2-Acetamido-2-de­oxy-3-O-β-d-galactopyranosyl-d-glucose dihydrate

Wada, M.; Kobayashi, K.; Nishimoto, M.; Kitaoka, M.; Noguchi, K.

doi:10.1107/S1600536809024775

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages o1781-o1782

doi:10.1107/S1600536809024775

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2-Acetamido-2-deoxy-3-O-β-D-galactopyranosyl-D-glucose dihydrate

Masahisa Wada,^a ^* Kayoko Kobayashi,^a Mamoru Nishimoto,^b Motomitsu Kitaoka ^b and Keiichi Noguchi ^c

^aDepartment of Biomaterials Science, Graduate School of Agricultural and Life Science, The University of Tokyo, Yayoi 1-1-1, Bunkyo-ku, Tokyo 113-8657, Japan, ^bNational Food Research Institute, National Agriculture and Food Research Organization, 2-1-12 Kanondai, Tsukuba, Ibaraki 305-8642, Japan, and ^cInstrumentaion Analysis Center, Tokyo University of Agriculture & Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan
^*Correspondence e-mail: awadam@mail.ecc.u-tokyo.ac.jp

(Received 16 June 2009; accepted 27 June 2009; online 4 July 2009)

In the title compound, C₁₄H₂₅NO₁₁·2H₂O, the primary hydroxyl group connected to the anomeric C atom of the N-acetyl-β-D-glucopyranose residue exhibits positional disorder, with occupancy factors for the α and β anomers of 0.77 and 0.23, respectively. The two torsion angles (Φ and Ψ) and the bridge angle (τ) that describe conformation of the glycosidic linkage between the galactopyranose and glucopyranose rings are Φ = −81.6 (3)°, Ψ = 118.1 (2)° and τ = 115.2 (2)°. Two water molecules stabilize the molecular packing by forming hydrogen bonds with the saccharide residues.

Related literature

For the synthesis of the title compound, see: Kitaoka et al. (2005 ); Nishimoto & Kitaoka (2007a ,b ). For the conformation of saccharide rings, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₄H₂₅NO₁₁·2H₂O
M_r = 419.38
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.284 (1) Å
b = 12.841 (1) Å
c = 17.503 (1) Å
V = 1861.9 (3) Å³
Z = 4
Synchrotron radiation
λ = 0.80000 Å
μ = 0.13 mm⁻¹
T = 95 K
0.10 × 0.10 × 0.10 mm

Data collection

ADSC Quantum 210r diffractometer
Absorption correction: none
25787 measured reflections
2153 independent reflections
2046 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.115
S = 1.06
2153 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond and torsion angles (°)

C1—O1—C9	115.2 (2)

O5—C1—O1—C9	−81.6 (3)
C2—C1—O1—C9	159.0 (2)
C1—O1—C9—C10	118.0 (2)
C1—O1—C9—C8	−123.3 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2Wⁱ	0.88	2.05	2.923 (3)	169
O2—H2O⋯O12ⁱⁱ	0.85	1.80	2.642 (3)	170
O3—H3O⋯O2W	0.85	1.86	2.702 (3)	169
O4—H4O⋯O13ⁱⁱ	0.93	1.95	2.803 (3)	150
O6—H6O⋯O1Wⁱⁱⁱ	0.85	1.79	2.624 (3)	168
O10—H10O⋯O6^iv	0.96	1.81	2.705 (3)	154
O1W—H11W⋯O10^iv	0.85	1.85	2.696 (3)	175
O12—H12O⋯O13^v	0.85	1.96	2.784 (3)	162
O1W—H12W⋯O4	0.87	1.90	2.759 (3)	173
O2W—H21W⋯O11^vi	0.90	1.94	2.772 (3)	154
O2W—H22W⋯O6^vii	0.85	1.91	2.757 (3)	171
O71—H71O⋯O2ⁱ	0.86	1.87	2.683 (3)	159
O72—H72O⋯O1W^v	0.84	2.04	2.545 (9)	119
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) x, y+1, z; (vii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: UGUI (Structural Biology Research Center, 2005 ); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ); data reduction: HKL-2000; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024775/is2433sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024775/is2433Isup2.hkl

checkCIF report

Comment top

It is widely accepted that oligosaccharides other than lactose in human milk (human milk oligosaccharides, HMOs) play a key role in the growth of Bifidobacteria in the gut. Bifidobacteria, Gram-positive anaerobes, are considered to be beneficial for human health. Recently, a unique metabolic pathway specific for lacto-N-biose I (Gal-β1→3GlcNAc, LNB) was found using Bifidobacteria (Kitaoka et al., 2005; Nishimoto & Kitaoka, 2007a). LNB is one of the basic core disaccharides of HMOs and is suggested to be a bifidus factor.

