XRD and VCD: a marriage of love or convenience? Honeymoon around a cyclic urea derivative

The structures and absolute configurations of the enantio­mers (3aR,8aR)-2,2-dimethyl-4,4,8,8-tetra­phenyl-4,5,6,7,8,8a-hexahydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 0.33-hydrate, C₃₂H₃₀N₂O₃·0.33H₂O, (Ia), and (3aS,8aS)-2,2-dimethyl-4,4,8,8-tetra­phenyl-4,5,6,7,8,8a-hexa­hydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 0.39-hydrate, C₃₂H₃₀N₂O₃·0.39H₂O, (Ib), have been elucidated unambiguously using the complementary power of single-crystal X-ray diffraction (XRD) and vibrational circular dichroism (VCD). The enantio­mers crystallize in the Sohncke space group P2₁2₁2 and pack as dimers stabilized by two symmetric hydrogen bonds involving one amide group each of the cyclic urea moiety. This double inter­action is capped by a water mol­ecule that partially occupies a site lying on the twofold axis and forms an uncommon hydrogen bond between the two monomers. A comparison between the solid-state VCD characterizations and the Bayesian statistics on Bijvoet differences determined from the XRD measurements reveals a tendency towards the correct determination of the absolute configuration by this latter method.

S1. Comment

The determination of the absolute configuration of molecules is of crucial importance in chemistry, biology and pharmaceutics, in industrial processes as well as in fundamental research. Several methods can lead more or less straightforwardly to this information, but among them single-crystal X-ray diffraction (XRD) and vibrational circular dichroism (VCD) are the two methods of reference when the concern is to obtain the information directly from experimental evidence (Flack & Bernardinelli, 2008a; He et al., 2011, and references therein). Each of these methods possesses its own advantages and drawbacks and they are now commonly coupled in studies involving absolute configuration determination. However, in most cases their association is restricted to a cross-validation process, where one method is used to confirm the results obtained by the other and vice versa: as in a marriage of convenience, the partners cohabit but do not interact much. The aim of this study is to show that much more structural information can be inferred from a process involving full collaboration and feedback between the two partners: a marriage for love. The starting point for the honeymoon journey was the synthesis and characterization of the (3aR,8aR) and (3aS,8aS) enantiomers of 2,2-dimethyl-4,4,8,8-tetraphenyl-4,5,6,7,8,8a-hexahydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one, (I), a new seven-membered ring urea derivative.

Cyclic urea-containing molecules are well known inhibitors of HIV-1 protease (Sussman et al., 2002; Duan et al., 2011, and references therein). In that context it has been proposed recently that the nature of the hydrogen-bond network between HIV-1 protease and urea-based inhibitors can be related to the efficiency of the latter (Li et al., 2011).

From enantiopure tartaric acid, we synthesized the (R,R) and (S,S) enantiomers of (I), hereinafter named (Ia) and (Ib), respectively, which were both obtained enantiopure as crystalline powders. A small amount of each sample was taken for crystallization by slow evaporation from ethanol and the remaining material was used for solid-state IR and VCD measurements.

The absolute configurations of (Ia) and (Ib) were known a priori from the synthetic process, but we decided to confirm them by solid-state VCD measurements (He et al., 2011, and references therein). The solid-state IR absorption spectra of both enantiomers revealed large bands in the C═O and C—N stretching regions (1600–1750 and 1350–1500 cm^-1, respectively) (Fig. 1). Based on literature data and density functional theory (DFT) calculations for interpretation of the IR spectra, it appeared that bands at 1371, 1379 and 1650 cm^-1 can not be related to an isolated molecule but rather are induced by interactions between two urea moieties. However, the second ν_C═O band at 1633 cm^-1, as well as bands at 1399, 1418, 1446 and 1496 cm^-1, can not be attributed to such a supramolecular structure. It was thus necessary to determine unambiguously the solid-state structure of (I) in order to calculate the correct VCD spectra. In particular, it was essential to determine the origin of the intense positive couplet (1616 and 1630 cm^-1) associated with the second stretching ν_C═O vibrational mode (Fig. 2).

We then carried out low-temperature XRD measurements in order to determine the supramolecular structure of (I), and these data were then used as new input for the calculation of the VCD spectra. As expected from the IR spectra, (I) crystallizes as a dimer (Fig. 3). However, the asymmetric unit is composed of one molecule of (I) in a general position and a water molecule lying on a twofold axis [Figs. 4 and 5 for enantiomers (Ia) and (Ib), respectively]. The molecule is built around the ring including the carbamide moiety. A survey of the Cambridge Structural Database (Version?; Allen, 2002) reports a few examples of ureas with this kind of seven-membered ring (Czochralska et al., 1977; Hodge et al., 1998; Schaffner et al., 2006; Aubert et al., 2007; Ejsmont et al., 2010). The geometric parameters within this ring in (Ia) and (Ib) are in agreement with those observed in the previously published structures, except for the angles around the N atoms of the carbamide: the C4—N1—C3 and C4—N2—C5 angles are 132.28 (16) and 131.58 (17)°, and 132.08 (11) and 131.13 (11)°, for (Ia) and (Ib), respectively, while the values reported in the literature range from 122 to 129°. Steric hindrance due to the presence of two bulky substituents on the C atoms bonded to the N atoms can explain the opening of these angles in the present compounds. Indeed, two phenyls are bonded to atoms C3 and C5, and each of these pairs of rings is oriented in such a way that they are involved in intramolecular C—H···π interactions. Although the values of the characteristic geometric parameters measured in our structures are at the limit of the range commonly admitted for this kind of contact (Nishio et al., 1998), it seems clear that the phenyl moieties adopt conformations that tend to optimize their interaction: the H16—C9 and H26—C27 distances range from 2.48 to 2.49 Å, while the C16—H16—C9 and C26—H26—C27 angles range from 104 to 105° in the two enantiomers. Moreover, the angle defined by the two planes of each pair of interacting phenyls is close to 70° in all cases. This observation was confirmed by DFT calculations. Indeed, similar orientations of the pairs of phenyl rings were obtained for the optimized structure of (I), starting from the X-ray geometry and using the cam-B3LYP/6-31 G(d) theoretical level (Fig. 6). The substitution of the cyclic urea is completed by the dimethyl dioxolane moiety, which adopts an envelope conformation (Cremer & Pople, 1975) imposed by its connectivity to chiral atoms C1 and C2.

Interestingly, enantiomers (Ia) and (Ib) crystallize as dimers that interact through a double hydrogen bond between atoms O1 and N1 of two symmetry-related molecules. This double hydrogen bond is itself capped by a weaker one between a water molecule and the two O atoms of the ureas, and the network built up by these interactions resembles that of bridged cyclic hydrocarbon compounds like norbornene derivatives (Figs. 3 and 6, and Tables 1 and 2). To our knowledge, this is the first example of this type of three-partner hydrogen-bond interaction involving a dimer and a water molecule.

The planes formed by the ureas within the dimers are neither coplanar nor twisted like those observed in three similar compounds described in the literature (Czochralska et al., 1977; Ejsmont et al., 2010; Aubert et al., 2007). In our molecules, the angles between the two moieties are close to 53° for both (Ia) and (Ib), and these values are comparable with those observed in other bent geometries in similar compounds (Schaffner et al., 2006) and with the simulated structures used for the VCD analysis (Fig. 6).

