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The dimeric condensation product of lactic acid, namely (S,S)-2-[(2-hy­droxy­propano­yl)­oxy]propanoic acid, C6H10O5, (I), crystallizes with two independent mol­ecules in the asymmetric unit, which both have an essentially planar backbone. The trimeric condensation product, namely (S,S,S)-3-hy­droxy­but-3-en-2-yl 2-[(2-hy­droxy­propano­yl)­oxy]propano­ate, C9H14O7, (II), has one mol­ecule in the asymmetric unit and consists of two essentially planar parts, with the central C-O bond in a gauche conformation. Both mol­ecules of the dimer are involved in inter­molecular hydrogen bonds, forming chains with a C(8) graph set. These chains are connected by D(2) hydrogen bonds to form a two-dimensional layer. The trimer forms hydrogen-bonded C(10) and C22(6) chains, which together result in a two-dimensional motif. The Hooft method [Hooft, Straver & Spek (2008). J. Appl. Cryst. 41, 96-103] was successfully applied to the determination of the absolute structure of (I).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110026193/bm3098sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110026193/bm3098Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110026193/bm3098IIsup3.hkl
Contains datablock II

CCDC references: 790641; 790642

Comment top

Lactic acid is the simplest 2-hydroxy acid with a chiral C atom. Hydroxy acids are known to form condensation polymers upon heating and removal of water (Probst et al., 1977). The crystal structures of the dimer, C6H10O5, (I), and the trimer, C9H14O7, (II), are reported here.

Today lactic acid is produced in general by fermentation. Both enantiomeric forms can be produced in this way: (S)-lactic acid, which is the natural form, but also (R)-lactic acid. Pure monomeric (S)-lactic acid has a melting point of 326 K (Borsook et al., 1933). However, due to the hygroscopicity of crystalline (S)-lactic acid, its high solubility in water and the phenomenon of condensation polymerization, the commercial product is not a solid, but a concentrated solution in water. A commercial solution of 90wt% lactic acid at equilibrium and 293 K contains about 65wt% of monomeric lactic acid, 15–20wt% of dimer and about 5wt% of higher oligomers. The crystal structure of lactic acid (Schouten et al., 1994) shows an almost planar molecule, with the hydroxy group coplanar with the carboxylic acid group.

Lactic acid and its derivatives are used in a wide range of applications (Datta, 2005). Lactic acid and its alkalimetal salts are used in food applications for reasons of pH control, taste and antimicrobial activity (Bogaert & Naidu, 2000; Shelef, 1994). Apart from food applications, lactic acid and its derivatives are also used in technical applications (e.g. lactic acid in household cleaning, ethyl lactate as a solvent in electronics), medical applications (e.g. sodium lactate in infusion liquor) and cosmetic applications. In the last decade, the application of lactic acid as monomer in the synthesis of poly(lactic acid) (PLA) has gained importance. PLA is used as a biobased polymer in packaging, but also in other polymer applications (Jem et al., 2010).

The condensation polymerization of lactic acid occurs at room temperature. The process starts with the formation of a dimer (lactoyllactic acid), followed by a trimer etc. (Holten, 1971). At high temperatures (473 K) and reduced pressure, a degree of polymerization of 10–20 can be achieved. As far as we know, no data on the pure solid dimer or trimer of (S)-lactic acid have been published previously.

Compound (I) crystallizes with two independent molecules in the asymmetric unit (Z' = 2). A plot of these molecules is shown in Fig. 1. The backbone of both molecules is essentially planar, with the torsion angles about C4x—O3x and O3x—C2x indicating trans conformations (Table 1; x = 1 or 2). The main differences between the two molecules are the conformations of the end groups, which are both involved in intermolecular hydrogen bonding (see below), and the differences can thus be ascribed to crystal packing effects. The torsion angles about C1x—C2x differ by about 15° between the two molecules; the torsion angles about C4x—C5x differ by about 25°. These differences can also be seen in an overlay plot of the two molecules (Fig. 2). Thermal motion analysis using the THMA11 program (Schomaker & Trueblood, 1998) reveals that the second molecule is more rigid than the first, with Rthma = 0.167 versus 0.280 (Rthma = {[Σ(wΔU)2]/[Σ(wUobs)2]}1/2). A possible explanation is the presence of an intramolecular O—H···O interaction in the second molecule, which makes the molecule more rigid. A comparison of the bond lengths in both molecules using a half-normal probability plot (Abrahams & Keve, 1971) is shown in Fig. 3 and reveals that the largest difference is 7.00σ. This difference is between the bonds C41—C51 in the first molecule and C42—C52 in the second molecule. The latter bond is part of the five-membered ring formed by the intramolecular hydrogen bond.

