Three 1,6-anhydro-β-D-glycopyranose derivatives

Two of the title compounds, 1,6-an­hydro-2,3-O-(S)-benzyl­idene-β-D-manno­pyran­ose, C₁₃H₁₄O₅, (I), and 1,6-an­hydro-4-O-benzyl-β-D-manno­pyran­ose, C₁₃H₁₆O₅, (II), are derived from β-D-manno­pyran­ose, while the third, 1,6-an­hydro-3,4-O-(S)-benzyl­idene-β-D-galacto­pyran­ose, C₁₃H₁₄O₅, (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.

S1. Comment

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 ų 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).

Related literature

For related literature, see: Allen & Kennard (1993); Bernstein et al. (1995); Boeyens (1978); Cano et al. (1984, 1985, 1986); Ceccarelli et al. (1980); Engelhardt et al. (1990); Flack (1983); Florent & Monneret (1980); Foces-Foces, Cano & Garcia-Blanco (1976); Jeffrey & Saenger (1991); Maluszynska et al. (1982); Martínez-Ripoll & Cano (1975); Motherwell et al. (1999, 2000); Noltemeyer & Saenger (1980); Reeves (1949); Subero et al. (1980); Zachariasen (1967).

S2. Experimental

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.

S3. Refinement

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 <F_o> or <sinθ/λ>: w = K/{[(a+b)F_o]²}[(c+d)sinθ/λ]. The parameters a, b, c and d were adjusted to flatten the initial trends (PESOS; Martínez-Ripoll & Cano, 1975).

Computing details

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.

Figures

	Fig. 1. The molecular structures of (a) (I), (b) (II) and (c) (III), displaying the numbering scheme and the conformations of the molecules. The displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (a) (I), (b) (II) and (c) (III), showing the secondary structure in the chains. Dotted lines represent hydrogen-bonding interactions; symmetry codes are as in Tables 2, 4 and 6.

(I) 1,6-anhydro-2,3-O-(S)-benzylidene-β-D-mannopyranose

Crystal data

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) Å^3	Rectangular prism, colourless
Z = 2	0.43 × 0.33 × 0.17 mm

