 | 1.379 (4) |
C1—H1 | 1.039 | C10—H10 | 1.040 |
C1—C2 | 1.515 (3) | C10—C11 | 1.382 (6) |
C2—H2 | 1.040 | C11—H11 | 1.039 |
C2—C3 | 1.527 (4) | C11—C12 | 1.377 (5) |
C3—H3 | 1.042 | C12—H12 | 1.032 |
C3—C4 | 1.538 (5) | C12—C13 | 1.393 (5) |
C4—H4 | 1.041 | C13—H13 | 1.040 |
C4—C5 | 1.516 (4) | | |
| | | |
H6a···H6b | 1.698 | H21···H2i | 2.87 (5) |
C2···H21 | 1.98 (5) | C12···H12iv | 2.874 |
O3···H7 | 2.023 | C7···H6b | 2.879 |
O5···H1 | 2.026 | H21···H1i | 2.90 (6) |
O1···H1 | 2.027 | O2···O5 | 2.905 (3) |
O2···H2 | 2.030 | H1···H11vi | 2.905 |
O5···H5 | 2.048 | O4···C6 | 2.936 (4) |
O4···H7 | 2.050 | O2···O5viii | 2.949 (4) |
O1···H6b | 2.051 | C13···H7v | 2.950 |
O1···H6a | 2.053 | C13···H12iv | 2.954 |
C8···H7 | 2.057 | C8···H7v | 2.972 |
O4···H4 | 2.061 | C13···H6b | 2.984 |
O5···H21i | 2.06 (5) | C1···H6a | 2.986 |
O3···H3 | 2.064 | C1···H21i | 2.99 (6) |
C11···H12 | 2.092 | H21···H10v | 3.00 (4) |
C2···H3 | 2.094 | C1···H6b | 3.002 |
C10···H9 | 2.095 | O4···H11iv | 3.003 |
C12···H11 | 2.098 | C5···H21i | 3.00 (5) |
C10···H11 | 2.099 | C7···H4 | 3.006 |
C5···H4 | 2.099 | H7···H7x | 3.009 |
C2···H1 | 2.101 | H7···H7v | 3.009 |
C1···H2 | 2.101 | O5···H6aiii | 3.011 |
C4···H3 | 2.104 | C5···H11iv | 3.013 |
C8···H9 | 2.104 | C7···H7v | 3.020 |
C3···H2 | 2.106) | O1···C3 | 3.020 (3) |
C11···H10 | 2.107 | C11···H12iv | 3.021 |
C9···H10 | 2.107 | O1···H5ix | 3.023 |
C13···H12 | 2.108 | C10···H1xi | 3.024 |
C4···H5 | 2.109 | O4···H9 | 3.039 |
C12···H13 | 2.112 | C3···H6b | 3.044 |
C8···H13 | 2.113 | C12···H9ii | 3.059 |
C3···H4 | 2.116 | C3···C6 | 3.064 (3) |
C5···H6a | 2.124 | C9···H12vii | 3.064 |
C5···H6b | 2.127 | O4···C9 | 3.080 (3) |
C6···H5 | 2.148 | C2···H4 | 3.100 |
H21···H2 | 2.20 (5) | C8···H6b | 3.110 |
C1···C5 | 2.219 (5) | C12···H3v | 3.113 |
C3···C7 | 2.228 (4) | H21···H3 | 3.12 (5) |
H3···H4 | 2.230 | C5···H6aiii | 3.127 |
H2···H4ii | 2.252 | O3···C6 | 3.130 (3) |
O3···O4 | 2.260 (4) | C2···C6 | 3.130 (4) |
O1···O5 | 2.267 (4) | C6···H5ix | 3.133 |
C1···C6 | 2.287 (5) | C6···H1 | 3.135 |
O5···C6 | 2.304 (4) | C1···H5 | 3.135 |
C4···C7 | 2.306 (4) | C5···H1 | 3.135 |
O3···C4 | 2.311 (4) | C11···H1xi | 3.139 |
H5···H6a | 2.330 | O3···H4 | 3.142 |
O1···C5 | 2.331 (4) | C1···H10vi | 3.151 |
O4···C3 | 2.339 (4) | C4···H21i | 3.15 (5) |
