Crystal structure of 4-nitro­phenyl 6-O-ethyl-β-d-galacto­pyran­oside monohydrate

Silva, B.L.; Alves, R.J.; Speziali, N.L.

doi:10.1107/S2056989017004595

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 4| April 2017| Pages 598-601

https://doi.org/10.1107/S2056989017004595

Open

access

Crystal structure of 4-nitrophenyl 6-O-ethyl-β-D-galactopyranoside monohydrate

Bruno Leonardo Silva,^a ^* Ricardo José Alves ^a and Nivaldo Lúcio Speziali ^b

^aDepartamento de Produtos Farmacêuticos – Faculdade de Farmácia – Universidade Federal de Minas Gerais – Avenida Antônio Carlos 6627, Belo Horizonte MG, 31.270-901, Brazil, and ^bDepartamento de Física – Instituto de Ciências Exatas – Universidade Federal de Minas Gerais – Avenida Antônio Carlos 6627, Belo Horizonte MG, 31.270-901, Brazil
^*Correspondence e-mail: brunoleoufmg@hotmail.com

Edited by G. Smith, Queensland University of Technology, Australia (Received 17 February 2017; accepted 22 March 2017; online 28 March 2017)

The synthesis and crystal structure of the title compound, C₁₄H₁₉NO₈·H₂O, prepared in three steps from 6-O-ethyl-1,2;3,4-di-O-isopropylidene-α-D-galactopyranose using protecting-group strategies employed in carbohydrate chemistry, is reported. The asymmetric unit consists of a single galactoside molecule, in which the pyranoid ring has a ⁴C₁ conformation and the 4-nitrophenyl moiety is essentially planar. In the crystal, each carbohydrate is surrounded by other D-galactose residues and water molecules, linked by O—H⋯O hydrogen bonds involving all hydroxy groups, giving a two-dimensional substructure lying parallel to (100) and extended into three dimensions by C—H⋯O interactions.

Keywords: crystal structure; D-galactose; nitrophenyl galactopyranosides; pyranoid ring; hydrogen bonding.

CCDC reference: 1539718

1. Chemical context

Small molecules containing D-galactose moieties substituted at non-anomeric positions have been assayed against galactosidases (Viana et al., 2011 ; McCarter et al., 1992 ; Huber & Gaunt, 1983 ) and lectins (Butera et al., 2009 ; Salameh et al., 2005 ). Trypanosoma cruzi trans-sialidase (TcTS) (Mendonça-Previato et al., 2010 ), an enzyme involved in Chagas's disease infection, is inhibited by β-D-galactopyranosides substituted at the C6 ring site, which are in general more potent than the corresponding analogues modified at other ring positions of the carbohydrate (Harrison et al., 2011 ). In this context, the title compound C₁₄H₁₉NO₈ was designed and synthesized to be evaluated against TcTS and T. cruzi invasion of host cells. The synthesis and crystal structure of this compound as the monohydrate (I) is reported herein.

