4-Nitro­phenyl α-l-rhamnopyran­oside hemihydrate

Peltier, P.; Daniellou, R.; Roisnel, T.; Nugier-Chauvin, C.; Ferrières, V.

doi:10.1107/S1600536807068195

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o379

doi:10.1107/S1600536807068195

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4-Nitrophenyl α-L-rhamnopyranoside hemihydrate

Pauline Peltier,^a Richard Daniellou,^a ^* Thierry Roisnel,^b Caroline Nugier-Chauvin ^a and Vincent Ferrières ^a

^aOrganic and Supramolecular Chemistry, Ecole Nationale Supérieure de Chimie, UMR CNRS 6226, Avenue du Général Leclerc, 35700 Rennes, France, and ^bCentre de Diffractométrie X, Université de Rennes 1, UMR CNRS 6226, 35042 Rennes, France
^*Correspondence e-mail: richard.daniellou@ensc-rennes.fr

(Received 21 November 2007; accepted 21 December 2007; online 9 January 2008)

In the title compound, C₁₂H₁₅NO₇·0.5H₂O, there are two independent molecules in the asymmetric unit, together with one water molecule. The pyranoside rings each have close to a ¹C₄ chair conformation and the nitro groups are almost coplanar with the benzene rings. The water molecule links the two independent molecules through O—H⋯O hydrogen bonds. All the hydroxyl groups are involved in hydrogen-bond interactions, giving rise to a three-dimensional network.

Related literature

For a related structure, see Fernandez-Castaño & Foces-Foces (1996 ). For related literature, see: Garegg et al. (1978 ).

Experimental

Crystal data

C₁₂H₁₅NO₇·0.5H₂O
M_r = 294.26
Monoclinic, P 2₁
a = 10.5371 (15) Å
b = 6.8681 (8) Å
c = 19.135 (3) Å
β = 101.543 (7)°
V = 1356.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 (2) K
0.6 × 0.58 × 0.23 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.923, T_max = 0.972
14281 measured reflections
3340 independent reflections
3147 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.080
S = 1.04
3340 reflections
396 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O202ⁱ	0.86 (3)	1.97 (7)	2.803 (7)	159 (9)
O1—H1B⋯O102ⁱⁱ	0.84 (8)	2.06 (1)	2.881 (8)	162 (7)
O102—H12⋯O104ⁱⁱⁱ	0.84 (5)	1.87 (3)	2.695 (6)	163 (8)
O103—H13⋯O203^iv	0.83 (0)	2.12 (3)	2.934 (2)	165 (6)
O104—H14⋯O203^iv	0.80 (8)	1.89 (5)	2.663 (7)	158 (5)
O202—H22⋯O1^iv	0.88 (0)	1.82 (0)	2.695 (8)	173 (0)
O203—H23⋯O204^v	0.83 (7)	1.80 (6)	2.641 (8)	176 (8)
O204—H24⋯O103^vi	0.79 (7)	1.99 (1)	2.776 (5)	168 (4)
Symmetry codes: (i) x+1, y-1, z; (ii) $[-x+1, y-{\script{3\over 2}}, -z+1]$ ; (iii) x, y+1, z; (iv) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (v) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (vi) x, y-1, z.

Data collection: SMART (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1995 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068195/bv2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068195/bv2086Isup2.hkl

checkCIF report

Comment top

α-L-Rhamnosidases (E.C. 3.2.1.40) catalyze the hydrolysis of L-rhamnose from polysaccharides and glycosides. During in vitro studies, the activity of these enzymes is determined most of the time using the title compound, (I), following the amount of p-nitrophenolate ions released by monitoring the emmision at 400 nm.

The stucture of (I) is shown in Fig. 1. The molecular packing (Fig. 2) is stabilized by hydrogen bonds between all the hydroxyl groups and the water molecules.

Related literature top

For a related structure, see Fernandez-Castaño & Foces-Foces (1996). For related literature, see: Garegg et al. (1978).