O2···H3 | 2.350 | C8···H12iv | 3.157 |
H4···H5 | 2.369 | C3···H21 | 3.16 (5) |
O5···C4 | 2.372 (3) | O1···C4 | 3.161 (3) |
O2···C3 | 2.381 (4) | O5···H6b | 3.164 |
C9···C11 | 2.381 (5) | H6b···H12iv | 3.183 |
O2···C1 | 2.391 (4) | C13···H3v | 3.185 |
C9···C13 | 2.392 (5) | O1···O3 | 3.186 (3) |
C10···C12 | 2.396 (6) | O3···C5 | 3.188 (4) |
C11···C13 | 2.400 (5) | O1···H5 | 3.195 |
C8···C12 | 2.402 (5) | C2···H4ii | 3.197 |
O5···C2 | 2.403 (4) | C2···H9v | 3.203 |
O4···C8 | 2.406 (4) | O1···H4ii | 3.205 |
C8···C10 | 2.407 (4) | H6a···H10xii | 3.210 |
H11···H12 | 2.409 | C11···H3v | 3.210 |
O1···C2 | 2.415 (3) | H6b···H10xii | 3.211 |
O4···C5 | 2.415 (3) | H7···H9v | 3.215 |
H9···H10 | 2.416 | H4···H7 | 3.215 |
H10···H11 | 2.419 | C2···H21i | 3.22 (6) |
O3···C8 | 2.421 (3) | O2···C1i | 3.224 (5) |
H5···H6aiii | 2.426 | C10···H12iv | 3.228 |
H12···H13 | 2.427 | H21···H1viii | 3.23 (6) |
O3···C2 | 2.435 (3) | H2···H10v | 3.240 |
H7···H9 | 2.439 | C13···H7 | 3.246 |
O3···H2 | 2.453 | H1···H6aix | 3.248 |
C7···C9 | 2.465 (4) | C9···H2x | 3.251 |
H1···H2 | 2.473 | O2···C2i | 3.254 (4) |
O3···H13 | 2.495 | H21···H5viii | 3.25 (5) |
H6b···H11iv | 2.497 | H10···H12vii | 3.279 |
O4···H6b | 2.505 | H9···H13vii | 3.279) |
H3···H9v | 2.507 | C4···H2vii | 3.286 |
O2···H1i | 2.518 | O5···H2 | 3.287 |
C1···C3 | 2.523 (4) | O3···C1 | 3.287 (3) |
C7···C13 | 2.530 (5) | C9···H12iv | 3.291 |
C3···C5 | 2.538 (4) | O2···H4viii | 3.296 |
O2···H1 | 2.540 | H1···H3viii | 3.308 |
H3···H7 | 2.543 | C1···H3 | 3.317 |
O3···H9v | 2.550 | C9···H11 | 3.321 |
C4···C6 | 2.552 (4) | C11···H9 | 3.322 |
H6a···H11iv | 2.559 | C10···H12 | 3.328 |
O1···H2 | 2.588 | O3···H4ii | 3.329 |
C9···H7 | 2.594 | C13···H9 | 3.335 |
C3···H7 | 2.594 | C10···H12vii | 3.337 |
C7···H3 | 2.601 | C8···H12 | 3.337 |
C2···C4 | 2.603 (5) | C12···H10 | 3.337 |
H6b···H13 | 2.613 | C9···H13 | 3.338 |
C4···H6b | 2.624 | C11···H13 | 3.338 |
C7···H9 | 2.629 | O2···O2i | 3.339 (4) |
H2···H3 | 2.630) | O2···O2viii | 3.339 (4) |
H5···H11iv | 2.631 | C13···H11 | 3.340 |
O5···H4 | 2.641 | C5···H3 | 3.341 |
O5···H10vi | 2.648 | C13···H9ii | 3.344 |
O3···H6b | 2.658 | C8···H10 | 3.348 |
O3···H7v | 2.667 | O2···C4 | 3.349 (4) |
H21···H1 | 2.67 (4) | H12···H12iv | 3.353 |
O4···H13vii | 2.679 | H12···H12xii | 3.353 |
