Cyclic water pentamers in triclinic crystals of brucinium L-glycerate

Brucinium L-glycerate 4.75-hydrate, C₂₃H₂₇N₂O₄⁺·C₃H₅O₄^-·4.75H₂O, was obtained by racemic resolution of DL-glyceric acid. This is the first report of triclinic crystals containing brucine. The water and L-glycerate anions form tapes built up of pentamers formed by water and carboxy O atoms, and this appears to be the reason for the low symmetry of the crystal.

S1. Comment

A special feature of water as a solvent is its ability to form aggregated hydrogen-bonded clusters, which are surrounded by non-hydrogen-bonded molecules (Scherega, 1979). Water clusters have, therefore, been the subject of a number of intense experimental and theoretical studies, as they can provide insight into fundamental biological and chemical systems. These studies have revealed ring-shaped tetramers, pentamers and hexamers as the building blocks for larger clusters (Ralf, 2001; Maheshwary et al., 2001; Liu et al., 1996). The lattice of a crystal host offers an attractive environment for stabilizing various topologies of water clusters, and thereby provides quantitative characterization of the hydrogen-bonding networks that exist in liquid water. Consequently, many studies have focused on the determination of the structural morphologies of water co-crystallizing with various chemical entities (Seanger, 1987; Custelcean et al., 2000; Raghuraman et al., 2003; Barbour et al., 1998). This paper reports the structure of the title compound, (I), containing cyclic water pentamers formed between brucinium–L-glycerate ionic sheets, and their self-assembly into a triclinic crystalline lattice.

In the structure of (I), there are two unique brucinium–glycerate ion pairs and 9.5 water molecules per unit cell. An overall view of both ion pairs, with the atomic numbering scheme, is presented in Fig. 1. The geometry of the brucine moieties is comparable with that found in other crystals (Cambridge Structural Database, Version?; Allen, 2002). The two unique L-glycerate anions have quite similar conformations, which are comparable with the molecular geometry of the glycerate anion in the crystal of ammonium DL-glycerate (Popek & Lis, 1996). The β-hydroxyl atom, O8 (or O8A), is +synclinal and -synclinal to the α-hydroxyl atom, O7 (or O7A), and atom C24 (or C24A), respectively (Table 1).

The crystal structure of (I) is composed of puckered sheets (Dijksma et al., 1998) of brucine, which are separated by solvent channels consisting of L-glycerate anions and water of crystallization (Fig. 2a). The puckered sheet is constructed from common parallel corrugated ribbons.

Among numerous crystal structures, to the best of our knowledge (Cambridge Structural Database, Version 5.24, November 2003; Allen, 2002), this is the first report of triclinic crystals containing brucine. Nevertheless, the corrugated ribbons observed in the present structure are also present in many crystal structures in which brucine molecules are related by a twofold screw symmetry axis (Toda et al., 1985; Glover et al., 1985; Quinkert et al., 1986; Sada et al., 1998; Boiadjiev et al., 1992; Wright et al., 1994; Chandramohan & Ravikumar, 1999; Krajewski & Ciunik, 1999; Dijksma et al., 1998; Pinkerton et al., 1993). Moreover, in the monoclinic crystals (space group C2) of brucinium hydrogen fumarate sesquihydrate (Dijksma et al., 1998), the same puckered sheet constructed from corrugated ribbons is related by parallel alternating twofold and twofold screw-axis symmetries. In the triclinic crystal under study, molecules of the brucine puckered sheet are related by similar local twofold and twofold screw axes parallel to the [110] direction (Fig. 2 b). Brucine molecules A [at (x, y, z)] and B [at (x − 1, y, z)] of the corrugated ribbon are related by a local twofold screw axis, and brucine corrugated ribbons of the puckered sheets are related by local twofold symmetry axes. Similar C—H···O and C—H···π(arene) contacts between the two unique brucine molecules confirm the parallel alternating twofold and twofold screw axes of the puckered sheet. The close environments of both crystallographically independent brucine cations, as L-glycerate anions, is quite similar. These anions participate, via both their carboxyl and β-hydroxyl groups, in hydrogen bonds to the protonated amine N and carbonyl O atoms of the brucine cations (Table 2).

The carboxyl groups of both crystallographically independent anions are directed towards the solvent channel and, together with eight water molecules, O1W, O2W, O3W, O4W, O5W, O7W, O8W and O9W, form an extended tape composed of units of four hydrogen-bonded five-membered rings along the brucine corrugated ribbons of the puckered sheets (Fig. 3). In one case, the carboxyl groups of both L-glycerate anions are linked by two water bridges (O1W and O7W) and join corrugated brucine ribbons of consecutive puckered sheets. In the other case, the pentamer is composed of three water molecules (O5W, O7W and O8W) and two carboxy atoms (O5 and O6) of one symmetry-independent anion. Four water molecules (O1W, O2W, O4W, O9W) and only one carboxy atom (O6A) of the other unique anion participate in formation of the next five-membered ring. The last pentamer of the extended tape is formed by five water molecules (O2W, O3W, O4W, O5W and O8W).

Neighbouring water tapes are linked by the α-hydroxyl groups of the two independent anions and, together with the remaining water molecules (O6W and O10W), contribute to one four-, two five- and three six-membered rings around the tape (Fig. 4).

The existence of the pentameric ring, O1W/O6/O7W/O5A/O6A, which involves the two carboxy O atoms of one independent L-glycerate anion and only one carboxy O atom of the other, causes the environment of these anions to be different and the crystal is triclinic. However, the same pentameric ring appears to determine the substructure of the water tape along the corrugated brucine ribbons as side-linked five-membered rings.

Table 1. Selected torsion angles of the two independent L-glycerate anions (°).

Table 2. Intermolecular hydrogen bonds (Å, °).

S2. Experimental

The synthesis of ammonium DL-glycerate was carried out as follows. Glycerine (about 0.53 mol, 40 ml) and water (50 ml) were placed in a 250 ml flask in an ice bath. Following this, fuming nitric acid (33 ml) was added while the whole mixture was stirred vigorously and its temperature kept below 283 K. The mixture was kept at 278 K for 5 d and then the solvents were evaporated using a hot water bath. The resulting syrup was left at room temperature for 3 d. Next, water (600 ml) and lead carbonate (140 g) were added and the mixture was stirred for about 24 d. The reaction mixture was concentrated in a hot water bath, cooled to room temperature, filtered by suction through a layer of cellite and left for crystallization. After several days, crystals of lead glycerate were separated from the mother liquor by filtration, washed with a very small quantity of a cold water–ethanol mixture (2:1) and dissolved in water, followed by the addition of excess aqueous ammonia. After vigorous stirring for several hours, the precipitate was filtered off and the solution of ammonium DL-glycerate was left for crystallization. Ammonium DL-glycerate (0.31 g, 2.5 mmol) was dissolved in a minimal quantity of water and passed through a column of Dowex-50X2 (3 × 40 cm, H⁺ form, 100 mesh). To the resulting eluate, an equimolar quantity of brucine (POCh, Poland) was added and the solution was left for crystallization. After a few weeks, the title brucinium salt started to crystallize as colourless plates.

