Concomitant polymorphism in the stereoselective synthesis of a β-benzyl-β-hy­droxy­aspartate analogue

Two concomitant polymorphs, (I) and (II), of a β-benzyl-β-hy­droxy­aspartate analogue [systematic name: dibenzyl 2-benzyl-2-hy­droxy-3-(4-methyl­phenyl­sulfonamido)­succinate], C₃₂H₃₁NO₇S, crystallize from a mixture of ethyl acetate and cyclo­hexane at ambient temperature. The structure of (I) has triclinic (P) symmetry and that of (II) monoclinic (P2₁/c) symmetry. Both crystal structures are made up of a stacking of homochiral racemic dimers (2S,3S and 2R,3R) which are inter­nally connected by a similar R₂²(9) hydrogen-bonding pattern consisting of inter­molecular N—H...O and O—H...O hydrogen bonds. The centroid of the racemic dimer lies on an inversion centre. The main structural difference between the two polymorphs is the conformational orientation of two of the four aromatic rings present in the mol­ecule. Polymorph (II) is found to be twinned by reticular merohedry with twin index 3 and twin fractions 0.854 (1) and 0.146 (1).

S1. Comment

Excitatory amino acid transporters (EAATs) play a key role in the regulation of glutamate as neurotransmitters in the mammalian central nervous system (CNS) (Danbolt, 2001). Therefore nontransportable blockers are indispensable tools for the investigation of the physiological roles of glutamate transporters (Maragakis & Rothstein, 2004; Esslinger et al., 2005). It was reported that several β-hydroxy aspartate analogues are potent pharmacophores for binding-site selectivity studies (Shimamoto et al., 2000). Following our interest in nonproteinogenic amino acids and CNS studies we propose regio- and stereoselective synthesis of a new β-substituted β-hydroxy aspartate to test its selectivity on EAAT1, EAAT2 and/or EAAT3. This new compound would mimic both the inhibitory effect of L-β-threo-hydroxy-Asp-OH with the free OH and L-β-threo-benzyl-Asp that are the most potent EAAT blockers (Esslinger et al., 2005). The title compound was synthesized using the strategy outlined in the reaction scheme below. Sharpless aminohydroxylation was used on dibenzyl 2-benzylfumarate (Li et al., 1996) and subsequent deprotection was carried out in an HBr/AcOH 33% mixture with phenol as scavenger. In order to confirm the regio- and stereoselective synthesis of the final β-benzyl β-hydroxy aspartate we have carried out an X-ray diffraction study on the synthetic intermediate dibenzyl 2-benzyl-2-hydroxy-3-(4-methylphenylsulfonamido)succinate. We have then demonstrated that the synthetic route was conducted with a total regioselectivity. However, the two polymorphic racemates obtained during the crystallization do not allow us to confirm the expected (2S,3S) enantioselectivity but only the relative one (threo-isomer).

Polymorphism occurs frequently in crystal chemistry (Mitscherlich, 1822; Bernstein, 2002, 2011) and has been extensively described in the literature (e.g. Dunitz, 1979; Glusker, 1994). The simultaneous formation of two different polymorphs of a compound in the same solvent system is called `concomitant polymorphism' (Bernstein et al., 1995; Jones et al., 2007), but it is reported less frequently than polymorphic structures grown in different solvents and/or at different temperatures or other external conditions. The reason is most probably, as also outlined by Jones et al. (2007), that the crystallographer in most cases tends to pick up the dominating crystals while neglecting the smaller and/or less well formed crystals in the batch. In our case we pursued our study because we had obtained a racemate in what was supposed to be the result of a stereoselective synthesis even if it was with a low enantiomeric excess (22% ee) of the (2S,3S) enantiomer (Mekki et al., 2011). Indeed a careful inspection of the batch revealed that there were very tiny needles in addition to larger prism-shaped crystals. Unluckily the structure of the needles appeared to be racemic as well.

Figs. 1 and 2 present the atomic displacement representations of the molecular structures of polymorphs (I) and (II), both in the arbitrarily chosen 2R,3R configuration. The molecule is an analogue of L-β-threo-benzyl-Asp-OH with two benzyl esters and a tosyl moiety acting as protecting groups for the carboxylate and amine functions of this amino acid. In order to describe the conformational orientation of the four aromatic rings present in the molecule, we consider ring 1 (C6–C11) from the β-benzyl chain, rings 2 (C13–C18) and 3 (C20–C25) from the two ester functions of the α and γ carboxyl groups, and ring 4 (C26–C31) from the tosyl moiety protecting the α-amino group. In polymorph (I) rings 3 and 4 are nearly coplanar with a dihedral angle of 5.93 (13)°; for (II) the dihedral angle between these two rings is 42.3 (3)°.

An examination of the mutual orientation of rings 1 and 2 reveals a larger deviation in (II) with a dihedral angle of 41.1 (4)° for (II) and 24.01 (15)° for (I).

Fig. 3 shows a superposition of the two (2R,3R) enantiomers as calculated by OLEX2 (Dolomanov et al., 2009) based on the overlapping for the three central atoms (N1, C2, C3). It is acknowledged that this is not the `best' superposition, which would take into account all nonhydrogen atoms giving a root-mean-square deviation of 1.743 Å. This figure highlights also that the main difference between the conformations of the two polymorphs lies in the orientation of aromatic rings 2 and 3. This is illustrated by the torsion angles C4—O5—C19—C20 and N1—C2—C1—O1 taken on the same enantiomers of both polymorphs (I) and (II), having values of 84.8 (2) and 178.1 (4)°, and 169.70 (18) and 1.5 (6)°, respectively. For the two other aromatic rings, viz. 1 and 4, the values of the torsion angles C2—C3—C5—C6 and C26—S1—N1—C2 are relatively similar at 177.4 (2), 172.0 (5)° and 88.66 (19), 81.0 (4)°, respectively. In both polymorphs the torsion angle S1—N1—H1—C2 [157.7° for (I) and 153.4° for (II)] implies a slight pyramidalization of the sulfonamide moiety.

Both polymorphs present the same hydrogen-bond pattern. They are composed of two intermolecular rings (···O4—C3—O3—H3···O7—S1—N1—H1···) forming the centrosymmetric dimer. This R₂² (9) hydrogen-bonding pattern associated with the different conformations described above leads [to] the dimer that looks like a `staircase step' for (I) and a `four-blade double helix' for (II) (Figs. 4 and 5; Tables 1 and 2). The hydrogen-bond interactions in both polymorphs are not particularly strong. Although the H···O distances range from 2.17 to 2.30 Å, being well below the sum of the van der Waals radii of H and O, the D—H···O angles are in the range 127–169°, where the hydrogen-bond interactions in (I) are stronger than in (II). A dimer association formed by two pTos—(NH)—C—(COH)—(C═O)— moieties is absent in the Cambridge Structural Database (CSD, Version 5.32; Allen, 2002). Only three structures present this moiety (DAZQAX, Streuff et al., 2005; PAQZIR, Zhao et al., 2005; QEJBIR, Streuff et al., 2006) and dimer association takes place only for PAQZIR, but in a different way, and moreover the latter structure is not an amino acid analogue.