H1···H10vi | 2.680 | O2···H10v | 3.359 |
H21···H4viii | 2.69 (5) | C8···H3v | 3.361 |
H5···H6b | 2.707 | C11···H6bxii | 3.367 |
O4···H5 | 2.741 | H4···H13vii | 3.373 |
C7···H13 | 2.748 | O4···C13 | 3.379 (5) |
O2···H21i | 2.75 (5) | O3···C9v | 3.381 (4) |
H9···H12vii | 2.752 | C10···H3v | 3.384 |
C9···C12 | 2.755 (5) | C1···H4 | 3.385 |
C8···C11 | 2.769 (5) | C4···H2 | 3.391 |
C6···H11iv | 2.775 | C4···H6a | 3.399 |
C10···C13 | 2.778 (5) | H21···H21viii | 3.41 (8) |
O1···H5ii | 2.786 | H21···H21i | 3.41 (8) |
O1···H6aix | 2.803 | C3···H1 | 3.406 |
H2···H9v | 2.803 | C5···C7 | 3.411 (4) |
O5···H6a | 2.807 | C7···H9v | 3.419 |
C4···H7 | 2.809 | O2···H4 | 3.423 |
O5···C3 | 2.810 (3) | C3···H5 | 3.430 |
O2···H2i | 2.811 | C6···H4 | 3.431 |
O3···C13 | 2.817 (4) | C9···H3v | 3.438 |
C3···H9v | 2.818 | C2···H6b | 3.449 |
O4···H3 | 2.825 | C1···H21viii | 3.46 (6) |
C1···C4 | 2.827 (5) | C10···H2x | 3.473 |
C1···H21 | 2.83 (5) | H12···H13xii | 3.476 |
H7···H13x | 2.843 | O5···H3 | 3.486 |
C2···C5 | 2.855 (5) | C3···H21i | 3.50 (5) |
| | | |
C1—O1—C6 | 106.8 (2) | O5—C5—C6 | 102.3 (3) |
H21—O2—C2 | 113 (3) | C4—C5—C6 | 114.4 (3) |
C7—O3—C3 | 103.5 (3) | H6b—C6—H6a | 109.3 |
C4—O4—C7 | 107.1 (2) | H6b—C6—O1 | 110.8 |
C1—O5—C5 | 101.7 (3) | H6b—C6—C5 | 111.0 |
H1—C1—O1 | 110.7 | H6a—C6—O1 | 110.9 |
H1—C1—O5 | 109.8 | H6a—C6—C5 | 110.7 |
H1—C1—C2 | 109.2 | O1—C6—C5 | 104.1 (2) |
O1—C1—O5 | 106.2 (2) | H7—C7—O3 | 110.7 |
O1—C1—C2 | 111.1 (2) | H7—C7—O4 | 110.5 |
O5—C1—C2 | 109.8 (3) | H7—C7—C8 | 107.2 |
H2—C2—O2 | 110.2 | O3—C7—O4 | 105.1 (2) |
H2—C2—C1 | 109.2 | O3—C7—C8 | 113.1 (3) |
H2—C2—C3 | 108.8 | O4—C7—C8 | 110.2 (2) |
O2—C2—C1 | 109.0 (2) | C9—C8—C13 | 119.4 (3) |
O2—C2—C3 | 107.7 (3) | C9—C8—C7 | 117.8 (3) |
C1—C2—C3 | 112.0 (2) | C13—C8—C7 | 122.8 (3) |
H3—C3—O3 | 112.3 | H9—C9—C10 | 119.2 |
H3—C3—C2 | 107.7 | H9—C9—C8 | 119.7 |
H3—C3—C4 | 107.7 | C10—C9—C8 | 121.1 (3) |
O3—C3—C2 | 110.8 (3) | H10—C10—C9 | 120.5 |
O3—C3—C4 | 102.2 (2) | H10—C10—C11 | 120.3 |
C2—C3—C4 | 116.3 (2) | C9—C10—C11 | 119.2 (3) |
H4—C4—O4 | 112.4 | H11—C11—C12 | 119.9 |
H4—C4—C5 | 108.9 | H11—C11—C10 | 119.6 |
H4—C4—C3 | 108.7 | C12—C11—C10 | 120.6 (3) |
O4—C4—C5 | 110.3 (2) | H12—C12—C11 | 119.9 |
O4—C4—C3 | 104.1 (2) | H12—C12—C13 | 120.1 |
C5—C4—C3 | 112.4 (3) | C11—C12—C13 | 120.1 (4) |