S3. Refinement

H atoms were found in Δρ maps. The H-atom parameters were refined with isotropic displacement parameters and were fixed before the last cycle of refinement. Friedel pairs were merged before the final refinement. The absolute configuration of (I) was chosen on the basis of the known absolute configuration of brucine. The occupancy factor for the water molecule O6W/H61W/H62W was refined and fixed at 0.5.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis RED (Oxford Diffraction, 2001); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 1999); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the two brucinium-glycerate ion pairs in (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. (a) The molecular packing of (I). For clarity, the water molecules have been omitted. (b) The local twofold and twofold screw axes of the puckered brucine sheet. Corrugated ribbons constructed of brucine puckered sheets are indicated by light and dark shading.
	Fig. 3. The water tape of five-membered rings along the corrugated brucine ribbons.
	Fig. 4. The water cluster around the tape.

brucinium L-glycerate 4.75 hydrate

Crystal data

C23H27N2O4^+·C3H5O4^−·4.75H2O	Z = 2
Mr = 586.11	F(000) = 627
Triclinic, P1	Dx = 1.403 Mg m^−3
a = 9.308 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.578 (3) Å	Cell parameters from 6626 reflections
c = 16.130 (4) Å	θ = 3.4–28.0°
α = 77.21 (3)°	µ = 0.11 mm^−1
β = 87.36 (3)°	T = 100 K
γ = 81.57 (3)°	Plate, colourless
V = 1387.1 (7) Å^3	0.75 × 0.30 × 0.07 mm

Data collection

Kuma KM4 CCD diffractometer	5944 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 28.0°, θmin = 3.4°
ω scans	h = −12→12
16810 measured reflections	k = −12→12
6655 independent reflections	l = −21→20