In order to understand semi-quantitatively the apparently easier formation of (I) with respect to (II) we have compared intermolecular energies of (I) and (II) calculated using the UNI potential developed by Gavezzotti (1994) and Gavezzotti & Filippini (1994) and implemented in Mercury (Macrae et al., 2006). Hydrogen distance normalization was used. Fig. 6 shows the distance–energy plot for (I) and (II), where the distance is between the centres of gravity of the central and surrounding molecules. The dominating cohesive force comes in both cases from the hydrogen-bonded dimer association and the interaction with one other molecule at even shorter distance than the dimer couples but at less negative interaction energy. Despite the overall similarity of the dispersion of the data points, i.e. the clustering in two groups, the data points of the two sets show only marginal correlation, proving that the packings, and thus the structures, are far from identical. This finding is reinforced by the calculation of the powder similarity index (PSI) of (I) and (II), using Mercury, which significantly differs from 1.0 (0.956), proving the absence of a strong correlation between the packings. Similar packings give in general PSIs in between 0.98 and 1.00, and lower values are a strong signature of the dissimilarity of the crystal packings. This is supported by the packing analysis of Chisholm & Motherwell (2005) with default parameters; this gives only one molecule in common, indicating that the packings are in fact very dissimilar. The packing energies – which are not identical to lattice energies but should give nevertheless some indications about the relative strengths – calculated for 200 interactions are -270.54 and -261.74 kJ mol^-1 for (I) and (II), respectively. This explains qualitatively the relative abundance of (I) with respect to (II).

Polymorphic P1 and P2₁/c pairs are not uncommon for organic structures. Out of 1420 P2₁/c organic polymorphic individuals (R < 0.10; no disordered structures, duplicates with the same space group removed) and 718 P1 individuals, 307 polymorphic pairs are found in the CSD (Version 5.32; Allen, 2002).

In summary, dibenzyl 2-benzyl-2-hydroxy-3-(4-methylphenylsulfonamido)succinate crystallizes as two racemic concomitant polymorphs, (I) and (II), of which (I) is much more abundant than (II). The striking feature of the structure of both polymorphs is the dimer association of the different enantiomers but, owing to the different orientation of two of the substituent groups, the crystal packing differs significantly.

Related literature

For related literature, see: Allen (2002); Bernstein (2002, 2011); Bernstein et al. (1995); Chisholm & Motherwell (2005); Danbolt (2001); Dolomanov et al. (2009); Dunitz (1979); Esslinger et al. (2005); Gavezzotti (1994); Gavezzotti & Filippini (1994); Glusker (1994); Jones et al. (2007); Li et al. (1996); Macrae et al. (2006); Maragakis & Rothstein (2004); Mekki et al. (2011); Mitscherlich (1822); Shimamoto et al. (2000); Streuff et al. (2005, 2006); Zhao et al. (2005).

S2. Experimental

The title compound was recrystallized from a mixture of ethyl acetate and cyclohexane at ambient temperature, yielding colourless crystals in the form of relatively large prisms [(I)] and tiny needles [(II)].

As the enantiopure material was indeed present in the batch and after resolution of the crude mixture at 22% ee by chiral high-pressure liquid chromatography we tried to grow crystals from one of these pure fractions (Mekki et al., 2011). Unfortunately, this enantiomeric pure fraction also crystallizes in the form of needles of even smaller size than those of polymorph (II). These crystals do not give any appreciable diffraction intensity even at long exposure times so that it should be concluded that it is apparently very difficult to grow crystals of sufficient size of the enantiopure material. Powder diffraction is therefore the only solution to confirm the molecular structure of the enantiopure material, but unfortunately this will not give more information about the absolute configuration of the main enantiomer.

S3. Refinement

All N- and O-bound H atoms were located in difference Fourier maps but were subsequently included as riding atoms [O—H = 0.82 Å and 1.5U_eq(O); N—H = 0.86 Å and 1.2U_eq(N)] in order to stabilize their coordinates during the final step of the refinement. All other H atoms were introduced at calculated positions and refined as riding atoms, with C—H = 0.96–0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl and 1.2U_eq(C) for all other H atoms. Polymorph (II) was found to be twinned by reticular merohedry with a twin index 3. The twin symmetry element is a twofold axis along the reciprocal c axis and the pseudo-orthorhombic lattice can be generated by a' = a, c' = 3c-a', c' = c. A merged HKLF5-type file was used for the refinements. The twin fractions were found to be 0.854/0.146.

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of polymorph (I), with displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
	Fig. 2. The asymmetric unit of polymorph (II), with displacement ellipsoids for the non-H atoms drawn at the 50% probability level.
	Fig. 3. A superposition of the molecular structures of polymorphs (I) and (II) based on the overlapping of the three central atoms (N1, C2 and C3). In the electronic version of the paper, polymorph (II) has been coloured in magenta to highlight differences between its conformation and that of polymorph (I).
	Fig. 4. The hydrogen-bonded dimer in polymorph (I) of the title compound. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Selected atoms of molecules present in the asymmetric unit are labelled to illustrate intermolecular N1—H···O4 and O3—H···O7 hydrogen bonds defining an R2^2(9) hydrogen-bonding motif. [Symmetry code: (i) -x, -y+2, -z.]
	Fig. 5. The hydrogen-bonded dimer in polymorph (II) of the title compound. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Selected atoms of molecules present in the asymmetric unit are labelled to illustrate intermolecular N1—H···O4 and O3—H···O7 hydrogen bonds defining an R2^2(9) hydrogen-bonding motif. [Symmetry code: (i) -x+1, -y, -z+1.]
	Fig. 6. A potential energy plot with respect to the distance between the centre of gravity of a central molecule and surrounding molecules.

(I) dibenzyl 2-benzyl-2-hydroxy-3-(4-methylphenylsulfonamido)succinate

Crystal data

C32H31NO7S	Z = 2
Mr = 573.64	F(000) = 604
Triclinic, P1	Dx = 1.341 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 10.8577 (4) Å	Cell parameters from 14932 reflections
b = 11.1342 (6) Å	θ = 4.3–69.1°
c = 12.3719 (6) Å	µ = 1.43 mm^−1
α = 87.928 (4)°	T = 173 K
β = 73.958 (4)°	Prism, colourless
γ = 81.354 (4)°	0.40 × 0.29 × 0.23 mm
V = 1421.06 (12) Å^3

Data collection

Agilent Xcalibur Sapphire3 Gemini diffractometer	5160 independent reflections
Radiation source: Enhance (Cu) X-ray Source	4541 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
Detector resolution: 16.0143 pixels mm^-1	θmax = 69.1°, θmin = 4.3°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→13
Tmin = 0.589, Tmax = 1.000	l = −14→14
43929 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.165	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0813P)^2 + 0.9611P] where P = (Fo^2 + 2Fc^2)/3
5160 reflections	(Δ/σ)max < 0.001
371 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.86 e Å^−3