Experimental top

The title compound is commercialy available (Sigma Chemical Company) or can be easily prepared following the described procedure of Garegg et al. (1978). The title compound, (I), was crystallized from methanol by slow evaporation of the solvent.

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SMART (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1995); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure and atom-labelling scheme for (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the structure, showing the network of hydrogen bonds (dotted lines).

4-Nitrophenyl α-L-rhamnopyranoside hemihydrate top

Crystal data top

C₁₂H₁₅NO₇·0.5H₂O	F(000) = 620
M_r = 294.26	D_x = 1.441 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8274 reflections
a = 10.5371 (15) Å	θ = 2.4–27.4°
b = 6.8681 (8) Å	µ = 0.12 mm⁻¹
c = 19.135 (3) Å	T = 100 K
β = 101.543 (7)°	Plate, colourless
V = 1356.8 (3) Å³	0.6 × 0.58 × 0.23 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	3147 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
CCD rotation images, thin slices scans	θ_max = 27.4°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −13→12
T_min = 0.923, T_max = 0.972	k = −8→8
14281 measured reflections	l = −24→21
3340 independent 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0398P)² + 0.2743P] where P = (F_o² + 2F_c²)/3
3340 reflections	(Δ/σ)_max = 0.001
396 parameters	Δρ_max = 0.38 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₅NO₇·0.5H₂O	V = 1356.8 (3) Å³
M_r = 294.26	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 10.5371 (15) Å	µ = 0.12 mm⁻¹
b = 6.8681 (8) Å	T = 100 K
c = 19.135 (3) Å	0.6 × 0.58 × 0.23 mm
β = 101.543 (7)°