H5—C5—O5 | 110.3 | H13—C13—C8 | 120.5 |
H5—C5—C4 | 109.8 | H13—C13—C12 | 119.8 |
H5—C5—C6 | 112.8 | C8—C13—C12 | 119.7 (3) |
O5—C5—C4 | 106.7 (2) | | |
| | | |
C6—O1—C1—O5 | 25.2 (3) | H3—C3—C4—O4 | 94.9 |
C6—O1—C1—C2 | −94.1 (3) | H3—C3—C4—C5 | −145.7 |
C6—O1—C1—H1 | 144.4 | H3—C3—C4—H4 | −25.1 |
C1—O1—C6—C5 | 1.1 (3) | O4—C4—C5—O5 | 168.7 (3) |
C1—O1—C6—H6a | −118.0 | O4—C4—C5—C6 | 56.3 (4) |
C1—O1—C6—H6b | 120.5 | O4—C4—C5—H5 | −71.7 |
H21—O2—C2—C1 | 91 (3) | C3—C4—C5—O5 | 53.0 (4) |
H21—O2—C2—C3 | −148 (3) | C3—C4—C5—C6 | −59.4 (4) |
H21—O2—C2—H2 | −29 (3) | C3—C4—C5—H5 | 172.6 |
C7—O3—C3—C2 | 164.4 (2) | H4—C4—C5—O5 | −67.5 |
C7—O3—C3—C4 | 39.9 (2) | H4—C4—C5—C6 | −179.9 |
C7—O3—C3—H3 | −75.2 | H4—C4—C5—H5 | 52.1 |
C3—O3—C7—O4 | −42.0 (2) | O5—C5—C6—O1 | −26.3 (3) |
C3—O3—C7—C8 | −162.3 (2) | O5—C5—C6—H6a | 92.9 |
C3—O3—C7—H7 | 77.3 | O5—C5—C6—H6b | −145.5 |
C7—O4—C4—C3 | −1.3 (3) | C4—C5—C6—O1 | 88.8 (3) |
C7—O4—C4—C5 | −122.1 (3) | C4—C5—C6—H6a | −152.1 |
C7—O4—C4—H4 | 116.2 | C4—C5—C6—H6b | −30.5 |
C4—O4—C7—O3 | 26.4 (3) | H5—C5—C6—O1 | −144.7 |
C4—O4—C7—C8 | 148.6 (2) | H5—C5—C6—H6a | −25.6 |
C4—O4—C7—H7 | −93.1 | H5—C5—C6—H6b | 96.0 |
C5—O5—C1—O1 | −42.1 (3) | O3—C7—C8—C9 | −166.5 (2) |
C5—O5—C1—C2 | 78.1 (3) | O3—C7—C8—C13 | 14.2 (3) |
C5—O5—C1—H1 | −161.8 | O4—C7—C8—C9 | 76.2 (3) |
C1—O5—C5—C4 | −79.5 (3) | O4—C7—C8—C13 | −103.1 (3) |
C1—O5—C5—C6 | 41.0 (3) | H7—C7—C8—C9 | −44.2 |
C1—O5—C5—H5 | 161.3 | H7—C7—C8—C13 | 136.5 |
O1—C1—C2—O2 | −172.3 (3) | C7—C8—C9—C10 | −178.1 (3) |
O1—C1—C2—C3 | 68.6 (4) | C7—C8—C9—H9 | 1.0 |
O1—C1—C2—H2 | −52.0 | C13—C8—C9—C10 | 1.3 (4) |
O5—C1—C2—O2 | 70.5 (3) | C13—C8—C9—H9 | −179.7 |
O5—C1—C2—C3 | −48.6 (3) | C7—C8—C13—C12 | 178.2 (2) |
O5—C1—C2—H2 | −169.2 | C7—C8—C13—H13 | −1.6 |
H1—C1—C2—O2 | −50.0 | C9—C8—C13—C12 | −1.1 (4) |
H1—C1—C2—C3 | −169.1 | C9—C8—C13—H13 | 179.1 |
H1—C1—C2—H2 | 70.4 | C8—C9—C10—C11 | −1.1 (5) |
O2—C2—C3—O3 | 146.1 (2) | C8—C9—C10—H10 | 179.7 |
O2—C2—C3—C4 | −97.9 (3) | H9—C9—C10—C11 | 179.9 |
O2—C2—C3—H3 | 23.0 | H9—C9—C10—H10 | 0.7 |
C1—C2—C3—O3 | −94.1 (3) | C9—C10—C11—C12 | 0.7 (5) |
C1—C2—C3—C4 | 21.9 (4) | C9—C10—C11—H11 | 180.0 |
C1—C2—C3—H3 | 142.8 | H10—C10—C11—C12 | 180.0 |
H2—C2—C3—O3 | 26.7 | H10—C10—C11—H11 | −0.7 |
H2—C2—C3—C4 | 142.7 | C10—C11—C12—C13 | −0.6 (5) |