Special details

Experimental. CrysAlisPro, Version 1.171.33.56 – release 18-01-2010 (Agilent Technologies UK Ltd, 2010) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.25145 (5)	1.05094 (5)	−0.20627 (5)	0.03001 (18)
O6	0.33812 (17)	1.13467 (16)	−0.20143 (14)	0.0379 (4)
O7	0.13185 (16)	1.09363 (16)	−0.23299 (14)	0.0358 (4)
O1	0.44831 (15)	0.83239 (14)	0.04969 (14)	0.0324 (4)
O2	0.32649 (18)	0.75934 (16)	−0.04675 (17)	0.0435 (5)
O3	0.14413 (15)	0.92342 (14)	0.16684 (14)	0.0323 (4)
H3	0.0663	0.9427	0.1746	0.049*
O5	0.17090 (15)	1.22042 (14)	0.04822 (14)	0.0321 (4)
O4	−0.00254 (15)	1.12424 (15)	0.12228 (14)	0.0339 (4)
N1	0.21102 (18)	0.98918 (17)	−0.08287 (16)	0.0276 (4)
H1	0.1532	0.9392	−0.0745	0.033*
C2	0.2939 (2)	0.9749 (2)	−0.00707 (19)	0.0292 (5)
H2	0.3627	1.0254	−0.0339	0.035*
C1	0.3557 (2)	0.8423 (2)	−0.0049 (2)	0.0308 (5)
C12	0.5207 (2)	0.7121 (2)	0.0542 (2)	0.0366 (6)
H12A	0.6047	0.7210	0.0636	0.044*
H12B	0.5353	0.6712	−0.0171	0.044*
C13	0.4549 (2)	0.6339 (2)	0.1470 (2)	0.0350 (5)
C14	0.3416 (3)	0.6749 (3)	0.2293 (2)	0.0420 (6)
H14	0.3007	0.7542	0.2274	0.050*
C15	0.2889 (3)	0.5962 (3)	0.3157 (3)	0.0516 (7)
H15	0.2134	0.6242	0.3710	0.062*
C16	0.3482 (3)	0.4776 (3)	0.3191 (3)	0.0541 (8)
H16	0.3125	0.4257	0.3759	0.065*
C17	0.4610 (4)	0.4370 (3)	0.2372 (3)	0.0547 (8)
H17	0.5018	0.3577	0.2393	0.066*
C18	0.5135 (3)	0.5138 (2)	0.1522 (2)	0.0457 (7)
H18	0.5891	0.4850	0.0974	0.055*
C3	0.2109 (2)	1.0192 (2)	0.11360 (19)	0.0275 (5)
C4	0.1130 (2)	1.1270 (2)	0.09634 (19)	0.0286 (5)
C19	0.0863 (3)	1.3212 (2)	0.0127 (2)	0.0367 (6)
H19A	0.0225	1.2886	−0.0148	0.044*
H19B	0.1379	1.3646	−0.0486	0.044*
C20	0.0176 (2)	1.4086 (2)	0.1086 (2)	0.0357 (5)
C21	0.0820 (3)	1.4966 (2)	0.1360 (2)	0.0420 (6)
H21	0.1682	1.4991	0.0977	0.050*
C22	0.0182 (3)	1.5812 (3)	0.2205 (3)	0.0480 (7)
H22	0.0615	1.6404	0.2383	0.058*
C23	−0.1102 (3)	1.5768 (3)	0.2782 (3)	0.0492 (7)
H23	−0.1530	1.6330	0.3349	0.059*
C24	−0.1746 (3)	1.4891 (3)	0.2515 (3)	0.0483 (7)
H24	−0.2605	1.4863	0.2906	0.058*
C25	−0.1111 (3)	1.4049 (2)	0.1661 (2)	0.0411 (6)
H25	−0.1549	1.3464	0.1477	0.049*
C5	0.2947 (2)	1.0569 (2)	0.1859 (2)	0.0320 (5)
H5A	0.3560	0.9871	0.1953	0.038*
H5B	0.3437	1.1189	0.1465	0.038*
C6	0.2146 (2)	1.1052 (2)	0.3011 (2)	0.0317 (5)
C7	0.1915 (3)	1.0285 (2)	0.3931 (2)	0.0385 (6)
H7	0.2248	0.9464	0.3840	0.046*
C8	0.1195 (3)	1.0727 (3)	0.4985 (2)	0.0474 (7)
H8	0.1061	1.0205	0.5597	0.057*
C9	0.0678 (3)	1.1939 (3)	0.5128 (2)	0.0544 (8)
H9	0.0184	1.2233	0.5833	0.065*
C10	0.0894 (3)	1.2713 (3)	0.4221 (3)	0.0529 (8)
H10	0.0542	1.3529	0.4316	0.063*
C11	0.1638 (3)	1.2278 (3)	0.3164 (2)	0.0455 (7)
H11	0.1796	1.2808	0.2560	0.055*
C26	0.3374 (2)	0.9362 (2)	−0.30536 (19)	0.0315 (5)
C27	0.2713 (2)	0.8524 (2)	−0.3380 (2)	0.0374 (6)
H27	0.1831	0.8537	−0.3050	0.045*
C28	0.3384 (3)	0.7671 (2)	−0.4201 (2)	0.0395 (6)
H28	0.2945	0.7110	−0.4420	0.047*
C29	0.4706 (2)	0.7640 (2)	−0.4704 (2)	0.0360 (5)
C30	0.5351 (2)	0.8470 (3)	−0.4351 (2)	0.0396 (6)
H30	0.6237	0.8445	−0.4667	0.048*
C31	0.4690 (2)	0.9337 (2)	−0.3530 (2)	0.0379 (6)
H31	0.5129	0.9894	−0.3304	0.045*
C32	0.5427 (3)	0.6728 (3)	−0.5619 (2)	0.0458 (7)
H32A	0.4858	0.6180	−0.5709	0.069*
H32B	0.6156	0.6278	−0.5417	0.069*