Data collection top

Bruker APEXII diffractometer	3340 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3147 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.972	R_int = 0.051
14281 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	1 restraint
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.38 e Å⁻³
3340 reflections	Δρ_min = −0.24 e Å⁻³
396 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
N113	0.06897 (18)	1.3356 (3)	−0.12305 (9)	0.0208 (4)
O114	−0.04061 (15)	1.3222 (3)	−0.16072 (8)	0.0285 (4)
O115	0.16860 (16)	1.3419 (3)	−0.14777 (8)	0.0320 (4)
C110	0.0816 (2)	1.3456 (3)	−0.04511 (10)	0.0169 (4)
C109	−0.0304 (2)	1.3374 (3)	−0.01675 (11)	0.0181 (4)
H109	−0.1132	1.326	−0.0471	0.022*
C108	−0.01818 (19)	1.3462 (3)	0.05646 (11)	0.0176 (4)
H108	−0.0933	1.3403	0.0768	0.021*
C107	0.10436 (19)	1.3638 (3)	0.10079 (10)	0.0154 (4)
C112	0.21624 (19)	1.3726 (3)	0.07163 (11)	0.0184 (4)
H112	0.2992	1.3849	0.1018	0.022*
C111	0.20393 (19)	1.3632 (3)	−0.00206 (11)	0.0179 (4)
H111	0.2786	1.3688	−0.0228	0.021*
O101	0.10387 (13)	1.3698 (2)	0.17252 (7)	0.0173 (3)
C101	0.21582 (18)	1.4443 (3)	0.22070 (10)	0.0150 (4)
H101	0.2387	1.574	0.203	0.018*
C102	0.17225 (19)	1.4730 (3)	0.29214 (10)	0.0143 (4)
H102	0.0905	1.551	0.2848	0.017*
O102	0.27280 (15)	1.5708 (2)	0.34038 (8)	0.0188 (3)
H12	0.259 (3)	1.692 (6)	0.3366 (17)	0.05*
C103	0.15121 (19)	1.2737 (3)	0.32381 (10)	0.0136 (4)
H103	0.0781	1.2065	0.2914	0.016*
O103	0.11609 (15)	1.3034 (2)	0.39202 (7)	0.0180 (3)
H13	0.115 (3)	1.197 (6)	0.4126 (18)	0.05*
C104	0.2735 (2)	1.1506 (3)	0.32928 (10)	0.0136 (4)
H104	0.3475	1.2151	0.3619	0.016*
O104	0.25457 (15)	0.9597 (2)	0.35459 (8)	0.0173 (3)
H14	0.246 (3)	0.959 (6)	0.3956 (19)	0.05*
C105	0.30432 (19)	1.1288 (3)	0.25488 (11)	0.0151 (4)
H105	0.2297	1.0641	0.2228	0.018*
C106	0.4262 (2)	1.0144 (3)	0.25400 (12)	0.0232 (5)
H10A	0.4425	1.0112	0.2054	0.035*
H10B	0.4157	0.8811	0.2703	0.035*
H10C	0.4995	1.0764	0.2858	0.035*
O105	0.32371 (13)	1.3205 (2)	0.22692 (7)	0.0154 (3)
N213	−0.39091 (16)	0.4276 (3)	0.01163 (9)	0.0194 (4)
O215	−0.32520 (14)	0.3120 (3)	−0.01531 (8)	0.0235 (3)
O214	−0.46481 (17)	0.5465 (3)	−0.02365 (8)	0.0322 (4)
C210	−0.38055 (19)	0.4233 (3)	0.08925 (10)	0.0168 (4)
C209	−0.4304 (2)	0.5769 (3)	0.12271 (11)	0.0190 (4)
H209	−0.4724	0.6827	0.0955	0.023*
C208	−0.41803 (19)	0.5738 (3)	0.19635 (11)	0.0180 (4)
H208	−0.4504	0.6787	0.2201	0.022*
C207	−0.35783 (18)	0.4156 (3)	0.23528 (10)	0.0146 (4)
C212	−0.3100 (2)	0.2609 (3)	0.20071 (11)	0.0180 (4)
H212	−0.2699	0.1532	0.2276	0.022*
C211	−0.32092 (19)	0.2644 (3)	0.12718 (11)	0.0178 (4)
H211	−0.2883	0.1602	0.1033	0.021*
O201	−0.34096 (13)	0.3963 (2)	0.30809 (7)	0.0153 (3)
C201	−0.37263 (19)	0.5583 (3)	0.34905 (10)	0.0141 (4)
H201	−0.4677	0.5847	0.3353	0.017*
C202	−0.34018 (18)	0.4911 (3)	0.42743 (10)	0.0139 (4)
H202	−0.3827	0.363	0.4323	0.017*
O202	−0.38516 (14)	0.6325 (2)	0.47115 (8)	0.0168 (3)
H22	−0.464 (3)	0.597 (6)	0.4737 (17)	0.05*
C203	−0.19271 (18)	0.4703 (3)	0.45089 (10)	0.0122 (4)
H203	−0.1636	0.355	0.4263	0.015*
O203	−0.16051 (13)	0.4396 (2)	0.52635 (7)	0.0148 (3)
H23	−0.114 (3)	0.341 (6)	0.5351 (17)	0.05*
C204	−0.12210 (17)	0.6509 (3)	0.43223 (10)	0.0123 (4)
H204	−0.1453	0.7623	0.4609	0.015*
O204	0.01541 (13)	0.6233 (2)	0.45107 (7)	0.0149 (3)
H24	0.036 (3)	0.533 (6)	0.4294 (18)	0.05*
C206	−0.1076 (2)	0.8921 (3)	0.33282 (11)	0.0202 (4)
H20A	−0.1367	0.9148	0.2815	0.03*