2. Structural commentary

In the structure of the title monohydrated compound (I) (Fig. 1), the pyranoid ring adopts a ⁴C₁ conformation, with puckering parameters Q = 0.569 (2) Å, θ = 4.6 (2)° and φ = 51 (3)°. The anomeric beta form and D-galacto configuration of the carbohydrate with C1(S), C2(R), C3(S), C4(R) and C5(R) are consistent with that expected from the synthesis. The length of the glycosidic bond is 1.408 (2) Å and the bond angles around the anomeric carbon atom (C1) range from 106.40 (16) to 111.35 (17)°. The 4-nitrophenyl substituent at C1 located in an equatorial position is essentially planar, with a r.m.s. deviation of 0.02 Å for non-hydrogen atoms [torsion angle C9—C10—N1—O11 = 179.0 (4)°]. The angle between the mean plane of the 4-nitrophenyl substituent (defined by atoms C7–C12/N1/O11/O12) and the mean sugar plane (defined by C1–C5/O5 atoms) is 57.45 (11)° [torsion angle O5—C1—O1—O7 = −79.8 (2)°]. An intramolecular C13—H13B⋯O5 interaction is also present (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯O6ⁱ	0.82	1.85	2.670 (2)	179
O3—H3B⋯O1Wⁱⁱ	0.82	1.91	2.711 (2)	167
O4—H4B⋯O3ⁱⁱⁱ	0.82	1.97	2.785 (2)	170
O1W—H1WA⋯O2^iv	0.89	1.90	2.776 (3)	166
O1W—H1WB⋯O3^v	0.89	2.39	3.208 (2)	154
C3—H3A⋯O4^vi	0.98	2.35	3.283 (3)	158
C13—H13A⋯O12^vii	0.97	2.55	3.167 (3)	121
C13—H13B⋯O5	0.97	2.53	3.173 (3)	123
Symmetry codes: (i) x, y-1, z; (ii) x-1, y-1, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) x, y+1, z; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (vi) x+1, y, z; (vii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, a carbohydrate moiety is connected to eight neighboring D-galactose residues by several direct and water-mediated classical hydrogen bonds (Table 1), establishing a network of interactions (Fig. 2). Regarding only the O—H⋯O interaction type, there are O2—H2B⋯O6ⁱ, O3—H3B⋯O1Wⁱⁱ and O4—H4B⋯O3ⁱⁱⁱ hydrogen bonds. In addition, there is a single-water bridge connecting O3 to O2 of a nearby galactoside molecule (O1W—H1WA⋯O2^iv and O1W—H1WB⋯O3^v; for symmetry codes, see Table 1). A two-dimensional substructure in the form of a sheet lying parallel to (100) is formed. The overall three-dimensional supramolecular aggregation is completed by intermolecular C—H⋯O interactions: C3—H3A⋯O4^vi connects carbohydrate rings stacked along the a axis and C13—H13A⋯O12^vii connects ethyl and nitro groups along the c axis. The 4-nitrophenyl substituent groups are arranged in parallel planes (Fig. 3), with an interplanar distance of 3.4355 (14) Å, but the slip angle (48.3°) prevents overlapping and therefore no π–π interactions are present [ring-centroid separation = 5.163 (2) Å].

Figure 2
Selected interactions in the crystal lattice with O—H⋯O hydrogen bonds shown as turquoise dashed lines and C—H⋯O interactions shown as blue dashed lines.

Figure 3
Crystal packing of the title compound, showing the stacked galactoside molecules along the a axis. For clarity, H atoms are not shown.

4. Database survey

To the best of our knowledge, this is the first report of the crystal structure of an aryl 6-O-substituted-β-D-galactopyranoside in the literature. In the Cambridge Structural Database (Version 5.38; Groom et al., 2016 ), the structural data for the closely related analogue 4-nitrophenyl β-D-galactopyranoside have been deposited (CSD Refcode VUCYO1; Gubica et al., 2009 ). Both galactosides are monohydrates and their molecular geometry and intermolecular interaction profiles in the crystal lattice are quite similar. The aromatic ring of the 6-unsubstituted galactoside is less planar due to the increased rotation of the N1—C10 bond, since the angle between the mean planes of the phenyl and nitro groups is ca 5.1°, compared to 2.6 (5)° in the title compound. According to the authors (Gubica et al., 2009), the deviation from coplanarity of these fragments in the 4-nitrophenyl β-D-galactopyranoside structure is due to intermolecular interactions involving the nitro group. In our crystallographic study on compound (I) we did not observe classical hydrogen bonds to 4-nitrophenyl O-atom acceptors, but only the weak C13—H13A⋯O12 interaction noted above.

5. Synthesis and crystallization

The chemical synthesis of 4-nitrophenyl 6-O-ethyl-β-D-galactopyranoside monohydrate (I) was achieved in three steps, as shown in Fig. 4.

Figure 4
Synthesis of the title compound (I)

: (i) AcCl, MeOH, HCl_(aq), room temperature, closed system; (ii) 4-nitrophenol, LiOH·H₂O, acetone/H₂O, room temperature; (iii) MeONa/MeOH, CH₂Cl₂, 273 K. The water molecule of crystallization of (I)

is not represented.

Initially the O-alkylation of 1,2;3,4-di-O-isopropylidene-α-D-galactopyranose was carried out as reported in the literature furnishing the 6-O-alkylated derivative (2) (Cironi & Varela, 2001 ; McKeown & Hayward, 1960 ). Next, the peracetylated α-D-galactopyranosyl chloride (3) was prepared in a three-step one-pot reaction as follows. To a solution of (2) (0.59 g, 2.06 mmol) in acetyl chloride (2.92 mL, 41.13 mmol) was added methanol (0.42 mL) under ice-bath conditions. The mixture was stirred at room temperature for 2h in a closed system and concentrated hydrochloric acid (0.34 mL) was then added and the resulting mixture was stirred at room temperature for 24 h, also in a closed system. The reaction was quenched with crushed ice (about 30 mL) and the mixture was extracted with dichloromethane (3 × 25 mL). The organic layers were washed with a saturated aqueous sodium bicarbonate solution (2 × 60 mL) and water (60 mL), then dried over anhydrous sodium sulfate and concentrated. The brown oil obtained (0.68 g, 94% yield) was used in the next step without further purification.