H32C	0.5724	0.7147	−0.6313	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0324 (3)	0.0297 (3)	0.0268 (3)	−0.0002 (2)	−0.0075 (2)	−0.0076 (2)
O6	0.0447 (10)	0.0359 (9)	0.0335 (9)	−0.0088 (8)	−0.0090 (7)	−0.0063 (7)
O7	0.0360 (9)	0.0374 (9)	0.0335 (9)	0.0040 (7)	−0.0131 (7)	−0.0044 (7)
O1	0.0302 (8)	0.0279 (8)	0.0386 (9)	0.0038 (6)	−0.0121 (7)	−0.0071 (7)
O2	0.0464 (10)	0.0317 (9)	0.0557 (12)	0.0039 (8)	−0.0226 (9)	−0.0171 (8)
O3	0.0292 (8)	0.0283 (8)	0.0374 (9)	0.0001 (6)	−0.0074 (7)	−0.0028 (7)
O5	0.0319 (8)	0.0258 (8)	0.0353 (9)	0.0023 (6)	−0.0065 (7)	−0.0056 (7)
O4	0.0286 (8)	0.0331 (9)	0.0376 (9)	0.0010 (7)	−0.0069 (7)	−0.0093 (7)
N1	0.0294 (9)	0.0270 (9)	0.0274 (10)	−0.0024 (7)	−0.0096 (8)	−0.0037 (8)
C2	0.0284 (11)	0.0294 (11)	0.0286 (12)	−0.0010 (9)	−0.0060 (9)	−0.0104 (9)
C1	0.0296 (11)	0.0299 (12)	0.0308 (12)	0.0013 (9)	−0.0065 (9)	−0.0091 (9)
C12	0.0336 (12)	0.0291 (12)	0.0448 (14)	0.0056 (10)	−0.0113 (11)	−0.0086 (10)
C13	0.0351 (12)	0.0332 (12)	0.0401 (13)	−0.0004 (10)	−0.0171 (10)	−0.0066 (10)
C14	0.0378 (13)	0.0416 (14)	0.0461 (15)	0.0016 (11)	−0.0142 (11)	−0.0008 (12)
C15	0.0429 (15)	0.067 (2)	0.0459 (16)	−0.0086 (14)	−0.0135 (13)	0.0041 (14)
C16	0.070 (2)	0.0501 (17)	0.0528 (18)	−0.0204 (15)	−0.0286 (16)	0.0094 (14)
C17	0.081 (2)	0.0306 (14)	0.0555 (18)	−0.0023 (14)	−0.0271 (16)	0.0000 (13)
C18	0.0574 (17)	0.0337 (14)	0.0448 (15)	0.0048 (12)	−0.0172 (13)	−0.0082 (12)
C3	0.0279 (11)	0.0253 (11)	0.0272 (11)	0.0001 (9)	−0.0056 (9)	−0.0062 (9)
C4	0.0290 (12)	0.0294 (11)	0.0257 (11)	0.0009 (9)	−0.0059 (9)	−0.0119 (9)
C19	0.0413 (13)	0.0296 (12)	0.0351 (13)	0.0067 (10)	−0.0094 (11)	−0.0043 (10)
C20	0.0390 (13)	0.0288 (12)	0.0355 (13)	0.0068 (10)	−0.0095 (10)	−0.0048 (10)
C21	0.0360 (13)	0.0401 (14)	0.0473 (15)	0.0040 (11)	−0.0109 (11)	−0.0085 (12)
C22	0.0465 (15)	0.0443 (15)	0.0565 (18)	0.0042 (12)	−0.0230 (13)	−0.0192 (13)
C23	0.0517 (16)	0.0445 (15)	0.0458 (16)	0.0078 (12)	−0.0100 (13)	−0.0180 (13)
C24	0.0400 (14)	0.0424 (15)	0.0522 (17)	0.0045 (12)	0.0003 (12)	−0.0115 (13)
C25	0.0416 (14)	0.0302 (12)	0.0482 (15)	−0.0006 (10)	−0.0083 (12)	−0.0074 (11)
C5	0.0305 (11)	0.0353 (12)	0.0301 (12)	0.0008 (9)	−0.0094 (9)	−0.0108 (10)
C6	0.0298 (11)	0.0378 (13)	0.0288 (12)	−0.0023 (9)	−0.0104 (9)	−0.0104 (10)
C7	0.0405 (13)	0.0408 (14)	0.0353 (13)	−0.0062 (11)	−0.0111 (11)	−0.0063 (11)
C8	0.0460 (15)	0.0658 (19)	0.0325 (14)	−0.0152 (14)	−0.0094 (11)	−0.0075 (13)
C9	0.0445 (15)	0.076 (2)	0.0381 (15)	−0.0043 (14)	−0.0031 (12)	−0.0288 (15)
C10	0.0646 (19)	0.0461 (16)	0.0440 (16)	0.0120 (14)	−0.0166 (14)	−0.0189 (13)
C11	0.0561 (17)	0.0406 (15)	0.0402 (15)	0.0048 (12)	−0.0180 (13)	−0.0145 (12)
C26	0.0344 (12)	0.0345 (12)	0.0240 (11)	−0.0004 (10)	−0.0069 (9)	−0.0067 (9)
C27	0.0333 (12)	0.0425 (14)	0.0339 (13)	−0.0065 (10)	−0.0031 (10)	−0.0093 (11)
C28	0.0418 (14)	0.0396 (14)	0.0356 (13)	−0.0065 (11)	−0.0065 (11)	−0.0111 (11)
C29	0.0386 (13)	0.0372 (13)	0.0292 (12)	0.0019 (10)	−0.0072 (10)	−0.0065 (10)
C30	0.0290 (12)	0.0498 (15)	0.0370 (13)	−0.0007 (11)	−0.0052 (10)	−0.0105 (12)
C31	0.0332 (12)	0.0451 (14)	0.0352 (13)	−0.0029 (10)	−0.0092 (10)	−0.0119 (11)
C32	0.0428 (14)	0.0492 (16)	0.0400 (15)	0.0051 (12)	−0.0062 (11)	−0.0171 (12)

