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Crystals of the title complex, C3H7NO2·C8H8O3·0.5H2O, were obtained from an aqueous solution containing racemic mandelic acid and (S)-alanine. The unit cell includes two independent molecular complexes and one water molecule. The structure formed by (R)-mandelic acid and (S)-alanine in a 1:1 molar ratio shows the successful optical separation of racemic mandelic acid. Strong hydrogen bonding, with a rather short O...O separation of 2.494 (3) Å, is observed between the carboxyl and carboxyl­ate groups. A structural comparison suggests that the strong hydrogen bonding affects the neighbouring covalent bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102015688/fr1385sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015688/fr1385Isup2.hkl
Contains datablock I

CCDC reference: 197339

Comment top

Optical resolution of racemic mandelic acid has been performed using some chiral separating reagents, such as S-2-benzylaminobutanol (Kozma et al., 2000) and (1R,3S)-camphoramic acid (Hu et al., 2001). Recently, we separated racemic mandelic acid using (S)-alanine as the separating reagent. The crystal structure of the title complex, (I), shows this successful optical resolution. \sch

The structure of (I) is shown in Fig. 1. The structure has two independent (R)-mandelic acid molecules, two independent (S)-alanine molecules and one water molecule in the unit cell.

Both (R)-mandelic acid molecules have almost identical structures. The CO(hydroxy) is syn to the CO bond of the carboxyl group, with an O(H)—C—CO torsion angle of 14.3 (3)° (in the C1-mandelic acid molecule) and 8.5 (3)° (in the C12 mandelic acid molecule). This is in agreement with data for (R)-mandelic acid reported previously by Wei & Ward (1977).

An intramolecular hydrogen bond (O3—H3···O2) between the hydroxy and carboxyl groups is observed in the C1-mandelic acid but not in the C12-mandelic acid, the hydroxy group (O8—H14) in the C12-mandelic acid forming an intermolecular hydrogen bond to a carboxyl group from the neighbouring mandelic acid, as shown in Fig. 1. This is the most distinct structural difference between the two mandelic acid molecules in (I).

Both (S)-alanine molecules display the normal inner salt structure (Destro et al., 1988). The difference of 0.017 (4) Å in the C—O bond distances observed in the C20-alanine agrees well with the difference of 0.016 (2) Å determined by neutron diffraction (Lehmann et al., 1972), but is significantly smaller than the difference of 0.040 (4) Å between C—O bond distances in the C9-alanine in (I). This may result from the strong hydrogen bonding, discussed below.

An extensive hydrogen-bond network exists in the crystal structure of (I), with all O and N atoms involved in the network. A stronger hydrogen bond with a rather short O1···O5 separation of 2.494 (3) Å is observed between the carboxyl group of the C1-mandelic acid and the carboxylate group of the C9-alanine, which is comparable with the value of 2.501 (2) Å found between mandelic acid and mandelate (Larsen & Lopez de Diego, 1993).

Several structures of compounds containing mandelic acid, mandelate or alanine have been reported to date, all with the carboxylate group involved in the hydrogen bonding (Larsen & Lopez de Diego, 1993; Lopez de Diego, 1995; Okamura et al., 1997). A structural comparison reveals that the shorter the donor···acceptor separation in the hydrogen bond, the larger the difference between the C—O bond distances in the carboxylate group. For example, the shorter O···O separation of 2.501 (2) Å in the hydrogen bond corresponds to the larger difference of 0.040 (2) Å between C—O bond distances in the carboxylate (Larsen & Lopez de Diego, 1993), whereas the longer (normal) N···O separation of 2.813 (1) Å in the hydrogen bond corresponds to the smaller difference of 0.016 (2) Å between C—O bond distances in the carboxylate (Lehmann et al., 1972). This conclusion also agrees well with the present work; the larger difference of 0.040 (4) Å between the O5—C9 and O4—C9 bonds corresponds to the shorter O1···O5 separation of 2.494 (3) Å, and the smaller difference of 0.017 (4) Å between the O9—C20 and O10—C20 bonds corresponds to the longer O6···O9 separation of 2.554 (3) Å. These facts may suggest the effect of the strong hydrogen bond on the neighbouring covalent bond (Larsen & Lopez de Diego, 1993).