Classical procedures in carbohydrate chemistry were employed in the next two steps (Conchie et al., 1957 ). The glycosylation of 4-nitrophenol with (3) in alkaline medium gave (4) in 46% yield. Treatment with sodium methoxide to remove the acetyl groups furnished (I) (as the monohydrate), in 84% yield. Colorless crystals of (I) (m.p. 424.1–424.9 K) suitable for X-ray diffraction analysis were obtained by slow evaporation of an acetone solution (about 0.7 mg/mL) at room temperature.

Spectrometric data. [α]_D²⁸ −46 (c 1.0, DMSO). IR $[\overline \nu]$ _max (cm⁻¹): 3354 (O—H), 1608, 1592, 1493 (C=C), 1511, 1349 (NO₂), 1249, 1074 (C—O), 846 (C—H aromatic out-of-plane bending). ¹H NMR (400 MHz, DMSO-d₆): δ_H 8.20 (d, 2H, J_ortho 9.2 Hz, CHCNO₂), 7.22 (d, 2H, J_ortho 9.2 Hz, OCCH), 5.28 (d, 1H, J_OH-2,2 5.2 Hz, OH-2), 5.05 (d, 1H, J_1,2 7.6 Hz, H-1), 4.91 (d, 1H, J_OH-3,3 5.7 Hz, OH-3), 4.64 (d, 1H, J_OH-4,4 4.6 Hz, OH-4), 3.85 (t, 1H, J_5,6a 5.4 Hz, J_5,6b 5.4 Hz, H-5), 3.71–3.66 (m, 1H, H-4), 3.63 (ddd, 1H, J_2,1 7.6 Hz, J_2,OH-2 5.2 Hz, J_2,3 9.2 Hz, H-2), 3.55 (dd, 1H, J_6a,5 5.4 Hz, J_6a,6b 10.2 Hz, H-6a), 3.50–3.39 (m, 4H, H-3, H-6b and OCH₂CH₃), 1.09 (t, 3H, J_ortho 6.9 Hz, OCH₂CH₃). ¹³C NMR (100 MHz, DMSO-d₆): δ_C 162.4 (OCCH), 141.6 (CHCNO₂), 125.6 (CHCNO₂), 116.5 (OCCH), 100.3 (C-1), 73.8 (C-5), 73.0 (C-3), 70.0 (C-2), 69.1 (C-6), 68.3 (C-4), 65.7 (OCH₂CH₃), 15.1 (OCH₂CH₃).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Oxygen-bound H atoms were located in a difference-Fourier map and refined with distance restraints of 0.82 Å (hydroxy group H) and 0.89 Å (water H) with U_iso(H) = 1.5 U_eq(O). Carbon-bound H atoms were constrained to an ideal geometry with C—H distances in the range 0.93–0.98 Å, U_iso(H) = 1.5 U_eq(C) for methyl H atoms and U_iso(H) = 1.2 U_eq(C) for other H atoms. In the absence of significant anomalous scattering effects, the Flack structure parameter (Flack, 1983 ) is essentially meaningless in this analysis and the absolute configuration is inferred from the known D-galacto configuration of the starting material, and remained unchanged during the synthesis. The beta configuration of C1 is confirmed by the coupling constant J_1,2 = 7.6 Hz, obtained from NMR spectroscopy.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₉NO₈·H₂O
M_r	347.32
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.1628 (3), 8.1593 (3), 38.5755 (16)
V (Å³)	1624.99 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Rigaku OD Xcalibur, Atlas, Gemini Ultra
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.835, 1.000
No. of measured, independent and observed [I > 2/s(I)] reflections	26976, 4265, 3597
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.108, 1.08
No. of reflections	4265
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.23
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1539718