Geometric parameters (Å, º)

S1—O6	1.4342 (18)	C21—C22	1.390 (4)
S1—O7	1.4360 (17)	C21—H21	0.93
S1—N1	1.625 (2)	C22—C23	1.387 (4)
S1—C26	1.769 (2)	C22—H22	0.93
O1—C1	1.348 (3)	C23—C24	1.381 (4)
O1—C12	1.455 (3)	C23—H23	0.93
O2—C1	1.198 (3)	C24—C25	1.395 (4)
O3—C3	1.419 (3)	C24—H24	0.9300
O3—H3	0.819 (9)	C25—H25	0.9300
O5—C4	1.333 (3)	C5—C6	1.518 (3)
O5—C19	1.475 (3)	C5—H5A	0.97
O4—C4	1.210 (3)	C5—H5B	0.97
N1—C2	1.458 (3)	C6—C7	1.388 (4)
N1—H1	0.882 (8)	C6—C11	1.392 (4)
C2—C1	1.529 (3)	C7—C8	1.386 (4)
C2—C3	1.569 (3)	C7—H7	0.93
C2—H2	0.98	C8—C9	1.379 (5)
C12—C13	1.500 (4)	C8—H8	0.93
C12—H12A	0.97	C9—C10	1.379 (5)
C12—H12B	0.97	C9—H9	0.93
C13—C14	1.389 (4)	C10—C11	1.393 (4)
C13—C18	1.399 (4)	C10—H10	0.93
C14—C15	1.408 (4)	C11—H11	0.93
C14—H14	0.93	C26—C31	1.383 (3)
C15—C16	1.384 (5)	C26—C27	1.392 (3)
C15—H15	0.93	C27—C28	1.385 (3)
C16—C17	1.383 (5)	C27—H27	0.93
C16—H16	0.93	C28—C29	1.394 (4)
C17—C18	1.383 (4)	C28—H28	0.93
C17—H17	0.93	C29—C30	1.388 (4)
C18—H18	0.93	C29—C32	1.510 (3)
C3—C4	1.530 (3)	C30—C31	1.392 (3)
C3—C5	1.548 (3)	C30—H30	0.93
C19—C20	1.512 (3)	C31—H31	0.93
C19—H19A	0.97	C32—H32A	0.96
C19—H19B	0.97	C32—H32B	0.96
C20—C25	1.387 (4)	C32—H32C	0.96
C20—C21	1.388 (4)
O6—S1—O7	120.04 (11)	C20—C21—C22	120.4 (3)
O6—S1—N1	107.02 (10)	C20—C21—H21	119.8
O7—S1—N1	105.71 (10)	C22—C21—H21	119.8
O6—S1—C26	107.98 (11)	C23—C22—C21	119.7 (3)
O7—S1—C26	107.15 (11)	C23—C22—H22	120.2
N1—S1—C26	108.51 (11)	C21—C22—H22	120.2
C1—O1—C12	116.98 (18)	C24—C23—C22	120.1 (2)
C3—O3—H3	109.5	C24—C23—H23	119.9
C4—O5—C19	115.55 (18)	C22—C23—H23	119.9
C2—N1—S1	123.19 (16)	C23—C24—C25	120.2 (3)
C2—N1—H1	117.5	C23—C24—H24	119.9
S1—N1—H1	115.1	C25—C24—H24	119.9
N1—C2—C1	110.44 (17)	C20—C25—C24	119.8 (3)
N1—C2—C3	109.00 (17)	C20—C25—H25	120.1
C1—C2—C3	110.79 (19)	C24—C25—H25	120.1
N1—C2—H2	108.9	C6—C5—C3	112.82 (18)
C1—C2—H2	108.9	C6—C5—H5A	109.0
C3—C2—H2	108.9	C3—C5—H5A	109.0
O2—C1—O1	124.9 (2)	C6—C5—H5B	109.0
O2—C1—C2	124.7 (2)	C3—C5—H5B	109.0
O1—C1—C2	110.39 (18)	H5A—C5—H5B	107.8
O1—C12—C13	114.13 (19)	C7—C6—C11	118.7 (2)
O1—C12—H12A	108.7	C7—C6—C5	120.8 (2)
C13—C12—H12A	108.7	C11—C6—C5	120.5 (2)
O1—C12—H12B	108.7	C8—C7—C6	120.9 (3)
C13—C12—H12B	108.7	C8—C7—H7	119.6
H12A—C12—H12B	107.6	C6—C7—H7	119.6
C14—C13—C18	118.5 (3)	C9—C8—C7	120.1 (3)
C14—C13—C12	123.7 (2)	C9—C8—H8	119.9
C18—C13—C12	117.7 (2)	C7—C8—H8	119.9
C13—C14—C15	119.9 (3)	C10—C9—C8	119.8 (3)
C13—C14—H14	120.0	C10—C9—H9	120.1
C15—C14—H14	120.0	C8—C9—H9	120.1
C16—C15—C14	120.6 (3)	C9—C10—C11	120.3 (3)
C16—C15—H15	119.7	C9—C10—H10	119.8
C14—C15—H15	119.7	C11—C10—H10	119.8
C17—C16—C15	119.3 (3)	C6—C11—C10	120.2 (3)
C17—C16—H16	120.3	C6—C11—H11	119.9
C15—C16—H16	120.3	C10—C11—H11	119.9
C16—C17—C18	120.4 (3)	C31—C26—C27	120.6 (2)
C16—C17—H17	119.8	C31—C26—S1	119.53 (19)
C18—C17—H17	119.8	C27—C26—S1	119.79 (18)
C17—C18—C13	121.2 (3)	C28—C27—C26	119.3 (2)
C17—C18—H18	119.4	C28—C27—H27	120.4
C13—C18—H18	119.4	C26—C27—H27	120.4
O3—C3—C4	109.48 (17)	C27—C28—C29	121.1 (2)
O3—C3—C5	109.89 (19)	C27—C28—H28	119.5
C4—C3—C5	110.72 (18)	C29—C28—H28	119.5
O3—C3—C2	108.12 (17)	C30—C29—C28	118.7 (2)
C4—C3—C2	106.10 (18)	C30—C29—C32	120.4 (2)
C5—C3—C2	112.41 (18)	C28—C29—C32	120.9 (2)
O4—C4—O5	125.4 (2)	C29—C30—C31	121.0 (2)
O4—C4—C3	122.7 (2)	C29—C30—H30	119.5
O5—C4—C3	111.83 (18)	C31—C30—H30	119.5