The molecular structure of compound (I) is shown in Fig. 1. There are two water molecules per LNB molecule in the crystal lattice. The primary hydroxyl group connected to the anomeric carbon atom of the GlcNAc residue exhibits disorder, with occupancy factors of O71 (α anomer) and O72 (β anomer) of 0.77 and 0.23, respectively.

The Gal ring is close to the ideal ⁴C₁ chair conformation with ring puckering parameters (Cremer & Pople, 1975) of Q = 0.556 (3) Å, Θ = 7.1 (3)° and Φ = 353 (2)° for the atom sequence O5—C1—C2—C3—C4—C5. The other GlcNAc ring is also close to the ideal chair conformation, with Q = 0.618 (3) Å, Θ = 3.8 (3)°, and Φ = 198 (4)° for the atom sequence O11—C7—C8—C9—C10—C11.

The conformation about the linkage between the Gal and GlcNAc rings is characterized by the torsion angles of Φ (O5—C1—O1—C9) and Ψ (C1—O1—C9—C10), and the bridge angle τ (C1—O1—C9). The values obtained in this study are Φ = -81.6 (3)°, Ψ = 118.1 (2)° and τ = 115.2 (2)° (Table 1).

The conformation of the hydroxymethyl group is defined by two sets of torsion angle: χ and χ'. The values for the Gal ring were χ (O5—C5—C6—O6) = 79.5 (3)° and χ' (C4—C5—C6—O6) = -157.9 (2)°, indicating values close to the gt conformation. The values for the GlcNAc ring are χ (O11—C11—C12—O12) = -64.1 (3)° and χ' (C10—C11—C12—O12) = 57.9 (3)°, indicating the gg conformation.

Both saccharide rings lie approximately parallel to the bc plane and the intermolecular hydrogen bonds were only along the a-axis (Table 2). Two water molecules stabilize the molecular packing by forming hydrogen bonds with sugar molecules in three dimensions.

Related literature top

For the synthesis of the title compound, see: Kitaoka et al. (2005); Nishimoto & Kitaoka (2007a,b). For the conformation of saccharide rings, see: Cremer & Pople (1975).

Experimental top

Compound (I) was synthesized from sucrose and GlcNAc by the concurrent action of four enzymes: sucrose phosphorylase, UDP-glucose-hexose-1-phosphate uridylyltransferase, UDP-glucose 4-epimerase, and lacto-N-biose phosphorylase (Nishimoto & Kitaoka, 2007b). Single crystals suitable for X-ray analysis were obtained by slow diffusion of ethanol into an aqueous solution.

Computing details top

Data collection: UGUI (Structural Biology Research Center, 2005); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000 (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Displacement ellipsoid plot and atomic numbering scheme of compound (I). The ellipsoids are drawn at the 50% probability level, and the H atoms are shown as small spheres with arbitrary radii. Broken lines indicate hydrogen bonds. The minor conformer of the disordered part has been omitted for clarity.

2-Acetamido-2-deoxy-3-O-β-D-galactopyranosyl-D- glucose dihydrate top

Crystal data top

C₁₄H₂₅NO₁₁·2H₂O	F(000) = 896
M_r = 419.38	D_x = 1.496 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Synchrotron radiation, λ = 0.80000 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25787 reflections
a = 8.284 (1) Å	θ = 2.2–30.0°
b = 12.841 (1) Å	µ = 0.13 mm⁻¹
c = 17.503 (1) Å	T = 95 K
V = 1861.9 (3) Å³	Block, colorless
Z = 4	0.10 × 0.10 × 0.10 mm

Data collection top

ADSC Quantum 210r diffractometer	2046 reflections with I > 2σ(I)
Radiation source: Photon Facrory NW12A	R_int = 0.047
Silicon monochromator	θ_max = 30.0°, θ_min = 2.2°
Detector resolution: 9.7466 pixels mm^-1	h = −10→10
ω scans	k = −16→16
25787 measured reflections	l = −21→21
2153 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap&geom
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0806P)² + 0.7215P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2153 reflections	Δρ_max = 0.27 e Å⁻³
264 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.084 (6)