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017004595/zs2376sup1.cif

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

4-Nitrophenyl 6-O-ethyl-β-D-galactopyranoside monohydrate top

Crystal data top

C₁₄H₁₉NO₈·H₂O	D_x = 1.420 Mg m⁻³
M_r = 347.32	Melting point: 424.5 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8847 reflections
a = 5.1628 (3) Å	θ = 2.5–28.5°
b = 8.1593 (3) Å	µ = 0.12 mm⁻¹
c = 38.5755 (16) Å	T = 293 K
V = 1624.99 (13) Å³	Rod, colourless
Z = 4	0.20 × 0.15 × 0.10 mm
F(000) = 736

Data collection top

Rigaku OD Xcalibur, Atlas, Gemini Ultra diffractometer	4265 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3597 reflections with I > 2/s(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 10.4186 pixels mm^-1	θ_max = 30.0°, θ_min = 2.5°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −11→11
T_min = 0.835, T_max = 1.000	l = −54→52
26976 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0448P)² + 0.4091P] where P = (F_o² + 2F_c²)/3
4265 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.2973 (3)	0.04259 (19)	0.13258 (4)	0.0359 (4)
O2	0.3964 (4)	−0.11807 (19)	0.06875 (4)	0.0413 (4)
H2B	0.3333	−0.1933	0.0800	0.062*
O3	0.1726 (3)	0.0335 (2)	0.00904 (4)	0.0331 (4)
H3B	0.0444	−0.0206	0.0142	0.050*
O4	−0.1450 (3)	0.2630 (2)	0.04353 (4)	0.0340 (4)
H4B	−0.2160	0.3194	0.0287	0.051*
O5	0.1951 (3)	0.27596 (18)	0.10442 (3)	0.0300 (3)
O6	0.1929 (4)	0.63541 (19)	0.10524 (4)	0.0388 (4)
O11	1.0131 (8)	0.2628 (5)	0.25526 (8)	0.1100 (12)
O12	0.7670 (9)	0.0893 (4)	0.28005 (6)	0.1237 (14)
N1	0.8375 (8)	0.1651 (4)	0.25473 (7)	0.0748 (10)
C1	0.3383 (4)	0.1298 (3)	0.10156 (5)	0.0285 (4)
H1	0.5228	0.1538	0.0984	0.034*
C2	0.2387 (5)	0.0236 (3)	0.07205 (5)	0.0283 (4)
H2A	0.0581	−0.0078	0.0762	0.034*
C3	0.2607 (4)	0.1215 (2)	0.03863 (5)	0.0257 (4)
H3A	0.4454	0.1433	0.0350	0.031*
C4	0.1277 (4)	0.2877 (3)	0.04194 (5)	0.0254 (4)
H4A	0.1685	0.3539	0.0215	0.030*
C5	0.2224 (4)	0.3771 (2)	0.07412 (5)	0.0266 (4)
H5	0.4057	0.4049	0.0711	0.032*
C6	0.0717 (5)	0.5319 (3)	0.08045 (6)	0.0340 (5)
H6A	0.0534	0.5910	0.0588	0.041*
H6B	−0.1005	0.5037	0.0886	0.041*
C7	0.4348 (5)	0.0860 (3)	0.16169 (6)	0.0350 (5)
C8	0.3682 (7)	−0.0008 (3)	0.19102 (6)	0.0521 (7)
H8	0.2354	−0.0778	0.1902	0.062*
C9	0.5004 (8)	0.0274 (4)	0.22159 (7)	0.0629 (9)
H9	0.4563	−0.0297	0.2416	0.076*
C10	0.6952 (6)	0.1392 (4)	0.22221 (6)	0.0515 (7)
C11	0.7581 (8)	0.2284 (5)	0.19380 (7)	0.0651 (9)
H11	0.8884	0.3069	0.1950	0.078*
C12	0.6266 (7)	0.2019 (4)	0.16305 (7)	0.0596 (9)
H12	0.6684	0.2623	0.1434	0.072*
C13	0.0993 (6)	0.6211 (3)	0.14011 (6)	0.0431 (6)
H13A	0.2266	0.6673	0.1558	0.052*
H13B	0.0799	0.5059	0.1458	0.052*
C14	−0.1538 (7)	0.7057 (5)	0.14554 (9)	0.0696 (10)
H14A	−0.1984	0.7024	0.1697	0.104*
H14B	−0.2858	0.6514	0.1323	0.104*
H14C	−0.1400	0.8177	0.1381	0.104*
O1W	0.7487 (4)	0.8396 (2)	0.01513 (5)	0.0579 (6)
H1WA	0.6231	0.8390	0.0309	0.087*
H1WB	0.7808	0.7339	0.0114	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0504 (10)	0.0340 (8)	0.0232 (7)	−0.0048 (8)	−0.0058 (7)	0.0061 (6)
O2	0.0589 (11)	0.0259 (8)	0.0391 (9)	0.0043 (8)	0.0131 (8)	0.0045 (7)
O3	0.0378 (8)	0.0389 (8)	0.0226 (7)	−0.0109 (7)	0.0029 (6)	−0.0054 (6)
O4	0.0266 (8)	0.0428 (9)	0.0326 (8)	−0.0055 (7)	−0.0060 (7)	0.0056 (7)
O5	0.0428 (9)	0.0267 (7)	0.0205 (6)	0.0025 (7)	−0.0005 (7)	0.0016 (6)
O6	0.0548 (11)	0.0289 (8)	0.0326 (8)	−0.0085 (8)	0.0020 (8)	−0.0043 (7)
O11	0.101 (2)	0.158 (3)	0.0708 (18)	−0.019 (3)	−0.0407 (17)	−0.029 (2)
O12	0.211 (4)	0.120 (2)	0.0396 (12)	−0.013 (3)	−0.0491 (19)	0.0032 (15)
N1	0.104 (3)	0.082 (2)	0.0393 (14)	0.021 (2)	−0.0273 (16)	−0.0178 (14)
C1	0.0346 (11)	0.0263 (10)	0.0247 (9)	−0.0019 (9)	−0.0023 (9)	0.0051 (8)
C2	0.0335 (11)	0.0256 (9)	0.0258 (9)	−0.0022 (9)	0.0035 (9)	0.0010 (8)
C3	0.0283 (10)	0.0289 (10)	0.0199 (8)	−0.0053 (9)	0.0013 (8)	−0.0012 (8)
C4	0.0275 (10)	0.0287 (10)	0.0200 (9)	−0.0053 (8)	−0.0007 (8)	0.0044 (8)
C5	0.0305 (11)	0.0259 (9)	0.0234 (9)	−0.0055 (9)	−0.0031 (8)	0.0034 (8)
C6	0.0435 (13)	0.0289 (10)	0.0296 (10)	0.0001 (10)	−0.0060 (9)	0.0001 (9)
C7	0.0494 (14)	0.0309 (11)	0.0248 (10)	0.0063 (10)	−0.0055 (10)	−0.0004 (9)
C8	0.085 (2)	0.0448 (15)	0.0267 (11)	−0.0106 (15)	−0.0050 (13)	0.0029 (10)
C9	0.109 (3)	0.0573 (17)	0.0229 (11)	−0.002 (2)	−0.0065 (15)	0.0044 (12)
C10	0.071 (2)	0.0533 (16)	0.0296 (12)	0.0133 (16)	−0.0161 (13)	−0.0103 (12)
C11	0.074 (2)	0.079 (2)	0.0422 (15)	−0.024 (2)	−0.0151 (15)	−0.0040 (15)
C12	0.076 (2)	0.069 (2)	0.0341 (13)	−0.0261 (18)	−0.0139 (14)	0.0098 (13)
C13	0.0567 (16)	0.0445 (14)	0.0282 (11)	−0.0012 (13)	0.0004 (11)	−0.0034 (11)
C14	0.0544 (19)	0.097 (3)	0.0570 (18)	0.0062 (19)	0.0048 (15)	−0.0203 (18)
O1W	0.0500 (11)	0.0482 (11)	0.0753 (13)	−0.0145 (10)	0.0207 (11)	−0.0187 (10)