The weakness of the hydrogen bonds involving the water molecule is not so much a question of geometric features as one of partial occupancy. On the one hand their geometric characteristics are within the range of typical hydrogen bonds (Tables 1 and 2), but on the other we observed with the room-temperature XRD measurements rather high anisotropic displacement parameters for atom O4 of the water molecule, despite the stability of the crystals. We therefore supposed that this molecule was weakly bonded and labile, and on the basis of the low-temperature measurements we could refine its occupancy factor to 0.66 for (Ia) and 0.78 for (Ib) (see Refinement). Thus, two types of geometry coexist in the crystalline state of (I): a homodimeric structure, consisting of the two urea derivatives linked by a symmetric double hydrogen bond, and an uncommon heterotrimeric structure, consisting of the homodimer and a water molecule.

All these observations are in agreement with the IR and VCD measurements. The ν_C═O band at 1633 cm^-1, which was missing on the spectrum calculated without a water molecule (model A), was correctly modelled in the spectrum including the water molecule (model B) (Figs. 1 and 2). In the same way, the simulation of the spectrum of model B introduced two ν_C—N bands (1415 and 1421 cm^-1) which were also missing from the spectrum of model A. Indeed, superimposing the spectra of models A and B shows good agreement with the measured spectrum, except for two bands, 1446 and 1496 cm^-1 (Fig. 1). These suggest a third structure which we could not assign precisely until now. However, the addition of the spectra corresponding to models A and B was sufficient to simulate the experimental VCD spectra correctly and thus to confirm the absolute configurations of (Ia) and (Ib) unambiguously (Fig. 2). As the samples used for VCD were derived directly from the crystalline material by crushing under a low vacuum, a partial loss or displacement of water hydrogen-bonded to the homodimer might have been induced by the mechanical constraints applied to the crystal and one can imagine that another supramolecular structure might appear and coexist with both the homodimer and the heterotrimer.

Stimulated by the fruitfulness of the union between XRD and VCD, we decided to extend the honeymoon journey a little further. The absolute configurations of both (Ia) and (Ib) were unambiguously determined by the VCD experiments and we were curious to know if the XRD analysis could give some indication about that information. It is often stated that the determination of absolute configuration (or absolute structure) by single-crystal XRD with an Mo Kα source is out of reach for compounds including only light atoms like O or N. This restriction has been generalized to enantiopure molecules for which the Friedif parameter is smaller than 80 (Flack & Bernardinelli, 2008b), which turns out to be the case in our study (Friedif = 5). However, it has been shown that, even if these strict requirements are not fulfilled, in many cases the absolute structure can be assigned correctly, or at least a clear indication can emerge from the data with the use of Bayesian statistics on Bijvoet differences (Hooft et al., 2008). We therefore decided to test our low-temperature measurements in this way, despite the meaningless (as far as their s.u.s) values of the refined Flack parameter. Refinements for both enantiomers were then performed by keeping the Bijvoet pairs separate (in contrast with the published refinements, where they were merged), and the results of the Bayesian statistics calculated by PLATON (Spek, 2009) are summarized in Table 3. Although some criteria were not optimum according to the statistics [e.g. the coverage of Bijvoet pairs was only 91% for (Ia) and 95% for (Ib)] or the normal plot probability slope was less than 1, a strong tendency towards the correct assignment of the absolute configuration emerged when the refinements were performed with the correct enantiomer. This is much more clear in the case of (Ib), where the Hooft parameter y = 0.0 (2) and the probabilities P2(true), P3(true) and P3(false) are 1.0, 0.947 and 0.0, respectively. The results obtained from the VCD measurements thus give much more confidence to these statistics than they would show in the absence of such experimental proofs. With an Mo X-ray source, more precise and complete experiments should be performed in order to enhance the anomalous signal, such as the acquisition of data with higher redundancy, or special measurements like the so-called Friedel strategy (Nonius, 1998) in order to obtain better discrimination between Bijvoet pairs. However, one can expect that further experience resulting from the accumulation of data obtained from various sources and laboratories, with coupled experiments such as XRD and VCD, will lead to increased confidence in the interpretation of Bayesian statistics and therefore to the determination of the absolute configuration of compounds of interest at the boundary of the method.

Related literature

For related literature, see: Allen (2002); Aubert et al. (2007); Cremer & Pople (1975); Czochralska et al. (1977); Duan et al. (2011); Ejsmont et al. (2010); Flack & Bernardinelli (2008a, 2008b); Frisch (2009); Gherase & Roussel (2012); He et al. (2011); Hodge et al. (1998); Hooft et al. (2008); Li et al. (2011); Nishio et al. (1998); Nonius (1998); Schaffner et al. (2006); Sheldrick (2008); Spek (2009); Sussman et al. (2002).

S2. Experimental

The cyclic urea, (I), was obtained by melting at 483 K a 1:1 mixture of isocyanate, A, obtained as described by Gherase & Roussel (2012), and taddamine, B, with an overall yield of 65% after purification [see scheme for the synthesis of (Ib)].

Compound (I), as a well homogenized solid mixture, obtained by evaporating a solution of isocyanate A (258 mg, 0.5 mmol) and taddamine B (232 mg, 0.5 mmol) in dichloromethane, was melted under argon at 483 K and kept at this temperature for 10 min. Purification by column chromatography (silica gel, diethyl ether) gave the cyclic urea, (I) (318 mg, 65%), as a colourless solid. Analysis: m.p. 528–529 K; R_F = 0.26 (1% MeOH–CH₂Cl₂); [α]_D²⁵ = -105.5 (c 1.00, CHCl₃); ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 7.64–7.62 (m, 4H, H_arom), 7.40–7.38 (m, 6H, H_arom), 7.26–7.25 (m, 6H, H_arom), 7.17–7.14 (m, 4H, H_arom), 5.19 (s, 2H, NH), 4.56 (s, 2H, CH), 1.27 (s, 6H, CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, p.p.m.): 160.33 (C═S), 144.67 (C_ipso), 140.99 (C_ipso), 129.18 (CH_arom), 128.71 (CH_arom), 128.16 (CH_arom), 127.91 (CH_arom), 127.84 (CH_arom), 127.65 (CH_arom), 110.01 (C₂), 79.31 (CH), 66.09 (C_Bz), 27.04 (CH₃). HRMS, calculated for C₃₂H₃₀N₂O₃ [M+H]⁺ 491.2329; found 491.2329. For the (3aR,8aR) enantiomer, the same procedure was employed; [α]_D²⁵ = 105.0 (c 1.01, CHCl₃).

Suitable crystals of the (R,R) and (S,S) enantiomers were obtained by slow evaporation from ethanol.