H2—C2—C3—H3 | −96.4 | C10—C11—C12—H12 | −179.9 |
O3—C3—C4—O4 | −23.5 (3) | H11—C11—C12—C13 | −179.9 |
O3—C3—C4—C5 | 95.9 (3) | H11—C11—C12—H12 | 0.8 |
O3—C3—C4—H4 | −143.5 | C11—C12—C13—C8 | 0.8 (4) |
C2—C3—C4—O4 | −144.2 (3) | C11—C12—C13—H13 | −179.4 |
C2—C3—C4—C5 | −24.8 (4) | H12—C12—C13—C8 | −179.9 |
C2—C3—C4—H4 | 95.8 | H12—C12—C13—H13 | −0.1 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, y+1, z; (iii) −x, y−1/2, −z+1; (iv) −x, y−1/2, −z+2; (v) −x+1, y+1/2, −z+2; (vi) x, y, z−1; (vii) x, y−1, z; (viii) −x+1, y+1/2, −z+1; (ix) −x, y+1/2, −z+1; (x) −x+1, y−1/2, −z+2; (xi) x, y, z+1; (xii) −x, y+1/2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O5viii | 0.91 (6) | 2.06 (5) | 2.950 (4) | 161 (4) |
C1—H1···O2viii | 1.04 | 2.52 | 3.224 (5) | 125 |
C9—H9···O3x | 1.04 | 2.55 | 3.381 (4) | 136 |
C3—H3···Cgx | 1.04 | 2.98 | 3.971 (3) | 160 |
C12—H12···Cgxii | 1.04 | 2.76 | 3.539 (3) | 132 |
Symmetry codes: (viii) −x+1, y+1/2, −z+1; (x) −x+1, y−1/2, −z+2; (xii) −x, y+1/2, −z+2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C13H14O5 | C13H16O5 | C13H14O5 |
Mr | 250.25 | 252.27 | 250.25 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, C2 | Monoclinic, P21 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 13.0265 (7), 7.0672 (3), 6.3376 (2) | 11.9752 (5), 5.7487 (2), 18.0759 (14) | 9.0956 (3), 5.8461 (2), 11.0603 (5) |
β (°) | 96.432 (4) | 100.295 (6) | 102.871 (4) |
V (Å3) | 579.77 (4) | 1224.34 (12) | 573.34 (4) |
Z | 2 | 4 | 2 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 0.93 | 0.88 | 0.94 |
Crystal size (mm) | 0.43 × 0.33 × 0.17 | 0.43 × 0.33 × 0.05 | 0.43 × 0.30 × 0.17 |
|
Data collection |
Diffractometer | Philips PW1100 four-circle diffractometer | Philips PW1100 four-circle diffractometer | Philips PW1100 four-circle diffractometer |
Absorption correction | ψ-scan (North et al., 1968) | ψ-scan (North et al., 1968) | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.776, 0.854 | 0.794, 0.957 | 0.760, 0.850 |
No. of measured, independent and observed (I > 0) reflections | 2488, 1148, 1148 | 2496, 1208, 1208 | 2368, 1127, 1127 |
Rint | 0.016 | 0.033 | 0.049 |
(sin θ/λ)max (Å−1) | 0.599 | 0.599 | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.032, 1.00 | 0.032, 0.040, 1.08 | 0.034, 0.043, 1.05 |
No. of reflections | 1148 | 1208 | 1127 |