Geometric parameters (Å, º) top

O1—C1	1.408 (2)	C5—H5	0.9800
O1—C7	1.375 (3)	C5—C6	1.504 (3)
O2—H2B	0.8200	C6—H6A	0.9700
O2—C2	1.420 (3)	C6—H6B	0.9700
O3—H3B	0.8201	C7—C8	1.379 (3)
O3—C3	1.423 (2)	C7—C12	1.370 (4)
O4—H4B	0.8199	C8—H8	0.9300
O4—C4	1.424 (3)	C8—C9	1.382 (4)
O5—C1	1.408 (3)	C9—H9	0.9300
O5—C5	1.438 (2)	C9—C10	1.358 (5)
O6—C6	1.421 (3)	C10—C11	1.355 (4)
O6—C13	1.434 (3)	C11—H11	0.9300
O11—N1	1.207 (5)	C11—C12	1.384 (4)
O12—N1	1.212 (4)	C12—H12	0.9300
N1—C10	1.469 (4)	C13—H13A	0.9700
C1—H1	0.9800	C13—H13B	0.9700
C1—C2	1.520 (3)	C13—C14	1.493 (4)
C2—H2A	0.9800	C14—H14A	0.9600
C2—C3	1.521 (3)	C14—H14B	0.9600
C3—H3A	0.9800	C14—H14C	0.9600
C3—C4	1.526 (3)	O1W—H1WA	0.8898
C4—H4A	0.9800	O1W—H1WB	0.8902
C4—C5	1.520 (3)