O5—C19—C20	111.5 (2)	C26—C31—C30	119.3 (2)
O5—C19—H19A	109.3	C26—C31—H31	120.3
C20—C19—H19A	109.3	C30—C31—H31	120.3
O5—C19—H19B	109.3	C29—C32—H32A	109.5
C20—C19—H19B	109.3	C29—C32—H32B	109.5
H19A—C19—H19B	108.0	H32A—C32—H32B	109.5
C25—C20—C21	119.7 (2)	C29—C32—H32C	109.5
C25—C20—C19	120.5 (2)	H32A—C32—H32C	109.5
C21—C20—C19	119.7 (2)	H32B—C32—H32C	109.5
O6—S1—N1—C2	−27.63 (19)	C25—C20—C21—C22	−0.2 (4)
O7—S1—N1—C2	−156.67 (16)	C19—C20—C21—C22	177.0 (3)
C26—S1—N1—C2	88.66 (19)	C20—C21—C22—C23	0.5 (5)
S1—N1—C2—C1	−105.3 (2)	C21—C22—C23—C24	−0.2 (5)
S1—N1—C2—C3	132.81 (17)	C22—C23—C24—C25	−0.3 (5)
C12—O1—C1—O2	2.2 (4)	C21—C20—C25—C24	−0.4 (4)
C12—O1—C1—C2	−177.13 (19)	C19—C20—C25—C24	−177.5 (3)
N1—C2—C1—O2	−9.6 (3)	C23—C24—C25—C20	0.6 (5)
C3—C2—C1—O2	111.2 (3)	O3—C3—C5—C6	−62.1 (2)
N1—C2—C1—O1	169.70 (18)	C4—C3—C5—C6	59.0 (3)
C3—C2—C1—O1	−69.4 (2)	C2—C3—C5—C6	177.4 (2)
C1—O1—C12—C13	−83.7 (3)	C3—C5—C6—C7	92.9 (3)
O1—C12—C13—C14	−6.4 (3)	C3—C5—C6—C11	−87.6 (3)
O1—C12—C13—C18	175.4 (2)	C11—C6—C7—C8	−0.1 (4)
C18—C13—C14—C15	0.4 (4)	C5—C6—C7—C8	179.4 (2)
C12—C13—C14—C15	−177.8 (2)	C6—C7—C8—C9	1.1 (4)
C13—C14—C15—C16	−0.6 (4)	C7—C8—C9—C10	−0.9 (4)
C14—C15—C16—C17	0.6 (5)	C8—C9—C10—C11	−0.3 (5)
C15—C16—C17—C18	−0.6 (5)	C7—C6—C11—C10	−1.1 (4)
C16—C17—C18—C13	0.4 (5)	C5—C6—C11—C10	179.4 (3)
C14—C13—C18—C17	−0.3 (4)	C9—C10—C11—C6	1.4 (5)
C12—C13—C18—C17	178.0 (3)	O6—S1—C26—C31	6.3 (2)
N1—C2—C3—O3	81.8 (2)	O7—S1—C26—C31	136.9 (2)
C1—C2—C3—O3	−39.9 (2)	N1—S1—C26—C31	−109.4 (2)
N1—C2—C3—C4	−35.6 (2)	O6—S1—C26—C27	−171.1 (2)
C1—C2—C3—C4	−157.29 (18)	O7—S1—C26—C27	−40.5 (2)
N1—C2—C3—C5	−156.72 (19)	N1—S1—C26—C27	73.2 (2)
C1—C2—C3—C5	81.6 (2)	C31—C26—C27—C28	−0.9 (4)
C19—O5—C4—O4	−7.6 (3)	S1—C26—C27—C28	176.5 (2)
C19—O5—C4—C3	171.10 (17)	C26—C27—C28—C29	−0.1 (4)
O3—C3—C4—O4	−2.3 (3)	C27—C28—C29—C30	1.3 (4)
C5—C3—C4—O4	−123.6 (2)	C27—C28—C29—C32	−178.5 (3)
C2—C3—C4—O4	114.1 (2)	C28—C29—C30—C31	−1.6 (4)
O3—C3—C4—O5	178.90 (17)	C32—C29—C30—C31	178.2 (3)
C5—C3—C4—O5	57.6 (2)	C27—C26—C31—C30	0.6 (4)
C2—C3—C4—O5	−64.6 (2)	S1—C26—C31—C30	−176.8 (2)
C4—O5—C19—C20	84.8 (2)	C29—C30—C31—C26	0.7 (4)
O5—C19—C20—C25	−101.7 (3)	S1—N1—H1—C2	157.7
O5—C19—C20—C21	81.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O7^i	0.82	2.17	2.914 (2)	152
N1—H1···O4^i	0.88	2.11	2.910 (2)	151

Symmetry code: (i) −x, −y+2, −z.

(II) dibenzyl 2-benzyl-2-hydroxy-3-(4-methylphenylsulfonamido)succinate

Crystal data

C32H31NO7S	F(000) = 1208
Mr = 573.64	Dx = 1.324 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 2973 reflections
a = 10.8712 (4) Å	θ = 4.2–51.5°
b = 19.8539 (6) Å	µ = 1.41 mm^−1
c = 13.8180 (4) Å	T = 173 K
β = 105.156 (3)°	Needle, colourless
V = 2878.68 (17) Å^3	0.21 × 0.02 × 0.02 mm
Z = 4

Data collection

Agilent Xcalibur Sapphire3 Gemini diffractometer	5477 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2878 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 16.0143 pixels mm^-1	θmax = 51.8°, θmin = 4.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −20→20
Tmin = 0.897, Tmax = 1.000	l = −13→12
5477 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.234	w = 1/[σ^2(Fo^2) + (0.1412P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.92	(Δ/σ)max < 0.001
5477 reflections	Δρmax = 0.79 e Å^−3
370 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0007 (3)