No. of parameters | 167 | 171 | 167 |
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 | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.13 | 0.13, −0.13 | 0.15, −0.12 |
Selected geometric parameters (Å, º) for (I) topO2—C2 | 1.436 (3) | O3—C3 | 1.437 (3) |
| | | |
O2—C2—C3 | 103.8 (2) | O4—C4—C5 | 110.8 (2) |
O3—C3—C2 | 102.5 (2) | O4—C4—C3 | 106.2 (2) |
O3—C3—C4 | 110.2 (2) | | |
| | | |
C7—O2—C2—C3 | −1.4 (2) | C3—O3—C7—O2 | 40.3 (2) |
C2—O2—C7—O3 | −23.7 (2) | O2—C2—C3—O3 | 25.2 (2) |
C7—O3—C3—C2 | −40.1 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H41···O2i | 0.96 (5) | 1.86 (5) | 2.803 (3) | 167 (4) |
C2—H2···O4ii | 1.04 | 2.59 | 3.317 (2) | 126 |
C7—H7···O1iii | 1.04 | 2.54 | 3.316 (2) | 131 |
C13—H13···O1 | 1.04 | 2.40 | 3.353 (3) | 152 |
C1—H1···O5iv | 1.04 | 2.54 | 3.317 (3) | 131 |
C4—H4···Cgi | 1.04 | 2.83 | 3.843 (3) | 165 |
C10—H10···Cgv | 1.04 | 2.90 | 3.752 (4) | 140 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y+1/2, −z+2; (iii) x, y, z+1; (iv) −x+1, y+1/2, −z+1; (v) −x, y+1/2, −z+2. |
Selected geometric parameters (Å, º) for (II) topO2—C2 | 1.420 (3) | O3—C3 | 1.412 (4) |
| | | |
O2—C2—C3 | 111.4 (2) | O4—C4—C5 | 105.6 (2) |
O3—C3—C2 | 112.3 (2) | O4—C4—C3 | 111.1 (2) |
O3—C3—C4 | 107.1 (2) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O1i | 0.94 (4) | 2.03 (2) | 2.761 (3) | 134 (3) |
O3—H31···O2ii | 0.93 (3) | 1.85 (3) | 2.741 (2) | 159 (4) |
C2—H2···O3iii | 1.04 | 2.60 | 3.305 (4) | 125 |
C7—H7b···O5iv | 1.04 | 2.43 | 3.409 (3) | 157 |
C5—H5···Cgv | 1.04 | 2.71 | 3.635 (3) | 148 |
Symmetry codes: (i) −x, y, −z+1; (ii) −x+1/2, y−1/2, −z+1; (iii) x, y+1, z; (iv) x+1/2, y−1/2, z; (v) x−1/2, y−1/2, z. |
Selected geometric parameters (Å, º) for (III) topO2—C2 | 1.421 (4) | O3—C3 | 1.431 (4) |
| | | |
O2—C2—C3 | 107.7 (3) | O4—C4—C5 | 110.3 (2) |
O3—C3—C2 | 110.8 (3) | O4—C4—C3 | 104.1 (2) |
O3—C3—C4 | 102.2 (2) | | |
| | | |
C7—O3—C3—C4 | 39.9 (2) | C4—O4—C7—O3 | 26.4 (3) |
C3—O3—C7—O4 | −42.0 (2) | O3—C3—C4—O4 | −23.5 (3) |
C7—O4—C4—C3 | −1.3 (3) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O5i | 0.91 (6) | 2.06 (5) | 2.950 (4) | 161 (4) |
C1—H1···O2i | 1.04 | 2.52 | 3.224 (5) | 125 |
C9—H9···O3ii | 1.04 | 2.55 | 3.381 (4) | 136 |