C7—O1—C1	119.10 (18)	C6—C5—H5	108.9
C2—O2—H2B	109.5	O6—C6—C5	112.37 (18)
C3—O3—H3B	109.5	O6—C6—H6A	109.1
C4—O4—H4B	109.4	O6—C6—H6B	109.1
C1—O5—C5	111.77 (15)	C5—C6—H6A	109.1
C6—O6—C13	115.74 (19)	C5—C6—H6B	109.1
O11—N1—O12	123.3 (3)	H6A—C6—H6B	107.9
O11—N1—C10	119.0 (3)	O1—C7—C8	114.2 (2)
O12—N1—C10	117.7 (4)	C12—C7—O1	125.6 (2)
O1—C1—H1	110.5	C12—C7—C8	120.2 (2)
O1—C1—C2	107.33 (16)	C7—C8—H8	120.3
O5—C1—O1	106.40 (16)	C7—C8—C9	119.5 (3)
O5—C1—H1	110.5	C9—C8—H8	120.3
O5—C1—C2	111.35 (17)	C8—C9—H9	120.2
C2—C1—H1	110.5	C10—C9—C8	119.5 (3)
O2—C2—C1	109.70 (18)	C10—C9—H9	120.2
O2—C2—H2A	110.3	C9—C10—N1	118.8 (3)
O2—C2—C3	107.99 (16)	C11—C10—N1	119.6 (3)
C1—C2—H2A	110.3	C11—C10—C9	121.6 (3)
C1—C2—C3	108.08 (16)	C10—C11—H11	120.3
C3—C2—H2A	110.3	C10—C11—C12	119.4 (3)
O3—C3—C2	113.03 (16)	C12—C11—H11	120.3
O3—C3—H3A	106.8	C7—C12—C11	119.7 (3)
O3—C3—C4	111.82 (17)	C7—C12—H12	120.1
C2—C3—H3A	106.8	C11—C12—H12	120.1
C2—C3—C4	111.25 (16)	O6—C13—H13A	109.0
C4—C3—H3A	106.8	O6—C13—H13B	109.0
O4—C4—C3	108.80 (17)	O6—C13—C14	112.9 (2)
O4—C4—H4A	109.0	H13A—C13—H13B	107.8
O4—C4—C5	110.55 (17)	C14—C13—H13A	109.0
C3—C4—H4A	109.0	C14—C13—H13B	109.0
C5—C4—C3	110.47 (17)	C13—C14—H14A	109.5
C5—C4—H4A	109.0	C13—C14—H14B	109.5
O5—C5—C4	110.93 (16)	C13—C14—H14C	109.5
O5—C5—H5	108.9	H14A—C14—H14B	109.5
O5—C5—C6	107.41 (17)	H14A—C14—H14C	109.5
C4—C5—H5	108.9	H14B—C14—H14C	109.5
C6—C5—C4	111.64 (17)	H1WA—O1W—H1WB	104.0