Several bifurcated hydrogen bonds are observed in the structure of (I). The O3—H3 hydroxy group, in addition to being the acceptor linking to an amine group from the adjacent alanine, acts as a bifurcated hydrogen-bond donor, intramolecularly to the C1O2 group and intermolecularly to a C20—O10 carboxyl group from an adjacent alanine. The other hydroxy group, O8—H14, is involved in a similar hydrogen-bonding network. In addition to being the donor linking to the C1—O2 carboxyl group from a neighbouring mandelic acid, the O8—H14 group also acts as a bifurcated hydrogen-bond acceptor, intermolecularly to both the adjacent N2-amine group and the solvate water. The water molecule also acts as both acceptor and donor, with both H atoms involved in the hydrogen bonding. It is notable that, of the carboxyl groups involved in the stronger hydrogen bonds, O1—H1 and O6—H12 serve only as donors.

Experimental top

Racemic mandelic acid (Mass?, 10 mmol) and (S)-alanine (Mass?, 10 mmol) were dissolved in turn in hot water (10 ml) with continuous stirring. The solution was kept at room temperature and powder crystals were obtained from the solution after 2 d. These powder crystals were separated from the solution and dried in vacuo at 333 K. The C, H and N content was analyzed using an Eager 200 elemental analysis instrument. Analysis calculated for C22H32N2O11: C 52.75, H 6.44, N 5.59%; found: C 52.80, H 6.40, N 5.60%. The specific optical rotation [α]D of -78.8° (H2O, c = 0.19) was determined using a Wzz-1 s instrument for the powder crystal sample. Recrystallization was performed from an aqueous solution at room temperature and well shaped single crystals of complex (I) were obtained after one week. A small amount of (I) was dissolved in water and the pH of the solution was adjusted to 2 with dilute HCl; the solution was then kept in a refrigerator. Colourless crystals of a different shape were obtained. The specific optical rotation [α]D of -153.9° (H2O, c = 0.35) agrees well with that of (R)-mandelic acid (Swinney et al., 1999), showing that the complex crystals do not include (S)-mandelic acid. This is not clear - was the crystal used here from the first batch, or the pH2 batch?

Refinement top

The H atoms were placed in calculated positions with C—H = 0.93–0.98 Å, O—H = 0.82 Å and N—H = 0.89 Å, guided by difference Fourier maps. The H atoms were included in the final cycles of the refinement in the riding mode, with Uiso(H) = 1.2Ueq of carrier atoms, except for the H atoms of the water molecules, which had fixed positional parameters and Uiso(H) = 0.08 Å2. A torsional parameter was refined for each CH3, NH3 and OH group. The absolute configuration was assigned based on that of the starting reagent, (S)-alanine, but could not be determined directly from the X-ray data. Friedel pairs were averaged.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994).