Crystal data top

C₁₄H₂₅NO₁₁·2H₂O	V = 1861.9 (3) Å³
M_r = 419.38	Z = 4
Orthorhombic, P2₁2₁2₁	Synchrotron radiation, λ = 0.80000 Å
a = 8.284 (1) Å	µ = 0.13 mm⁻¹
b = 12.841 (1) Å	T = 95 K
c = 17.503 (1) Å	0.10 × 0.10 × 0.10 mm

Data collection top

ADSC Quantum 210r diffractometer	2046 reflections with I > 2σ(I)
25787 measured reflections	R_int = 0.047
2153 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	Δρ_max = 0.27 e Å⁻³
2153 reflections	Δρ_min = −0.31 e Å⁻³
264 parameters

Special details top

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

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.7021 (3)	0.32502 (19)	0.34879 (14)	0.0205 (5)
H1	0.8227	0.3214	0.3471	0.025*
C2	0.6435 (3)	0.4253 (2)	0.31127 (15)	0.0211 (5)
H2	0.5234	0.4232	0.3059	0.025*
C3	0.6921 (3)	0.52070 (19)	0.35853 (15)	0.0215 (5)
H3	0.8113	0.5310	0.3535	0.026*
C4	0.6518 (3)	0.5082 (2)	0.44263 (16)	0.0226 (6)
H4	0.7071	0.5646	0.4721	0.027*
C5	0.7119 (4)	0.4031 (2)	0.47122 (15)	0.0235 (6)
H5	0.8323	0.4017	0.4671	0.028*
C6	0.6658 (4)	0.3832 (2)	0.55375 (16)	0.0279 (6)
H61	0.6722	0.4494	0.5826	0.033*
H62	0.5526	0.3585	0.5559	0.033*
O1	0.6358 (2)	0.24111 (13)	0.30922 (11)	0.0217 (4)
O2	0.7150 (2)	0.43673 (14)	0.23805 (11)	0.0241 (4)
H2O	0.6648	0.4055	0.2024	0.029*
O3	0.6135 (3)	0.61167 (14)	0.33229 (11)	0.0261 (5)
H3O	0.6709	0.6420	0.2988	0.031*
O4	0.4818 (3)	0.51573 (15)	0.45519 (11)	0.0268 (5)
H4O	0.4508	0.5788	0.4331	0.032*
O5	0.6475 (2)	0.31996 (13)	0.42597 (10)	0.0219 (4)
O6	0.7678 (3)	0.30802 (14)	0.58916 (11)	0.0266 (5)
H6O	0.7491	0.2462	0.5742	0.032*
C7	0.8597 (3)	−0.00264 (19)	0.25298 (15)	0.0220 (5)
H71	0.8919	−0.0327	0.2025	0.026*	0.77
H72	0.9533	0.0120	0.2874	0.026*	0.23
C8	0.7699 (3)	0.10082 (19)	0.24040 (15)	0.0213 (5)
H8	0.6707	0.0870	0.2094	0.026*
C9	0.7191 (3)	0.14403 (19)	0.31837 (15)	0.0206 (5)
H9	0.8171	0.1549	0.3508	0.025*
C10	0.6100 (3)	0.06275 (19)	0.35568 (15)	0.0213 (5)
H10	0.5151	0.0491	0.3218	0.026*
C11	0.7058 (3)	−0.03748 (19)	0.36589 (15)	0.0218 (5)
H11	0.8047	−0.0211	0.3964	0.026*
C12	0.6157 (4)	−0.1242 (2)	0.40603 (16)	0.0248 (6)
H121	0.6855	−0.1866	0.4092	0.030*
H122	0.5888	−0.1022	0.4587	0.030*
O71	0.9959 (3)	0.01943 (18)	0.29538 (14)	0.0217 (5)	0.77
H71O	1.0752	−0.0218	0.2860	0.026*	0.77
O72	0.9226 (12)	−0.0517 (7)	0.1856 (5)	0.031 (2)	0.23
H72O	0.8861	−0.0216	0.1467	0.037*	0.23
O10	0.5548 (3)	0.09459 (15)	0.42885 (11)	0.0251 (5)
H10O	0.4729	0.1468	0.4241	0.030*
O11	0.7561 (2)	−0.07395 (14)	0.29198 (11)	0.0229 (4)
O12	0.4722 (3)	−0.1495 (2)	0.36648 (17)	0.0485 (7)
H12O	0.4325	−0.2091	0.3760	0.058*
N1	0.8734 (3)	0.17181 (16)	0.19831 (13)	0.0214 (5)
H1N	0.9621	0.1942	0.2205	0.026*
C13	0.8410 (3)	0.20474 (19)	0.12798 (16)	0.0220 (6)
O13	0.7167 (3)	0.18034 (14)	0.09211 (11)	0.0258 (4)
C14	0.9628 (4)	0.2771 (2)	0.09275 (17)	0.0312 (7)
H141	1.0519	0.2884	0.1287	0.047*
H142	0.9112	0.3438	0.0810	0.047*
H143	1.0048	0.2461	0.0456	0.047*
O1W	0.2143 (3)	0.39008 (16)	0.43738 (13)	0.0370 (6)
H11W	0.1688	0.3974	0.4806	0.044*
H12W	0.2950	0.4330	0.4398	0.044*
O2W	0.8087 (2)	0.72473 (14)	0.24058 (11)	0.0247 (4)
H21W	0.7630	0.7867	0.2498	0.030*
H22W	0.7901	0.7083	0.1942	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0228 (13)	0.0155 (11)	0.0234 (12)	−0.0008 (11)	0.0008 (11)	−0.0003 (9)
C2	0.0226 (13)	0.0174 (12)	0.0234 (12)	−0.0030 (10)	0.0052 (11)	0.0017 (10)
C3	0.0216 (12)	0.0146 (11)	0.0284 (13)	−0.0008 (10)	0.0015 (11)	0.0010 (10)
C4	0.0235 (13)	0.0161 (11)	0.0282 (13)	0.0002 (11)	0.0020 (11)	0.0000 (10)
C5	0.0270 (13)	0.0168 (11)	0.0266 (13)	−0.0004 (11)	−0.0002 (11)	0.0000 (10)
C6	0.0334 (16)	0.0232 (13)	0.0271 (14)	0.0061 (12)	0.0018 (12)	0.0011 (11)
O1	0.0240 (10)	0.0130 (8)	0.0280 (9)	0.0006 (8)	−0.0020 (8)	−0.0001 (7)
O2	0.0269 (10)	0.0221 (9)	0.0233 (9)	−0.0041 (8)	0.0020 (8)	0.0008 (7)
O3	0.0302 (11)	0.0151 (8)	0.0329 (10)	0.0033 (8)	0.0029 (9)	0.0043 (7)
O4	0.0272 (10)	0.0196 (9)	0.0336 (10)	0.0058 (8)	0.0065 (9)	0.0026 (8)
O5	0.0286 (10)	0.0147 (8)	0.0225 (9)	0.0002 (8)	0.0013 (8)	−0.0005 (7)
O6	0.0311 (11)	0.0193 (9)	0.0293 (10)	0.0021 (8)	−0.0036 (8)	0.0022 (8)
C7	0.0244 (13)	0.0165 (11)	0.0251 (12)	−0.0016 (11)	0.0001 (11)	0.0006 (10)
C8	0.0255 (13)	0.0146 (11)	0.0237 (12)	−0.0025 (11)	0.0002 (11)	0.0029 (10)
C9	0.0212 (12)	0.0138 (11)	0.0268 (12)	0.0010 (11)	−0.0009 (11)	0.0000 (10)
C10	0.0254 (14)	0.0160 (11)	0.0225 (12)	0.0003 (11)	0.0018 (11)	−0.0005 (10)
C11	0.0252 (13)	0.0162 (11)	0.0241 (12)	0.0004 (11)	0.0004 (11)	−0.0004 (10)
C12	0.0257 (14)	0.0182 (12)	0.0304 (13)	0.0001 (11)	−0.0022 (12)	0.0039 (11)
O71	0.0196 (11)	0.0169 (11)	0.0284 (12)	0.0029 (10)	−0.0022 (10)	−0.0015 (9)
O72	0.039 (5)	0.024 (4)	0.028 (4)	0.008 (4)	0.011 (4)	0.001 (4)
O10	0.0307 (11)	0.0200 (9)	0.0246 (9)	0.0042 (8)	0.0048 (8)	0.0018 (8)
O11	0.0289 (10)	0.0153 (8)	0.0246 (9)	−0.0021 (8)	0.0027 (8)	−0.0012 (7)
O12	0.0368 (13)	0.0384 (12)	0.0703 (17)	−0.0204 (11)	−0.0240 (13)	0.0300 (12)
N1	0.0208 (10)	0.0168 (10)	0.0268 (11)	−0.0020 (9)	0.0010 (9)	0.0007 (9)
C13	0.0235 (13)	0.0148 (11)	0.0278 (12)	−0.0005 (10)	−0.0005 (11)	0.0002 (10)
O13	0.0256 (10)	0.0232 (9)	0.0286 (10)	−0.0046 (8)	−0.0015 (8)	0.0015 (8)
C14	0.0330 (16)	0.0308 (14)	0.0298 (14)	−0.0107 (13)	0.0024 (12)	0.0058 (12)
O1W	0.0484 (14)	0.0261 (10)	0.0365 (12)	−0.0066 (11)	0.0090 (11)	−0.0014 (9)
O2W	0.0292 (10)	0.0169 (8)	0.0280 (9)	0.0031 (8)	−0.0015 (9)	−0.0020 (7)