IR and vibrational circular dichroism (VCD) spectra were recorded on a Bruker PMA 50 accessory coupled to a Vertex70 FT–IR spectrometer. A photoelastic modulator (Hinds PEM 90) set at l/4 retardation was used to modulate the handedness of the circular polarized light at 50 kHz. Demodulation was performed by a lock-in amplifier (SR830 DSP). An optical low-pass filter (<1800 cm^-1) before the photoelastic modulator was used to enhance the signal-to-noise ratio. KBr pellets were prepared by finely mixing crystals of (Ia) or (Ib) (1 mg) with dry purified KBr (400 mg) in an agate mortar and compressing the mixture in a mechanical press. For the individual spectrum of each enantiomer, about 1333 scans were averaged at 4 cm^-1 resolution (corresponding to 20 min measurement time). The linear dichroism (LD) contributions to the VCD spectra were shown to be negligible from measurements of the LD spectra of the two pellets. For the IR spectra, the empty holder served as a reference. The spectra are presented without smoothing or further data processing.

All calculations were performed on enantiomer (Ia) with absolute configuration (R,R). The geometry optimizations, vibrational frequencies, IR absorption and VCD intensities were calculated using density functional theory (DFT) with M06L and cam-B3LYP functionals combined with, respectively, 4-31G(d) and 6-31G(d) basis sets. However, only the best results, obtained at the cam-B3LYP/6-31G(d) level, are presented in this work. IR absorption and VCD spectra were constructed from calculated dipole and rotational strengths, assuming a Lorentzian band shape with a half-width at half maximum of 6 cm^-1. A scaling factor of 0.94 was applied to the frequencies. All calculations were performed using GAUSSIAN09 (Revision A02; Frisch et al., 2009).

S3. Refinement

All H atoms were located in difference Fourier syntheses, but only the coordinates of the N-bound H atoms were refined freely, with U_iso(H) = 1.2U_eq(N). All C-bound H atoms were placed in calculated positions, with C—H = 0.93, 0.98 or 0.96 Å for aromatic, methine or methyl H atoms, respectively, and refined as rigid groups. The methyl H atoms were allowed to rotate, with U_iso(H) = 1.5U_eq(C), and for the other C-bonded H atoms U_iso(H) = 1.2U_eq(C). The position of the H atom of the water molecule was derived from a comparison between the peaks observed in the difference Fourier synthesis, the analysis of intermolecular interactions within the crystal structure and the positions of the H atoms calculated in the models for the VCD analysis. The O—H distance was fixed at 0.90 Å for both enantiomers and refined as a rigid group, with U_iso(H) = 1.5U_eq(O4).

For both (Ia) and (Ib), the Bijvoet pairs were merged before the final refinements. Some low-resolution reflections [six for (Ia) and seven for (Ib)] were found to be partially cancelled by the beam stop and were omitted from the final cycles of refinement. The occupancy factor for the water molecule in both (Ia) and (Ib) was refined by introducing a free variable via the FVAR instruction (SHELXL97; Sheldrick, 2008) and assigning site-occupancy factors of 21 and 22 to O and H, respectively.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 (Farrugia, 1997) for (Ia); ORTEP-3(Farrugia, 1997) for (Ib). For both compounds, software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The solid-state IR absorption spectra for (Ia). Lower trace: measured data (red in the electronic version of the journal). Upper traces: data calculated without water (model A; black) or with water (model B; blue) at the cam-B3LYP/6-31G(d) theoretical level. A scaling factor correction of 0.94 was applied to the calculated frequencies.
	Fig. 2. The solid-state VCD spectra. Lower traces: measured for (Ia) (green in the electronic version of the journal) and (Ib) (red). Upper traces: calculated for (Ia) without water (model A; black) or with water (model B; blue) at the cam-B3LYP/6-31G(d) theoretical level. A scaling factor correction of 0.94 was applied to the calculated frequencies.
	Fig. 3. A representation of the dimer of (Ia), with the hydrogen bonding to the water molecule shown with dashed bonds.
	Fig. 4. The molecular structure of (Ia), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. The molecular structure of (Ib), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 6. A superposition of the X-ray (grey) and simulated (black) structures of (Ia). The r.m.s. deviation calculated by fitting all the non H-atoms of the five- and seven-membered rings is 0.342 Å. H atoms have been omitted for clarity. Dashed lines indicate hydrogen bonds.

(Ia) (3aR,8aR)-2,2-dimethyl-4,4,8,8-tetraphenyl-4,5,6,7,8,8a- hexahydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 0.33-hydrate

Crystal data

C32H30N2O3·0.33H20	F(000) = 1053
Mr = 496.44	Dx = 1.276 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 33303 reflections
a = 14.2076 (2) Å	θ = 2.9–36.3°
b = 15.9721 (3) Å	µ = 0.08 mm^−1
c = 11.3920 (2) Å	T = 173 K
V = 2585.13 (8) Å^3	Prism, colourless
Z = 4	0.4 × 0.32 × 0.12 mm

Data collection

Nonius KappaCCD area-detector diffractometer	Rint = 0.06
Graphite monochromator	θmax = 36.3°, θmin = 2.9°
ω and ϕ scans	h = −22→23
33303 measured reflections	k = −26→26
6619 independent reflections	l = −18→18
4774 reflections with I > 2σ(I)