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.043P)^2] where P = (Fo^2 + 2Fc^2)/3
6655 reflections	(Δ/σ)max = 0.002
739 parameters	Δρmax = 0.22 e Å^−3
3 restraints	Δρmin = −0.20 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	−0.32321 (17)	1.07379 (19)	0.66635 (11)	0.0203 (4)
O2	0.44291 (18)	0.38697 (18)	0.82568 (12)	0.0224 (4)
O3	0.37620 (18)	0.49669 (18)	0.95732 (11)	0.0203 (4)
O4	−0.04590 (17)	0.89874 (18)	0.91407 (11)	0.0193 (4)
N1	−0.0566 (2)	0.7843 (2)	0.80531 (12)	0.0148 (4)
N2	−0.1057 (2)	0.6556 (2)	0.54934 (13)	0.0184 (4)
H2	−0.0771	0.5786	0.5166	0.033*
C1	0.2203 (3)	0.5106 (3)	0.75278 (15)	0.0175 (5)
H1	0.2403	0.4641	0.7049	0.014*
C2	0.3152 (3)	0.4790 (2)	0.82028 (16)	0.0165 (5)
C3	0.2805 (2)	0.5421 (2)	0.89177 (15)	0.0163 (5)
C4	0.1571 (2)	0.6429 (2)	0.89267 (15)	0.0164 (5)
H4	0.1364	0.6935	0.9426	0.018*
C5	0.0678 (2)	0.6772 (3)	0.82190 (15)	0.0159 (5)
C6	0.0961 (2)	0.6105 (2)	0.75420 (14)	0.0150 (4)
C7	−0.0263 (2)	0.6576 (2)	0.69114 (15)	0.0156 (5)
C8	−0.1067 (2)	0.7961 (2)	0.71739 (15)	0.0146 (4)
H8	−0.2118	0.7929	0.7171	0.013*
C9	−0.0915 (2)	0.8983 (3)	0.84341 (15)	0.0161 (5)
C10	−0.1937 (3)	1.0244 (3)	0.79371 (16)	0.0175 (5)
H10A	−0.2970	1.0040	0.8074	0.014*
H10B	−0.1733	1.1053	0.8153	0.017*
C11	−0.1780 (2)	1.0601 (3)	0.69569 (16)	0.0176 (5)
H11	−0.1424	1.1548	0.6770	0.016*
C12	−0.3404 (3)	1.1251 (3)	0.57635 (17)	0.0246 (5)
H12A	−0.4327	1.1831	0.5672	0.022*
H12B	−0.2710	1.1939	0.5549	0.015*
C13	−0.3206 (3)	1.0007 (3)	0.53225 (16)	0.0223 (5)
H13	−0.4067	0.9812	0.5071	0.030*
C14	−0.1928 (3)	0.9177 (3)	0.53037 (15)	0.0195 (5)
C15	−0.1737 (3)	0.7911 (3)	0.48849 (16)	0.0217 (5)
H15A	−0.2650	0.7714	0.4699	0.014*
H15B	−0.1112	0.8093	0.4393	0.024*
C16	−0.2135 (3)	0.5927 (3)	0.61528 (17)	0.0225 (5)
H16A	−0.2915	0.6801	0.6184	0.015*
H16B	−0.2566	0.5196	0.5952	0.020*
C17	−0.1282 (3)	0.5422 (3)	0.69703 (16)	0.0186 (5)
H17A	−0.1980	0.5339	0.7488	0.018*
H17B	−0.0775	0.4499	0.6999	0.017*
C18	−0.0713 (2)	0.9418 (2)	0.66628 (15)	0.0154 (4)
H18	0.0251	0.9596	0.6854	0.019*
C19	−0.0576 (2)	0.9451 (3)	0.56985 (15)	0.0175 (5)
H19	−0.0336	1.0427	0.5407	0.025*
C20	0.0684 (2)	0.8273 (3)	0.55867 (15)	0.0182 (5)
H20A	0.1496	0.8408	0.5892	0.018*
H20B	0.0941	0.8329	0.5018	0.017*
C21	0.0241 (2)	0.6811 (3)	0.59729 (15)	0.0170 (5)
H21	0.1009	0.6052	0.5914	0.017*
C22	0.4914 (3)	0.3369 (3)	0.75073 (19)	0.0315 (7)
H22A	0.4238	0.2769	0.7328	0.026*
H22B	0.4971	0.4208	0.7007	0.030*
H22C	0.5902	0.2809	0.7660	0.028*
C23	0.3455 (3)	0.5625 (3)	1.02841 (17)	0.0238 (5)
H23A	0.2511	0.5359	1.0569	0.018*
H23B	0.4224	0.5287	1.0705	0.021*
H23C	0.3426	0.6664	1.0122	0.025*
O1A	0.02633 (18)	1.30966 (18)	1.02618 (11)	0.0215 (4)
O2A	0.67660 (18)	0.61936 (18)	0.86709 (11)	0.0207 (4)
O3A	0.51900 (17)	0.73214 (19)	0.73484 (11)	0.0195 (4)
O4A	0.13090 (18)	1.13867 (19)	0.77405 (11)	0.0205 (4)
N1A	0.2877 (2)	1.1089 (2)	0.88310 (13)	0.0162 (4)
N2A	0.5053 (2)	1.0615 (2)	1.14170 (13)	0.0185 (4)
H2A	0.5807	1.0200	1.1743	0.027*
C1A	0.5806 (2)	0.8146 (3)	0.93868 (15)	0.0162 (5)
H1A	0.6441	0.7775	0.9904	0.016*
C2A	0.5867 (2)	0.7448 (3)	0.87170 (16)	0.0170 (5)
C3A	0.4976 (2)	0.8039 (3)	0.79981 (15)	0.0155 (5)
C4A	0.3968 (2)	0.9270 (3)	0.79748 (15)	0.0159 (5)
H4A	0.3333	0.9634	0.7544	0.012*
C5A	0.3887 (2)	0.9907 (2)	0.86770 (15)	0.0157 (5)
C6A	0.4810 (2)	0.9391 (3)	0.93600 (15)	0.0160 (5)
C7A	0.4564 (2)	1.0352 (2)	0.99889 (15)	0.0155 (4)
C8A	0.3054 (2)	1.1244 (2)	0.97194 (15)	0.0155 (4)
H8A	0.3128	1.2265	0.9674	0.021*
C9A	0.1569 (2)	1.1576 (3)	0.84517 (15)	0.0170 (5)
C10A	0.0468 (2)	1.2413 (3)	0.89480 (15)	0.0166 (5)
H10C	0.0743	1.3421	0.8836	0.027*
H10D	−0.0416	1.2477	0.8683	0.023*
C11A	0.0390 (2)	1.1819 (3)	0.99192 (16)	0.0179 (5)
H11A	−0.0459	1.1321	1.0084	0.011*
C12A	0.0052 (3)	1.2860 (3)	1.11673 (17)	0.0246 (6)
H12C	−0.0507	1.3837	1.1238	0.029*
H12D	−0.0455	1.2016	1.1358	0.025*
C13A	0.1490 (3)	1.2579 (3)	1.16057 (16)	0.0225 (5)
H13A	0.1794	1.3288	1.1863	0.016*
C14A	0.2404 (3)	1.1382 (3)	1.15885 (16)	0.0191 (5)
C15A	0.3859 (3)	1.1073 (3)	1.20094 (16)	0.0210 (5)
H15C	0.4118	1.1960	1.2179	0.014*
H15D	0.3856	1.0331	1.2488	0.017*
C16A	0.5496 (3)	1.1882 (3)	1.07694 (17)	0.0221 (5)
H16C	0.4672	1.2732	1.0723	0.023*
H16D	0.6328	1.2230	1.0969	0.026*
C17A	0.5749 (2)	1.1353 (3)	0.99455 (16)	0.0193 (5)
H17C	0.5595	1.2173	0.9447	0.016*
H17D	0.6706	1.0790	0.9910	0.012*
C18A	0.1733 (2)	1.0701 (2)	1.02164 (15)	0.0152 (4)
H18A	0.1576	0.9856	1.0015	0.015*
C19A	0.2006 (3)	1.0205 (3)	1.11784 (15)	0.0178 (5)
H19A	0.1171	0.9836	1.1466	0.026*