Figures top
[Figure 1] Fig. 1. The structure of (I), drawn with 50% probability displacement ellipsoids. The dashed lines indicate the intermolecular hydrogen bonds [symmetry code: (i) 1 + x, y, z].
(R)-mandelic acid (S)-alanine hemihydrate top
Crystal data top
C3H7NO2·C8H8O3·0.5H2OZ = 2
Mr = 250.25F(000) = 266
Triclinic, P1Dx = 1.348 Mg m3
a = 6.0193 (11) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.2285 (10) ÅCell parameters from 20 reflections
c = 12.5811 (11) Åθ = 4.9–9.8°
α = 82.545 (9)°µ = 0.11 mm1
β = 86.000 (14)°T = 298 K
γ = 89.752 (13)°Prism, colourless
V = 616.36 (15) Å30.60 × 0.55 × 0.30 mm
Data collection top
Rigaku AFC-7S
diffractometer
Rint = 0.016
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 2.5°
Graphite monochromatorh = 07
ω/2θ scansk = 1010
2617 measured reflectionsl = 1515
2436 independent reflections3 standard reflections every 150 reflections
2011 reflections with I > 2σ(I) intensity decay: 0.3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0474P)2 + 0.0307P]
where P = (Fo2 + 2Fc2)/3
2436 reflections(Δ/σ)max = 0.010
324 parametersΔρmax = 0.14 e Å3
3 restraintsΔρmin = 0.15 e Å3
Crystal data top
C3H7NO2·C8H8O3·0.5H2Oγ = 89.752 (13)°
Mr = 250.25V = 616.36 (15) Å3
Triclinic, P1Z = 2
a = 6.0193 (11) ÅMo Kα radiation
b = 8.2285 (10) ŵ = 0.11 mm1
c = 12.5811 (11) ÅT = 298 K
α = 82.545 (9)°0.60 × 0.55 × 0.30 mm
β = 86.000 (14)°
Data collection top
Rigaku AFC-7S
diffractometer
Rint = 0.016
2617 measured reflections3 standard reflections every 150 reflections
2436 independent reflections intensity decay: 0.3%
2011 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0303 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.04Δρmax = 0.14 e Å3
2436 reflectionsΔρmin = 0.15 e Å3
324 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
xyzUiso*/Ueq
O10.2598 (3)0.7048 (2)0.33142 (17)0.0506 (5)
H10.25900.60430.34220.061*
O20.0021 (3)0.6777 (2)0.46728 (16)0.0484 (5)
O30.0541 (3)0.9997 (2)0.45949 (16)0.0471 (5)
H30.12490.92250.49330.057*
C10.1100 (4)0.7614 (3)0.39579 (19)0.0352 (5)
C20.0752 (4)0.9446 (3)0.3734 (2)0.0374 (5)
H20.22120.99850.36760.045*
C30.0296 (4)0.9859 (3)0.2672 (2)0.0375 (5)
C40.2352 (5)0.9231 (4)0.2519 (3)0.0506 (7)
H40.30970.85420.30740.061*
C50.3323 (6)0.9608 (5)0.1555 (3)0.0671 (9)
H50.47030.91680.14570.080*
C60.2221 (7)1.0646 (5)0.0738 (3)0.0752 (11)
H60.28711.09100.00890.090*
C70.0199 (7)1.1286 (5)0.0872 (3)0.0672 (10)
H70.05261.19850.03160.081*
C80.0787 (5)1.0899 (4)0.1837 (2)0.0507 (7)
H80.21751.13350.19260.061*
O40.4347 (3)0.1919 (2)0.46812 (17)0.0486 (5)
O50.2715 (3)0.4006 (2)0.37551 (17)0.0470 (5)
N10.8234 (3)0.3378 (2)0.46222 (17)0.0381 (5)
H9A0.81570.22940.46460.046*
H9B0.79200.36520.52770.046*
H9C0.96030.37210.43860.046*