Compound (II) crystallizes with one independent molecule in the asymmetric unit (Z' = 1), which is shown in Fig. 4. The molecule consists of two essentially planar parts, with the torsion angles about C2—O3, O3—C4, C4—C5 and O5—C7 corresponding to trans conformations. The central C5—O5 bond adopts a gauche conformation (Table 3). If a segmented model is applied in the rigid-body analysis in THMA11 and the molecule is allowed to move about this C5—O5 bond, Rthma drops from 0.263 to 0.148. Segementation about other bonds of the molecule does not lead to such a large improvement. We therefore consider this as a strong indication that the two planar parts of the molecule are independent rigid groups.

The two independent molecules in (I) form hydrogen-bonded chains in the direction of the crystallographic a axis. Carboxylic acid atom O21 acts as donor and ester atom O51 of the translated molecule is the acceptor (Table 2). An identical situation is found for the second residue and the graph-set descriptors (Bernstein et al., 1995) for the two chains are consequently both C(8). The two chains are linked, with hydroxy groups O51 and O52 of one chain as donors and carboxylic acid atoms O12 and O11 of the other chain as acceptors, best described with the graph-set descriptor D(2). The overall pattern formed by intermolecular hydrogen bonding is thus a two-dimensional network in the ac plane (Fig. 5). The hydroxy group at O52 is actually bifurcated, with an angle sum of 357 (2)° at H52O. This additionally forms an intramolecular hydrogen bond with atom O42 as acceptor, thereby imparting molecular rigidity (see above); here the graph-set notation is S(5). The corresponding interaction at O51 is considered much weaker, due to an O—H···O angle of only 94.9 (12)° and a very long H···O distance of 2.625 (16) Å.

In (II) we also find a two-dimensional hydrogen-bonding pattern (Fig. 6). Chains with graph-set descriptor C(10) run along the [110] diagonal. Carboxylic acid atom O2 is the hydrogen-bond donor and ester atom O6 the acceptor (Table 4). Atom H2O is bifurcated, with an angle sum of 361 (5)°, and also involved in a hydrogen-bonded chain in the b direction. In this chain, atom O2 is the donor and hydroxy group O7 the acceptor. In a cooperative fashion, atom O7 is then also a donor, with carboxylic atom O1 as acceptor. Consequently, the graph-set descriptor here is C22(6). The combination of the [110] and the [010] chains results in a two-dimensional network in the ab plane.

Both molecules (I) and (II) only consist of the very weak anomalous scatterers C, H and O. For Mo Kα radiation the a priori estimation of the Bijvoet differences (Flack & Shmueli, 2007) results in the very low value of Friedif = 7 for both structures. The standard uncertainties in the Flack parameters (Flack, 1983), x = 0.0 (3) for (I) and x = -0.1 (8) for (II), were so large that the absolute structure could not be determined reliably by this method (Flack & Bernardinelli, 2000). For the least-squares refinement of both structures the Friedel pairs have therefore been averaged. Interestingly, using the method of Hooft et al. (2008) on the unmerged data allowed the absolute structure of (I) to be confirmed. Here, the absolute structure is not determined during the least-squares refinement as with the Flack parameter, but likelihood calculations are applied on the Bijvoet differences. For (I), the Hooft parameter yields a value of y = -0.02 (9) based on all 3024 Bijvoet pairs and assuming a Gaussian distribution of errors. The probability that the absolute configuration is correct is 1.000. In the case of (II), the standard uncertainty in the Hooft parameter y = 0.2 (2) is too high to draw reliable conclusions. Here, a probability of 0.987 for the correct absolute structure is only attained by making the assumption that the crystal is enantiomerically pure. Allowing the possibility of an inversion twin reduces the probability to 0.536.

Related literature top

For related literature, see: Abrahams & Keve (1971); Bernstein et al. (1995); Bogaert & Naidu (2000); Borsook et al. (1933); Datta (2005); Flack (1983); Flack & Bernardinelli (2000); Flack & Shmueli (2007); Holten (1971); Hooft et al. (2008); Jem et al. (2010); Probst et al. (1977); Schomaker & Trueblood (1998); Schouten et al. (1994); Shelef (1994).

Experimental top

(S,S)-Lactoyllactic acid, (I), was prepared as follows. (S,S)-Lactide (401 g) was mixed with demineralized water (100 g) and acetone (161 g). The mixture was refluxed for 5 h and afterwards cooled to about 313 K. The excess water, the acetone and some monomeric lactic acid were then removed by means of a short-path distillation (KDL-4, UIC). The resulting product contained about 90wt% of (S,S)-lactoyllactic acid. The crude product (398 g) was mixed with diisopropyl ether (112 g), cooled to 288 K and seeded. After 2.5 h at 288 K the crystals were separated off using a filtering centrifuge. The crystals were dried in vacuo at room temperature. The yield was 177 g of dried solids (differential scanning calorimetry m.p. 318.7 K, heat of fusion 93 kJ kg-1).