C20A	0.3266 (3)	0.8957 (3)	1.12935 (15)	0.0191 (5)
H20C	0.3010	0.8224	1.1021	0.020*
H20D	0.3394	0.8477	1.1897	0.019*
C21A	0.4643 (3)	0.9529 (3)	1.09258 (15)	0.0175 (5)
H21A	0.5417	0.8746	1.1008	0.019*
C22A	0.7538 (3)	0.5462 (3)	0.94277 (17)	0.0266 (6)
H22D	0.8292	0.6035	0.9545	0.028*
H22E	0.6833	0.5199	0.9941	0.023*
H22F	0.8000	0.4474	0.9329	0.023*
C23A	0.4217 (3)	0.7856 (3)	0.66515 (17)	0.0229 (5)
H23D	0.3238	0.7811	0.6854	0.026*
H23E	0.4406	0.8832	0.6367	0.014*
H23F	0.4410	0.7202	0.6264	0.022*
O5	−0.11449 (19)	0.4851 (2)	0.43795 (12)	0.0250 (4)
O6	−0.0597 (2)	0.2627 (2)	0.41413 (13)	0.0262 (4)
O7	0.16182 (19)	0.50466 (19)	0.46890 (12)	0.0239 (4)
H71	0.1719	0.5620	0.4201	0.026*
O8	0.0737 (2)	0.2986 (2)	0.60593 (12)	0.0267 (4)
H81	0.1061	0.2481	0.6530	0.029*
C24	−0.0276 (3)	0.3729 (3)	0.43506 (15)	0.0190 (5)
C25	0.1319 (3)	0.3682 (3)	0.45835 (16)	0.0196 (5)
H25	0.1878	0.3412	0.4117	0.027*
C26	0.1702 (3)	0.2594 (3)	0.54080 (17)	0.0214 (5)
H26A	0.1609	0.1637	0.5329	0.013*
H26B	0.2735	0.2598	0.5592	0.027*
O5A	0.73808 (19)	0.98905 (19)	0.24806 (12)	0.0227 (4)
O6A	0.97024 (18)	0.89743 (19)	0.27340 (11)	0.0221 (4)
O7A	0.67287 (18)	0.73748 (19)	0.21906 (12)	0.0220 (4)
H72	0.6227	0.7634	0.2661	0.027*
O8A	0.8440 (2)	0.8674 (2)	0.08107 (11)	0.0268 (4)
H82	0.8815	0.8631	0.0331	0.025*
C24A	0.8445 (3)	0.8906 (3)	0.25138 (15)	0.0175 (5)
C25A	0.8228 (3)	0.7493 (3)	0.22702 (16)	0.0193 (5)
H25A	0.8639	0.6616	0.2709	0.019*
C26A	0.8991 (3)	0.7408 (3)	0.14239 (17)	0.0222 (5)
H26C	0.8776	0.6514	0.1231	0.017*
H26D	1.0066	0.7358	0.1479	0.023*
O1W	0.11184 (19)	0.0383 (2)	0.36902 (12)	0.0263 (4)
H11W	0.0546	0.1186	0.3822	0.023*
H12W	0.0641	0.0133	0.3317	0.021*
O2W	0.20073 (19)	0.68878 (19)	0.31836 (12)	0.0245 (4)
H21W	0.1279	0.7599	0.3007	0.026*
H22W	0.2802	0.7215	0.3299	0.050*
O3W	0.3403 (2)	0.4559 (2)	0.25326 (13)	0.0297 (4)
H31W	0.3002	0.5408	0.2657	0.039*
H32W	0.4272	0.4730	0.2280	0.075*
O4W	0.4748 (2)	0.7596 (2)	0.35034 (13)	0.0278 (4)
H41W	0.5099	0.6781	0.3869	0.048*
H42W	0.4470	0.8296	0.3873	0.041*
O5W	0.5931 (2)	0.4967 (2)	0.44411 (19)	0.0502 (7)
H51W	0.5641	0.4229	0.4268	0.097*
H52W	0.6995	0.4829	0.4508	0.093*
O6W	0.3996 (4)	0.5221 (5)	0.5625 (3)	0.0358 (10)	0.50
H61W	0.4562	0.5096	0.5238	0.015*	0.50
H62W	0.3171	0.5144	0.5333	0.025*	0.50
O7W	0.7404 (2)	0.24146 (19)	0.29997 (13)	0.0263 (4)
H71W	0.8007	0.2511	0.3372	0.079*
H72W	0.7607	0.1577	0.2891	0.035*
O8W	0.4834 (2)	0.2614 (2)	0.38974 (13)	0.0299 (4)
H81W	0.5659	0.2413	0.3569	0.071*
H82W	0.4303	0.3227	0.3460	0.049*
O9W	0.3840 (2)	0.9841 (2)	0.42763 (13)	0.0297 (4)
H91W	0.2863	1.0061	0.4081	0.016*
H92W	0.4118	1.0677	0.4154	0.031*
O10W	0.6170 (2)	0.4796 (2)	0.17967 (13)	0.0278 (4)
H1W	0.6693	0.4041	0.2161	0.082*
H2W	0.6354	0.5599	0.1951	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0144 (8)	0.0242 (9)	0.0204 (9)	0.0012 (7)	−0.0037 (7)	−0.0024 (7)
O2	0.0169 (8)	0.0188 (9)	0.0277 (10)	0.0054 (7)	−0.0005 (7)	−0.0019 (7)
O3	0.0191 (8)	0.0168 (8)	0.0232 (9)	0.0010 (7)	−0.0075 (7)	−0.0015 (7)
O4	0.0191 (8)	0.0211 (9)	0.0182 (9)	−0.0008 (7)	−0.0019 (7)	−0.0065 (7)
N1	0.0141 (9)	0.0159 (10)	0.0135 (10)	−0.0005 (7)	−0.0007 (7)	−0.0025 (7)
N2	0.0156 (9)	0.0237 (11)	0.0178 (10)	−0.0048 (8)	−0.0004 (8)	−0.0069 (8)
C1	0.0179 (11)	0.0159 (11)	0.0171 (12)	−0.0018 (9)	0.0030 (9)	−0.0012 (9)
C2	0.0157 (11)	0.0111 (10)	0.0208 (12)	−0.0005 (9)	0.0008 (9)	−0.0002 (9)
C3	0.0154 (11)	0.0140 (11)	0.0182 (12)	−0.0037 (9)	−0.0022 (9)	0.0009 (9)
C4	0.0165 (11)	0.0162 (11)	0.0164 (11)	−0.0031 (9)	−0.0012 (9)	−0.0024 (9)
C5	0.0122 (10)	0.0164 (11)	0.0172 (12)	−0.0010 (9)	0.0007 (9)	−0.0007 (9)
C6	0.0140 (10)	0.0158 (11)	0.0139 (11)	−0.0008 (8)	−0.0018 (9)	−0.0012 (9)
C7	0.0144 (11)	0.0158 (11)	0.0160 (11)	−0.0008 (9)	−0.0003 (9)	−0.0028 (9)
C8	0.0129 (10)	0.0166 (11)	0.0138 (11)	−0.0007 (8)	−0.0015 (8)	−0.0027 (9)
C9	0.0120 (10)	0.0199 (12)	0.0171 (12)	−0.0044 (9)	0.0020 (9)	−0.0044 (9)
C10	0.0149 (11)	0.0171 (11)	0.0202 (12)	0.0004 (9)	0.0007 (9)	−0.0050 (9)
C11	0.0150 (11)	0.0157 (11)	0.0213 (12)	−0.0018 (9)	−0.0021 (9)	−0.0020 (9)
C12	0.0217 (12)	0.0246 (13)	0.0236 (13)	0.0035 (10)	−0.0075 (10)	−0.0002 (10)
C13	0.0184 (12)	0.0297 (14)	0.0169 (12)	−0.0024 (10)	−0.0039 (10)	−0.0008 (10)
C14	0.0192 (12)	0.0241 (13)	0.0140 (11)	−0.0028 (10)	−0.0017 (9)	−0.0011 (9)
C15	0.0209 (12)	0.0288 (14)	0.0157 (12)	−0.0015 (10)	−0.0056 (10)	−0.0057 (10)
C16	0.0176 (11)	0.0290 (13)	0.0231 (13)	−0.0076 (10)	0.0004 (10)	−0.0081 (11)
C17	0.0200 (12)	0.0181 (12)	0.0189 (12)	−0.0030 (9)	0.0031 (9)	−0.0068 (9)