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)] = 0.053	Hydrogen site location: difference Fourier map
wR(F^2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0498P)^2 + 1.1048P] where P = (Fo^2 + 2Fc^2)/3
6619 reflections	(Δ/σ)max < 0.001
344 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
C1	0.52198 (12)	0.20986 (11)	0.78333 (17)	0.0232 (3)
H1	0.5204	0.1862	0.7021	0.028*
C2	0.43402 (13)	0.26161 (12)	0.80454 (17)	0.0229 (3)
H2	0.4458	0.3011	0.8711	0.027*
C3	0.40041 (12)	0.31176 (11)	0.69702 (17)	0.0219 (3)
C4	0.56374 (13)	0.38243 (12)	0.66568 (17)	0.0243 (3)
C5	0.61429 (13)	0.25894 (11)	0.80133 (18)	0.0239 (3)
C6	0.41502 (14)	0.12892 (12)	0.8857 (2)	0.0292 (4)
C7	0.38197 (16)	0.05255 (14)	0.8197 (3)	0.0430 (6)
H7A	0.3992	0.0579	0.7368	0.064*
H7B	0.3134	0.0476	0.8268	0.064*
H7C	0.4118	0.0025	0.8528	0.064*
C8	0.40104 (18)	0.12239 (17)	1.0170 (2)	0.0415 (6)
H8A	0.4375	0.0751	1.0474	0.062*
H8B	0.3341	0.1137	1.0341	0.062*
H8C	0.4224	0.1742	1.0546	0.062*
C9	0.39165 (14)	0.25600 (12)	0.58773 (18)	0.0257 (3)
C10	0.44616 (16)	0.26817 (15)	0.4884 (2)	0.0331 (4)
H10	0.4907	0.3125	0.4867	0.040*
C11	0.4364 (2)	0.21615 (18)	0.3907 (2)	0.0447 (6)
H11	0.4743	0.2253	0.3232	0.054*
C12	0.3720 (2)	0.15158 (17)	0.3917 (2)	0.0477 (6)
H12	0.3659	0.1159	0.3255	0.057*
C13	0.3166 (2)	0.13912 (15)	0.4895 (3)	0.0448 (6)
H13	0.2719	0.0949	0.4904	0.054*
C14	0.32565 (16)	0.19094 (14)	0.5869 (2)	0.0343 (4)
H14	0.2867	0.1821	0.6535	0.041*
C15	0.30621 (13)	0.35583 (12)	0.72422 (18)	0.0239 (3)
C16	0.23801 (16)	0.36555 (16)	0.6385 (2)	0.0363 (5)
H16	0.2481	0.3428	0.5625	0.044*
C17	0.15461 (17)	0.40849 (18)	0.6626 (3)	0.0455 (6)
H17	0.1084	0.4148	0.6030	0.055*
C18	0.13909 (16)	0.44155 (16)	0.7719 (3)	0.0406 (6)
H18	0.0821	0.4704	0.7883	0.049*
C19	0.20653 (18)	0.43270 (15)	0.8579 (2)	0.0393 (5)
H19	0.1960	0.4555	0.9338	0.047*
C20	0.28975 (16)	0.39060 (14)	0.8342 (2)	0.0338 (4)
H20	0.3361	0.3855	0.8939	0.041*
C21	0.69943 (13)	0.20016 (12)	0.78717 (18)	0.0259 (4)
C22	0.70447 (16)	0.14609 (14)	0.6914 (2)	0.0333 (4)
H22	0.6536	0.1436	0.6375	0.040*
C23	0.78307 (17)	0.09569 (15)	0.6738 (2)	0.0379 (5)
H23	0.7849	0.0583	0.6090	0.045*
C24	0.85881 (16)	0.09961 (16)	0.7504 (2)	0.0391 (5)
H24	0.9129	0.0659	0.7376	0.047*
C25	0.85464 (16)	0.15278 (17)	0.8448 (2)	0.0406 (5)
H25	0.9062	0.1556	0.8978	0.049*
C26	0.77552 (14)	0.20275 (15)	0.8639 (2)	0.0336 (4)
H26	0.7736	0.2389	0.9300	0.040*
C27	0.61549 (13)	0.30441 (12)	0.92015 (18)	0.0256 (3)
C28	0.61881 (16)	0.39133 (14)	0.9288 (2)	0.0330 (4)
H28	0.6210	0.4244	0.8596	0.040*
C29	0.61895 (19)	0.43003 (16)	1.0384 (2)	0.0420 (5)
H29	0.6201	0.4894	1.0430	0.050*
C30	0.61738 (18)	0.38347 (18)	1.1404 (2)	0.0420 (5)
H30	0.6172	0.4103	1.2148	0.050*
C31	0.61602 (17)	0.29714 (17)	1.1326 (2)	0.0370 (5)
H31	0.6164	0.2643	1.2022	0.044*
C32	0.61407 (15)	0.25808 (14)	1.02401 (19)	0.0307 (4)
H32	0.6117	0.1987	1.0202	0.037*
N1	0.46834 (11)	0.38119 (10)	0.68101 (15)	0.0243 (3)
H1N	0.4395 (8)	0.4301 (14)	0.6551 (7)	0.029*
N2	0.62077 (12)	0.31744 (11)	0.70072 (16)	0.0264 (3)
H2N	0.6807 (18)	0.3292 (4)	0.6857 (5)	0.032*
O1	0.60102 (10)	0.44380 (9)	0.61762 (15)	0.0318 (3)
O2	0.36656 (9)	0.20079 (9)	0.84016 (14)	0.0284 (3)
O3	0.51347 (9)	0.14399 (9)	0.86627 (14)	0.0279 (3)
O4	0.5000	0.5000	0.4183 (3)	0.0502 (14)	0.655 (9)
H1W	0.4614	0.5298	0.4655	0.075*	0.655 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0192 (7)	0.0208 (7)	0.0296 (8)	0.0006 (6)	0.0000 (6)	0.0017 (7)
C2	0.0198 (7)	0.0209 (7)	0.0280 (8)	0.0007 (6)	−0.0005 (6)	0.0032 (7)
C3	0.0203 (7)	0.0193 (7)	0.0262 (8)	0.0013 (6)	0.0001 (6)	0.0017 (6)
C4	0.0228 (8)	0.0219 (7)	0.0282 (8)	−0.0003 (6)	0.0018 (7)	−0.0010 (7)
C5	0.0204 (8)	0.0206 (7)	0.0307 (9)	0.0001 (6)	0.0003 (7)	0.0032 (7)
C6	0.0225 (8)	0.0230 (8)	0.0421 (11)	−0.0002 (6)	0.0025 (8)	0.0073 (8)
C7	0.0288 (10)	0.0241 (9)	0.0761 (19)	−0.0004 (8)	−0.0060 (12)	−0.0028 (11)
C8	0.0342 (11)	0.0458 (13)	0.0446 (13)	0.0047 (10)	0.0073 (10)	0.0161 (11)
C9	0.0250 (8)	0.0239 (8)	0.0280 (8)	0.0030 (7)	−0.0029 (7)	−0.0006 (7)
C10	0.0317 (10)	0.0348 (11)	0.0327 (10)	0.0037 (9)	0.0006 (8)	−0.0027 (9)
C11	0.0499 (14)	0.0517 (14)	0.0326 (11)	0.0120 (12)	0.0003 (10)	−0.0079 (11)
C12	0.0612 (17)	0.0403 (12)	0.0415 (13)	0.0122 (12)	−0.0126 (12)	−0.0145 (11)
C13	0.0524 (15)	0.0308 (11)	0.0511 (15)	−0.0051 (10)	−0.0184 (12)	−0.0058 (11)
C14	0.0338 (10)	0.0316 (10)	0.0374 (11)	−0.0037 (8)	−0.0071 (9)	−0.0002 (9)
C15	0.0191 (7)	0.0217 (7)	0.0309 (9)	0.0015 (6)	0.0017 (6)	0.0032 (7)
C16	0.0301 (10)	0.0452 (12)	0.0337 (10)	0.0121 (9)	−0.0025 (8)	0.0004 (10)
C17	0.0289 (11)	0.0545 (15)	0.0531 (15)	0.0152 (10)	−0.0076 (10)	0.0001 (13)
C18	0.0258 (10)	0.0376 (11)	0.0583 (15)	0.0108 (9)	0.0097 (10)	0.0025 (12)
C19	0.0405 (12)	0.0357 (11)	0.0418 (12)	0.0119 (9)	0.0082 (10)	−0.0025 (10)
C20	0.0336 (10)	0.0335 (10)	0.0344 (10)	0.0089 (8)	−0.0020 (8)	−0.0039 (9)
C21	0.0200 (8)	0.0251 (8)	0.0325 (9)	0.0021 (6)	0.0026 (7)	0.0057 (7)
C22	0.0283 (9)	0.0347 (10)	0.0368 (10)	0.0055 (8)	0.0000 (8)	0.0005 (9)
C23	0.0357 (11)	0.0338 (11)	0.0440 (13)	0.0099 (9)	0.0077 (10)	0.0011 (10)
C24	0.0288 (10)	0.0396 (11)	0.0489 (13)	0.0129 (9)	0.0104 (9)	0.0140 (11)
C25	0.0237 (9)	0.0508 (14)	0.0472 (13)	0.0099 (9)	0.0005 (9)	0.0098 (12)
C26	0.0228 (9)	0.0383 (11)	0.0398 (11)	0.0045 (8)	0.0000 (8)	0.0022 (10)
C27	0.0184 (7)	0.0272 (8)	0.0313 (9)	0.0012 (7)	−0.0008 (7)	−0.0001 (7)
C28	0.0338 (10)	0.0279 (9)	0.0374 (11)	−0.0009 (8)	−0.0052 (9)	−0.0013 (8)
C29	0.0446 (13)	0.0343 (11)	0.0471 (13)	0.0001 (10)	−0.0075 (11)	−0.0111 (10)
C30	0.0365 (11)	0.0521 (14)	0.0375 (12)	−0.0030 (11)	−0.0019 (10)	−0.0122 (11)
C31	0.0307 (10)	0.0483 (13)	0.0321 (10)	−0.0030 (10)	0.0001 (9)	0.0031 (10)
C32	0.0261 (9)	0.0328 (10)	0.0333 (10)	−0.0001 (8)	−0.0012 (8)	0.0020 (8)
N1	0.0202 (7)	0.0203 (6)	0.0322 (8)	0.0014 (5)	0.0002 (6)	0.0024 (6)
N2	0.0185 (7)	0.0261 (7)	0.0345 (8)	−0.0003 (6)	0.0014 (6)	0.0059 (7)
O1	0.0261 (7)	0.0241 (6)	0.0452 (9)	−0.0010 (5)	0.0043 (6)	0.0084 (6)
O2	0.0195 (6)	0.0231 (6)	0.0427 (8)	0.0009 (5)	0.0028 (6)	0.0083 (6)
O3	0.0205 (6)	0.0230 (6)	0.0401 (8)	0.0008 (5)	−0.0001 (6)	0.0086 (6)
O4	0.067 (3)	0.054 (3)	0.0293 (19)	−0.016 (2)	0.000	0.000