Data collection

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

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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···H4^i	2.883
O2···H41^i	1.86 (5)	O5···H3^iii	2.884
C4···H41	1.91 (5)	O3···H13	2.907
O3···H7	2.022	H41···H2^v	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···H7^xi	2.96 (5)
O1···H6b	2.049	C1···H6a	2.967
O1···H6a	2.050	C2···H41^i	2.98 (5)
O2···H7	2.050	O1···C3	3.001 (2)
O3···H3	2.069	C1···H7^iii	3.011
C8···H7	2.069	H1···H3^iii	3.017
O2···H2	2.082	O3···C13	3.019 (3)
C2···H3	2.096	C1···H6b	3.023
C4···H3	2.097	H6b···H11^vii	3.030
C11···H10	2.097	H1···H5^x	3.037
C10···H11	2.098	O1···O3	3.041 (2)
C12···H11	2.099	C13···H4^i	3.043
C1···H2	2.100	C7···H2	3.048
C12···H13	2.102	O5···H41^x	3.06 (4)
C13···H12	2.103	C3···H6b	3.058
C11···H12	2.104	H2···H3^xii	3.061
C8···H9	2.104	C3···C6	3.065 (3)
C3···H2	2.107	H12···H13^ii	3.071
C10···H9	2.108	C4···H2	3.073
C5···H4	2.108	H3···H6a^vi	3.081
C3···H4	2.111	C12···H10^viii	3.103
C8···H13	2.111	C12···H6b^ii	3.103
C4···H5	2.111	H41···H2^xi	3.12 (5)
C9···H10	2.112	C9···H6a^xiii	3.119
C2···H1	2.117	O1···H11^vii	3.121
C5···H6a	2.119	C5···H1^iv	3.127
C5···H6b	2.120	C1···H5	3.127
C6···H5	2.150	H9···H12^vi	3.128
H41···H4	2.18 (4)	C13···H11^vii	3.129
C1···C5	2.216 (4)	C6···H1	3.132
H2···H3	2.232	C13···H10^viii	3.132
C3···C7	2.236 (4)	C10···H6a^xiii	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···H10^viii	3.175
O4···H3	2.333	O2···H4^i	3.186
H5···H6a	2.336	C6···H13	3.190
O4···C3	2.363 (4)	H6a···H11^vii	3.192
O5···C2	2.374 (3)	O1···H5	3.197
H1···H2	2.378	O1···H9^iii	3.204
C11···C13	2.389 (4)	C8···H41^i	3.22 (4)
C10···C12	2.391 (4)	H41···H3	3.22 (5)
C9···C11	2.397 (3)	H4···H6a^vi	3.225
C9···C13	2.397 (3)	C8···H10^viii	3.241
O1···H13	2.400	C1···H3^iii	3.245
O3···C8	2.401 (3)	O2···H5^i	3.246
C8···C10	2.402 (4)	C10···H4^i	3.252
C8···C12	2.407 (3)	O3···C5	3.257 (3)
H10···H11	2.410	C11···H13^ii	3.268
O2···C8	2.415 (3)	C6···H11^vii	3.274
H4···H6b	2.416	C13···H9^iii	3.274
H11···H12	2.418	C10···H12^vi	3.275
H12···H13	2.420	C10···H10^viii	3.284
H11···H13^ii	2.421	O5···C2^iv	3.287 (3)
O2···C1	2.421 (3)	H2···H7	3.294
H9···H10	2.429	C10···H11^viii	3.294
O4···C5	2.429 (3)	C12···H11^vii	3.299
O5···C4	2.430 (3)	O4···C2	3.302 (4)
O3···C4	2.433 (3)	C11···H6b^ii	3.303