O1—C1—C2—O2	−67.1 (2)	C1—O5—C5—C6	−177.75 (17)
O1—C1—C2—C3	175.37 (17)	C1—C2—C3—O3	179.94 (18)
O1—C7—C8—C9	177.4 (3)	C1—C2—C3—C4	−53.3 (2)
O1—C7—C12—C11	−177.0 (3)	C2—C3—C4—O4	−70.0 (2)
O2—C2—C3—O3	61.3 (2)	C2—C3—C4—C5	51.5 (2)
O2—C2—C3—C4	−171.91 (17)	C3—C4—C5—O5	−53.3 (2)
O3—C3—C4—O4	57.4 (2)	C3—C4—C5—C6	−173.06 (17)
O3—C3—C4—C5	178.97 (16)	C4—C5—C6—O6	−166.46 (18)
O4—C4—C5—O5	67.2 (2)	C5—O5—C1—O1	179.69 (16)
O4—C4—C5—C6	−52.6 (2)	C5—O5—C1—C2	−63.7 (2)
O5—C1—C2—O2	176.81 (16)	C6—O6—C13—C14	−77.1 (3)
O5—C1—C2—C3	59.3 (2)	C7—O1—C1—O5	−79.8 (2)
O5—C5—C6—O6	71.7 (2)	C7—O1—C1—C2	160.93 (19)
O11—N1—C10—C9	179.0 (4)	C7—C8—C9—C10	−0.5 (5)
O11—N1—C10—C11	−2.0 (5)	C8—C7—C12—C11	1.6 (5)
O12—N1—C10—C9	−2.8 (5)	C8—C9—C10—N1	−178.7 (3)
O12—N1—C10—C11	176.2 (4)	C8—C9—C10—C11	2.3 (5)
N1—C10—C11—C12	178.9 (3)	C9—C10—C11—C12	−2.1 (5)
C1—O1—C7—C8	176.3 (2)	C10—C11—C12—C7	0.1 (6)
C1—O1—C7—C12	−4.9 (4)	C12—C7—C8—C9	−1.4 (5)
C1—O5—C5—C4	60.0 (2)	C13—O6—C6—C5	−96.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O6ⁱ	0.82	1.85	2.670 (2)	179
O3—H3B···O1Wⁱⁱ	0.82	1.91	2.711 (2)	167
O4—H4B···O3ⁱⁱⁱ	0.82	1.97	2.785 (2)	170
O1W—H1WA···O2^iv	0.89	1.90	2.776 (3)	166
O1W—H1WB···O3^v	0.89	2.39	3.208 (2)	154
C3—H3A···O4^vi	0.98	2.35	3.283 (3)	158
C13—H13A···O12^vii	0.97	2.55	3.167 (3)	121
C13—H13B···O5	0.97	2.53	3.173 (3)	123

Symmetry codes: (i) x, y−1, z; (ii) x−1, y−1, z; (iii) x−1/2, −y+1/2, −z; (iv) x, y+1, z; (v) x+1/2, −y+1/2, −z; (vi) x+1, y, z; (vii) −x+1, y+1/2, −z+1/2.

Funding information

Funding for this research was provided by: Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq).

References

Butera, A. P., Filho, J. de S., Prado, M. A. F., Lisboa, M. P. & Alves, R. J. (2009). Helv. Chim. Acta, 92, 176–187. CrossRef CAS Google Scholar
Cironi, P. & Varela, O. (2001). J. Braz. Chem. Soc. 12, 667–672. CrossRef CAS Google Scholar
Conchie, J., Levvy, G. A. & Marsh, C. A. (1957). Adv. Carbohydr. Chem. 12, 157–187. PubMed CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gubica, T., Temeriusz, A., Paradowska, K., Ostrowski, A., Klimentowska, P. & Cyrański, M. K. (2009). Carbohydr. Res. 344, 1734–1744. CSD CrossRef PubMed CAS Google Scholar
Harrison, J. A., Kartha, K. P. R., Fournier, E. J. L., Lowary, T. L., Malet, C., Nilsson, U. J., Hindsgaul, O., Schenkman, S., Naismith, J. H. & Field, R. A. (2011). Org. Biomol. Chem. 9, 1653–1660. CrossRef CAS PubMed Google Scholar
Huber, R. E. & Gaunt, M. T. (1983). Arch. Biochem. Biophys. 220, 263–271. CrossRef CAS PubMed Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
McCarter, J. D., Adam, M. J. & Withers, S. G. (1992). Biochem. J. 286, 721–727. CrossRef PubMed CAS Google Scholar
McKeown, G. G. & Hayward, L. D. (1960). Can. J. Chem. 38, 174–175. CrossRef CAS Google Scholar
Mendonça-Previato, L., Todeschini, A. R., Freire de Lima, L. & Previato, J. O. (2010). Open Parasitol. J. 4, 111–115. Google Scholar
Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Salameh, B. A., Leffler, H. & Nilsson, U. J. (2005). Bioorg. Med. Chem. Lett. 15, 3344–3346. CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Viana, P. A., de Rezende, S. T., Alves, A. de A., Manfrini, R. M., Alves, R. J., Bemquerer, M. P., Santoro, M. M. & Guimarães, V. M. (2011). Carbohydr. Res. 346, 602–605. CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.