Geometric parameters (Å, º)

C1—O3	1.419 (2)	C15—C16	1.385 (3)
C1—C2	1.518 (3)	C15—C20	1.390 (3)
C1—C5	1.542 (3)	C16—C17	1.396 (3)
C1—H1	1.0000	C16—H16	0.9500
C2—O2	1.424 (2)	C17—C18	1.370 (4)
C2—C3	1.539 (3)	C17—H17	0.9500
C2—H2	1.0000	C18—C19	1.377 (4)
C3—N1	1.481 (2)	C18—H18	0.9500
C3—C9	1.536 (3)	C19—C20	1.387 (3)
C3—C15	1.543 (3)	C19—H19	0.9500
C4—O1	1.241 (2)	C20—H20	0.9500
C4—N1	1.367 (2)	C21—C26	1.391 (3)
C4—N2	1.376 (3)	C21—C22	1.393 (3)
C5—N2	1.482 (3)	C22—C23	1.391 (3)
C5—C27	1.536 (3)	C22—H22	0.9500
C5—C21	1.540 (3)	C23—C24	1.386 (4)
C6—O2	1.436 (2)	C23—H23	0.9500
C6—O3	1.437 (2)	C24—C25	1.372 (4)
C6—C7	1.508 (3)	C24—H24	0.9500
C6—C8	1.512 (3)	C25—C26	1.395 (3)
C7—H7A	0.9800	C25—H25	0.9500
C7—H7B	0.9800	C26—H26	0.9500
C7—H7C	0.9800	C27—C28	1.393 (3)
C8—H8A	0.9800	C27—C32	1.396 (3)
C8—H8B	0.9800	C28—C29	1.393 (3)
C8—H8C	0.9800	C28—H28	0.9500
C9—C10	1.385 (3)	C29—C30	1.380 (4)
C9—C14	1.400 (3)	C29—H29	0.9500
C10—C11	1.395 (3)	C30—C31	1.382 (4)
C10—H10	0.9500	C30—H30	0.9500
C11—C12	1.378 (4)	C31—C32	1.386 (3)
C11—H11	0.9500	C31—H31	0.9500
C12—C13	1.379 (4)	C32—H32	0.9500
C12—H12	0.9500	N1—H1N	0.93 (2)
C13—C14	1.390 (3)	N2—H2N	0.89 (2)
C13—H13	0.9500	O4—H1W	0.9032
C14—H14	0.9500
O3—C1—C2	103.16 (14)	C16—C15—C20	118.23 (18)
O3—C1—C5	111.15 (15)	C16—C15—C3	121.09 (18)
C2—C1—C5	113.73 (15)	C20—C15—C3	120.60 (17)
O3—C1—H1	109.5	C15—C16—C17	120.7 (2)
C2—C1—H1	109.5	C15—C16—H16	119.7
C5—C1—H1	109.5	C17—C16—H16	119.7
O2—C2—C1	103.19 (14)	C18—C17—C16	120.3 (2)
O2—C2—C3	111.89 (15)	C18—C17—H17	119.8
C1—C2—C3	114.34 (16)	C16—C17—H17	119.8
O2—C2—H2	109.1	C17—C18—C19	119.6 (2)
C1—C2—H2	109.1	C17—C18—H18	120.2
C3—C2—H2	109.1	C19—C18—H18	120.2
N1—C3—C9	112.77 (16)	C18—C19—C20	120.3 (2)
N1—C3—C2	106.58 (15)	C18—C19—H19	119.9
C9—C3—C2	111.62 (14)	C20—C19—H19	119.9
N1—C3—C15	104.38 (14)	C19—C20—C15	120.8 (2)
C9—C3—C15	110.91 (15)	C19—C20—H20	119.6
C2—C3—C15	110.28 (15)	C15—C20—H20	119.6
O1—C4—N1	119.40 (18)	C26—C21—C22	118.06 (19)
O1—C4—N2	118.19 (17)	C26—C21—C5	121.80 (19)
N1—C4—N2	122.41 (18)	C22—C21—C5	120.03 (18)
N2—C5—C27	112.50 (15)	C23—C22—C21	120.9 (2)
N2—C5—C21	104.75 (15)	C23—C22—H22	119.6
C27—C5—C21	111.83 (16)	C21—C22—H22	119.6
N2—C5—C1	105.70 (15)	C24—C23—C22	120.4 (2)
C27—C5—C1	111.54 (16)	C24—C23—H23	119.8
C21—C5—C1	110.15 (15)	C22—C23—H23	119.8
O2—C6—O3	106.08 (15)	C25—C24—C23	119.2 (2)
O2—C6—C7	108.48 (18)	C25—C24—H24	120.4
O3—C6—C7	111.21 (18)	C23—C24—H24	120.4
O2—C6—C8	110.48 (19)	C24—C25—C26	120.7 (2)
O3—C6—C8	106.99 (18)	C24—C25—H25	119.6
C7—C6—C8	113.4 (2)	C26—C25—H25	119.6
C6—C7—H7A	109.5	C21—C26—C25	120.8 (2)
C6—C7—H7B	109.5	C21—C26—H26	119.6
H7A—C7—H7B	109.5	C25—C26—H26	119.6
C6—C7—H7C	109.5	C28—C27—C32	118.0 (2)
H7A—C7—H7C	109.5	C28—C27—C5	122.29 (19)
H7B—C7—H7C	109.5	C32—C27—C5	119.74 (17)
C6—C8—H8A	109.5	C27—C28—C29	120.4 (2)
C6—C8—H8B	109.5	C27—C28—H28	119.8
H8A—C8—H8B	109.5	C29—C28—H28	119.8
C6—C8—H8C	109.5	C30—C29—C28	121.0 (2)
H8A—C8—H8C	109.5	C30—C29—H29	119.5
H8B—C8—H8C	109.5	C28—C29—H29	119.5
C10—C9—C14	118.2 (2)	C29—C30—C31	119.0 (2)
C10—C9—C3	122.40 (18)	C29—C30—H30	120.5
C14—C9—C3	119.36 (19)	C31—C30—H30	120.5
C9—C10—C11	120.8 (2)	C30—C31—C32	120.4 (2)
C9—C10—H10	119.6	C30—C31—H31	119.8
C11—C10—H10	119.6	C32—C31—H31	119.8
C12—C11—C10	120.3 (3)	C31—C32—C27	121.2 (2)
C12—C11—H11	119.8	C31—C32—H32	119.4
C10—C11—H11	119.8	C27—C32—H32	119.4
C11—C12—C13	119.6 (2)	C4—N1—C3	132.28 (16)
C11—C12—H12	120.2	C4—N1—H1N	112.6 (8)
C13—C12—H12	120.2	C3—N1—H1N	112.4 (9)
C12—C13—C14	120.4 (2)	C4—N2—C5	131.58 (17)
C12—C13—H13	119.8	C4—N2—H2N	110.4 (6)
C14—C13—H13	119.8	C5—N2—H2N	110.0 (6)
C13—C14—C9	120.7 (2)	C2—O2—C6	109.01 (14)
C13—C14—H14	119.7	C1—O3—C6	108.06 (14)
C9—C14—H14	119.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.93 (2)	2.14 (2)	3.051 (2)	166.7 (12)
O4—H1W···O1^i	0.9	1.99	2.832 (3)	154