Special details

Experimental. CrysAlisPro, Version 1.171.33.56 – release 18-01-2010 (Agilent Technologies UK Ltd, 2010) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Twin by reticular merohedry with twin index 3 It is noted that the Crysalis software outputs a hklf5 reflection file with merged reflection intensities (contrary to Bruker software) RINT ANALYSIS FOR OVERLAPPED REFLECTIONS Components measured kept unique redundancy F2/sig(F2) Rint Rsigma —————————————————————————— 1,2 3799 3351 1102 3.04 16.24 0.049 0.062

RINT ANALYSIS FOR ISOLATED REFLECTIONS Component measured kept unique redundancy F2/sig(F2) Rint Rsigma —————————————————————————— 1 7815 7408 2287 3.24 12.47 0.048 0.069 2 7855 7691 2293 3.35 2.91 0.152 0.322

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.19111 (13)	0.13864 (7)	0.49979 (9)	0.0361 (4)
O6	0.2530 (4)	0.15103 (18)	0.4225 (2)	0.0447 (10)
O7	0.0650 (3)	0.16364 (18)	0.4905 (3)	0.0427 (10)
O1	0.3563 (4)	0.02570 (19)	0.6710 (3)	0.0476 (11)
O2	0.4688 (4)	−0.0424 (2)	0.5948 (3)	0.0553 (12)
O3	0.1547 (3)	−0.07994 (18)	0.5269 (2)	0.0386 (10)
H3	0.1307	−0.1187	0.5129	0.058*
O5	0.1355 (3)	0.00349 (19)	0.2945 (3)	0.0400 (10)
O4	−0.0176 (4)	−0.04333 (18)	0.3532 (3)	0.0397 (10)
N1	0.1801 (3)	0.05847 (17)	0.5100 (2)	0.0353 (11)
H1	0.1344	0.0481	0.5520	0.042*
C2	0.2768 (3)	0.01082 (17)	0.4966 (2)	0.0334 (13)
H2	0.3196	0.0303	0.4471	0.040*
C1	0.3786 (6)	−0.0061 (3)	0.5922 (4)	0.0402 (14)
C12	0.4496 (6)	0.0183 (3)	0.7680 (4)	0.0562 (17)
H12A	0.4738	0.0633	0.7977	0.067*
H12B	0.5273	−0.0037	0.7585	0.067*
C13	0.3954 (5)	−0.0231 (3)	0.8376 (4)	0.0460 (16)
C14	0.3875 (8)	−0.0917 (4)	0.8268 (5)	0.074 (2)
H14	0.4148	−0.1126	0.7741	0.089*
C15	0.3402 (8)	−0.1307 (4)	0.8915 (6)	0.085 (3)
H15	0.3332	−0.1782	0.8831	0.102*
C16	0.3030 (7)	−0.0996 (4)	0.9692 (6)	0.072 (2)
H16	0.2723	−0.1260	1.0152	0.087*
C17	0.3100 (6)	−0.0321 (4)	0.9798 (5)	0.0608 (19)
H17	0.2826	−0.0111	1.0324	0.073*
C18	0.3569 (6)	0.0065 (4)	0.9144 (5)	0.0549 (17)
H18	0.3626	0.0540	0.9226	0.066*
C3	0.2037 (5)	−0.0536 (3)	0.4503 (4)	0.0336 (13)
C4	0.0929 (6)	−0.0310 (3)	0.3625 (4)	0.0326 (13)
C19	0.0399 (6)	0.0335 (3)	0.2134 (4)	0.0506 (17)
H19A	−0.0143	0.0645	0.2404	0.061*
H19B	−0.0151	−0.0020	0.1740	0.061*
C20	0.1057 (6)	0.0716 (3)	0.1476 (4)	0.0454 (16)
C21	0.2217 (7)	0.1012 (3)	0.1847 (5)	0.0578 (19)
H21	0.2648	0.0959	0.2536	0.069*
C22	0.2776 (8)	0.1390 (4)	0.1229 (5)	0.076 (2)
H22	0.3581	0.1597	0.1496	0.091*
C23	0.2169 (11)	0.1464 (4)	0.0242 (6)	0.083 (3)
H23	0.2544	0.1726	−0.0180	0.099*
C24	0.1010 (10)	0.1157 (5)	−0.0142 (6)	0.081 (3)
H24	0.0594	0.1201	−0.0835	0.097*
C25	0.0449 (7)	0.0786 (4)	0.0463 (5)	0.065 (2)
H25	−0.0355	0.0578	0.0191	0.078*
C5	0.2851 (5)	−0.1057 (3)	0.4115 (4)	0.0415 (15)
H5A	0.3301	−0.0828	0.3671	0.050*
H5B	0.3502	−0.1245	0.4692	0.050*
C6	0.2064 (6)	−0.1625 (3)	0.3547 (4)	0.0452 (16)
C7	0.1563 (6)	−0.2122 (3)	0.4040 (5)	0.0563 (18)
H7	0.1756	−0.2116	0.4752	0.068*
C8	0.0789 (8)	−0.2623 (4)	0.3516 (7)	0.080 (2)
H8	0.0431	−0.2943	0.3875	0.096*
C9	0.0528 (9)	−0.2672 (5)	0.2514 (8)	0.097 (3)
H9	0.0013	−0.3028	0.2168	0.117*
C10	0.1024 (8)	−0.2194 (5)	0.1998 (6)	0.087 (3)
H10	0.0850	−0.2224	0.1288	0.104*
C11	0.1784 (7)	−0.1662 (4)	0.2504 (5)	0.067 (2)
H11	0.2104	−0.1331	0.2137	0.081*
C26	0.2883 (5)	0.1723 (3)	0.6114 (4)	0.0349 (14)
C27	0.4161 (5)	0.1842 (3)	0.6207 (4)	0.0398 (15)
H27	0.4525	0.1728	0.5674	0.048*
C28	0.4906 (6)	0.2125 (3)	0.7070 (4)	0.0456 (15)
H28	0.5783	0.2207	0.7126	0.055*
C29	0.4401 (6)	0.2292 (3)	0.7858 (4)	0.0447 (15)
C30	0.3119 (6)	0.2164 (3)	0.7765 (4)	0.0467 (16)
H30	0.2756	0.2276	0.8299	0.056*
C31	0.2373 (6)	0.1877 (3)	0.6910 (4)	0.0419 (15)
H31	0.1502	0.1783	0.6861	0.050*
C32	0.5205 (7)	0.2634 (4)	0.8789 (5)	0.068 (2)
H32A	0.5170	0.2372	0.9382	0.102*
H32B	0.4876	0.3088	0.8839	0.102*
H32C	0.6090	0.2662	0.8747	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0410 (9)	0.0343 (8)	0.0328 (8)	−0.0040 (7)	0.0094 (6)	0.0003 (6)
O6	0.057 (3)	0.044 (2)	0.034 (2)	−0.011 (2)	0.0144 (19)	0.0010 (18)
O7	0.042 (2)	0.039 (2)	0.043 (2)	0.0004 (19)	0.0044 (18)	0.0030 (18)
O1	0.055 (3)	0.049 (3)	0.034 (2)	0.002 (2)	0.004 (2)	−0.0016 (19)
O2	0.034 (2)	0.079 (3)	0.052 (3)	0.010 (2)	0.0099 (19)	0.002 (2)
O3	0.046 (2)	0.032 (2)	0.039 (2)	−0.0036 (18)	0.0141 (18)	−0.0030 (17)
O5	0.036 (2)	0.047 (2)	0.040 (2)	0.0019 (19)	0.0150 (19)	0.0081 (19)
O4	0.028 (2)	0.046 (2)	0.046 (2)	−0.0017 (19)	0.0111 (18)	−0.0003 (18)
N1	0.030 (3)	0.041 (3)	0.037 (2)	−0.004 (2)	0.013 (2)	−0.005 (2)
C2	0.031 (3)	0.035 (3)	0.037 (3)	−0.003 (3)	0.015 (3)	0.001 (3)
C1	0.032 (4)	0.039 (4)	0.048 (4)	−0.009 (3)	0.007 (3)	0.006 (3)
C12	0.063 (4)	0.056 (4)	0.042 (4)	−0.010 (4)	0.000 (3)	0.001 (3)
C13	0.046 (4)	0.053 (4)	0.032 (3)	0.001 (3)	−0.002 (3)	0.005 (3)
C14	0.116 (7)	0.047 (5)	0.071 (5)	−0.005 (4)	0.045 (5)	−0.003 (4)
C15	0.122 (7)	0.046 (5)	0.104 (6)	0.003 (5)	0.060 (6)	0.008 (4)
C16	0.067 (5)	0.080 (6)	0.076 (5)	0.004 (4)	0.031 (4)	0.019 (5)
C17	0.045 (4)	0.085 (6)	0.054 (4)	0.005 (4)	0.016 (3)	0.000 (4)
C18	0.047 (4)	0.059 (4)	0.054 (4)	0.003 (3)	0.004 (3)	−0.010 (4)
C3	0.039 (3)	0.036 (3)	0.028 (3)	0.003 (3)	0.013 (3)	0.006 (3)
C4	0.039 (4)	0.027 (3)	0.036 (3)	0.004 (3)	0.017 (3)	−0.004 (2)
C19	0.043 (4)	0.059 (4)	0.048 (4)	0.009 (3)	0.008 (3)	0.017 (3)
C20	0.059 (4)	0.038 (4)	0.044 (4)	0.014 (3)	0.022 (3)	0.008 (3)
C21	0.091 (6)	0.047 (4)	0.041 (3)	−0.023 (4)	0.028 (4)	−0.007 (3)
C22	0.121 (7)	0.059 (5)	0.060 (5)	−0.040 (5)	0.046 (5)	−0.017 (4)
C23	0.162 (9)	0.040 (4)	0.069 (6)	0.009 (5)	0.073 (6)	0.009 (4)
C24	0.112 (7)	0.083 (6)	0.052 (5)	0.042 (6)	0.030 (5)	0.030 (4)
C25	0.055 (4)	0.090 (6)	0.051 (4)	0.024 (4)	0.017 (3)	0.026 (4)
C5	0.041 (4)	0.045 (4)	0.041 (3)	0.011 (3)	0.013 (3)	0.004 (3)
C6	0.046 (4)	0.046 (4)	0.038 (4)	0.018 (3)	0.001 (3)	−0.017 (3)
C7	0.067 (4)	0.036 (4)	0.057 (4)	0.015 (4)	−0.001 (4)	−0.006 (3)
C8	0.092 (6)	0.040 (4)	0.089 (6)	0.006 (4)	−0.011 (5)	−0.015 (4)
C9	0.105 (7)	0.055 (6)	0.105 (8)	0.018 (5)	−0.020 (6)	−0.026 (5)
C10	0.093 (6)	0.094 (7)	0.049 (5)	0.049 (6)	−0.025 (4)	−0.038 (5)
C11	0.075 (5)	0.072 (5)	0.052 (4)	0.040 (4)	0.010 (4)	−0.004 (4)
C26	0.037 (4)	0.030 (3)	0.040 (3)	0.003 (3)	0.014 (3)	0.003 (2)
C27	0.047 (4)	0.040 (4)	0.037 (3)	0.001 (3)	0.019 (3)	−0.007 (3)
C28	0.035 (3)	0.050 (4)	0.050 (4)	0.001 (3)	0.007 (3)	−0.008 (3)
C29	0.047 (4)	0.040 (4)	0.041 (4)	0.006 (3)	0.000 (3)	−0.005 (3)
C30	0.059 (4)	0.049 (4)	0.033 (3)	0.002 (3)	0.014 (3)	−0.005 (3)
C31	0.039 (3)	0.053 (4)	0.037 (3)	−0.004 (3)	0.016 (3)	0.001 (3)
C32	0.062 (5)	0.076 (5)	0.056 (4)	0.003 (4)	−0.002 (4)	−0.021 (4)