C90.4379 (4)0.3278 (3)0.4153 (2)0.0332 (5)
C100.6606 (4)0.4159 (3)0.3883 (2)0.0330 (5)
H100.64240.53080.39990.040*
C110.7425 (5)0.4094 (5)0.2723 (2)0.0573 (8)
H11A0.89230.45070.26040.069*
H11B0.64800.47530.22580.069*
H11C0.73920.29810.25720.069*
O60.8102 (3)0.2952 (2)0.80887 (17)0.0486 (5)
H120.79810.20580.78750.058*
O71.0561 (4)0.3416 (2)0.66728 (16)0.0517 (5)
O81.1004 (4)0.6560 (3)0.68694 (18)0.0604 (6)
H141.03580.66320.63130.073*
C120.9498 (4)0.3873 (3)0.7430 (2)0.0378 (5)
C130.9705 (5)0.5607 (3)0.7703 (2)0.0426 (6)
H130.82160.60870.77670.051*
C141.0802 (4)0.5645 (3)0.8747 (2)0.0400 (6)
C151.2837 (5)0.4886 (4)0.8900 (2)0.0492 (7)
H151.35050.43170.83720.059*
C161.3867 (6)0.4976 (5)0.9834 (3)0.0629 (9)
H161.52280.44620.99380.075*
C171.2874 (6)0.5832 (5)1.0619 (3)0.0656 (9)
H171.35760.58921.12480.079*
C181.0902 (6)0.6577 (4)1.0475 (3)0.0607 (8)
H181.02560.71581.10030.073*
C190.9831 (5)0.6482 (4)0.9544 (2)0.0492 (7)
H190.84560.69820.94550.059*
O90.7927 (3)0.0223 (3)0.7333 (2)0.0570 (6)
O100.6338 (3)0.1422 (2)0.63425 (17)0.0487 (5)
N20.2377 (3)0.0029 (3)0.65009 (17)0.0353 (4)
H20A0.24140.11120.65070.042*
H20B0.26830.04580.58330.042*
H20C0.10280.02670.67390.042*
C200.6294 (4)0.0320 (3)0.6924 (2)0.0358 (5)
C210.4047 (4)0.0467 (3)0.7204 (2)0.0330 (5)
H210.42210.16610.70700.040*
C220.3296 (5)0.0014 (5)0.8374 (2)0.0570 (8)
H22A0.42850.04610.88160.068*
H22B0.33160.11860.85390.068*
H22C0.18120.03770.85100.068*
O110.5440 (4)0.5155 (3)0.6117 (2)0.0666 (6)
H1W0.57230.62810.60070.080*
H2W0.40910.49770.63790.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0498 (11)0.0432 (10)0.0552 (12)0.0078 (9)0.0110 (9)0.0012 (9)
O20.0568 (11)0.0405 (10)0.0450 (10)0.0023 (9)0.0087 (9)0.0016 (8)
O30.0586 (12)0.0393 (10)0.0428 (10)0.0012 (9)0.0066 (9)0.0082 (8)
C10.0317 (12)0.0403 (13)0.0337 (12)0.0012 (10)0.0061 (10)0.0029 (10)
C20.0357 (12)0.0390 (13)0.0374 (13)0.0019 (10)0.0005 (10)0.0057 (10)
C30.0420 (13)0.0301 (12)0.0400 (13)0.0055 (10)0.0004 (10)0.0045 (10)
C40.0433 (15)0.0535 (17)0.0545 (16)0.0008 (12)0.0072 (12)0.0033 (13)
C50.058 (2)0.071 (2)0.077 (2)0.0111 (17)0.0285 (18)0.0156 (19)
C60.093 (3)0.083 (3)0.052 (2)0.021 (2)0.0273 (19)0.0078 (19)
C70.091 (3)0.068 (2)0.0380 (16)0.013 (2)0.0077 (17)0.0015 (15)
C80.0506 (16)0.0519 (16)0.0473 (16)0.0033 (13)0.0071 (13)0.0033 (13)
O40.0438 (10)0.0371 (10)0.0616 (12)0.0090 (8)0.0032 (9)0.0062 (9)
O50.0278 (9)0.0433 (10)0.0699 (13)0.0023 (7)0.0065 (8)0.0057 (9)
N10.0329 (10)0.0358 (11)0.0450 (12)0.0042 (8)0.0095 (9)0.0003 (9)
C90.0294 (11)0.0325 (12)0.0389 (12)0.0011 (9)0.0005 (10)0.0111 (10)
C100.0292 (11)0.0281 (11)0.0412 (13)0.0011 (9)0.0032 (10)0.0023 (10)
C110.0402 (15)0.084 (2)0.0416 (15)0.0056 (15)0.0030 (12)0.0097 (15)