C18	0.0131 (10)	0.0163 (11)	0.0167 (11)	−0.0024 (8)	−0.0004 (9)	−0.0033 (9)
C19	0.0142 (11)	0.0211 (12)	0.0164 (11)	−0.0033 (9)	−0.0008 (9)	−0.0015 (9)
C20	0.0148 (11)	0.0255 (13)	0.0135 (11)	−0.0038 (9)	0.0019 (9)	−0.0023 (9)
C21	0.0114 (10)	0.0222 (12)	0.0177 (12)	−0.0010 (9)	−0.0006 (9)	−0.0055 (9)
C22	0.0254 (14)	0.0308 (15)	0.0313 (15)	0.0099 (12)	0.0053 (12)	−0.0018 (12)
C23	0.0222 (12)	0.0252 (13)	0.0234 (13)	−0.0003 (10)	−0.0066 (10)	−0.0046 (10)
O1A	0.0221 (9)	0.0200 (9)	0.0213 (9)	0.0027 (7)	−0.0009 (7)	−0.0059 (7)
O2A	0.0175 (8)	0.0199 (9)	0.0226 (9)	0.0046 (7)	−0.0009 (7)	−0.0045 (7)
O3A	0.0144 (8)	0.0253 (9)	0.0199 (9)	−0.0001 (7)	−0.0022 (7)	−0.0086 (7)
O4A	0.0167 (8)	0.0262 (9)	0.0175 (9)	−0.0007 (7)	−0.0037 (7)	−0.0032 (7)
N1A	0.0141 (9)	0.0173 (10)	0.0154 (10)	−0.0006 (7)	−0.0016 (7)	−0.0005 (8)
N2A	0.0186 (10)	0.0186 (10)	0.0183 (10)	−0.0024 (8)	−0.0042 (8)	−0.0029 (8)
C1A	0.0131 (10)	0.0188 (11)	0.0157 (11)	−0.0036 (9)	−0.0014 (9)	−0.0004 (9)
C2A	0.0116 (10)	0.0169 (11)	0.0206 (12)	−0.0023 (9)	0.0007 (9)	−0.0002 (9)
C3A	0.0101 (10)	0.0198 (12)	0.0179 (12)	−0.0054 (9)	0.0021 (8)	−0.0051 (9)
C4A	0.0119 (10)	0.0188 (11)	0.0167 (12)	−0.0025 (9)	−0.0038 (9)	−0.0020 (9)
C5A	0.0111 (10)	0.0160 (11)	0.0180 (12)	−0.0016 (8)	−0.0008 (9)	0.0007 (9)
C6A	0.0127 (10)	0.0188 (11)	0.0161 (11)	−0.0025 (9)	0.0006 (9)	−0.0030 (9)
C7A	0.0126 (10)	0.0151 (11)	0.0176 (11)	0.0003 (8)	−0.0009 (9)	−0.0023 (9)
C8A	0.0153 (10)	0.0154 (11)	0.0156 (11)	−0.0030 (9)	−0.0022 (8)	−0.0020 (9)
C9A	0.0147 (11)	0.0174 (11)	0.0180 (12)	−0.0040 (9)	−0.0013 (9)	−0.0007 (9)
C10A	0.0115 (10)	0.0212 (12)	0.0167 (12)	−0.0012 (9)	−0.0032 (9)	−0.0037 (9)
C11A	0.0126 (10)	0.0202 (12)	0.0209 (12)	−0.0017 (9)	0.0005 (9)	−0.0046 (10)
C12A	0.0246 (13)	0.0287 (14)	0.0207 (13)	0.0031 (11)	0.0008 (10)	−0.0107 (11)
C13A	0.0268 (13)	0.0224 (13)	0.0177 (12)	−0.0007 (10)	−0.0014 (10)	−0.0044 (10)
C14A	0.0218 (12)	0.0181 (12)	0.0162 (11)	−0.0038 (9)	0.0002 (9)	−0.0009 (9)
C15A	0.0247 (12)	0.0206 (12)	0.0172 (12)	0.0018 (10)	−0.0044 (10)	−0.0052 (10)
C16A	0.0243 (12)	0.0191 (12)	0.0226 (13)	−0.0059 (10)	−0.0062 (10)	−0.0006 (10)
C17A	0.0145 (11)	0.0189 (12)	0.0233 (13)	−0.0014 (9)	−0.0040 (9)	−0.0022 (10)
C18A	0.0150 (11)	0.0135 (11)	0.0169 (11)	−0.0018 (9)	−0.0014 (9)	−0.0024 (9)
C19A	0.0196 (11)	0.0160 (11)	0.0170 (12)	−0.0033 (9)	0.0003 (9)	−0.0013 (9)
C20A	0.0237 (12)	0.0159 (11)	0.0166 (12)	−0.0023 (9)	−0.0016 (10)	−0.0012 (9)
C21A	0.0209 (11)	0.0164 (11)	0.0147 (11)	−0.0017 (9)	−0.0030 (9)	−0.0027 (9)
C22A	0.0231 (13)	0.0258 (14)	0.0254 (14)	0.0089 (11)	−0.0028 (11)	−0.0016 (11)
C23A	0.0171 (12)	0.0286 (14)	0.0236 (13)	0.0007 (10)	−0.0045 (10)	−0.0091 (11)
O5	0.0209 (9)	0.0269 (10)	0.0279 (10)	0.0015 (7)	−0.0061 (7)	−0.0095 (8)
O6	0.0245 (9)	0.0221 (9)	0.0342 (11)	−0.0002 (7)	−0.0065 (8)	−0.0115 (8)
O7	0.0240 (9)	0.0243 (9)	0.0242 (9)	−0.0096 (7)	0.0025 (7)	−0.0034 (7)
O8	0.0234 (9)	0.0306 (10)	0.0205 (9)	0.0043 (8)	0.0006 (7)	0.0010 (8)
C24	0.0208 (12)	0.0203 (12)	0.0155 (12)	−0.0027 (10)	−0.0014 (9)	−0.0028 (9)
C25	0.0177 (11)	0.0224 (12)	0.0199 (12)	−0.0042 (10)	0.0025 (9)	−0.0065 (10)
C26	0.0169 (11)	0.0205 (12)	0.0258 (14)	−0.0006 (9)	−0.0008 (10)	−0.0042 (10)
O5A	0.0200 (8)	0.0235 (9)	0.0261 (10)	0.0006 (7)	−0.0046 (7)	−0.0099 (7)
O6A	0.0176 (8)	0.0244 (9)	0.0258 (10)	−0.0035 (7)	−0.0031 (7)	−0.0079 (7)
O7A	0.0161 (8)	0.0227 (9)	0.0268 (10)	−0.0050 (7)	−0.0029 (7)	−0.0030 (7)
O8A	0.0291 (10)	0.0301 (10)	0.0175 (9)	0.0037 (8)	0.0024 (7)	−0.0030 (7)
C24A	0.0192 (11)	0.0173 (11)	0.0141 (11)	−0.0013 (9)	−0.0001 (9)	−0.0006 (9)
C25A	0.0186 (11)	0.0167 (12)	0.0219 (12)	−0.0010 (9)	−0.0043 (10)	−0.0027 (9)
C26A	0.0206 (12)	0.0199 (12)	0.0252 (13)	0.0032 (10)	−0.0021 (10)	−0.0067 (10)
O1W	0.0227 (9)	0.0289 (10)	0.0292 (10)	0.0007 (8)	−0.0065 (8)	−0.0122 (8)
O2W	0.0189 (8)	0.0220 (9)	0.0298 (10)	−0.0021 (7)	−0.0008 (7)	−0.0002 (7)
O3W	0.0261 (10)	0.0281 (10)	0.0362 (11)	−0.0024 (8)	−0.0005 (8)	−0.0107 (9)
O4W	0.0225 (9)	0.0247 (10)	0.0335 (11)	0.0000 (7)	−0.0001 (8)	−0.0027 (8)
O5W	0.0304 (12)	0.0251 (11)	0.092 (2)	−0.0016 (9)	−0.0278 (12)	−0.0021 (11)
O6W	0.031 (2)	0.055 (3)	0.027 (2)	−0.0085 (19)	0.0006 (17)	−0.0199 (19)
O7W	0.0244 (9)	0.0205 (9)	0.0348 (11)	0.0021 (7)	−0.0079 (8)	−0.0099 (8)
O8W	0.0233 (9)	0.0315 (11)	0.0334 (11)	−0.0026 (8)	−0.0021 (8)	−0.0047 (9)
O9W	0.0218 (9)	0.0265 (10)	0.0399 (12)	−0.0029 (8)	−0.0094 (8)	−0.0041 (8)
O10W	0.0272 (10)	0.0255 (10)	0.0310 (11)	−0.0038 (8)	−0.0043 (8)	−0.0061 (8)