H41···H5	2.44 (4)	C11···H12^ii	3.303
O1···C2	2.442 (2)	O1···H3^iii	3.307
O3···H4	2.463	O5···H4	3.312
H4···H5	2.477	C9···H10^viii	3.315
C7···C9	2.497 (4)	O1···C7^iii	3.315 (2)
C7···C13	2.507 (3)	O4···C2^v	3.317 (2)
C9···H7	2.527	O1···H2	3.317
C3···C5	2.527 (3)	O5···C1^iv	3.317 (3)
C1···C3	2.540 (3)	H4···H9^xi	3.320
O1···H7^iii	2.540	C13···H11	3.328
C4···C6	2.542 (3)	C12···H10	3.329
O5···H1^iv	2.544	C11···H13	3.330
H3···H7	2.571	C10···H12	3.333
H1···H7^iii	2.572	H6b···H10^ix	3.334
O4···H1^iv	2.581	C11···H9	3.335
C2···C4	2.593 (4)	C5···H2^iv	3.336
O4···H2^v	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···H11^viii	3.340
C3···H7	2.615	C4···H1^iv	3.340
H3···H4	2.619	C13···H7	3.340
H9···H13^vi	2.634	C13···H9	3.341
H6b···H12^vii	2.634	C13···H12^vii	3.341
O5···H2	2.636	C8···H10	3.343
H10···H12^vi	2.639	O4···H2	3.345
C5···H41	2.64 (4)	C8···H12	3.349
C7···H9	2.687	C3···H6a^vi	3.349
C7···H13	2.690	O1···O3^iii	3.349 (2)
H5···H6b	2.696	C1···H3	3.352
H41···H3^v	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···H11^viii	2.750	C4···H6a	3.390
H5···H9^ix	2.756	C2···H4	3.392
C10···C13	2.763 (4)	C12···H4^i	3.394
C9···C12	2.768 (3)	C1···C7	3.398 (3)
O5···H6a	2.769	O1···C7	3.402 (2)
H6a···H9^ix	2.771	C6···H9^ix	3.403
C8···H4^i	2.772	C7···H4^i	3.406
C8···C11	2.773 (4)	C1···H41^x	3.41 (4)
O2···H13	2.774	C3···H5	3.412
O4···H3^v	2.782	H6a···H7^iii	3.415
H11···H12^ii	2.786	O2···C4^i	3.415 (4)
O5···H2^iv	2.791	O4···C1^iv	3.418 (3)
H41···H1^iv	2.80 (4)	C3···H1	3.431
C7···H41^i	2.80 (5)	C12···H6b^i	3.444
O2···O4^i	2.803 (3)	O4···O5^iv	3.446 (3)
O1···O2	2.804 (2)	O3···C9	3.455 (4)
O2···H3	2.808	C9···H13^vi	3.462
H6a···H10^ix	2.811	C12···H10^iii	3.476
C2···C5	2.824 (4)	O2···O5^x	3.479 (2)
O5···C3	2.832 (3)	C5···H9^ix	3.480
C9···H11^viii	2.834	C11···H6a^ii	3.485
C2···H7	2.844	O4···H7^v	3.487
H2···H5^x	2.845	H5···H13^xi	3.490
C1···C4	2.858 (4)	C11···H4^i	3.491
O3···H6a^vi	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)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2^xi	0.96 (5)	1.86 (5)	2.803 (3)	167 (4)
C2—H2···O4^xii	1.04	2.59	3.317 (2)	126
C7—H7···O1^vi	1.04	2.54	3.316 (2)	131
C13—H13···O1	1.04	2.40	3.353 (3)	152
C1—H1···O5^x	1.04	2.54	3.317 (3)	131
C4—H4···Cg^xi	1.04	2.83	3.843 (3)	165
C10—H10···Cg^xiv	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