O60.0479 (11)0.0449 (11)0.0533 (11)0.0076 (9)0.0048 (9)0.0123 (9)
O70.0602 (12)0.0465 (11)0.0476 (11)0.0052 (9)0.0049 (10)0.0080 (9)
O80.0847 (16)0.0488 (12)0.0470 (11)0.0188 (11)0.0228 (11)0.0071 (10)
C120.0376 (13)0.0410 (13)0.0362 (13)0.0050 (11)0.0082 (11)0.0078 (11)
C130.0425 (14)0.0413 (14)0.0455 (14)0.0045 (11)0.0107 (11)0.0078 (11)
C140.0417 (14)0.0395 (13)0.0397 (13)0.0044 (11)0.0048 (11)0.0072 (11)
C150.0448 (15)0.0571 (17)0.0479 (15)0.0038 (13)0.0069 (12)0.0137 (13)
C160.0544 (18)0.078 (2)0.0586 (19)0.0046 (16)0.0235 (15)0.0058 (17)
C170.080 (2)0.079 (2)0.0415 (16)0.009 (2)0.0163 (16)0.0124 (16)
C180.077 (2)0.065 (2)0.0405 (15)0.0046 (17)0.0051 (15)0.0155 (14)
C190.0482 (15)0.0492 (16)0.0509 (16)0.0010 (12)0.0044 (13)0.0127 (13)
O90.0251 (9)0.0560 (12)0.0964 (16)0.0001 (8)0.0083 (9)0.0324 (12)
O100.0364 (9)0.0440 (10)0.0701 (13)0.0042 (8)0.0001 (9)0.0256 (9)
N20.0285 (10)0.0371 (10)0.0406 (11)0.0024 (8)0.0045 (8)0.0051 (9)
C200.0279 (11)0.0334 (12)0.0459 (14)0.0005 (9)0.0007 (10)0.0057 (11)
C210.0271 (11)0.0333 (12)0.0396 (13)0.0012 (9)0.0014 (9)0.0092 (10)
C220.0412 (15)0.089 (2)0.0413 (15)0.0060 (15)0.0000 (12)0.0130 (16)
O110.0722 (15)0.0612 (14)0.0682 (14)0.0127 (12)0.0043 (12)0.0197 (11)
Geometric parameters (Å, º) top
O1—C11.296 (3)O6—H120.8200
O1—H10.8200O7—C121.210 (3)
O2—C11.223 (3)O8—C131.416 (4)
O3—C21.412 (3)O8—H140.8200
O3—H30.8200C12—C131.518 (4)
C1—C21.514 (4)C13—C141.515 (4)
C2—C31.515 (4)C13—H130.9800
C2—H20.9800C14—C191.384 (4)
C3—C41.378 (4)C14—C151.386 (4)
C3—C81.392 (4)C15—C161.376 (4)
C4—C51.382 (5)C15—H150.9300
C4—H40.9300C16—C171.387 (5)
C5—C61.381 (6)C16—H160.9300
C5—H50.9300C17—C181.346 (5)
C6—C71.358 (6)C17—H170.9300
C6—H60.9300C18—C191.387 (5)
C7—C81.388 (5)C18—H180.9300
C7—H70.9300C19—H190.9300
C8—H80.9300O9—C201.252 (3)
O4—C91.224 (3)O10—C201.235 (3)
O5—C91.264 (3)N2—C211.476 (3)
N1—C101.485 (3)N2—H20A0.8900
N1—H9A0.8900N2—H20B0.8900
N1—H9B0.8900N2—H20C0.8900
N1—H9C0.8900C20—C211.536 (3)
C9—C101.523 (3)C21—C221.512 (4)
C10—C111.515 (4)C21—H210.9800
C10—H100.9800C22—H22A0.9600
C11—H11A0.9600C22—H22B0.9600
C11—H11B0.9600C22—H22C0.9600
C11—H11C0.9600O11—H1W0.934
O6—C121.309 (3)O11—H2W0.861
C1—O1—H1109.5C13—O8—H14109.5
C2—O3—H3109.5O7—C12—O6124.5 (3)
O2—C1—O1124.8 (3)O7—C12—C13121.7 (2)
O2—C1—C2121.0 (2)O6—C12—C13113.8 (2)
O1—C1—C2114.2 (2)O8—C13—C14108.5 (2)
O3—C2—C1110.0 (2)O8—C13—C12109.3 (2)
O3—C2—C3112.3 (2)C14—C13—C12111.8 (2)
C1—C2—C3109.8 (2)O8—C13—H13109.0
O3—C2—H2108.2C14—C13—H13109.0
C1—C2—H2108.2C12—C13—H13109.0
C3—C2—H2108.2C19—C14—C15119.2 (3)
C4—C3—C8118.7 (3)C19—C14—C13120.6 (2)
C4—C3—C2120.7 (2)C15—C14—C13120.2 (2)
C8—C3—C2120.6 (2)C16—C15—C14120.0 (3)
C3—C4—C5121.0 (3)C16—C15—H15120.0
C3—C4—H4119.5C14—C15—H15120.0