H20B	−0.0128	0.8843	0.3443	0.03*
H20C	−0.1365	0.9997	0.3595	0.03*
C205	−0.16438 (18)	0.7030 (3)	0.35314 (10)	0.0131 (4)
H205	−0.1398	0.5948	0.3234	0.016*
O205	−0.30423 (13)	0.7267 (2)	0.33721 (7)	0.0142 (3)
O1	0.62208 (15)	0.0270 (2)	0.50941 (9)	0.0203 (3)
H1A	0.628 (3)	−0.084 (6)	0.4891 (18)	0.05*
H1B	0.664 (3)	0.021 (6)	0.5520 (19)	0.05*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N113	0.0260 (9)	0.0160 (8)	0.0201 (9)	−0.0018 (7)	0.0036 (7)	−0.0005 (7)
O114	0.0280 (8)	0.0352 (9)	0.0194 (7)	−0.0047 (7)	−0.0025 (6)	−0.0013 (7)
O115	0.0295 (9)	0.0478 (11)	0.0201 (8)	−0.0030 (8)	0.0083 (7)	−0.0006 (8)
C110	0.0221 (10)	0.0125 (9)	0.0154 (9)	−0.0003 (8)	0.0023 (8)	0.0008 (7)
C109	0.0173 (10)	0.0138 (9)	0.0216 (10)	−0.0015 (8)	0.0003 (7)	−0.0003 (8)
C108	0.0162 (9)	0.0151 (9)	0.0222 (10)	−0.0013 (8)	0.0057 (8)	0.0005 (8)
C107	0.0174 (9)	0.0125 (9)	0.0163 (9)	0.0001 (8)	0.0030 (7)	0.0007 (7)
C112	0.0153 (9)	0.0205 (10)	0.0185 (10)	−0.0014 (8)	0.0014 (7)	0.0014 (8)
C111	0.0184 (10)	0.0166 (10)	0.0195 (10)	−0.0010 (8)	0.0056 (8)	0.0022 (8)
O101	0.0152 (7)	0.0213 (7)	0.0151 (7)	−0.0021 (6)	0.0026 (5)	0.0011 (6)
C101	0.0138 (9)	0.0137 (9)	0.0169 (9)	−0.0009 (7)	0.0019 (7)	0.0010 (7)
C102	0.0155 (9)	0.0105 (8)	0.0160 (9)	0.0034 (7)	0.0010 (7)	0.0014 (7)
O102	0.0267 (8)	0.0091 (6)	0.0192 (7)	0.0000 (6)	0.0010 (6)	−0.0003 (5)
C103	0.0157 (9)	0.0122 (8)	0.0135 (9)	−0.0005 (7)	0.0039 (7)	−0.0007 (7)
O103	0.0260 (8)	0.0131 (7)	0.0170 (7)	0.0042 (6)	0.0097 (6)	0.0012 (6)
C104	0.0168 (9)	0.0079 (8)	0.0166 (9)	0.0004 (7)	0.0045 (7)	0.0003 (7)
O104	0.0280 (8)	0.0092 (6)	0.0171 (7)	0.0004 (6)	0.0105 (6)	0.0006 (5)
C105	0.0173 (10)	0.0111 (8)	0.0183 (10)	−0.0007 (8)	0.0067 (7)	−0.0004 (7)
C106	0.0255 (11)	0.0168 (10)	0.0317 (12)	0.0061 (8)	0.0163 (9)	0.0045 (9)
O105	0.0153 (7)	0.0131 (6)	0.0189 (7)	0.0008 (5)	0.0057 (5)	0.0033 (5)
N213	0.0159 (8)	0.0243 (9)	0.0178 (8)	−0.0008 (7)	0.0029 (7)	−0.0022 (7)
O215	0.0200 (7)	0.0317 (8)	0.0196 (7)	0.0015 (7)	0.0057 (6)	−0.0045 (7)
O214	0.0348 (9)	0.0422 (10)	0.0171 (8)	0.0156 (8)	−0.0009 (6)	0.0026 (7)
C210	0.0132 (9)	0.0226 (10)	0.0139 (9)	−0.0016 (8)	0.0012 (7)	−0.0024 (8)
C209	0.0160 (10)	0.0201 (10)	0.0190 (10)	0.0038 (8)	−0.0008 (8)	0.0002 (8)
C208	0.0161 (10)	0.0176 (9)	0.0194 (10)	0.0042 (8)	0.0013 (8)	−0.0018 (8)
C207	0.0120 (9)	0.0158 (9)	0.0150 (9)	−0.0021 (7)	0.0001 (7)	−0.0034 (7)
C212	0.0174 (9)	0.0155 (9)	0.0199 (10)	0.0024 (8)	0.0006 (8)	−0.0006 (8)
C211	0.0165 (10)	0.0189 (10)	0.0179 (10)	0.0019 (8)	0.0035 (8)	−0.0046 (8)
O201	0.0176 (7)	0.0136 (7)	0.0136 (7)	0.0015 (6)	0.0008 (5)	−0.0013 (5)
C201	0.0128 (9)	0.0138 (9)	0.0152 (9)	0.0001 (8)	0.0013 (7)	−0.0033 (7)
C202	0.0127 (9)	0.0130 (9)	0.0162 (9)	0.0000 (7)	0.0031 (7)	−0.0021 (7)
O202	0.0157 (7)	0.0159 (7)	0.0197 (7)	0.0000 (6)	0.0061 (6)	−0.0038 (6)
C203	0.0143 (9)	0.0118 (8)	0.0102 (8)	0.0014 (7)	0.0014 (7)	0.0001 (7)
O203	0.0185 (7)	0.0143 (7)	0.0114 (6)	0.0026 (6)	0.0027 (5)	0.0018 (5)
C204	0.0102 (8)	0.0124 (8)	0.0141 (9)	0.0011 (7)	0.0017 (7)	−0.0005 (7)
O204	0.0110 (6)	0.0140 (7)	0.0185 (7)	0.0012 (5)	0.0005 (5)	−0.0024 (6)
C206	0.0226 (10)	0.0194 (10)	0.0169 (10)	−0.0050 (9)	0.0001 (8)	0.0052 (8)
C205	0.0123 (9)	0.0135 (8)	0.0130 (9)	0.0011 (7)	0.0016 (7)	0.0003 (7)
O205	0.0127 (7)	0.0133 (7)	0.0155 (7)	0.0011 (5)	0.0003 (5)	0.0011 (5)
O1	0.0191 (7)	0.0178 (8)	0.0238 (8)	0.0025 (6)	0.0032 (6)	−0.0006 (6)