(S,S,S)-Lactoyllactoyllactic acid, (II), was prepared as follows. (S,S)-Lactide (637 g) was mixed with (S)-lactic acid (230 g). The mixture was heated to 423 K and allowed to react for 1 h, then cooled rapidly to 353 K. Further overnight cooling to room temperature resulted in crystallization of the excess lactide. The viscous suspension was separated by means of a filtering centrifuge, resulting in a viscous filtrate containing lactic acid and oligomers up to a degree of polymerization of about 12, and some lactide. The viscous liquid was separated by means of a short-path distillation at low pressure (1 mbara; 1 bar = 100000 Pa) to remove lactic acid, lactide and some of the lactoyllactic acid. After distillation, the residue, containing about 25% of trimer, was used for further processing by means of preparative chromatography (Sepacor, Buchi). Separation of the oligomer mixture was achieved with a solvent gradient from water–methanol 85:15 (v/v) to methanol–acetonitrile 40:60 (v/v). The fractions containing the (S)-lactic acid trimer were combined and evaporated to dryness at 303 K and 20 mbara. Each 10 g of crude oligomer mixture resulted in 2.2 g of pure (S)-lactic acid trimer after chromatography. The product crystallized slowly after concentration and had a purity of 95–97% [differential scanning calorimetry m.p. 346.2 K (onset); heat of fusion 83 kJ kg-1].