Crystal data

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) Å^3	Rectangular plate, colourless
Z = 4	0.43 × 0.33 × 0.05 mm

Data collection

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

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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···H31^i	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···H12^x	2.819
O4···H7b	2.013	H5···H7b^iv	2.825
O1···H21^ii	2.03 (3)	C7···H3	2.857
O4···H4	2.034	H3···H6a^vi	2.858
O5···H5	2.036	H7a···H13^ix	2.882
O1···H6a	2.049	H6a···H7b^viii	2.886
O1···H6b	2.049	O5···H6a^v	2.887
O1···H1	2.052	C3···H7b	2.889
C8···H7a	2.087	O5···C3	2.895 (3)
C8···H7b	2.088	H10···H11^iii	2.895
C12···H13	2.093	H10···H10^iii	2.905
C11···H10	2.093	H1···H3^iv	2.911
C10···H9	2.097	C4···H2	2.923
C11···H12	2.099	C9···H7a	2.932
C12···H11	2.100	C10···H5^vi	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···H21^ii	2.95 (4)
C1···H2	2.105	C9···H5^vi	2.965
C8···H9	2.106	O1···O2	2.968 (2)
C4···H5	2.110	C12···H7a^v	2.975
C2···H3	2.114	C1···H6b	2.979
C3···H2	2.114	H21···H1^ii	2.98 (4)
C2···H1	2.115	H31···H1^ix	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···H5^vi	3.004
C4···H3	2.129	H4···H9^viii	3.005
C6···H5	2.156	C1···H21^ii	3.01 (3)
C1···C5	2.205 (4)	C12···H12^x	3.018
H31···H3	2.24 (4)	C2···H31^i	3.02 (3)
O1···O5	2.252 (3)	C1···H6a	3.024
H3···H7b	2.278	C5···H7b^iv	3.039
O5···C6	2.292 (4)	O4···H6b^vi	3.039
H4···H7a	2.294	H6b···H7b^iv	3.040
H2···H3	2.298	H31···H2^xi	3.04 (3)
C1···C6	2.300 (5)	H21···H2^xi	3.04 (3)
O1···C5	2.323 (3)	H3···H6b^vi	3.043
H5···H6b	2.346	C13···H7a	3.044
O4···C5	2.348 (3)	C10···H12^x	3.045
H11···H11^iii	2.349	O4···H2	3.054
H21···H31	2.36 (6)	C8···H5^vi	3.088
C4···C7	2.373 (4)	C13···H7a^v	3.095
O5···C2	2.376 (3)	C1···H6a^v	3.106
C10···C12	2.378 (5)	C12···H5^vi	3.112
O4···C8	2.380 (3)	C1···H5	3.118
C9···C13	2.381 (4)	C6···H2^viii	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···H5^vi	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···H1^ii	3.148
H1···H2	2.413	O4···C2	3.151 (3)
H11···H12	2.414	C5···H9^iv	3.151
H9···H10	2.415	O5···H6a	3.159
H10···H11	2.416	H11···H12^x	3.159
H21···H31^i	2.42 (5)	H6b···H7b^viii	3.163
O2···C1	2.422 (3)	C11···H11^iii	3.164
O5···H7b^iv	2.426	C6···H21^ii	3.17 (3)
H4···H5	2.429	C3···C7	3.172 (4)
H1···H6a^v	2.431	O2···H3^i	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···H21^xi	3.19 (3)
O3···C2	2.445 (4)	O1···H5	3.195
O1···C2	2.446 (3)	C9···H4^vi	3.201
H2···H6b^vi	2.446	O1···H3^iv	3.210
O4···C3	2.454 (3)	C4···H31	3.22 (4)
C7···H4	2.462	O2···H2^xi	3.232
H7b···H9	2.468	H21···H3	3.24 (3)
O3···H6a	2.474	C11···H10^iii	3.244
C7···C9	2.502 (4)	C10···H10^iii	3.259
C1···H21	2.51 (3)	C10···H7a^vi	3.262
H4···H6a	2.527	H31···H6a	3.26 (3)
C7···C13	2.528 (5)	H5···H7a^iv	3.275
C2···C4	2.535 (3)	C10···H13^vii	3.280
C1···C3	2.535 (4)	C13···H11^x	3.287
O4···H5	2.538	H31···H4	3.29 (3)
C3···C5	2.539 (3)	C13···H10^iv	3.288
C4···C6	2.548 (3)	C2···H31^v	3.29 (4)
O4···H3	2.549	O5···H4^v	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···H13^vii	2.575	O2···H1^ii	3.297
H7a···H10^viii	2.583	H2···H6a^vi	3.298
O2···H31	2.60 (4)	O5···H3^iv	3.300
O3···H2^ix	2.597	O5···H4	3.301
H31···H2^ix	2.60 (4)	C1···H3^iv	3.301
C4···H7b	2.607	O3···C2^ix	3.305 (4)
C4···H7a	2.608	H11···H13^xii	3.305
O5···H2	2.608	O2···H21^i	3.31 (4)
C4···H6a	2.616	O3···C1^ix	3.310 (4)
O2···H1	2.627	C8···H6b^vi	3.313
C9···H7b	2.636	C10···H12	3.319
H5···H9^iv	2.644	C12···H10	3.320
H7a···H12^ix	2.658	C13···H9	3.324
H4···H7b	2.665	C11···H13	3.325
H9···H13^vii	2.674	C9···H13^vii	3.325
C7···H9	2.680	O1···H2	3.326
H10···H12^vii	2.680	C9···H13	3.327
C3···H21	2.69 (3)	C13···H11	3.327
H5···H6a	2.703	O2···H31^v	3.33 (4)
O3···H1^ix	2.715	C11···H9	3.327
C7···H13	2.721	O1···H2^viii	3.330
H21···H2	2.72 (4)	C12···H10^iv	3.330
C2···H31	2.74 (4)	H3···H6b^vii	3.334
O2···O3^i	2.741 (2)	C9···H11	3.335
O5···H9^iv	2.743	H4···H10^viii	3.338
C10···C13	2.744 (4)	C8···H12	3.348
C9···C12	2.755 (5)	C8···H10	3.348
O1···O2^ii	2.761 (3)	H21···H6b^ii	3.35 (3)
H21···H1	2.76 (3)	C7···H6b^vi	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)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H21···O1^ii	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···O2^xi	0.93 (3)	1.85 (3)	2.741 (2)	159 (4)
C2—H2···O3^v	1.04	2.60	3.305 (4)	125
C7—H7b···O5^vii	1.04	2.43	3.409 (3)	157
C5—H5···Cg^viii	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