Geometric parameters (Å, º) top

N113—O115	1.236 (2)	N213—O215	1.232 (2)
N113—O114	1.236 (2)	N213—C210	1.468 (3)
N113—C110	1.472 (3)	C210—C211	1.389 (3)
C110—C111	1.389 (3)	C210—C209	1.390 (3)
C110—C109	1.395 (3)	C209—C208	1.389 (3)
C109—C108	1.382 (3)	C209—H209	0.95
C109—H109	0.95	C208—C207	1.396 (3)
C108—C107	1.401 (3)	C208—H208	0.95
C108—H108	0.95	C207—O201	1.375 (2)
C107—O101	1.374 (2)	C207—C212	1.398 (3)
C107—C112	1.403 (3)	C212—C211	1.389 (3)
C112—C111	1.391 (3)	C212—H212	0.95
C112—H112	0.95	C211—H211	0.95
C111—H111	0.95	O201—C201	1.438 (2)
O101—C101	1.438 (2)	C201—O205	1.405 (2)
C101—O105	1.406 (2)	C201—C202	1.541 (3)
C101—C102	1.539 (3)	C201—H201	1
C101—H101	1	C202—O202	1.424 (2)
C102—O102	1.426 (2)	C202—C203	1.535 (3)
C102—C103	1.531 (3)	C202—H202	1
C102—H102	1	O202—H22	0.88 (3)
O102—H12	0.85 (4)	C203—O203	1.431 (2)
C103—O103	1.440 (2)	C203—C204	1.525 (3)
C103—C104	1.527 (3)	C203—H203	1
C103—H103	1	O203—H23	0.84 (4)
O103—H13	0.83 (4)	C204—O204	1.434 (2)
C104—O104	1.426 (2)	C204—C205	1.532 (3)
C104—C105	1.530 (3)	C204—H204	1
C104—H104	1	O204—H24	0.80 (4)
O104—H14	0.81 (4)	C206—C205	1.513 (3)
C105—O105	1.450 (2)	C206—H20A	0.98
C105—C106	1.508 (3)	C206—H20B	0.98
C105—H105	1	C206—H20C	0.98
C106—H10A	0.98	C205—O205	1.453 (2)
C106—H10B	0.98	C205—H205	1
C106—H10C	0.98	O1—H1A	0.86 (4)
N213—O214	1.232 (2)	O1—H1B	0.85 (4)