Symmetry code: (i) −x+1, −y+1, z.

(Ib) (3aS,8aS)-2,2-dimethyl-4,4,8,8-tetraphenyl-4,5,6,7,8,8a- hexahydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 0.39-hydrate

Crystal data

C32H30N2O3·0.39H2O	F(000) = 1056
Mr = 497.79	Dx = 1.276 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 44308 reflections
a = 14.2212 (2) Å	θ = 2.9–36.3°
b = 15.9917 (2) Å	µ = 0.08 mm^−1
c = 11.3920 (2) Å	T = 173 K
V = 2590.78 (7) Å^3	Prism, colourless
Z = 4	0.5 × 0.4 × 0.34 mm

Data collection

Nonius KappaCCD area-detector diffractometer	Rint = 0.041
Graphite monochromator	θmax = 36.3°, θmin = 2.9°
ω and ϕ scans	h = −23→23
44308 measured reflections	k = −25→25
6613 independent reflections	l = −18→18
5684 reflections with I > 2σ(I)

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)] = 0.049	Hydrogen site location: difference Fourier map
wR(F^2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0808P)^2 + 0.2579P] where P = (Fo^2 + 2Fc^2)/3
6613 reflections	(Δ/σ)max < 0.001
344 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.52 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
C1	0.47837 (8)	0.79014 (8)	0.21586 (12)	0.0190 (2)
H1	0.4798	0.8137	0.2972	0.023*
C2	0.56661 (9)	0.73836 (8)	0.19472 (12)	0.0185 (2)
H2	0.5550	0.6989	0.1282	0.022*
C3	0.59988 (9)	0.68826 (8)	0.30274 (12)	0.0180 (2)
C4	0.43706 (9)	0.61806 (8)	0.33350 (12)	0.0204 (2)
C5	0.38626 (9)	0.74061 (8)	0.19765 (12)	0.0196 (2)
C6	0.58517 (10)	0.87122 (9)	0.11383 (15)	0.0244 (3)
C7	0.61807 (13)	0.94738 (10)	0.1800 (2)	0.0395 (4)
H7A	0.6004	0.9421	0.2629	0.059*
H7B	0.5886	0.9974	0.1467	0.059*
H7C	0.6866	0.9521	0.1736	0.059*
C8	0.59938 (13)	0.87787 (13)	−0.01775 (17)	0.0378 (4)
H8A	0.5617	0.9243	−0.0485	0.057*
H8B	0.5797	0.8256	−0.0553	0.057*
H8C	0.6660	0.8881	−0.0345	0.057*
C9	0.60858 (10)	0.74407 (8)	0.41182 (12)	0.0217 (2)
C10	0.55411 (12)	0.73184 (10)	0.51153 (14)	0.0291 (3)
H10	0.5095	0.6876	0.5134	0.035*
C11	0.56438 (16)	0.78395 (14)	0.60902 (16)	0.0404 (4)
H11	0.5269	0.7747	0.6768	0.049*
C12	0.62841 (17)	0.84877 (13)	0.60784 (18)	0.0437 (5)
H12	0.6342	0.8847	0.6739	0.052*
C13	0.68406 (16)	0.86116 (11)	0.51014 (18)	0.0408 (4)
H13	0.7289	0.9052	0.5094	0.049*
C14	0.67485 (12)	0.80926 (10)	0.41245 (15)	0.0304 (3)
H14	0.7137	0.8181	0.3457	0.036*
C15	0.69389 (9)	0.64453 (8)	0.27545 (12)	0.0196 (2)
C16	0.76182 (12)	0.63423 (12)	0.36173 (15)	0.0330 (3)
H16	0.7513	0.6564	0.4380	0.040*
C17	0.84529 (13)	0.59173 (14)	0.33790 (19)	0.0418 (4)
H17	0.8913	0.5856	0.3977	0.050*
C18	0.86136 (12)	0.55860 (11)	0.22809 (18)	0.0367 (4)
H18	0.9183	0.5298	0.2119	0.044*
C19	0.79419 (13)	0.56764 (11)	0.14202 (17)	0.0359 (4)
H19	0.8048	0.5449	0.0661	0.043*
C20	0.71077 (12)	0.60989 (10)	0.16568 (15)	0.0300 (3)
H20	0.6647	0.6151	0.1058	0.036*
C21	0.30097 (9)	0.79945 (9)	0.21164 (13)	0.0216 (2)
C22	0.29571 (11)	0.85345 (10)	0.30780 (15)	0.0287 (3)
H22	0.3463	0.8560	0.3621	0.034*
C23	0.21680 (12)	0.90353 (11)	0.32467 (17)	0.0334 (3)
H23	0.2147	0.9409	0.3894	0.040*
C24	0.14147 (12)	0.89944 (11)	0.24840 (17)	0.0339 (3)
H24	0.0873	0.9330	0.2612	0.041*
C25	0.14579 (11)	0.84608 (13)	0.15327 (17)	0.0354 (4)
H25	0.0944	0.8431	0.1001	0.042*
C26	0.22513 (10)	0.79657 (11)	0.13474 (15)	0.0291 (3)
H26	0.2274	0.7604	0.0687	0.035*
C27	0.38532 (10)	0.69533 (9)	0.07898 (13)	0.0219 (2)
C28	0.38193 (12)	0.60839 (10)	0.07052 (15)	0.0295 (3)
H28	0.3799	0.5755	0.1399	0.035*
C29	0.38148 (15)	0.56929 (12)	−0.03867 (17)	0.0378 (4)
H29	0.3798	0.5100	−0.0429	0.045*