Crystal data

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) Å^3	Rectangular prism, colourless
Z = 2	0.43 × 0.30 × 0.17 mm

Data collection

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

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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···H2^i	2.87 (5)
C2···H21	1.98 (5)	C12···H12^iv	2.874
O3···H7	2.023	C7···H6b	2.879
O5···H1	2.026	H21···H1^i	2.90 (6)
O1···H1	2.027	O2···O5	2.905 (3)
O2···H2	2.030	H1···H11^vi	2.905
O5···H5	2.048	O4···C6	2.936 (4)
O4···H7	2.050	O2···O5^viii	2.949 (4)
O1···H6b	2.051	C13···H7^v	2.950
O1···H6a	2.053	C13···H12^iv	2.954
C8···H7	2.057	C8···H7^v	2.972
O4···H4	2.061	C13···H6b	2.984
O5···H21^i	2.06 (5)	C1···H6a	2.986
O3···H3	2.064	C1···H21^i	2.99 (6)
C11···H12	2.092	H21···H10^v	3.00 (4)
C2···H3	2.094	C1···H6b	3.002
C10···H9	2.095	O4···H11^iv	3.003
C12···H11	2.098	C5···H21^i	3.00 (5)
C10···H11	2.099	C7···H4	3.006
C5···H4	2.099	H7···H7^x	3.009
C2···H1	2.101	H7···H7^v	3.009
C1···H2	2.101	O5···H6a^iii	3.011
C4···H3	2.104	C5···H11^iv	3.013
C8···H9	2.104	C7···H7^v	3.020
C3···H2	2.106)	O1···C3	3.020 (3)
C11···H10	2.107	C11···H12^iv	3.021
C9···H10	2.107	O1···H5^ix	3.023
C13···H12	2.108	C10···H1^xi	3.024
C4···H5	2.109	O4···H9	3.039
C12···H13	2.112	C3···H6b	3.044
C8···H13	2.113	C12···H9^ii	3.059
C3···H4	2.116	C3···C6	3.064 (3)
C5···H6a	2.124	C9···H12^vii	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···H3^v	3.113
C3···C7	2.228 (4)	H21···H3	3.12 (5)
H3···H4	2.230	C5···H6a^iii	3.127
H2···H4^ii	2.252	O3···C6	3.130 (3)
O3···O4	2.260 (4)	C2···C6	3.130 (4)
O1···O5	2.267 (4)	C6···H5^ix	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···H1^xi	3.139
H5···H6a	2.330	O3···H4	3.142
O1···C5	2.331 (4)	C1···H10^vi	3.151
O4···C3	2.339 (4)	C4···H21^i	3.15 (5)
O2···H3	2.350	C8···H12^iv	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···H12^iv	3.183
O2···C1	2.391 (4)	C13···H3^v	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···H4^ii	3.197
O5···C2	2.403 (4)	C2···H9^v	3.203
O4···C8	2.406 (4)	O1···H4^ii	3.205
C8···C10	2.407 (4)	H6a···H10^xii	3.210
H11···H12	2.409	C11···H3^v	3.210
O1···C2	2.415 (3)	H6b···H10^xii	3.211
O4···C5	2.415 (3)	H7···H9^v	3.215
H9···H10	2.416	H4···H7	3.215
H10···H11	2.419	C2···H21^i	3.22 (6)
O3···C8	2.421 (3)	O2···C1^i	3.224 (5)