O115—N113—O114	123.06 (18)	O214—N213—C210	118.61 (17)
O115—N113—C110	118.34 (17)	O215—N213—C210	118.43 (17)
O114—N113—C110	118.61 (17)	C211—C210—C209	121.90 (18)
C111—C110—C109	121.97 (19)	C211—C210—N213	118.60 (18)
C111—C110—N113	119.34 (18)	C209—C210—N213	119.49 (18)
C109—C110—N113	118.69 (17)	C208—C209—C210	119.23 (19)
C108—C109—C110	118.56 (18)	C208—C209—H209	120.4
C108—C109—H109	120.7	C210—C209—H209	120.4
C110—C109—H109	120.7	C209—C208—C207	119.57 (19)
C109—C108—C107	120.32 (18)	C209—C208—H208	120.2
C109—C108—H108	119.8	C207—C208—H208	120.2
C107—C108—H108	119.8	O201—C207—C208	124.66 (18)
O101—C107—C108	114.84 (17)	O201—C207—C212	114.85 (18)
O101—C107—C112	124.57 (17)	C208—C207—C212	120.49 (18)
C108—C107—C112	120.59 (18)	C211—C212—C207	120.10 (19)
C111—C112—C107	119.06 (18)	C211—C212—H212	119.9
C111—C112—H112	120.5	C207—C212—H212	119.9
C107—C112—H112	120.5	C210—C211—C212	118.68 (18)
C110—C111—C112	119.49 (18)	C210—C211—H211	120.7
C110—C111—H111	120.3	C212—C211—H211	120.7
C112—C111—H111	120.3	C207—O201—C201	118.71 (15)
C107—O101—C101	118.97 (15)	O205—C201—O201	111.51 (15)
O105—C101—O101	112.63 (16)	O205—C201—C202	112.49 (16)
O105—C101—C102	112.46 (15)	O201—C201—C202	105.56 (15)
O101—C101—C102	105.23 (15)	O205—C201—H201	109.1
O105—C101—H101	108.8	O201—C201—H201	109.1
O101—C101—H101	108.8	C202—C201—H201	109.1
C102—C101—H101	108.8	O202—C202—C203	109.15 (15)
O102—C102—C103	108.21 (15)	O202—C202—C201	109.41 (15)
O102—C102—C101	108.67 (16)	C203—C202—C201	109.08 (15)
C103—C102—C101	109.26 (15)	O202—C202—H202	109.7
O102—C102—H102	110.2	C203—C202—H202	109.7
C103—C102—H102	110.2	C201—C202—H202	109.7
C101—C102—H102	110.2	C202—O202—H22	106 (2)
C102—O102—H12	108 (2)	O203—C203—C204	109.13 (14)
O103—C103—C104	112.48 (15)	O203—C203—C202	109.29 (15)
O103—C103—C102	108.43 (15)	C204—C203—C202	111.63 (15)
C104—C103—C102	109.58 (16)	O203—C203—H203	108.9
O103—C103—H103	108.8	C204—C203—H203	108.9
C104—C103—H103	108.8	C202—C203—H203	108.9
C102—C103—H103	108.8	C203—O203—H23	109 (2)
C103—O103—H13	110 (2)	O204—C204—C203	110.44 (15)
O104—C104—C103	111.05 (16)	O204—C204—C205	111.02 (15)
O104—C104—C105	107.24 (15)	C203—C204—C205	111.23 (15)
C103—C104—C105	108.90 (16)	O204—C204—H204	108
O104—C104—H104	109.9	C203—C204—H204	108
C103—C104—H104	109.9	C205—C204—H204	108
C105—C104—H104	109.9	C204—O204—H24	110 (2)
C104—O104—H14	113 (3)	C205—C206—H20A	109.5
O105—C105—C106	106.61 (16)	C205—C206—H20B	109.5
O105—C105—C104	109.04 (15)	H20A—C206—H20B	109.5
C106—C105—C104	113.64 (17)	C205—C206—H20C	109.5
O105—C105—H105	109.2	H20A—C206—H20C	109.5
C106—C105—H105	109.2	H20B—C206—H20C	109.5
C104—C105—H105	109.2	O205—C205—C206	106.63 (15)
C105—C106—H10A	109.5	O205—C205—C204	108.41 (14)
C105—C106—H10B	109.5	C206—C205—C204	113.74 (16)
H10A—C106—H10B	109.5	O205—C205—H205	109.3
C105—C106—H10C	109.5	C206—C205—H205	109.3
H10A—C106—H10C	109.5	C204—C205—H205	109.3
H10B—C106—H10C	109.5	C201—O205—C205	113.88 (14)
C101—O105—C105	114.15 (14)	H1A—O1—H1B	109 (3)
O214—N213—O215	122.95 (17)