Geometric parameters (Å, º)

O1—C11	1.431 (3)	C5A—C6A	1.385 (3)
O1—C12	1.434 (3)	C6A—C7A	1.503 (3)
O2—C2	1.366 (3)	C7A—C21A	1.542 (3)
O2—C22	1.428 (3)	C7A—C17A	1.553 (3)
O3—C3	1.367 (3)	C7A—C8A	1.560 (3)
O3—C23	1.425 (3)	C8A—C18A	1.529 (3)
O4—C9	1.236 (3)	C8A—H8A	0.9765
N1—C9	1.360 (3)	C9A—C10A	1.517 (3)
N1—C5	1.423 (3)	C10A—C11A	1.546 (3)
N1—C8	1.489 (3)	C10A—H10C	1.0106
N2—C16	1.515 (3)	C10A—H10D	0.9329
N2—C15	1.517 (3)	C11A—C18A	1.541 (3)
N2—C21	1.541 (3)	C11A—H11A	0.9781
N2—H2	0.9979	C12A—C13A	1.504 (4)
C1—C2	1.387 (3)	C12A—H12C	1.0283
C1—C6	1.391 (3)	C12A—H12D	0.9793
C1—H1	0.9719	C13A—C14A	1.329 (4)
C2—C3	1.420 (3)	C13A—H13A	0.9513
C3—C4	1.389 (3)	C14A—C15A	1.504 (4)
C4—C5	1.394 (3)	C14A—C19A	1.523 (4)
C4—H4	1.0249	C15A—H15C	1.0120
C5—C6	1.380 (3)	C15A—H15D	0.9272
C6—C7	1.513 (3)	C16A—C17A	1.521 (4)
C7—C21	1.542 (3)	C16A—H16C	1.0259
C7—C17	1.544 (3)	C16A—H16D	0.9807
C7—C8	1.558 (3)	C17A—H17C	0.9905
C8—C18	1.529 (3)	C17A—H17D	0.9780
C8—H8	0.9834	C18A—C19A	1.541 (3)
C9—C10	1.520 (3)	C18A—H18A	0.9682
C10—C11	1.547 (3)	C19A—C20A	1.533 (3)
C10—H10A	1.0136	C19A—H19A	0.9585
C10—H10B	0.9618	C20A—C21A	1.512 (3)
C11—C18	1.536 (3)	C20A—H20C	0.9681
C11—H11	0.9914	C20A—H20D	0.9844
C12—C13	1.503 (4)	C21A—H21A	0.9522
C12—H12A	0.9510	C22A—H22D	1.0003
C12—H12B	0.9868	C22A—H22E	1.0421
C13—C14	1.333 (4)	C22A—H22F	1.0233
C13—H13	0.9746	C23A—H23D	0.9582
C14—C15	1.499 (4)	C23A—H23E	0.9832
C14—C19	1.518 (3)	C23A—H23F	0.9717
C15—H15A	0.9717	O5—C24	1.255 (3)
C15—H15B	0.9621	O6—C24	1.256 (3)
C16—C17	1.518 (4)	O7—C25	1.423 (3)
C16—H16A	1.0338	O7—H71	0.8645
C16—H16B	0.9748	O8—C26	1.428 (3)
C17—H17A	1.0305	O8—H81	0.8470
C17—H17B	0.9321	C24—C25	1.540 (3)
C18—C19	1.549 (3)	C25—C26	1.518 (4)
C18—H18	1.0115	C25—H25	0.9559
C19—C20	1.537 (3)	C26—H26A	0.9691
C19—H19	1.0008	C26—H26B	1.0202
C20—C21	1.509 (4)	O5A—C24A	1.258 (3)
C20—H20A	0.9602	O6A—C24A	1.254 (3)
C20—H20B	0.9288	O7A—C25A	1.431 (3)
C21—H21	0.9597	O7A—H72	0.9330
C22—H22A	1.0034	O8A—C26A	1.431 (3)
C22—H22B	1.0103	O8A—H82	0.8418
C22—H22C	1.0065	C24A—C25A	1.533 (3)
C23—H23A	1.0119	C25A—C26A	1.522 (4)
C23—H23B	0.9785	C25A—H25A	1.0101
C23—H23C	0.9679	C26A—H26C	1.0221
O1A—C12A	1.436 (3)	C26A—H26D	1.0017
O1A—C11A	1.438 (3)	O1W—H11W	0.9283
O2A—C2A	1.374 (3)	O1W—H12W	0.8586
O2A—C22A	1.432 (3)	O2W—H21W	0.8951
O3A—C3A	1.367 (3)	O2W—H22W	0.8870
O3A—C23A	1.431 (3)	O3W—H31W	0.9042
O4A—C9A	1.240 (3)	O3W—H32W	0.9090
N1A—C9A	1.360 (3)	O4W—H41W	0.8959
N1A—C5A	1.421 (3)	O4W—H42W	0.9927
N1A—C8A	1.492 (3)	O5W—H51W	0.8940
N2A—C16A	1.510 (3)	O5W—H52W	0.9877
N2A—C15A	1.512 (3)	O6W—H61W	0.8154
N2A—C21A	1.537 (3)	O6W—H62W	0.9394
N2A—H2A	0.8871	O7W—H71W	0.8689
C1A—C2A	1.386 (3)	O7W—H72W	0.8516
C1A—C6A	1.393 (3)	O8W—H81W	0.9338
C1A—H1A	1.0121	O8W—H82W	0.9215
C2A—C3A	1.419 (3)	O9W—H91W	0.9554
C3A—C4A	1.390 (3)	O9W—H92W	0.8561
C4A—C5A	1.395 (3)	O10W—H1W	0.9164
C4A—H4A	0.9079	O10W—H2W	0.9005
C11—O1—C12	115.02 (19)	C3A—C4A—H4A	123.1
C2—O2—C22	116.6 (2)	C5A—C4A—H4A	119.4
C3—O3—C23	116.00 (18)	C6A—C5A—C4A	122.2 (2)
C9—N1—C5	126.2 (2)	C6A—C5A—N1A	110.0 (2)
C9—N1—C8	119.49 (19)	C4A—C5A—N1A	127.8 (2)
C5—N1—C8	109.25 (18)	C5A—C6A—C1A	120.2 (2)
C16—N2—C15	112.42 (18)	C5A—C6A—C7A	110.8 (2)
C16—N2—C21	107.48 (18)	C1A—C6A—C7A	129.0 (2)
C15—N2—C21	112.84 (19)	C6A—C7A—C21A	114.1 (2)
C16—N2—H2	104.0	C6A—C7A—C17A	113.42 (19)
C15—N2—H2	108.4	C21A—C7A—C17A	101.75 (19)
C21—N2—H2	111.4	C6A—C7A—C8A	102.10 (18)
C2—C1—C6	119.1 (2)	C21A—C7A—C8A	114.58 (19)
C2—C1—H1	120.6	C17A—C7A—C8A	111.38 (19)
C6—C1—H1	120.3	N1A—C8A—C18A	105.67 (19)
O2—C2—C1	125.1 (2)	N1A—C8A—C7A	104.37 (18)
O2—C2—C3	115.0 (2)	C18A—C8A—C7A	116.47 (19)
C1—C2—C3	119.8 (2)	N1A—C8A—H8A	105.5
O3—C3—C4	123.9 (2)	C18A—C8A—H8A	115.5
O3—C3—C2	115.32 (19)	C7A—C8A—H8A	108.1
C4—C3—C2	120.8 (2)	O4A—C9A—N1A	122.5 (2)
C3—C4—C5	117.7 (2)	O4A—C9A—C10A	122.4 (2)
C3—C4—H4	120.5	N1A—C9A—C10A	115.1 (2)
C5—C4—H4	121.7	C9A—C10A—C11A	116.59 (19)
C6—C5—C4	122.0 (2)	C9A—C10A—H10C	105.5
C6—C5—N1	110.1 (2)	C11A—C10A—H10C	109.0
C4—C5—N1	127.9 (2)	C9A—C10A—H10D	105.1
C5—C6—C1	120.4 (2)	C11A—C10A—H10D	112.8
C5—C6—C7	110.38 (19)	H10C—C10A—H10D	107.3
C1—C6—C7	129.2 (2)	O1A—C11A—C18A	114.57 (19)
C6—C7—C21	114.21 (19)	O1A—C11A—C10A	103.49 (19)
C6—C7—C17	112.80 (19)	C18A—C11A—C10A	110.46 (19)
C21—C7—C17	102.18 (19)	O1A—C11A—H11A	110.2
C6—C7—C8	102.39 (18)	C18A—C11A—H11A	106.6
C21—C7—C8	114.30 (19)	C10A—C11A—H11A	111.7
C17—C7—C8	111.36 (18)	O1A—C12A—C13A	110.5 (2)
N1—C8—C18	105.82 (18)	O1A—C12A—H12C	102.0
N1—C8—C7	104.26 (17)	C13A—C12A—H12C	110.2
C18—C8—C7	117.25 (19)	O1A—C12A—H12D	108.8
N1—C8—H8	110.7	C13A—C12A—H12D	108.9
C18—C8—H8	110.3	H12C—C12A—H12D	116.2
C7—C8—H8	108.2	C14A—C13A—C12A	120.6 (2)
O4—C9—N1	122.6 (2)	C14A—C13A—H13A	118.7
O4—C9—C10	122.1 (2)	C12A—C13A—H13A	120.6
N1—C9—C10	115.2 (2)	C13A—C14A—C15A	122.1 (2)
C9—C10—C11	117.88 (19)	C13A—C14A—C19A	121.8 (2)
C9—C10—H10A	108.1	C15A—C14A—C19A	116.0 (2)
C11—C10—H10A	106.7	C14A—C15A—N2A	111.2 (2)
C9—C10—H10B	103.2	C14A—C15A—H15C	111.3
C11—C10—H10B	109.2	N2A—C15A—H15C	107.0
H10A—C10—H10B	111.8	C14A—C15A—H15D	110.1
O1—C11—C18	114.5 (2)	N2A—C15A—H15D	107.9
O1—C11—C10	104.26 (18)	H15C—C15A—H15D	109.2