C30	0.38338 (14)	0.61574 (13)	−0.14107 (17)	0.0380 (4)
H30	0.3834	0.5887	−0.2153	0.046*
C31	0.38520 (13)	0.70234 (13)	−0.13382 (15)	0.0334 (3)
H31	0.3853	0.7349	−0.2035	0.040*
C32	0.38688 (11)	0.74161 (10)	−0.02487 (14)	0.0275 (3)
H32	0.3891	0.8009	−0.0211	0.033*
N1	0.53212 (8)	0.61902 (7)	0.31873 (11)	0.0199 (2)
H1N	0.5607 (7)	0.5744 (11)	0.3501 (8)	0.024*
N2	0.37967 (8)	0.68261 (8)	0.29857 (11)	0.0220 (2)
H2N	0.3172 (15)	0.6730 (2)	0.3182 (5)	0.026*
O1	0.39951 (8)	0.55652 (7)	0.38200 (11)	0.0277 (2)
O2	0.63384 (7)	0.79932 (6)	0.15913 (11)	0.0246 (2)
O3	0.48698 (7)	0.85588 (6)	0.13310 (10)	0.0241 (2)
O4	0.5000	0.5000	0.5819 (2)	0.0481 (9)	0.784 (8)
H1W	0.5386	0.4702	0.5352	0.072*	0.784 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0145 (4)	0.0177 (5)	0.0250 (5)	0.0009 (4)	0.0005 (4)	0.0025 (4)
C2	0.0144 (4)	0.0183 (5)	0.0226 (5)	0.0009 (4)	0.0008 (4)	0.0035 (4)
C3	0.0153 (4)	0.0167 (5)	0.0219 (5)	0.0009 (4)	0.0002 (4)	0.0014 (4)
C4	0.0184 (5)	0.0179 (5)	0.0248 (5)	0.0004 (4)	0.0013 (4)	0.0013 (4)
C5	0.0148 (4)	0.0186 (5)	0.0254 (5)	0.0009 (4)	−0.0002 (4)	0.0023 (4)
C6	0.0180 (5)	0.0180 (5)	0.0372 (7)	0.0008 (4)	0.0021 (5)	0.0063 (5)
C7	0.0267 (7)	0.0216 (6)	0.0703 (13)	−0.0009 (5)	−0.0057 (8)	−0.0037 (7)
C8	0.0311 (7)	0.0429 (9)	0.0393 (8)	0.0048 (7)	0.0077 (7)	0.0175 (7)
C9	0.0208 (5)	0.0199 (5)	0.0245 (5)	0.0025 (4)	−0.0029 (5)	−0.0017 (4)
C10	0.0275 (7)	0.0312 (7)	0.0285 (6)	0.0030 (6)	0.0017 (6)	−0.0031 (6)
C11	0.0447 (10)	0.0481 (10)	0.0286 (7)	0.0106 (8)	0.0006 (7)	−0.0100 (7)
C12	0.0560 (12)	0.0374 (8)	0.0376 (9)	0.0106 (8)	−0.0137 (9)	−0.0138 (7)
C13	0.0490 (11)	0.0289 (7)	0.0444 (9)	−0.0045 (7)	−0.0187 (9)	−0.0051 (7)
C14	0.0300 (7)	0.0284 (6)	0.0328 (7)	−0.0057 (6)	−0.0074 (6)	0.0000 (6)
C15	0.0155 (5)	0.0179 (5)	0.0255 (5)	0.0016 (4)	0.0010 (4)	0.0024 (4)
C16	0.0257 (6)	0.0433 (9)	0.0299 (7)	0.0131 (6)	−0.0039 (6)	−0.0004 (7)
C17	0.0260 (7)	0.0529 (11)	0.0464 (10)	0.0185 (7)	−0.0067 (7)	−0.0002 (9)
C18	0.0232 (6)	0.0339 (8)	0.0530 (10)	0.0108 (6)	0.0070 (7)	0.0018 (8)
C19	0.0350 (8)	0.0347 (8)	0.0378 (8)	0.0136 (7)	0.0084 (7)	−0.0028 (7)
C20	0.0293 (7)	0.0306 (7)	0.0300 (7)	0.0106 (6)	−0.0013 (6)	−0.0040 (6)
C21	0.0164 (5)	0.0211 (5)	0.0274 (6)	0.0026 (4)	0.0020 (4)	0.0040 (5)
C22	0.0243 (6)	0.0314 (7)	0.0304 (6)	0.0062 (5)	0.0008 (5)	−0.0015 (6)
C23	0.0301 (7)	0.0316 (7)	0.0386 (8)	0.0099 (6)	0.0074 (6)	−0.0005 (6)
C24	0.0257 (6)	0.0346 (7)	0.0412 (8)	0.0124 (6)	0.0088 (6)	0.0122 (7)
C25	0.0200 (6)	0.0473 (9)	0.0389 (8)	0.0100 (6)	0.0010 (6)	0.0079 (8)
C26	0.0188 (5)	0.0347 (7)	0.0338 (7)	0.0043 (5)	−0.0014 (5)	0.0008 (6)
C27	0.0152 (5)	0.0227 (5)	0.0279 (6)	0.0008 (4)	−0.0012 (5)	−0.0011 (5)
C28	0.0311 (7)	0.0235 (6)	0.0338 (7)	−0.0005 (5)	−0.0065 (6)	−0.0028 (5)
C29	0.0416 (9)	0.0302 (7)	0.0417 (9)	0.0000 (7)	−0.0074 (8)	−0.0115 (7)
C30	0.0333 (8)	0.0477 (10)	0.0329 (7)	−0.0032 (8)	−0.0012 (7)	−0.0132 (7)
C31	0.0271 (7)	0.0445 (9)	0.0288 (7)	−0.0032 (7)	0.0000 (6)	0.0000 (7)
C32	0.0241 (6)	0.0289 (6)	0.0296 (7)	−0.0002 (5)	−0.0009 (6)	0.0020 (5)
N1	0.0161 (4)	0.0156 (4)	0.0279 (5)	0.0008 (3)	0.0011 (4)	0.0037 (4)
N2	0.0154 (4)	0.0223 (5)	0.0283 (5)	0.0006 (4)	0.0025 (4)	0.0058 (4)
O1	0.0221 (4)	0.0210 (4)	0.0401 (6)	−0.0014 (4)	0.0049 (4)	0.0088 (4)
O2	0.0157 (4)	0.0203 (4)	0.0378 (5)	0.0007 (3)	0.0032 (4)	0.0097 (4)
O3	0.0168 (4)	0.0196 (4)	0.0360 (5)	0.0010 (3)	0.0001 (4)	0.0089 (4)
O4	0.0628 (19)	0.0552 (17)	0.0264 (11)	−0.0176 (14)	0.000	0.000

Geometric parameters (Å, º)