C3—H3···Cgii | 1.04 | 2.98 | 3.971 (3) | 160 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+2. |
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The crystal structure determinations of the three title 1,6-anhydro-β-D-glycopyranose derivatives, (I), (II) and (III), were carried out within a project on hydrogen-bonding and cooperativity effects on the assembly of carbohydrates (Lopez de la Paz et al., 1998). Carbohydrates are biomolecules that contain enough hydroxyl groups to form chains and cycles of cooperative O—H···O—H hydrogen bonds, and evidence of this cooperativity in the solid state has been reported previously (Jeffrey & Saenger, 1991; Noltemeyer & Saenger, 1980). The main aim of this report is to explore the ability of the OH group to form intramolecular hydrogen bonds depending on the relative configuration of the OH group and its position on the pyranose ring. Compounds (I) to (III) were selected to study the influence of a second hydroxyl group, as present in (II), in the crystal packing. \sch
A comparison of the geometrical parameters of the three compounds (Tables 1, 3 and 5) reveals that the substitution at positions O3 and/or O2/O4 introduces significant changes in the molecular dimensions, such as in O—C bond distances and in the angles around C2, C3 and C4. These differences can be explained by the dissimilar participation of the O atoms in the hydrogen bonding and by the conformation of the O4R group in (I) and (II), trans to C3 versus gauche, respectively [H41/C7—O4—C4—C3 = 167 (3) in (I) and 87.1 (3)° in (II)]. Furthermore, the greatest differences between (I) and the previously reported analogue 4-O-acetyl-1,6-anhydro-2,3-O-(S)-benzylidene-β-D-mannopyranose [Cano et al., 1986; Cambridge Structural Database (CSD; Allen & Kennard, 1993) reference FOJMEW] are for the bond distances and angles around O4, where the hydroxyl group is protected with an acetyl one. Similar features are found between (III) and 2-O-acetyl-1,6-anhydro-3,4-O-(S)-benzylidene-β-D-galactopyranose (Cano et al., 1986; CSD reference FOJLUL).
In compounds (I) to (III), the pyranose ring is in a 1C4 conformation distorted towards an E6 envelope, less puckering at C3 (Boeyens, 1978). The anhydro and dioxolane rings are in an envelope conformation, with flaps at O5 and O3, respectively (Tables 1, 3 and 5).