Refinement top

Friedel pairs were merged prior to refinement. H atoms were located in difference Fourier maps. Thereafter, hydroxy H atoms were refined freely with isotropic displacement parameters and all other H atoms were refined using a riding model, with C—H = 0.98 for methyl H atoms or 1.00 Å for the other H atoms, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) for the other H atoms.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: PEAKREF (Schreurs, 2005); data reduction: EVAL15 (Schreurs et al., 2010) and SADABS (Sheldrick, 2008a); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: manual editing of CIF from SHELXL97 (Sheldrick, 2008b).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), showing the two independent molecules and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. In the electronic version of the paper, O atoms are drawn in red.
[Figure 2] Fig. 2. A quaternion fit of the two independent molecules in (I) (x = 1, 2), calculated by PLATON (Spek, 2009) using an algorithm of Mackay (1984). The fit is based on all non-H atoms except O1x, O2x, O5x and C6x, resulting in an r.m.s. fit of 0.027 Å for the seven fitted atoms.
[Figure 3] Fig. 3. A half-normal probability plot (Abrahams & Keve, 1971) of the bond distances in the two independent molecules of (I). The slope is 3.59 and the intercept is 0.56.
[Figure 4] Fig. 4. A view of the asymmetric unit of (II), with atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. In the electronic version of the paper, O atoms are drawn in red.
[Figure 5] Fig. 5. A view of the two-dimensional hydrogen-bonding pattern in (I), viewed along the b axis. C-bound H atoms have been omitted for clarity. Chains with graph set C(8) (coloured grey in the electronic version of the paper) run along a axis. Hydrogen bonds forming connections along the c direction (coloured green in the electronic version of the paper) have graph set D(2). Hydrogen-bond geometry and symmetry operations are given in Table 2.
[Figure 6] Fig. 6. A view of the two-dimensional hydrogen-bonding pattern in (II), viewed along the c axis. C-bound H atoms have been omitted for clarity. Chains with graph-set notation C(10) (coloured grey in the electronic version of the paper) run along the [110] direction. Chains in the b direction (coloured green in the electronic version of the paper) have graph-set notation C22(6). Hydrogen-bond geometry and symmetry operations are given in Table 4.
(I) (S,S)-2-[(2-Hydroxypropanoyl)oxy]propanoic acid top
Crystal data top
C6H10O5F(000) = 688
Mr = 162.14Dx = 1.376 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 62696 reflections
a = 7.94437 (7) Åθ = 1.7–35.0°
b = 11.71472 (17) ŵ = 0.12 mm1
c = 16.82348 (12) ÅT = 150 K
V = 1565.70 (3) Å3Block, colourless
Z = 80.38 × 0.36 × 0.24 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3856 independent reflections
Radiation source: rotating anode3674 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ϕ and ω scansθmax = 35.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 1212
Tmin = 0.703, Tmax = 0.747k = 1818
69491 measured reflectionsl = 2727
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)] = 0.026Hydrogen site location: difference Fourier map
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.0671P]
where P = (Fo2 + 2Fc2)/3
3856 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C6H10O5V = 1565.70 (3) Å3
Mr = 162.14Z = 8
Orthorhombic, P212121Mo Kα radiation
a = 7.94437 (7) ŵ = 0.12 mm1
b = 11.71472 (17) ÅT = 150 K
c = 16.82348 (12) Å0.38 × 0.36 × 0.24 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3856 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
3674 reflections with I > 2σ(I)
Tmin = 0.703, Tmax = 0.747Rint = 0.026
69491 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.31 e Å3
3856 reflectionsΔρmin = 0.20 e Å3
219 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O110.82164 (10)0.42378 (6)0.10719 (5)0.03150 (16)
O210.89807 (9)0.27881 (6)0.18537 (5)0.02953 (14)
H21O0.983 (3)0.3293 (17)0.2025 (12)0.054 (5)*
O310.49795 (7)0.32710 (6)0.10479 (3)0.02104 (11)
O410.49862 (12)0.34578 (10)0.23757 (4)0.0457 (2)