O115—N113—C110—C111	0.4 (3)	O214—N213—C210—C211	165.9 (2)
O114—N113—C110—C111	−179.17 (19)	O215—N213—C210—C211	−14.1 (3)
O115—N113—C110—C109	−179.6 (2)	O214—N213—C210—C209	−14.0 (3)
O114—N113—C110—C109	0.8 (3)	O215—N213—C210—C209	166.02 (19)
C111—C110—C109—C108	−0.3 (3)	C211—C210—C209—C208	1.3 (3)
N113—C110—C109—C108	179.77 (18)	N213—C210—C209—C208	−178.75 (17)
C110—C109—C108—C107	0.3 (3)	C210—C209—C208—C207	−1.0 (3)
C109—C108—C107—O101	−179.59 (18)	C209—C208—C207—O201	−179.57 (18)
C109—C108—C107—C112	0.0 (3)	C209—C208—C207—C212	0.0 (3)
O101—C107—C112—C111	179.37 (18)	O201—C207—C212—C211	−179.71 (17)
C108—C107—C112—C111	−0.1 (3)	C208—C207—C212—C211	0.6 (3)
C109—C110—C111—C112	0.1 (3)	C209—C210—C211—C212	−0.7 (3)
N113—C110—C111—C112	−179.95 (18)	N213—C210—C211—C212	179.43 (17)
C107—C112—C111—C110	0.1 (3)	C207—C212—C211—C210	−0.3 (3)
C108—C107—O101—C101	−161.68 (17)	C208—C207—O201—C201	−7.9 (3)
C112—C107—O101—C101	18.8 (3)	C212—C207—O201—C201	172.50 (17)
C107—O101—C101—O105	−69.4 (2)	C207—O201—C201—O205	−56.3 (2)
C107—O101—C101—C102	167.78 (16)	C207—O201—C201—C202	−178.77 (15)
O105—C101—C102—O102	64.6 (2)	O205—C201—C202—O202	66.1 (2)
O101—C101—C102—O102	−172.44 (15)	O201—C201—C202—O202	−172.04 (14)
O105—C101—C102—C103	−53.3 (2)	O205—C201—C202—C203	−53.2 (2)
O101—C101—C102—C103	69.69 (19)	O201—C201—C202—C203	68.62 (19)
O102—C102—C103—O103	59.34 (19)	O202—C202—C203—O203	51.0 (2)
C101—C102—C103—O103	177.50 (14)	C201—C202—C203—O203	170.50 (15)
O102—C102—C103—C104	−63.78 (19)	O202—C202—C203—C204	−69.81 (19)
C101—C102—C103—C104	54.4 (2)	C201—C202—C203—C204	49.7 (2)
O103—C103—C104—O104	62.8 (2)	O203—C203—C204—O204	62.33 (19)
C102—C103—C104—O104	−176.49 (15)	C202—C203—C204—O204	−176.76 (14)
O103—C103—C104—C105	−179.32 (15)	O203—C203—C204—C205	−173.93 (14)
C102—C103—C104—C105	−58.6 (2)	C202—C203—C204—C205	−53.0 (2)
O104—C104—C105—O105	179.73 (15)	O204—C204—C205—O205	179.33 (14)
C103—C104—C105—O105	59.5 (2)	C203—C204—C205—O205	55.92 (19)
O104—C104—C105—C106	−61.5 (2)	O204—C204—C205—C206	−62.3 (2)
C103—C104—C105—C106	178.25 (17)	C203—C204—C205—C206	174.33 (16)
O101—C101—O105—C105	−61.5 (2)	O201—C201—O205—C205	−57.5 (2)
C102—C101—O105—C105	57.2 (2)	C202—C201—O205—C205	60.9 (2)
C106—C105—O105—C101	177.03 (16)	C206—C205—O205—C201	176.29 (15)
C104—C105—O105—C101	−59.9 (2)	C204—C205—O205—C201	−60.88 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O202ⁱ	0.86 (3)	1.97 (7)	2.803 (7)	159 (9)
O1—H1B···O102ⁱⁱ	0.84 (8)	2.06 (1)	2.881 (8)	162 (7)
O102—H12···O104ⁱⁱⁱ	0.84 (5)	1.87 (3)	2.695 (6)	163 (8)
O103—H13···O203^iv	0.83 (1)	2.12 (3)	2.934 (2)	165 (6)
O104—H14···O203^iv	0.80 (8)	1.89 (5)	2.663 (7)	158 (5)
O202—H22···O1^iv	0.88 (1)	1.82 (1)	2.695 (8)	173 (0)
O203—H23···O204^v	0.83 (7)	1.80 (6)	2.641 (8)	176 (8)
O204—H24···O103^vi	0.79 (7)	1.99 (1)	2.776 (5)	168 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₇·0.5H₂O
M_r	294.26
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	10.5371 (15), 6.8681 (8), 19.135 (3)
β (°)	101.543 (7)
V (Å³)	1356.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.6 × 0.58 × 0.23