In the crystal packing of 1–6-anhydro-β-D-mannopyranose and 1–6-anhydro-β-D-galactopyranose, the endocyclic O atoms compete with the hydroxyl groups in the formation of hydrogen bonds, and this is also seen in the title compounds (Tables 2, 4 and 6) and those reported above. The hydrogen-bond networks have been analysed by means of the graph-set approach (Bernstein et al., 1995), as implemented in the RPLUTO program (June 2000 version; Motherwell et al., 1999, 2000).
In (I), the packing can be described as pairs of chains related by a 21 axis (Table 2 and Fig. 2a). The O4—H···O2 bond is responsible for the formation of each chain [graph set C(6)], while C—H···O interactions between atoms O1 and O5 are reinforced by C—H···π contacts.
The hydrogen bonding in (II) differs from that in (I), since molecules of (II) form dimers through three-centre O2—H···O1/O3 hydrogen bonds. Such dimers (Table 4 and Fig. 2 b) are in turn connected into sheets by O3—H···O2 hydrogen bonds, graph set C22(8) C(5)[R22(10)]. The inter- and intramolecular geometry is similar to that reported for 1,6-anhydro-β-D-mannopyranose (Maluszynska et al., 1982; CSD reference BIFTUF). According to the results of a search of the CSD, structure (II) represents an unusual case in pyranoses in which two contiguous hydroxyl groups allow hydrogen bonds, leading to the formation of cyclic dimers. Only one similar cyclic dimer without intermolecular O—H···O hydrogen bonds between them [graph set R22(10), ignoring the D and S patterns] has been previously observed, in 6,7-anhydro-2,3-di-O-benzyl-8-deoxy-α-D-threo-D-galacto-octopyranoside (Engelhardt et al., 1990; CSD reference KIDDEG).
In (III), an O2—H2···O5 hydrogen bond links the molecules into chains (Table 6 and Fig. 2c) in a way similar [graph set C(5)] to that reported for the analogue 1,6-anhydro-3,4-O-isopropylidene-β-D-galactopyranose (Cano et al., 1984; CSD reference COHJIS). However, when the only hydroxyl group in the molecule is attached at C4, as in 2,3-di-O-acetyl-1,6-anhydro-β-D-galactopyranose (Foces-Foces et al., 1976; CSD reference ACHGAL), the hydroxyl group acts as a hydrogen-bond donor to the anhydro O1 atom (O4—H···O1), giving rise to a C(6) motif. Moreover, in 1,6-anhydro-β-D-galactopyranose (Ceccarelli et al., 1980; CSD reference AHGALP), the O5 atoms in the three independent molecules accept hydrogen bonds, whereas only one O1 atom is involved in a hydrogen bond, either in discrete (D) or chain [C(6)] first-level motifs.
Despite the scarcity of 1,6-anhydro-galactopyranose structures reported in the literature, it seems that when only one hydroxyl group is present in the structure at C2 or C4, the O5 or O1 atom is the acceptor of the corresponding O—H···O hydrogen bond. However, both can be acceptors at the same time when there is more than one hydroxyl group in the molecular structure, as mentioned above and as observed in BIFTUF, where the O5 of one of the two independent molecules and the O1 of the other are involved in discrete (D) first-level motifs.
The volumes per non-H atom of 16.10, 17.00 and 15.93 Å3 for (I), (II) and (III), respectively, also reflect the differences in the crystal packing. Compound (II) shows the least efficient packing in spite of depicting the shortest O···O distances.
It can be concluded that although these molecules (I) and (III) present similar secondary structure as a whole, the greater number of acceptor groups than donors in the molecular structure allows different linkages of the molecules within it. Several weak interactions (C—H···O and C—H···π), other than van der Waals ones, hold the chains together (in Tables 2, 4 and 6, Cg represents the centroid of the phenyl ring).