H5···H6a^iii	2.426	C10···H12^iv	3.228
H12···H13	2.427	H21···H1^viii	3.23 (6)
O3···C2	2.435 (3)	H2···H10^v	3.240
H7···H9	2.439	C13···H7	3.246
O3···H2	2.453	H1···H6a^ix	3.248
C7···C9	2.465 (4)	C9···H2^x	3.251
H1···H2	2.473	O2···C2^i	3.254 (4)
O3···H13	2.495	H21···H5^viii	3.25 (5)
H6b···H11^iv	2.497	H10···H12^vii	3.279
O4···H6b	2.505	H9···H13^vii	3.279)
H3···H9^v	2.507	C4···H2^vii	3.286
O2···H1^i	2.518	O5···H2	3.287
C1···C3	2.523 (4)	O3···C1	3.287 (3)
C7···C13	2.530 (5)	C9···H12^iv	3.291
C3···C5	2.538 (4)	O2···H4^viii	3.296
O2···H1	2.540	H1···H3^viii	3.308
H3···H7	2.543	C1···H3	3.317
O3···H9^v	2.550	C9···H11	3.321
C4···C6	2.552 (4)	C11···H9	3.322
H6a···H11^iv	2.559	C10···H12	3.328
O1···H2	2.588	O3···H4^ii	3.329
C9···H7	2.594	C13···H9	3.335
C3···H7	2.594	C10···H12^vii	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···O2^i	3.339 (4)
H2···H3	2.630)	O2···O2^viii	3.339 (4)
H5···H11^iv	2.631	C13···H11	3.340
O5···H4	2.641	C5···H3	3.341
O5···H10^vi	2.648	C13···H9^ii	3.344
O3···H6b	2.658	C8···H10	3.348
O3···H7^v	2.667	O2···C4	3.349 (4)
H21···H1	2.67 (4)	H12···H12^iv	3.353
O4···H13^vii	2.679	H12···H12^xii	3.353
H1···H10^vi	2.680	O2···H10^v	3.359
H21···H4^viii	2.69 (5)	C8···H3^v	3.361
H5···H6b	2.707	C11···H6b^xii	3.367
O4···H5	2.741	H4···H13^vii	3.373
C7···H13	2.748	O4···C13	3.379 (5)
O2···H21^i	2.75 (5)	O3···C9^v	3.381 (4)
H9···H12^vii	2.752	C10···H3^v	3.384
C9···C12	2.755 (5)	C1···H4	3.385
C8···C11	2.769 (5)	C4···H2	3.391
C6···H11^iv	2.775	C4···H6a	3.399
C10···C13	2.778 (5)	H21···H21^viii	3.41 (8)
O1···H5^ii	2.786	H21···H21^i	3.41 (8)
O1···H6a^ix	2.803	C3···H1	3.406
H2···H9^v	2.803	C5···C7	3.411 (4)
O5···H6a	2.807	C7···H9^v	3.419
C4···H7	2.809	O2···H4	3.423
O5···C3	2.810 (3)	C3···H5	3.430
O2···H2^i	2.811	C6···H4	3.431
O3···C13	2.817 (4)	C9···H3^v	3.438
C3···H9^v	2.818	C2···H6b	3.449
O4···H3	2.825	C1···H21^viii	3.46 (6)
C1···C4	2.827 (5)	C10···H2^x	3.473
C1···H21	2.83 (5)	H12···H13^xii	3.476
H7···H13^x	2.843	O5···H3	3.486
C2···C5	2.855 (5)	C3···H21^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H21···O5^viii	0.91 (6)	2.06 (5)	2.950 (4)	161 (4)
C1—H1···O2^viii	1.04	2.52	3.224 (5)	125
C9—H9···O3^x	1.04	2.55	3.381 (4)	136
C3—H3···Cg^x	1.04	2.98	3.971 (3)	160
C12—H12···Cg^xii	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.