C1—O3	1.4174 (16)	C15—C16	1.388 (2)
C1—C2	1.5227 (18)	C15—C20	1.389 (2)
C1—C5	1.5447 (18)	C16—C17	1.395 (2)
C1—H1	1.0000	C16—H16	0.9500
C2—O2	1.4243 (16)	C17—C18	1.378 (3)
C2—C3	1.5428 (18)	C17—H17	0.9500
C2—H2	1.0000	C18—C19	1.377 (3)
C3—N1	1.4792 (16)	C18—H18	0.9500
C3—C9	1.5349 (19)	C19—C20	1.392 (2)
C3—C15	1.5405 (18)	C19—H19	0.9500
C4—O1	1.2486 (16)	C20—H20	0.9500
C4—N1	1.3624 (17)	C21—C26	1.390 (2)
C4—N2	1.3748 (17)	C21—C22	1.397 (2)
C5—N2	1.4802 (18)	C22—C23	1.392 (2)
C5—C27	1.534 (2)	C22—H22	0.9500
C5—C21	1.5433 (18)	C23—C24	1.381 (3)
C6—O3	1.4347 (17)	C23—H23	0.9500
C6—O2	1.4378 (17)	C24—C25	1.381 (3)
C6—C7	1.507 (2)	C24—H24	0.9500
C6—C8	1.516 (2)	C25—C26	1.395 (2)
C7—H7A	0.9800	C25—H25	0.9500
C7—H7B	0.9800	C26—H26	0.9500
C7—H7C	0.9800	C27—C28	1.395 (2)
C8—H8A	0.9800	C27—C32	1.396 (2)
C8—H8B	0.9800	C28—C29	1.392 (2)
C8—H8C	0.9800	C28—H28	0.9500
C9—C10	1.389 (2)	C29—C30	1.383 (3)
C9—C14	1.405 (2)	C29—H29	0.9500
C10—C11	1.396 (2)	C30—C31	1.387 (3)
C10—H10	0.9500	C30—H30	0.9500
C11—C12	1.380 (3)	C31—C32	1.391 (2)
C11—H11	0.9500	C31—H31	0.9500
C12—C13	1.380 (3)	C32—H32	0.9500
C12—H12	0.9500	N1—H1N	0.897 (15)
C13—C14	1.394 (2)	N2—H2N	0.93 (2)
C13—H13	0.9500	O4—H1W	0.9008
C14—H14	0.9500
O3—C1—C2	103.12 (10)	C16—C15—C20	118.04 (13)
O3—C1—C5	111.36 (10)	C16—C15—C3	121.00 (13)
C2—C1—C5	113.50 (10)	C20—C15—C3	120.85 (12)
O3—C1—H1	109.6	C15—C16—C17	120.82 (16)
C2—C1—H1	109.6	C15—C16—H16	119.6
C5—C1—H1	109.6	C17—C16—H16	119.6
O2—C2—C1	103.06 (10)	C18—C17—C16	120.37 (17)
O2—C2—C3	112.12 (10)	C18—C17—H17	119.8
C1—C2—C3	114.14 (10)	C16—C17—H17	119.8
O2—C2—H2	109.1	C19—C18—C17	119.42 (15)
C1—C2—H2	109.1	C19—C18—H18	120.3
C3—C2—H2	109.1	C17—C18—H18	120.3
N1—C3—C9	112.83 (11)	C18—C19—C20	120.31 (17)
N1—C3—C15	104.50 (10)	C18—C19—H19	119.8
C9—C3—C15	110.94 (10)	C20—C19—H19	119.8
N1—C3—C2	106.69 (10)	C15—C20—C19	121.03 (15)
C9—C3—C2	111.63 (10)	C15—C20—H20	119.5
C15—C3—C2	109.94 (10)	C19—C20—H20	119.5
O1—C4—N1	119.21 (12)	C26—C21—C22	118.24 (13)
O1—C4—N2	117.77 (12)	C26—C21—C5	121.63 (13)
N1—C4—N2	123.02 (12)	C22—C21—C5	119.99 (12)
N2—C5—C27	112.84 (11)	C23—C22—C21	120.47 (15)
N2—C5—C21	104.61 (10)	C23—C22—H22	119.8
C27—C5—C21	111.84 (11)	C21—C22—H22	119.8
N2—C5—C1	105.71 (10)	C24—C23—C22	120.75 (17)
C27—C5—C1	111.58 (11)	C24—C23—H23	119.6
C21—C5—C1	109.88 (10)	C22—C23—H23	119.6
O3—C6—O2	106.07 (10)	C25—C24—C23	119.25 (15)
O3—C6—C7	111.33 (13)	C25—C24—H24	120.4
O2—C6—C7	108.49 (13)	C23—C24—H24	120.4
O3—C6—C8	107.04 (13)	C24—C25—C26	120.38 (16)
O2—C6—C8	110.29 (13)	C24—C25—H25	119.8
C7—C6—C8	113.37 (15)	C26—C25—H25	119.8
C6—C7—H7A	109.5	C21—C26—C25	120.89 (16)
C6—C7—H7B	109.5	C21—C26—H26	119.6
H7A—C7—H7B	109.5	C25—C26—H26	119.6
C6—C7—H7C	109.5	C28—C27—C32	118.08 (14)
H7A—C7—H7C	109.5	C28—C27—C5	122.14 (14)
H7B—C7—H7C	109.5	C32—C27—C5	119.78 (12)
C6—C8—H8A	109.5	C29—C28—C27	120.64 (16)
C6—C8—H8B	109.5	C29—C28—H28	119.7
H8A—C8—H8B	109.5	C27—C28—H28	119.7
C6—C8—H8C	109.5	C30—C29—C28	120.82 (16)
H8A—C8—H8C	109.5	C30—C29—H29	119.6
H8B—C8—H8C	109.5	C28—C29—H29	119.6
C10—C9—C14	118.32 (14)	C29—C30—C31	119.09 (17)
C10—C9—C3	122.37 (13)	C29—C30—H30	120.5
C14—C9—C3	119.31 (13)	C31—C30—H30	120.5
C9—C10—C11	120.54 (16)	C30—C31—C32	120.26 (17)
C9—C10—H10	119.7	C30—C31—H31	119.9
C11—C10—H10	119.7	C32—C31—H31	119.9
C12—C11—C10	120.65 (18)	C31—C32—C27	121.10 (15)
C12—C11—H11	119.7	C31—C32—H32	119.5
C10—C11—H11	119.7	C27—C32—H32	119.4
C11—C12—C13	119.62 (17)	C4—N1—C3	132.08 (11)
C11—C12—H12	120.2	C4—N1—H1N	113.1 (7)
C13—C12—H12	120.2	C3—N1—H1N	110.5 (8)
C12—C13—C14	120.29 (18)	C4—N2—C5	131.13 (11)
C12—C13—H13	119.9	C4—N2—H2N	112.0 (4)
C14—C13—H13	119.9	C5—N2—H2N	110.6 (5)
C13—C14—C9	120.57 (17)	C2—O2—C6	109.05 (10)
C13—C14—H14	119.7	C1—O3—C6	108.22 (10)
C9—C14—H14	119.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.897 (15)	2.198 (17)	3.0570 (16)	160.3 (11)
O4—H1W···O1^i	0.9	2.00	2.836 (2)	154

Symmetry code: (i) −x+1, −y+1, z.