C18—C11—C10	110.16 (18)	N2A—C16A—C17A	105.3 (2)
O1—C11—H11	108.6	N2A—C16A—H16C	108.4
C18—C11—H11	109.9	C17A—C16A—H16C	112.3
C10—C11—H11	109.2	N2A—C16A—H16D	110.7
O1—C12—C13	110.6 (2)	C17A—C16A—H16D	115.4
O1—C12—H12A	107.7	H16C—C16A—H16D	104.6
C13—C12—H12A	113.6	C16A—C17A—C7A	102.8 (2)
O1—C12—H12B	109.1	C16A—C17A—H17C	110.7
C13—C12—H12B	111.8	C7A—C17A—H17C	110.4
H12A—C12—H12B	103.8	C16A—C17A—H17D	113.1
C14—C13—C12	121.7 (2)	C7A—C17A—H17D	109.2
C14—C13—H13	121.6	H17C—C17A—H17D	110.4
C12—C13—H13	116.7	C8A—C18A—C19A	112.54 (19)
C13—C14—C15	121.8 (2)	C8A—C18A—C11A	107.93 (18)
C13—C14—C19	122.5 (2)	C19A—C18A—C11A	118.16 (19)
C15—C14—C19	115.7 (2)	C8A—C18A—H18A	105.8
C14—C15—N2	110.49 (19)	C19A—C18A—H18A	106.9
C14—C15—H15A	112.6	C11A—C18A—H18A	104.4
N2—C15—H15A	107.6	C14A—C19A—C20A	108.8 (2)
C14—C15—H15B	110.0	C14A—C19A—C18A	113.98 (19)
N2—C15—H15B	108.5	C20A—C19A—C18A	106.84 (19)
H15A—C15—H15B	107.6	C14A—C19A—H19A	109.1
N2—C16—C17	104.81 (19)	C20A—C19A—H19A	107.7
N2—C16—H16A	103.7	C18A—C19A—H19A	110.2
C17—C16—H16A	111.3	C21A—C20A—C19A	109.26 (19)
N2—C16—H16B	109.4	C21A—C20A—H20C	112.5
C17—C16—H16B	116.8	C19A—C20A—H20C	108.1
H16A—C16—H16B	109.9	C21A—C20A—H20D	110.5
C16—C17—C7	103.4 (2)	C19A—C20A—H20D	111.3
C16—C17—H17A	110.2	H20C—C20A—H20D	105.2
C7—C17—H17A	114.3	C20A—C21A—N2A	110.43 (19)
C16—C17—H17B	110.5	C20A—C21A—C7A	115.5 (2)
C7—C17—H17B	112.5	N2A—C21A—C7A	104.97 (19)
H17A—C17—H17B	106.1	C20A—C21A—H21A	108.3
C8—C18—C11	107.31 (18)	N2A—C21A—H21A	106.1
C8—C18—C19	111.86 (19)	C7A—C21A—H21A	111.2
C11—C18—C19	118.22 (19)	O2A—C22A—H22D	110.4
C8—C18—H18	109.1	O2A—C22A—H22E	111.7
C11—C18—H18	102.2	H22D—C22A—H22E	113.2
C19—C18—H18	107.5	O2A—C22A—H22F	106.7
C14—C19—C20	108.9 (2)	H22D—C22A—H22F	111.2
C14—C19—C18	114.73 (19)	H22E—C22A—H22F	103.3
C20—C19—C18	106.62 (18)	O3A—C23A—H23D	109.4
C14—C19—H19	108.9	O3A—C23A—H23E	108.6
C20—C19—H19	110.2	H23D—C23A—H23E	114.0
C18—C19—H19	107.4	O3A—C23A—H23F	107.5
C21—C20—C19	108.84 (19)	H23D—C23A—H23F	106.8
C21—C20—H20A	109.0	H23E—C23A—H23F	110.4
C19—C20—H20A	107.4	C25—O7—H71	110.6
C21—C20—H20B	110.1	C26—O8—H81	107.2
C19—C20—H20B	111.8	O5—C24—O6	125.2 (2)
H20A—C20—H20B	109.7	O5—C24—C25	118.2 (2)
C20—C21—N2	110.31 (19)	O6—C24—C25	116.5 (2)
C20—C21—C7	116.0 (2)	O7—C25—C26	107.4 (2)
N2—C21—C7	104.70 (18)	O7—C25—C24	112.12 (19)
C20—C21—H21	110.8	C26—C25—C24	111.2 (2)
N2—C21—H21	105.7	O7—C25—H25	109.9
C7—C21—H21	108.8	C26—C25—H25	111.0
O2—C22—H22A	113.1	C24—C25—H25	105.2
O2—C22—H22B	110.9	O8—C26—C25	108.07 (19)
H22A—C22—H22B	105.2	O8—C26—H26A	111.5
O2—C22—H22C	103.9	C25—C26—H26A	108.8
H22A—C22—H22C	112.5	O8—C26—H26B	107.5
H22B—C22—H22C	111.4	C25—C26—H26B	112.1
O3—C23—H23A	110.0	H26A—C26—H26B	109.0
O3—C23—H23B	110.6	C25A—O7A—H72	107.9
H23A—C23—H23B	107.9	C26A—O8A—H82	109.6
O3—C23—H23C	111.6	O6A—C24A—O5A	125.2 (2)
H23A—C23—H23C	111.1	O6A—C24A—C25A	115.8 (2)
H23B—C23—H23C	105.6	O5A—C24A—C25A	119.0 (2)
C12A—O1A—C11A	115.11 (19)	O7A—C25A—C26A	108.2 (2)
C2A—O2A—C22A	116.27 (19)	O7A—C25A—C24A	112.52 (19)
C3A—O3A—C23A	115.35 (18)	C26A—C25A—C24A	109.6 (2)
C9A—N1A—C5A	126.1 (2)	O7A—C25A—H25A	106.3
C9A—N1A—C8A	118.91 (19)	C26A—C25A—H25A	108.1
C5A—N1A—C8A	108.79 (18)	C24A—C25A—H25A	112.0
C16A—N2A—C15A	112.36 (19)	O8A—C26A—C25A	107.92 (19)
C16A—N2A—C21A	107.33 (19)	O8A—C26A—H26C	109.1
C15A—N2A—C21A	113.27 (19)	C25A—C26A—H26C	110.1
C16A—N2A—H2A	108.8	O8A—C26A—H26D	110.0
C15A—N2A—H2A	106.1	C25A—C26A—H26D	110.3
C21A—N2A—H2A	108.9	H26C—C26A—H26D	109.4
C2A—C1A—C6A	119.0 (2)	H11W—O1W—H12W	105.2
C2A—C1A—H1A	122.6	H21W—O2W—H22W	112.6
C6A—C1A—H1A	118.4	H31W—O3W—H32W	105.1
O2A—C2A—C1A	125.1 (2)	H41W—O4W—H42W	103.6
O2A—C2A—C3A	114.7 (2)	H51W—O5W—H52W	111.5
C1A—C2A—C3A	120.2 (2)	H61W—O6W—H62W	94.5
O3A—C3A—C4A	123.6 (2)	H71W—O7W—H72W	109.4
O3A—C3A—C2A	115.5 (2)	H81W—O8W—H82W	96.1
C4A—C3A—C2A	120.9 (2)	H91W—O9W—H92W	101.5
C3A—C4A—C5A	117.4 (2)	H1W—O10W—H2W	105.4
C22—O2—C2—C1	9.7 (3)	O2A—C2A—C3A—O3A	−3.1 (3)
C22—O2—C2—C3	−171.7 (2)	C1A—C2A—C3A—O3A	175.7 (2)
C6—C1—C2—O2	−177.8 (2)	O2A—C2A—C3A—C4A	177.1 (2)
C6—C1—C2—C3	3.7 (3)	C1A—C2A—C3A—C4A	−4.1 (3)
C23—O3—C3—C4	−1.8 (3)	O3A—C3A—C4A—C5A	−178.7 (2)
C23—O3—C3—C2	178.1 (2)	C2A—C3A—C4A—C5A	1.0 (3)
O2—C2—C3—O3	−3.0 (3)	C3A—C4A—C5A—C6A	2.9 (3)
C1—C2—C3—O3	175.8 (2)	C3A—C4A—C5A—N1A	−174.5 (2)
O2—C2—C3—C4	177.0 (2)	C9A—N1A—C5A—C6A	−158.4 (2)
C1—C2—C3—C4	−4.3 (3)	C8A—N1A—C5A—C6A	−6.7 (3)
O3—C3—C4—C5	−178.9 (2)	C9A—N1A—C5A—C4A	19.3 (4)
C2—C3—C4—C5	1.2 (3)	C8A—N1A—C5A—C4A	171.0 (2)
C3—C4—C5—C6	2.5 (3)	C4A—C5A—C6A—C1A	−3.9 (3)
C3—C4—C5—N1	−174.5 (2)	N1A—C5A—C6A—C1A	174.0 (2)
C9—N1—C5—C6	−159.1 (2)	C4A—C5A—C6A—C7A	175.3 (2)
C8—N1—C5—C6	−4.6 (3)	N1A—C5A—C6A—C7A	−6.8 (3)
C9—N1—C5—C4	18.3 (4)	C2A—C1A—C6A—C5A	0.8 (3)
C8—N1—C5—C4	172.7 (2)	C2A—C1A—C6A—C7A	−178.3 (2)
C4—C5—C6—C1	−3.2 (4)	C5A—C6A—C7A—C21A	140.7 (2)
N1—C5—C6—C1	174.3 (2)	C1A—C6A—C7A—C21A	−40.2 (3)
C4—C5—C6—C7	174.2 (2)	C5A—C6A—C7A—C17A	−103.4 (2)
N1—C5—C6—C7	−8.3 (3)	C1A—C6A—C7A—C17A	75.7 (3)
C2—C1—C6—C5	0.0 (3)	C5A—C6A—C7A—C8A	16.5 (2)
C2—C1—C6—C7	−176.8 (2)	C1A—C6A—C7A—C8A	−164.4 (2)
C5—C6—C7—C21	140.9 (2)	C9A—N1A—C8A—C18A	47.3 (3)
C1—C6—C7—C21	−42.0 (3)	C5A—N1A—C8A—C18A	−106.7 (2)