O510.15854 (8)0.41356 (7)0.21850 (4)0.02722 (13)
H51O0.200 (2)0.4338 (15)0.2641 (11)0.042 (4)*
C110.79636 (9)0.33017 (6)0.13505 (4)0.01769 (11)
C210.64675 (10)0.25651 (6)0.11113 (4)0.01838 (12)
H210.62860.19440.15100.022*
C310.67689 (11)0.20615 (7)0.02930 (5)0.02385 (14)
H31A0.69020.26800.00940.036*
H31B0.58070.15850.01420.036*
H31C0.77920.15950.03020.036*
C410.43711 (11)0.36720 (9)0.17371 (5)0.02484 (15)
C510.28349 (10)0.44303 (8)0.16164 (5)0.02380 (15)
H510.23730.42880.10720.029*
C610.33359 (14)0.56804 (10)0.16788 (7)0.03360 (19)
H61A0.23320.61610.16260.050*
H61B0.41340.58670.12540.050*
H61C0.38640.58190.21960.050*
O120.26701 (9)0.46502 (5)0.37050 (4)0.02352 (12)
O220.38102 (9)0.36903 (7)0.47259 (4)0.02930 (14)
H22O0.464 (2)0.4222 (16)0.4669 (11)0.048 (5)*
O320.01762 (7)0.33292 (5)0.38147 (3)0.02008 (10)
O420.04579 (9)0.44065 (7)0.49146 (4)0.03008 (15)
O520.35923 (8)0.50074 (6)0.45163 (4)0.02718 (13)
H52O0.294 (2)0.5170 (16)0.4907 (11)0.046 (5)*
C120.26684 (9)0.38520 (6)0.41660 (5)0.01832 (12)
C220.13758 (10)0.28996 (7)0.41478 (5)0.02043 (13)
H220.11730.26100.46990.025*
C320.19469 (13)0.19297 (7)0.36180 (7)0.03069 (18)
H32A0.21820.22240.30840.046*
H32B0.10580.13510.35880.046*
H32C0.29700.15870.38390.046*
C420.09660 (9)0.40899 (7)0.42739 (5)0.01950 (12)
C520.25657 (10)0.45373 (7)0.39000 (5)0.02163 (13)
H520.31800.38890.36440.026*
C620.21641 (15)0.54314 (10)0.32719 (7)0.0359 (2)
H62A0.32120.57770.30820.054*
H62B0.15770.50690.28260.054*
H62C0.14440.60240.35040.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0341 (3)0.0207 (2)0.0397 (4)0.0083 (2)0.0153 (3)0.0088 (3)
O210.0240 (3)0.0263 (3)0.0383 (3)0.0023 (2)0.0122 (3)0.0091 (3)
O310.0167 (2)0.0304 (3)0.0160 (2)0.0013 (2)0.00005 (17)0.0028 (2)
O410.0386 (4)0.0800 (7)0.0185 (3)0.0281 (5)0.0068 (3)0.0092 (3)
O510.0161 (2)0.0440 (4)0.0215 (2)0.0047 (2)0.0009 (2)0.0040 (3)
C110.0169 (3)0.0180 (3)0.0182 (3)0.0002 (2)0.0006 (2)0.0005 (2)
C210.0173 (3)0.0191 (3)0.0187 (3)0.0022 (2)0.0016 (2)0.0001 (2)
C310.0253 (3)0.0239 (3)0.0224 (3)0.0042 (3)0.0036 (3)0.0069 (3)
C410.0186 (3)0.0386 (4)0.0173 (3)0.0040 (3)0.0014 (2)0.0058 (3)
C510.0160 (3)0.0389 (4)0.0165 (3)0.0026 (3)0.0010 (2)0.0046 (3)
C610.0281 (4)0.0392 (5)0.0334 (4)0.0015 (4)0.0070 (4)0.0002 (4)
O120.0267 (3)0.0233 (2)0.0205 (2)0.0041 (2)0.0009 (2)0.0022 (2)
O220.0186 (2)0.0362 (3)0.0331 (3)0.0004 (2)0.0068 (2)0.0082 (3)
O320.0157 (2)0.0224 (2)0.0221 (2)0.00249 (19)0.00024 (18)0.00292 (19)
O420.0240 (3)0.0446 (4)0.0217 (3)0.0080 (3)0.0034 (2)0.0093 (3)
O520.0150 (2)0.0355 (3)0.0310 (3)0.0033 (2)0.0005 (2)0.0106 (3)
C120.0154 (3)0.0211 (3)0.0185 (3)0.0025 (2)0.0019 (2)0.0006 (2)
C220.0164 (3)0.0198 (3)0.0251 (3)0.0014 (2)0.0015 (2)0.0034 (2)
C320.0285 (4)0.0192 (3)0.0443 (5)0.0056 (3)0.0015 (4)0.0035 (3)
C420.0147 (3)0.0237 (3)0.0201 (3)0.0010 (2)0.0013 (2)0.0017 (2)
C520.0155 (3)0.0255 (3)0.0239 (3)0.0018 (2)0.0027 (2)0.0051 (3)
C620.0357 (5)0.0390 (5)0.0331 (4)0.0080 (4)0.0004 (4)0.0091 (4)
Geometric parameters (Å, º) top
O11—C111.2093 (10)O12—C121.2148 (10)
O21—C111.3159 (10)O22—C121.3213 (10)
O21—H21O0.94 (2)O22—H22O0.912 (19)
O31—C411.3411 (10)O32—C421.3359 (9)
O31—C211.4467 (10)O32—C221.4449 (10)
O41—C411.2068 (11)O42—C421.2093 (10)
O51—C511.4212 (11)O52—C521.4295 (10)
O51—H51O0.869 (18)O52—H52O0.857 (19)
C11—C211.5229 (11)C12—C221.5167 (11)
C21—C311.5169 (11)C22—C321.5136 (12)
C21—H211.0000C22—H221.0000
C31—H31A0.9800C32—H32A0.9800
C31—H31B0.9800C32—H32B0.9800
C31—H31C0.9800C32—H32C0.9800
C41—C511.5231 (12)C42—C521.5117 (11)
C51—C611.5212 (15)C52—C621.5216 (14)
C51—H511.0000C52—H521.0000
C61—H61A0.9800C62—H62A0.9800
C61—H61B0.9800C62—H62B0.9800
C61—H61C0.9800C62—H62C0.9800
C11—O21—H21O110.5 (12)C12—O22—H22O108.9 (12)
C41—O31—C21115.52 (6)C42—O32—C22114.13 (6)
C51—O51—H51O105.1 (12)C52—O52—H52O107.4 (12)
O11—C11—O21124.19 (8)O12—C12—O22124.38 (8)
O11—C11—C21122.75 (7)O12—C12—C22123.65 (7)
O21—C11—C21112.96 (7)O22—C12—C22111.95 (7)
O31—C21—C31106.52 (6)O32—C22—C32106.79 (7)
O31—C21—C11109.47 (6)O32—C22—C12109.23 (6)
C31—C21—C11109.69 (6)C32—C22—C12111.17 (7)
O31—C21—H21110.4O32—C22—H22109.9
C31—C21—H21110.4C32—C22—H22109.9
C11—C21—H21110.4C12—C22—H22109.9
C21—C31—H31A109.5C22—C32—H32A109.5
C21—C31—H31B109.5C22—C32—H32B109.5
H31A—C31—H31B109.5H32A—C32—H32B109.5
C21—C31—H31C109.5C22—C32—H32C109.5
H31A—C31—H31C109.5H32A—C32—H32C109.5
H31B—C31—H31C109.5H32B—C32—H32C109.5
O41—C41—O31123.44 (8)O42—C42—O32124.28 (7)
O41—C41—C51124.36 (8)O42—C42—C52123.04 (7)
O31—C41—C51112.20 (7)O32—C42—C52112.67 (7)
O51—C51—C61111.72 (7)O52—C52—C42108.14 (7)
O51—C51—C41109.16 (7)O52—C52—C62110.99 (8)
C61—C51—C41110.04 (8)C42—C52—C62110.57 (7)
O51—C51—H51108.6O52—C52—H52109.0
C61—C51—H51108.6C42—C52—H52109.0
C41—C51—H51108.6C62—C52—H52109.0
C51—C61—H61A109.5C52—C62—H62A109.5
C51—C61—H61B109.5C52—C62—H62B109.5
H61A—C61—H61B109.5H62A—C62—H62B109.5
C51—C61—H61C109.5C52—C62—H62C109.5
H61A—C61—H61C109.5H62A—C62—H62C109.5
H61B—C61—H61C109.5H62B—C62—H62C109.5
C41—O31—C21—C31171.34 (7)C42—O32—C22—C32171.42 (7)
C41—O31—C21—C1170.13 (9)C42—O32—C22—C1268.27 (8)
O11—C11—C21—O3141.75 (10)O12—C12—C22—O3227.49 (10)
O21—C11—C21—O31141.63 (7)O22—C12—C22—O32154.31 (7)
O11—C11—C21—C3174.79 (10)O12—C12—C22—C3290.10 (10)
O21—C11—C21—C31101.83 (8)O22—C12—C22—C3288.10 (9)
C21—O31—C41—O411.00 (15)C22—O32—C42—O420.05 (12)
C21—O31—C41—C51178.52 (7)C22—O32—C42—C52178.90 (6)
O41—C41—C51—O5144.90 (14)O42—C42—C52—O5220.96 (12)
O31—C41—C51—O51135.58 (8)O32—C42—C52—O52160.08 (7)
O41—C41—C51—C6178.04 (13)O42—C42—C52—C62100.74 (11)
O31—C41—C51—C61101.48 (9)O32—C42—C52—C6278.22 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H21O···O51i0.94 (2)1.73 (2)2.6617 (10)169.4 (19)
O51—H51O···O120.869 (18)1.902 (18)2.7650 (9)171.7 (17)
O22—H22O···O52i0.912 (19)1.698 (19)2.6006 (10)169.6 (18)
O52—H52O···O420.857 (19)2.168 (18)2.6730 (9)117.4 (15)
O52—H52O···O11ii0.857 (19)2.090 (19)2.7785 (11)136.9 (16)
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1, z+1/2.
(II) (S,S,S)-3-Hydroxybut-3-en-2-yl 2-[(2-hydroxypropanoyl)oxy]propanoate top
Crystal data top
C9H14O7F(000) = 496
Mr = 234.20Dx = 1.371 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 17211 reflections
a = 17.3594 (5) Åθ = 1.8–27.5°
b = 5.62712 (17) ŵ = 0.12 mm1
c = 13.9888 (6) ÅT = 150 K
β = 123.861 (1)°Needle, colourless
V = 1134.71 (7) Å30.48 × 0.12 × 0.09 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
1443 independent reflections
Radiation source: rotating anode1358 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ϕ and ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 2222
Tmin = 0.707, Tmax = 0.746k = 77
19858 measured reflectionsl = 1818
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)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.069H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0318P)2 + 0.5155P]
where P = (Fo2 + 2Fc2)/3
1443 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.17 e Å3
1 restraintΔρmin = 0.15 e Å3
Crystal data top
C9H14O7V = 1134.71 (7) Å3
Mr = 234.20Z = 4
Monoclinic, C2Mo Kα radiation
a = 17.3594 (5) ŵ = 0.12 mm1
b = 5.62712 (17) ÅT = 150 K
c = 13.9888 (6) Å0.48 × 0.12 × 0.09 mm
β = 123.861 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1443 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
1358 reflections with I > 2σ(I)
Tmin = 0.707, Tmax = 0.746Rint = 0.028
19858 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0281 restraint
wR(F2) = 0.069H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.17 e Å3
1443 reflectionsΔρmin = 0.15 e Å3
156 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.17066 (10)0.4613 (3)0.73316 (11)0.0382 (3)
O20.11475 (11)0.7716 (3)0.61303 (13)0.0438 (4)
H2O0.100 (2)0.823 (8)0.661 (3)0.085 (10)*
O30.25546 (7)0.2979 (2)0.62751 (10)0.0277 (3)
O40.35275 (9)0.6008 (3)0.72761 (12)0.0344 (3)
O50.49699 (7)0.2950 (3)0.85280 (9)0.0276 (3)
O60.50562 (9)0.3483 (3)0.70013 (11)0.0324 (3)
O70.68303 (10)0.5210 (3)0.84047 (14)0.0395 (4)
H7O0.6698 (19)0.645 (6)0.803 (2)0.055 (8)*
C10.15700 (12)0.5649 (3)0.64948 (15)0.0275 (4)
C20.17984 (11)0.4664 (4)0.56672 (14)0.0258 (4)
H20.19730.59830.53440.031*
C30.09807 (12)0.3285 (4)0.47044 (15)0.0339 (4)
H3A0.08170.20000.50330.051*
H3B0.11480.26090.41970.051*
H3C0.04490.43540.42610.051*
C40.33751 (12)0.3925 (3)0.70986 (15)0.0249 (4)
C50.40548 (11)0.1942 (3)0.77945 (14)0.0247 (4)
H50.40500.07290.72690.030*
C60.38168 (12)0.0789 (4)0.85764 (15)0.0311 (4)
H6A0.38390.19850.91000.047*
H6B0.42660.04740.90250.047*
H6C0.31920.01080.81100.047*
C70.53842 (12)0.3725 (3)0.80130 (15)0.0251 (4)
C80.63027 (12)0.4907 (4)0.88781 (16)0.0334 (4)
H80.66560.38370.95620.040*
C90.61305 (18)0.7229 (6)0.9273 (3)0.0732 (10)
H9A0.58280.83500.86280.110*
H9B0.67230.78930.98990.110*
H9C0.57290.69470.95490.110*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0537 (8)0.0336 (8)0.0374 (7)0.0070 (7)0.0316 (7)0.0096 (6)
O20.0722 (10)0.0341 (8)0.0475 (8)0.0209 (8)0.0472 (8)0.0135 (7)
O30.0223 (5)0.0263 (7)0.0298 (6)0.0011 (5)0.0116 (5)0.0027 (5)
O40.0326 (7)0.0265 (7)0.0439 (8)0.0043 (6)0.0212 (6)0.0046 (6)
O50.0208 (5)0.0392 (8)0.0254 (5)0.0048 (6)0.0145 (5)0.0005 (6)
O60.0372 (7)0.0366 (8)0.0339 (6)0.0003 (6)0.0262 (6)0.0004 (6)
O70.0396 (7)0.0311 (8)0.0697 (10)0.0041 (7)0.0440 (8)0.0097 (8)
C10.0289 (8)0.0272 (9)0.0294 (8)0.0018 (8)0.0181 (7)0.0028 (7)
C20.0250 (8)0.0263 (9)0.0277 (8)0.0039 (7)0.0156 (7)0.0032 (7)
C30.0287 (9)0.0370 (11)0.0286 (8)0.0039 (9)0.0115 (7)0.0008 (8)
C40.0250 (8)0.0282 (9)0.0266 (8)0.0033 (7)0.0176 (7)0.0033 (7)
C50.0214 (7)0.0301 (10)0.0250 (7)0.0020 (7)0.0144 (7)0.0019 (7)
C60.0266 (8)0.0389 (11)0.0312 (9)0.0060 (8)0.0182 (7)0.0018 (9)
C70.0259 (8)0.0243 (8)0.0336 (8)0.0055 (7)0.0217 (7)0.0043 (7)
C80.0234 (8)0.0439 (12)0.0401 (9)0.0028 (9)0.0221 (8)0.0023 (10)
C90.0515 (13)0.087 (2)0.105 (2)0.0405 (15)0.0586 (15)0.066 (2)
Geometric parameters (Å, º) top
O1—C11.207 (2)C3—H3B0.9800
O2—C11.317 (2)C3—H3C0.9800
O2—H2O0.89 (3)C4—C51.518 (3)
O3—C41.346 (2)C5—C61.514 (2)
O3—C21.450 (2)C5—H51.0000
O4—C41.197 (2)C6—H6A0.9800
O5—C71.3430 (19)C6—H6B0.9800
O5—C51.443 (2)C6—H6C0.9800
O6—C71.203 (2)C7—C81.516 (3)
O7—C81.408 (2)C8—C91.512 (4)
O7—H7O0.83 (3)C8—H81.0000
C1—C21.522 (2)C9—H9A0.9800
C2—C31.517 (2)C9—H9B0.9800
C2—H21.0000C9—H9C0.9800
C3—H3A0.9800
C1—O2—H2O109 (3)O5—C5—H5110.2
C4—O3—C2115.09 (15)C6—C5—H5110.2
C7—O5—C5116.91 (13)C4—C5—H5110.2
C8—O7—H7O112.4 (19)C5—C6—H6A109.5
O1—C1—O2124.60 (17)C5—C6—H6B109.5
O1—C1—C2124.65 (17)H6A—C6—H6B109.5
O2—C1—C2110.61 (15)C5—C6—H6C109.5
O3—C2—C3106.24 (16)H6A—C6—H6C109.5
O3—C2—C1109.06 (13)H6B—C6—H6C109.5
C3—C2—C1110.50 (14)O6—C7—O5123.38 (16)
O3—C2—H2110.3O6—C7—C8125.91 (15)
C3—C2—H2110.3O5—C7—C8110.71 (14)
C1—C2—H2110.3O7—C8—C9112.3 (2)
C2—C3—H3A109.5O7—C8—C7110.38 (15)
C2—C3—H3B109.5C9—C8—C7109.68 (16)
H3A—C3—H3B109.5O7—C8—H8108.1
C2—C3—H3C109.5C9—C8—H8108.1
H3A—C3—H3C109.5C7—C8—H8108.1
H3B—C3—H3C109.5C8—C9—H9A109.5
O4—C4—O3124.84 (18)C8—C9—H9B109.5
O4—C4—C5125.72 (17)H9A—C9—H9B109.5
O3—C4—C5109.38 (15)C8—C9—H9C109.5
O5—C5—C6106.87 (13)H9A—C9—H9C109.5
O5—C5—C4108.75 (15)H9B—C9—H9C109.5
C6—C5—C4110.54 (14)
C4—O3—C2—C3173.83 (14)O4—C4—C5—O513.1 (2)
C4—O3—C2—C167.06 (18)O3—C4—C5—O5169.56 (12)
O1—C1—C2—O326.7 (2)O4—C4—C5—C6103.9 (2)
O2—C1—C2—O3157.42 (15)O3—C4—C5—C673.41 (17)
O1—C1—C2—C389.7 (2)C5—O5—C7—O64.7 (3)
O2—C1—C2—C386.2 (2)C5—O5—C7—C8175.50 (16)
C2—O3—C4—O47.0 (2)O6—C7—C8—O713.6 (3)
C2—O3—C4—C5170.40 (13)O5—C7—C8—O7166.21 (16)
C7—O5—C5—C6169.37 (16)O6—C7—C8—C9110.7 (2)
C7—O5—C5—C471.28 (18)O5—C7—C8—C969.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O6i0.89 (3)2.00 (3)2.7986 (19)149 (3)
O2—H2O···O7i0.89 (3)2.37 (3)3.049 (2)134 (3)
O7—H7O···O1ii0.83 (3)2.03 (3)2.843 (2)166 (3)
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC6H10O5C9H14O7
Mr162.14234.20
Crystal system, space groupOrthorhombic, P212121Monoclinic, C2
Temperature (K)150150
a, b, c (Å)7.94437 (7), 11.71472 (17), 16.82348 (12)17.3594 (5), 5.62712 (17), 13.9888 (6)
α, β, γ (°)90, 90, 9090, 123.861 (1), 90
V3)1565.70 (3)1134.71 (7)
Z84
Radiation typeMo KαMo Kα
µ (mm1)0.120.12
Crystal size (mm)0.38 × 0.36 × 0.240.48 × 0.12 × 0.09
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008a)
Multi-scan
(SADABS; Sheldrick, 2008a)
Tmin, Tmax0.703, 0.7470.707, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
69491, 3856, 3674 19858, 1443, 1358
Rint0.0260.028
(sin θ/λ)max1)0.8070.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.076, 1.07 0.028, 0.069, 1.07
No. of reflections38561443
No. of parameters219156
No. of restraints01
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.200.17, 0.15

Computer programs: COLLECT (Nonius, 1999), PEAKREF (Schreurs, 2005), EVAL15 (Schreurs et al., 2010) and SADABS (Sheldrick, 2008a), SHELXS97 (Sheldrick, 2008b), PLATON (Spek, 2009), manual editing of CIF from SHELXL97 (Sheldrick, 2008b).

Selected geometric parameters (Å, º) for (I) top
C41—C511.5231 (12)C42—C521.5117 (11)
C41—O31—C21—C31171.34 (7)C42—O32—C22—C32171.42 (7)
O11—C11—C21—O3141.75 (10)O12—C12—C22—O3227.49 (10)
C21—O31—C41—C51178.52 (7)C22—O32—C42—C52178.90 (6)
O31—C41—C51—O51135.58 (8)O32—C42—C52—O52160.08 (7)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O21—H21O···O51i0.94 (2)1.73 (2)2.6617 (10)169.4 (19)
O51—H51O···O120.869 (18)1.902 (18)2.7650 (9)171.7 (17)
O22—H22O···O52i0.912 (19)1.698 (19)2.6006 (10)169.6 (18)
O52—H52O···O420.857 (19)2.168 (18)2.6730 (9)117.4 (15)
O52—H52O···O11ii0.857 (19)2.090 (19)2.7785 (11)136.9 (16)
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1, z+1/2.
Selected torsion angles (º) for (II) top
C4—O3—C2—C3173.83 (14)O3—C4—C5—O5169.56 (12)
C2—O3—C4—C5170.40 (13)C5—O5—C7—C8175.50 (16)
C7—O5—C5—C471.28 (18)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O6i0.89 (3)2.00 (3)2.7986 (19)149 (3)
O2—H2O···O7i0.89 (3)2.37 (3)3.049 (2)134 (3)
O7—H7O···O1ii0.83 (3)2.03 (3)2.843 (2)166 (3)
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y+1/2, z.
 

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