C5—C4—H4119.5C15—C16—C17120.0 (3)
C6—C5—C4119.2 (3)C15—C16—H16120.0
C6—C5—H5120.4C17—C16—H16120.0
C4—C5—H5120.4C18—C17—C16120.4 (3)
C7—C6—C5120.8 (3)C18—C17—H17119.8
C7—C6—H6119.6C16—C17—H17119.8
C5—C6—H6119.6C17—C18—C19120.3 (3)
C6—C7—C8120.1 (3)C17—C18—H18119.9
C6—C7—H7120.0C19—C18—H18119.9
C8—C7—H7120.0C14—C19—C18120.2 (3)
C7—C8—C3120.1 (3)C14—C19—H19119.9
C7—C8—H8119.9C18—C19—H19119.9
C3—C8—H8119.9C21—N2—H20A109.5
C10—N1—H9A109.5C21—N2—H20B109.5
C10—N1—H9B109.5H20A—N2—H20B109.5
H9A—N1—H9B109.5C21—N2—H20C109.5
C10—N1—H9C109.5H20A—N2—H20C109.5
H9A—N1—H9C109.5H20B—N2—H20C109.5
H9B—N1—H9C109.5O10—C20—O9126.1 (2)
O4—C9—O5125.5 (2)O10—C20—C21118.6 (2)
O4—C9—C10118.7 (2)O9—C20—C21115.2 (2)
O5—C9—C10115.7 (2)N2—C21—C22110.8 (2)
N1—C10—C11110.7 (2)N2—C21—C20109.28 (19)
N1—C10—C9108.32 (19)C22—C21—C20110.9 (2)
C11—C10—C9111.3 (2)N2—C21—H21108.6
N1—C10—H10108.8C22—C21—H21108.6
C11—C10—H10108.8C20—C21—H21108.6
C9—C10—H10108.8C21—C22—H22A109.5
C10—C11—H11A109.5C21—C22—H22B109.5
C10—C11—H11B109.5H22A—C22—H22B109.5
H11A—C11—H11B109.5C21—C22—H22C109.5
C10—C11—H11C109.5H22A—C22—H22C109.5
H11A—C11—H11C109.5H22B—C22—H22C109.5
H11B—C11—H11C109.5H1W—O11—H2W109.5
C12—O6—H12109.5
O2—C1—C2—O314.3 (3)O6—C12—C13—O8172.1 (2)
O1—C1—C2—O3167.8 (2)O7—C12—C13—C14111.7 (3)
O2—C1—C2—C3109.7 (3)O6—C12—C13—C1467.7 (3)
O1—C1—C2—C368.2 (3)O8—C13—C14—C19109.9 (3)
O3—C2—C3—C461.9 (3)C12—C13—C14—C19129.4 (3)
C1—C2—C3—C460.7 (3)O8—C13—C14—C1567.8 (3)
O3—C2—C3—C8117.2 (3)C12—C13—C14—C1552.9 (3)
C1—C2—C3—C8120.1 (3)C19—C14—C15—C160.2 (4)
C8—C3—C4—C50.6 (4)C13—C14—C15—C16177.6 (3)
C2—C3—C4—C5179.7 (3)C14—C15—C16—C170.3 (5)
C3—C4—C5—C60.7 (5)C15—C16—C17—C180.1 (6)
C4—C5—C6—C70.4 (6)C16—C17—C18—C190.6 (6)
C5—C6—C7—C80.1 (6)C15—C14—C19—C180.9 (4)
C6—C7—C8—C30.2 (5)C13—C14—C19—C18176.8 (3)
C4—C3—C8—C70.1 (4)C17—C18—C19—C141.2 (5)
C2—C3—C8—C7179.2 (3)O10—C20—C21—N212.6 (3)
O4—C9—C10—N117.9 (3)O9—C20—C21—N2168.3 (2)
O5—C9—C10—N1165.6 (2)O10—C20—C21—C22109.8 (3)
O4—C9—C10—C11104.0 (3)O9—C20—C21—C2269.2 (3)
O5—C9—C10—C1172.5 (3)O3—C2—C1—O214.3 (3)
O7—C12—C13—O88.5 (3)O8—C13—C12—O78.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O50.821.682.494 (3)174
O11—H1W···O10i0.932.032.924 (3)160
O11—H2W···O7ii0.862.473.263 (3)154
O11—H2W···O8ii0.862.363.045 (4)137
O3—H3···O20.822.202.656 (3)115
O3—H3···O10iii0.822.222.916 (3)142
N1—H9A···O3iv0.892.052.879 (3)155
N1—H9C···O5v0.891.992.861 (3)168
N1—H9B···O70.892.443.024 (3)124
N1—H9B···O110.892.232.959 (3)139
O6—H12···O90.821.742.554 (3)175
O8—H14···O2v0.822.082.856 (3)158
N2—H20A···O8vi0.892.082.899 (3)152
N2—H20B···O40.891.982.811 (3)156
N2—H20C···O9ii0.891.962.824 (3)163
Symmetry codes: (i) x, y+1, z; (ii) x1, y, z; (iii) x1, y+1, z; (iv) x+1, y1, z; (v) x+1, y, z; (vi) x1, y1, z.