C5—C6—C7—C17	−103.0 (2)	C9A—N1A—C8A—C7A	170.7 (2)
C1—C6—C7—C17	74.1 (3)	C5A—N1A—C8A—C7A	16.6 (2)
C5—C6—C7—C8	16.8 (2)	C6A—C7A—C8A—N1A	−19.3 (2)
C1—C6—C7—C8	−166.1 (2)	C21A—C7A—C8A—N1A	−143.2 (2)
C9—N1—C8—C18	47.0 (2)	C17A—C7A—C8A—N1A	102.0 (2)
C5—N1—C8—C18	−109.5 (2)	C6A—C7A—C8A—C18A	96.7 (2)
C9—N1—C8—C7	171.25 (19)	C21A—C7A—C8A—C18A	−27.2 (3)
C5—N1—C8—C7	14.8 (2)	C17A—C7A—C8A—C18A	−141.9 (2)
C6—C7—C8—N1	−18.4 (2)	C5A—N1A—C9A—O4A	−25.3 (4)
C21—C7—C8—N1	−142.44 (19)	C8A—N1A—C9A—O4A	−174.5 (2)
C17—C7—C8—N1	102.4 (2)	C5A—N1A—C9A—C10A	156.8 (2)
C6—C7—C8—C18	98.2 (2)	C8A—N1A—C9A—C10A	7.7 (3)
C21—C7—C8—C18	−25.9 (3)	O4A—C9A—C10A—C11A	141.1 (2)
C17—C7—C8—C18	−141.0 (2)	N1A—C9A—C10A—C11A	−41.0 (3)
C5—N1—C9—O4	−23.3 (4)	C12A—O1A—C11A—C18A	−64.4 (3)
C8—N1—C9—O4	−175.4 (2)	C12A—O1A—C11A—C10A	175.23 (19)
C5—N1—C9—C10	158.0 (2)	C9A—C10A—C11A—O1A	137.7 (2)
C8—N1—C9—C10	5.9 (3)	C9A—C10A—C11A—C18A	14.6 (3)
O4—C9—C10—C11	145.6 (2)	C11A—O1A—C12A—C13A	90.5 (2)
N1—C9—C10—C11	−35.7 (3)	O1A—C12A—C13A—C14A	−67.3 (3)
C12—O1—C11—C18	−67.1 (3)	C12A—C13A—C14A—C15A	179.2 (2)
C12—O1—C11—C10	172.45 (19)	C12A—C13A—C14A—C19A	−3.9 (4)
C9—C10—C11—O1	131.6 (2)	C13A—C14A—C15A—N2A	−131.6 (2)
C9—C10—C11—C18	8.3 (3)	C19A—C14A—C15A—N2A	51.3 (3)
C11—O1—C12—C13	89.8 (3)	C16A—N2A—C15A—C14A	78.2 (3)
O1—C12—C13—C14	−66.2 (3)	C21A—N2A—C15A—C14A	−43.6 (3)
C12—C13—C14—C15	178.3 (2)	C15A—N2A—C16A—C17A	−140.5 (2)
C12—C13—C14—C19	−2.0 (4)	C21A—N2A—C16A—C17A	−15.4 (2)
C13—C14—C15—N2	−127.1 (2)	N2A—C16A—C17A—C7A	35.9 (2)
C19—C14—C15—N2	53.2 (3)	C6A—C7A—C17A—C16A	−165.23 (19)
C16—N2—C15—C14	76.4 (2)	C21A—C7A—C17A—C16A	−42.3 (2)
C21—N2—C15—C14	−45.4 (3)	C8A—C7A—C17A—C16A	80.3 (2)
C15—N2—C16—C17	−140.8 (2)	N1A—C8A—C18A—C19A	156.93 (18)
C21—N2—C16—C17	−16.0 (2)	C7A—C8A—C18A—C19A	41.6 (3)
N2—C16—C17—C7	36.0 (2)	N1A—C8A—C18A—C11A	−70.9 (2)
C6—C7—C17—C16	−165.10 (19)	C7A—C8A—C18A—C11A	173.79 (19)
C21—C7—C17—C16	−42.0 (2)	O1A—C11A—C18A—C8A	−77.1 (2)
C8—C7—C17—C16	80.4 (2)	C10A—C11A—C18A—C8A	39.2 (3)
N1—C8—C18—C11	−72.0 (2)	O1A—C11A—C18A—C19A	51.9 (3)
C7—C8—C18—C11	172.32 (19)	C10A—C11A—C18A—C19A	168.3 (2)
N1—C8—C18—C19	156.84 (17)	C13A—C14A—C19A—C20A	−178.0 (2)
C7—C8—C18—C19	41.1 (3)	C15A—C14A—C19A—C20A	−1.0 (3)
O1—C11—C18—C8	−73.6 (2)	C13A—C14A—C19A—C18A	62.9 (3)
C10—C11—C18—C8	43.5 (2)	C15A—C14A—C19A—C18A	−120.0 (2)
O1—C11—C18—C19	54.0 (3)	C8A—C18A—C19A—C14A	59.2 (3)
C10—C11—C18—C19	171.11 (19)	C11A—C18A—C19A—C14A	−67.7 (3)
C13—C14—C19—C20	178.3 (2)	C8A—C18A—C19A—C20A	−60.9 (2)
C15—C14—C19—C20	−2.0 (3)	C11A—C18A—C19A—C20A	172.2 (2)
C13—C14—C19—C18	58.9 (3)	C14A—C19A—C20A—C21A	−56.1 (2)
C15—C14—C19—C18	−121.4 (2)	C18A—C19A—C20A—C21A	67.4 (2)
C8—C18—C19—C14	59.3 (3)	C19A—C20A—C21A—N2A	63.5 (2)
C11—C18—C19—C14	−66.1 (3)	C19A—C20A—C21A—C7A	−55.3 (3)
C8—C18—C19—C20	−61.3 (2)	C16A—N2A—C21A—C20A	−136.4 (2)
C11—C18—C19—C20	173.3 (2)	C15A—N2A—C21A—C20A	−11.8 (3)
C14—C19—C20—C21	−56.2 (2)	C16A—N2A—C21A—C7A	−11.3 (2)
C18—C19—C20—C21	68.1 (2)	C15A—N2A—C21A—C7A	113.3 (2)
C19—C20—C21—N2	63.5 (2)	C6A—C7A—C21A—C20A	−82.9 (2)
C19—C20—C21—C7	−55.3 (3)	C17A—C7A—C21A—C20A	154.6 (2)
C16—N2—C21—C20	−135.6 (2)	C8A—C7A—C21A—C20A	34.3 (3)
C15—N2—C21—C20	−11.1 (3)	C6A—C7A—C21A—N2A	155.24 (18)
C16—N2—C21—C7	−10.2 (2)	C17A—C7A—C21A—N2A	32.7 (2)
C15—N2—C21—C7	114.3 (2)	C8A—C7A—C21A—N2A	−87.6 (2)
C6—C7—C21—C20	−84.3 (2)	O5—C24—C25—O7	−8.3 (3)
C17—C7—C21—C20	153.5 (2)	O5—C24—C25—C26	111.9 (3)
C8—C7—C21—C20	33.1 (3)	O6—C24—C25—O7	171.4 (2)
C6—C7—C21—N2	153.86 (19)	O6—C24—C25—C26	−68.4 (3)
C17—C7—C21—N2	31.7 (2)	O7—C25—C26—O8	65.1 (2)
C8—C7—C21—N2	−88.7 (2)	C24—C25—C26—O8	−57.9 (3)
C22A—O2A—C2A—C1A	9.3 (3)	O5A—C24A—C25A—O7A	−11.6 (3)
C22A—O2A—C2A—C3A	−172.0 (2)	O5A—C24A—C25A—C26A	108.8 (2)
C6A—C1A—C2A—O2A	−178.2 (2)	O6A—C24A—C25A—O7A	168.4 (2)
C6A—C1A—C2A—C3A	3.1 (3)	O6A—C24A—C25A—C26A	−71.2 (3)
C23A—O3A—C3A—C4A	−4.7 (3)	O7A—C25A—C26A—O8A	67.1 (2)
C23A—O3A—C3A—C2A	175.5 (2)	C24A—C25A—C26A—O8A	−55.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	1.00	1.78	2.694 (3)	150.5
N2—H2···O7	1.00	2.38	3.075 (3)	126.1
N2A—H2A···O5A^i	0.89	1.88	2.738 (3)	162.7
O7—H71···O2W	0.86	1.85	2.711 (3)	176.9
O8—H81···O4A^ii	0.85	2.01	2.835 (3)	165.5
O7A—H72···O4W	0.93	1.89	2.766 (3)	155.9
O8A—H82···O4^iii	0.84	1.98	2.806 (2)	167.4
O1W—H11W···O6	0.93	1.77	2.698 (3)	175.6
O1W—H12W···O6A^iv	0.86	1.92	2.750 (3)	161.2
O2W—H21W···O6A^v	0.90	1.82	2.714 (3)	174.7
O2W—H22W···O4W	0.89	1.96	2.832 (3)	169.0
O3W—H31W···O2W	0.90	1.91	2.798 (3)	165.3
O3W—H32W···O10W	0.91	1.90	2.804 (3)	171.8
O4W—H41W···O5W	0.90	1.85	2.738 (3)	169.2
O4W—H42W···O9W	0.99	1.76	2.730 (3)	165.1
O5W—H51W···O8W	0.89	2.03	2.919 (3)	175.8
O5W—H52W···O5^vi	0.99	1.74	2.706 (3)	166.0
O6W—H61W···O5W	0.82	1.78	2.590 (5)	172.7
O6W—H62W···O7	0.94	1.84	2.781 (4)	175.9
O7W—H71W···O6^vi	0.87	1.87	2.736 (3)	176.0
O7W—H72W···O5A^ii	0.85	1.92	2.731 (3)	159.3
O8W—H81W···O7W	0.93	1.83	2.743 (3)	165.7
O8W—H82W···O3W	0.92	1.88	2.796 (3)	173.9
O9W—H91W···O1W^vii	0.96	1.73	2.683 (3)	176.6
O9W—H92W···O8W^vii	0.86	2.01	2.869 (3)	177.8
O10W—H1W···O7W	0.92	1.88	2.786 (3)	168.6
O10W—H2W···O7A	0.90	1.91	2.807 (3)	175.6

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