Geometric parameters (Å, º) top

C1—O1	1.394 (3)	C8—N1	1.452 (3)
C1—O5	1.426 (3)	C8—C9	1.532 (4)
C1—C2	1.525 (3)	C8—H8	1.0000
C1—H1	1.0000	C9—C10	1.528 (4)
C2—O2	1.419 (3)	C9—H9	1.0000
C2—C3	1.532 (3)	C10—O10	1.420 (3)
C2—H2	1.0000	C10—C11	1.523 (3)
C3—O3	1.414 (3)	C10—H10	1.0000
C3—C4	1.518 (4)	C11—O11	1.437 (3)
C3—H3	1.0000	C11—C12	1.514 (4)
C4—O4	1.429 (3)	C11—H11	1.0000
C4—C5	1.523 (3)	C12—O12	1.413 (4)
C4—H4	1.0000	C12—H121	0.9900
C5—O5	1.432 (3)	C12—H122	0.9900
C5—C6	1.516 (4)	O71—H71O	0.8594
C5—H5	1.0000	O72—H72O	0.8400
C6—O6	1.425 (3)	O10—H10O	0.9571
C6—H61	0.9900	O12—H12O	0.8497
C6—H62	0.9900	N1—C13	1.329 (4)
O1—C9	1.434 (3)	N1—H1N	0.8800
O2—H2O	0.8500	C13—O13	1.246 (4)
O3—H3O	0.8500	C13—C14	1.504 (4)
O4—H4O	0.9338	C14—H141	0.9800
O6—H6O	0.8499	C14—H142	0.9800
C7—O71	1.380 (4)	C14—H143	0.9800
C7—O11	1.428 (3)	O1W—H11W	0.8500
C7—O72	1.435 (9)	O1W—H12W	0.8676
C7—C8	1.538 (3)	O2W—H21W	0.8963
C7—H71	1.0000	O2W—H22W	0.8523
C7—H72	1.0000

O1—C1—O5	108.1 (2)	O72—C7—H72	107.2
O1—C1—C2	108.3 (2)	C8—C7—H72	107.4
O5—C1—C2	110.2 (2)	N1—C8—C9	112.7 (2)
O1—C1—H1	110.1	N1—C8—C7	109.2 (2)
O5—C1—H1	110.1	C9—C8—C7	108.5 (2)
C2—C1—H1	110.1	N1—C8—H8	108.8
O2—C2—C1	110.1 (2)	C9—C8—H8	108.8
O2—C2—C3	107.2 (2)	C7—C8—H8	108.8
C1—C2—C3	111.0 (2)	O1—C9—C10	110.9 (2)
O2—C2—H2	109.5	O1—C9—C8	110.3 (2)
C1—C2—H2	109.5	C10—C9—C8	107.2 (2)
C3—C2—H2	109.5	O1—C9—H9	109.5
O3—C3—C4	107.5 (2)	C10—C9—H9	109.5
O3—C3—C2	111.3 (2)	C8—C9—H9	109.5
C4—C3—C2	112.4 (2)	O10—C10—C11	107.8 (2)
O3—C3—H3	108.5	O10—C10—C9	112.3 (2)
C4—C3—H3	108.5	C11—C10—C9	108.6 (2)
C2—C3—H3	108.5	O10—C10—H10	109.4
O4—C4—C3	111.0 (2)	C11—C10—H10	109.4
O4—C4—C5	109.4 (2)	C9—C10—H10	109.4
C3—C4—C5	109.9 (2)	O11—C11—C12	108.7 (2)
O4—C4—H4	108.8	O11—C11—C10	108.7 (2)
C3—C4—H4	108.8	C12—C11—C10	114.8 (2)
C5—C4—H4	108.8	O11—C11—H11	108.2
O5—C5—C6	107.9 (2)	C12—C11—H11	108.2
O5—C5—C4	110.9 (2)	C10—C11—H11	108.2
C6—C5—C4	112.3 (2)	O12—C12—C11	110.9 (2)
O5—C5—H5	108.5	O12—C12—H121	109.5
C6—C5—H5	108.5	C11—C12—H121	109.5
C4—C5—H5	108.5	O12—C12—H122	109.5
O6—C6—C5	112.3 (2)	C11—C12—H122	109.5
O6—C6—H61	109.2	H121—C12—H122	108.0
C5—C6—H61	109.2	C7—O71—H71O	113.3
O6—C6—H62	109.2	C7—O72—H72O	109.5
C5—C6—H62	109.2	C10—O10—H10O	110.6
H61—C6—H62	107.9	C7—O11—C11	113.28 (19)
C1—O1—C9	115.2 (2)	C12—O12—H12O	115.9
C2—O2—H2O	114.2	C13—N1—C8	123.4 (2)
C3—O3—H3O	110.2	C13—N1—H1N	118.3
C4—O4—H4O	105.5	C8—N1—H1N	118.3
C1—O5—C5	111.8 (2)	O13—C13—N1	123.6 (3)
C6—O6—H6O	113.0	O13—C13—C14	120.2 (2)
O71—C7—O11	111.5 (2)	N1—C13—C14	116.2 (2)
O11—C7—O72	109.2 (4)	C13—C14—H141	109.5
O71—C7—C8	107.1 (2)	C13—C14—H142	109.5
O11—C7—C8	109.4 (2)	H141—C14—H142	109.5
O72—C7—C8	115.9 (4)	C13—C14—H143	109.5
O71—C7—H71	109.6	H141—C14—H143	109.5
O11—C7—H71	109.6	H142—C14—H143	109.5
C8—C7—H71	109.6	H11W—O1W—H12W	103.1
O11—C7—H72	107.4	H21W—O2W—H22W	108.4

O1—C1—C2—O2	−69.5 (3)	O11—C7—C8—C9	58.8 (3)
O5—C1—C2—O2	172.4 (2)	O72—C7—C8—C9	−177.2 (5)
O1—C1—C2—C3	171.9 (2)	C1—O1—C9—C10	118.0 (2)
O5—C1—C2—C3	53.9 (3)	C1—O1—C9—C8	−123.3 (2)
O2—C2—C3—O3	70.7 (3)	N1—C8—C9—O1	58.5 (3)
C1—C2—C3—O3	−169.0 (2)	C7—C8—C9—O1	179.6 (2)
O2—C2—C3—C4	−168.6 (2)	N1—C8—C9—C10	179.3 (2)
C1—C2—C3—C4	−48.3 (3)	C7—C8—C9—C10	−59.5 (3)
O3—C3—C4—O4	50.3 (3)	O1—C9—C10—O10	−59.4 (3)
C2—C3—C4—O4	−72.6 (3)	C8—C9—C10—O10	−179.9 (2)
O3—C3—C4—C5	171.5 (2)	O1—C9—C10—C11	−178.5 (2)
C2—C3—C4—C5	48.6 (3)	C8—C9—C10—C11	61.0 (3)
O4—C4—C5—O5	66.6 (3)	O10—C10—C11—O11	177.2 (2)
C3—C4—C5—O5	−55.5 (3)	C9—C10—C11—O11	−60.9 (3)
O4—C4—C5—C6	−54.2 (3)	O10—C10—C11—C12	55.2 (3)
C3—C4—C5—C6	−176.4 (2)	C9—C10—C11—C12	177.1 (2)
O5—C5—C6—O6	79.5 (3)	O11—C11—C12—O12	−64.1 (3)
C4—C5—C6—O6	−157.9 (2)	C10—C11—C12—O12	57.9 (3)
O5—C1—O1—C9	−81.6 (3)	O71—C7—O11—C11	57.6 (3)
C2—C1—O1—C9	159.0 (2)	O72—C7—O11—C11	171.4 (5)
O1—C1—O5—C5	179.3 (2)	C8—C7—O11—C11	−60.7 (3)
C2—C1—O5—C5	−62.6 (3)	C12—C11—O11—C7	−172.7 (2)
C6—C5—O5—C1	−172.6 (2)	C10—C11—O11—C7	61.8 (3)
C4—C5—O5—C1	64.0 (3)	C9—C8—N1—C13	−125.0 (3)
O71—C7—C8—N1	61.1 (3)	C7—C8—N1—C13	114.2 (3)
O11—C7—C8—N1	−178.0 (2)	C8—N1—C13—O13	2.1 (4)
O72—C7—C8—N1	−53.9 (5)	C8—N1—C13—C14	−179.2 (2)
O71—C7—C8—C9	−62.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2Wⁱ	0.88	2.05	2.923 (3)	169
O2—H2O···O12ⁱⁱ	0.85	1.80	2.642 (3)	170
O3—H3O···O2W	0.85	1.86	2.702 (3)	169
O4—H4O···O13ⁱⁱ	0.93	1.95	2.803 (3)	150
O6—H6O···O1Wⁱⁱⁱ	0.85	1.79	2.624 (3)	168
O10—H10O···O6^iv	0.96	1.81	2.705 (3)	154
O1W—H11W···O10^iv	0.85	1.85	2.696 (3)	175
O12—H12O···O13^v	0.85	1.96	2.784 (3)	162
O1W—H12W···O4	0.87	1.90	2.759 (3)	173
O2W—H21W···O11^vi	0.90	1.94	2.772 (3)	154
O2W—H22W···O6^vii	0.85	1.91	2.757 (3)	171
O71—H71O···O2ⁱ	0.86	1.87	2.683 (3)	159
O72—H72O···O1W^v	0.84	2.04	2.545 (9)	119

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, −z+1; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1, y−1/2, −z+1/2; (vi) x, y+1, z; (vii) −x+3/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₂₅NO₁₁·2H₂O
M_r	419.38
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	95
a, b, c (Å)	8.284 (1), 12.841 (1), 17.503 (1)
V (Å³)	1861.9 (3)
Z	4
Radiation type	Synchrotron, λ = 0.80000 Å
µ (mm⁻¹)	0.13
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	ADSC Quantum 210r diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	25787, 2153, 2046
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.115, 1.06
No. of reflections	2153
No. of parameters	264
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.31

Computer programs: UGUI (Structural Biology Research Center, 2005), HKL-2000 (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Selected bond and torsion angles (º) top

C1—O1—C9	115.2 (2)

O5—C1—O1—C9	−81.6 (3)	C1—O1—C9—C10	118.0 (2)
C2—C1—O1—C9	159.0 (2)	C1—O1—C9—C8	−123.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2Wⁱ	0.88	2.05	2.923 (3)	169
O2—H2O···O12ⁱⁱ	0.85	1.80	2.642 (3)	170
O3—H3O···O2W	0.85	1.86	2.702 (3)	169
O4—H4O···O13ⁱⁱ	0.93	1.95	2.803 (3)	150
O6—H6O···O1Wⁱⁱⁱ	0.85	1.79	2.624 (3)	168
O10—H10O···O6^iv	0.96	1.81	2.705 (3)	154
O1W—H11W···O10^iv	0.85	1.85	2.696 (3)	175
O12—H12O···O13^v	0.85	1.96	2.784 (3)	162
O1W—H12W···O4	0.87	1.90	2.759 (3)	173
O2W—H21W···O11^vi	0.90	1.94	2.772 (3)	154
O2W—H22W···O6^vii	0.85	1.91	2.757 (3)	171
O71—H71O···O2ⁱ	0.86	1.87	2.683 (3)	159
O72—H72O···O1W^v	0.84	2.04	2.545 (9)	119

Acknowledgements

This study was supported in part by a grant from the Promotion of Basic Research Activities for Innovative Biosciences (PROBRAIN) of Japan.

References

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