Experimental details

Crystal data
Chemical formulaC3H7NO2·C8H8O3·0.5H2O
Mr250.25
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)6.0193 (11), 8.2285 (10), 12.5811 (11)
α, β, γ (°)82.545 (9), 86.000 (14), 89.752 (13)
V3)616.36 (15)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.60 × 0.55 × 0.30
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2617, 2436, 2011
Rint0.016
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.084, 1.04
No. of reflections2436
No. of parameters324
No. of restraints3
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.15

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994).

Selected geometric parameters (Å, º) top
O1—C11.296 (3)O6—C121.309 (3)
O2—C11.223 (3)O7—C121.210 (3)
O4—C91.224 (3)O9—C201.252 (3)
O5—C91.264 (3)O10—C201.235 (3)
O2—C1—O1124.8 (3)O7—C12—O6124.5 (3)
O4—C9—O5125.5 (2)O10—C20—O9126.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O50.821.682.494 (3)174
O11—H1W···O10i0.932.032.924 (3)160
O11—H2W···O7ii0.862.473.263 (3)154
O11—H2W···O8ii0.862.363.045 (4)137
O3—H3···O20.822.202.656 (3)115
O3—H3···O10iii0.822.222.916 (3)142
N1—H9A···O3iv0.892.052.879 (3)155
N1—H9C···O5v0.891.992.861 (3)168
N1—H9B···O70.892.443.024 (3)124
N1—H9B···O110.892.232.959 (3)139
O6—H12···O90.821.742.554 (3)175
O8—H14···O2v0.822.082.856 (3)158
N2—H20A···O8vi0.892.082.899 (3)152
N2—H20B···O40.891.982.811 (3)156
N2—H20C···O9ii0.891.962.824 (3)163
Symmetry codes: (i) x, y+1, z; (ii) x1, y, z; (iii) x1, y+1, z; (iv) x+1, y1, z; (v) x+1, y, z; (vi) x1, y1, z.
 

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