Geometric parameters (Å, º)

S1—O6	1.425 (4)	C21—C22	1.391 (9)
S1—O7	1.432 (4)	C21—H21	0.9500
S1—N1	1.605 (4)	C22—C23	1.358 (11)
S1—C26	1.758 (5)	C22—H22	0.9500
O1—C1	1.335 (7)	C23—C24	1.376 (12)
O1—C12	1.460 (7)	C23—H23	0.9500
O2—C1	1.209 (7)	C24—C25	1.371 (11)
O3—C3	1.405 (6)	C24—H24	0.9500
O3—H3	0.8200	C25—H25	0.9500
O5—C4	1.339 (6)	C5—C6	1.506 (8)
O5—C19	1.444 (7)	C5—H5A	0.9900
O4—C4	1.200 (6)	C5—H5B	0.9900
N1—C2	1.461 (8)	C6—C7	1.389 (9)
N1—H1	0.881 (5)	C6—C11	1.395 (8)
C2—C1	1.523 (7)	C7—C8	1.380 (9)
C2—C3	1.552 (6)	C7—H7	0.9500
C2—H2	1.0000	C8—C9	1.343 (12)
C12—C13	1.499 (8)	C8—H8	0.9500
C12—H12A	0.9900	C9—C10	1.378 (13)
C12—H12B	0.9900	C9—H9	0.9500
C13—C18	1.369 (8)	C10—C11	1.409 (11)
C13—C14	1.370 (9)	C10—H10	0.9500
C14—C15	1.381 (10)	C11—H11	0.9500
C14—H14	0.9500	C26—C27	1.381 (8)
C15—C16	1.387 (10)	C26—C31	1.389 (7)
C15—H15	0.9500	C27—C28	1.375 (8)
C16—C17	1.347 (10)	C27—H27	0.9500
C16—H16	0.9500	C28—C29	1.382 (8)
C17—C18	1.381 (9)	C28—H28	0.9500
C17—H17	0.9500	C29—C30	1.389 (8)
C18—H18	0.9500	C29—C32	1.513 (8)
C3—C4	1.536 (7)	C30—C31	1.370 (8)
C3—C5	1.546 (7)	C30—H30	0.9500
C19—C20	1.500 (8)	C31—H31	0.9500
C19—H19A	0.9900	C32—H32A	0.9800
C19—H19B	0.9900	C32—H32B	0.9800
C20—C21	1.364 (9)	C32—H32C	0.9800
C20—C25	1.390 (9)
O6—S1—O7	120.1 (2)	C20—C21—C22	120.7 (6)
O6—S1—N1	107.3 (2)	C20—C21—H21	119.7
O7—S1—N1	105.1 (2)	C22—C21—H21	119.7
O6—S1—C26	107.4 (2)	C23—C22—C21	120.0 (8)
O7—S1—C26	106.8 (2)	C23—C22—H22	120.0
N1—S1—C26	110.0 (2)	C21—C22—H22	120.0
C1—O1—C12	118.0 (5)	C22—C23—C24	119.7 (7)
C3—O3—H3	109.5	C22—C23—H23	120.2
C4—O5—C19	116.4 (4)	C24—C23—H23	120.2
C2—N1—S1	123.90 (12)	C25—C24—C23	120.7 (7)
C2—N1—H1	118.7	C25—C24—H24	119.6
S1—N1—H1	111.0	C23—C24—H24	119.6
N1—C2—C1	114.6 (3)	C24—C25—C20	119.9 (8)
N1—C2—C3	106.1 (2)	C24—C25—H25	120.1
C1—C2—C3	110.7 (4)	C20—C25—H25	120.1
N1—C2—H2	108.4	C6—C5—C3	112.6 (4)
C1—C2—H2	108.4	C6—C5—H5A	109.1
C3—C2—H2	108.4	C3—C5—H5A	109.1
O2—C1—O1	125.2 (5)	C6—C5—H5B	109.1
O2—C1—C2	123.9 (5)	C3—C5—H5B	109.1
O1—C1—C2	111.0 (5)	H5A—C5—H5B	107.8
O1—C12—C13	110.4 (5)	C7—C6—C11	117.5 (6)
O1—C12—H12A	109.6	C7—C6—C5	121.2 (5)
C13—C12—H12A	109.6	C11—C6—C5	121.3 (6)
O1—C12—H12B	109.6	C8—C7—C6	121.2 (7)
C13—C12—H12B	109.6	C8—C7—H7	119.4
H12A—C12—H12B	108.1	C6—C7—H7	119.4
C18—C13—C14	119.2 (6)	C9—C8—C7	121.9 (9)
C18—C13—C12	120.9 (6)	C9—C8—H8	119.0
C14—C13—C12	119.9 (6)	C7—C8—H8	119.0
C13—C14—C15	120.7 (7)	C8—C9—C10	118.6 (8)
C13—C14—H14	119.7	C8—C9—H9	120.7
C15—C14—H14	119.7	C10—C9—H9	120.7
C14—C15—C16	119.0 (7)	C9—C10—C11	121.1 (7)
C14—C15—H15	120.5	C9—C10—H10	119.4
C16—C15—H15	120.5	C11—C10—H10	119.4
C17—C16—C15	120.5 (7)	C6—C11—C10	119.6 (8)
C17—C16—H16	119.7	C6—C11—H11	120.2
C15—C16—H16	119.7	C10—C11—H11	120.2
C16—C17—C18	120.0 (6)	C27—C26—C31	119.3 (5)
C16—C17—H17	120.0	C27—C26—S1	120.4 (4)
C18—C17—H17	120.0	C31—C26—S1	120.3 (4)
C13—C18—C17	120.6 (7)	C28—C27—C26	120.1 (5)
C13—C18—H18	119.7	C28—C27—H27	120.0
C17—C18—H18	119.7	C26—C27—H27	120.0
O3—C3—C4	109.3 (4)	C27—C28—C29	121.1 (6)
O3—C3—C5	112.1 (4)	C27—C28—H28	119.5
C4—C3—C5	108.9 (4)	C29—C28—H28	119.5
O3—C3—C2	104.5 (3)	C28—C29—C30	118.6 (5)
C4—C3—C2	107.2 (4)	C28—C29—C32	121.1 (6)
C5—C3—C2	114.6 (4)	C30—C29—C32	120.2 (6)
O4—C4—O5	123.4 (5)	C31—C30—C29	120.7 (5)
O4—C4—C3	125.5 (5)	C31—C30—H30	119.7
O5—C4—C3	111.1 (5)	C29—C30—H30	119.7
O5—C19—C20	108.6 (5)	C30—C31—C26	120.3 (6)
O5—C19—H19A	110.0	C30—C31—H31	119.8
C20—C19—H19A	110.0	C26—C31—H31	119.8
O5—C19—H19B	110.0	C29—C32—H32A	109.5
C20—C19—H19B	110.0	C29—C32—H32B	109.5
H19A—C19—H19B	108.4	H32A—C32—H32B	109.5
C21—C20—C25	119.0 (6)	C29—C32—H32C	109.5
C21—C20—C19	122.0 (5)	H32A—C32—H32C	109.5
C25—C20—C19	119.0 (6)	H32B—C32—H32C	109.5
O6—S1—N1—C2	35.4 (2)	C25—C20—C21—C22	1.3 (10)
O7—S1—N1—C2	164.28 (16)	C19—C20—C21—C22	−176.8 (6)
C26—S1—N1—C2	−81.1 (2)	C20—C21—C22—C23	−0.5 (11)
S1—N1—C2—C1	90.7 (3)	C21—C22—C23—C24	−0.8 (12)
S1—N1—C2—C3	−146.8 (3)	C22—C23—C24—C25	1.2 (12)
C12—O1—C1—O2	2.0 (8)	C23—C24—C25—C20	−0.4 (11)
C12—O1—C1—C2	−176.2 (4)	C21—C20—C25—C24	−0.9 (10)
N1—C2—C1—O2	−176.8 (4)	C19—C20—C25—C24	177.3 (6)
C3—C2—C1—O2	63.2 (6)	O3—C3—C5—C6	69.0 (6)
N1—C2—C1—O1	1.4 (5)	C4—C3—C5—C6	−52.0 (6)
C3—C2—C1—O1	−118.5 (4)	C2—C3—C5—C6	−172.0 (4)
C1—O1—C12—C13	−110.2 (6)	C3—C5—C6—C7	−73.3 (7)
O1—C12—C13—C18	−105.0 (6)	C3—C5—C6—C11	105.0 (6)
O1—C12—C13—C14	76.9 (8)	C11—C6—C7—C8	−1.7 (9)
C18—C13—C14—C15	0.6 (11)	C5—C6—C7—C8	176.7 (6)
C12—C13—C14—C15	178.7 (7)	C6—C7—C8—C9	2.9 (11)
C13—C14—C15—C16	−1.2 (13)	C7—C8—C9—C10	−1.8 (12)
C14—C15—C16—C17	1.6 (12)	C8—C9—C10—C11	−0.3 (12)
C15—C16—C17—C18	−1.3 (11)	C7—C6—C11—C10	−0.4 (9)
C14—C13—C18—C17	−0.3 (10)	C5—C6—C11—C10	−178.8 (5)
C12—C13—C18—C17	−178.4 (6)	C9—C10—C11—C6	1.4 (11)
C16—C17—C18—C13	0.7 (10)	O6—S1—C26—C27	−20.5 (5)
N1—C2—C3—O3	−67.8 (3)	O7—S1—C26—C27	−150.5 (4)
C1—C2—C3—O3	57.1 (5)	N1—S1—C26—C27	96.0 (5)
N1—C2—C3—C4	48.1 (3)	O6—S1—C26—C31	159.1 (4)
C1—C2—C3—C4	173.0 (4)	O7—S1—C26—C31	29.1 (5)
N1—C2—C3—C5	169.1 (3)	N1—S1—C26—C31	−84.4 (5)
C1—C2—C3—C5	−66.0 (5)	C31—C26—C27—C28	−1.6 (8)
C19—O5—C4—O4	7.8 (7)	S1—C26—C27—C28	177.9 (4)
C19—O5—C4—C3	−173.8 (4)	C26—C27—C28—C29	0.4 (9)
O3—C3—C4—O4	−11.0 (7)	C27—C28—C29—C30	0.4 (9)
C5—C3—C4—O4	111.8 (6)	C27—C28—C29—C32	−177.1 (6)
C2—C3—C4—O4	−123.7 (5)	C28—C29—C30—C31	0.1 (9)
O3—C3—C4—O5	170.8 (4)	C32—C29—C30—C31	177.6 (6)
C5—C3—C4—O5	−66.5 (5)	C29—C30—C31—C26	−1.4 (9)
C2—C3—C4—O5	58.0 (5)	C27—C26—C31—C30	2.2 (8)
C4—O5—C19—C20	178.1 (4)	S1—C26—C31—C30	−177.4 (4)
O5—C19—C20—C21	−30.8 (8)	S1—N1—H1—C2	−153.0
O5—C19—C20—C25	151.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O7^i	0.82	2.30	2.868 (5)	127
N1—H1···O4^i	0.88	2.05	2.920 (5)	169

Symmetry code: (i) −x, −y, −z+1.