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.923, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	14281, 3340, 3147
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.080, 1.04
No. of reflections	3340
No. of parameters	396
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.24

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), SIR97 (Altomare et al., 1995), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O202ⁱ	0.86 (3)	1.97 (7)	2.803 (7)	159 (9)
O1—H1B···O102ⁱⁱ	0.84 (8)	2.06 (1)	2.881 (8)	162 (7)
O102—H12···O104ⁱⁱⁱ	0.84 (5)	1.87 (3)	2.695 (6)	163 (8)
O103—H13···O203^iv	0.83 (0)	2.12 (3)	2.934 (2)	165 (6)
O104—H14···O203^iv	0.80 (8)	1.89 (5)	2.663 (7)	158 (5)
O202—H22···O1^iv	0.88 (0)	1.82 (0)	2.695 (8)	173 (0)
O203—H23···O204^v	0.83 (7)	1.80 (6)	2.641 (8)	176 (8)
O204—H24···O103^vi	0.79 (7)	1.99 (1)	2.776 (5)	168 (4)

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

Acknowledgements

PP is grateful to the Région Bretagne for a grant.

References

Altomare, A., Burla, M. C., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G. & Polidori, G. (1995). J. Appl. Cryst. 28, 842–846. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fernandez-Castaño, C. & Foces-Foces, C. (1996). Acta Cryst. C52, 1586–1588. CSD CrossRef Web of Science IUCr Journals Google Scholar
Garegg, P. J., Hultberg, C. & Iversen, T. (1978). Carbohydr. Res. 62, 173–174. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2002). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar