Strychninium N-phthaloyl-β-alaninate N-phthaloyl-β-alanine and brucinium N-phthaloyl-β-alaninate 5.67-hydrate

Comparison of the structures of strychninium N-phthaloyl-β-alaninate N-phthaloyl-β-alanine, C₂₁H₂₃N₂O₂⁺·C₁₁H₈NO₄⁻·C₁₁H₉NO₄, and brucinium N-phthaloyl-β-alaninate 5.67-hydrate, C₂₃H₂₇N₂O₄⁺·C₁₁H₈NO₄⁻·5.67H₂O, reveals that, unlike strychninium cations, brucinium cations display a tendency to produce stacking inter­actions with cocrystallizing guests.

S1. Comment

Strychnine and its dimethoxy derivative, brucine, are well known as resolving agents of racemic acids by fractional crystallization of diastereomeric salts (Jacques et al., 1991; Eliel & Wilen, 1994). Recently, we demonstrated the matching of donor/acceptor properties of both resolved compounds at the surface of self-assembed resolving agents during racemic resolution of N-benzoyl- and N-phthaloyl-α-alanine by strychnine and brucine (Bialonska & Ciunik, 2004). In addition, various D– or L-enantiomers of the α-alanine derivative were recognized by the surfaces of self-assembled strychnine and brucine. We describe here the molecular recognition of N-phthaloyl-β-alanine by both strychnine and brucine in the title compounds, (1) and (2) (Fig. 1).

In (1), the N-phthaloyl-β-alanine molecules and N-phthaloyl-β-alaninate anions are linked by O—H···O and C—H···O hydrogen bonds, and π–π interactions, to form three-dimensional networks with large channels extending along the [100] direction (Fig. 2). The channels are occupied by columns of strychninium cations linked by C—H···O and C—H···π hydrogen bonds. A similar strychnine self-assembly is present in crystals of (-)-strychninium (+)-neopentyl phthalate chloroform solvate (Yuan et al., 1994). The strychninium cations and N-phthaloyl-β-alaninate anions are linked by N—H⁺···O⁻ hydrogen bonds, formed between the protonated tertiary amine atom N2 of the cation and atom O3 of the deprotonated carboxyl group of the anion (Table 1). The structure is additionally stabilized by a number of weak C—H···O hydrogen bonds.

In (2), the protonated tertiary amine atom N2 of the brucinium cation is a hydrogen-bond donor, and atom O5, or atoms O5A and O6A, of the deprotonated, disordered, carboxyl group of the N-phthaloyl-β-alaninate anion are the acceptors (Table 2). The arene ring of the brucinium cation and the phthaloyl group of the β-alanine derivative participate in π–π interactions extending along the [010] direction. Channels are present between the neighboring columns, resulting from the π–π stacking of the arene rings of the brucinium cations and the phthaloyl groups of the N-phthaloyl-β-alaninate anions. The shortest and longest diameters of the channel are approximately 5.25 and 11.25 Å, respectively (Fig. 3). The channels are occupied by hydrogen-bonded water molecules.

Atoms O5 and O6 of the anion, carbonyl atom O4 of the brucinium cation, and the water molecules form a hydrogen-bonded tape of type 3T6(2) (Infantes & Motherwell, 2002) that extends along the [010] direction. The 3T6(2) tape is constructed from three T6(2) tapes, linked by their edges. ???The T6(2) tapes are formed by six-membered rings, with two neighboring six-membered rings sharing one side. In (2), the O1W, O3W, O4W and O5W water molecules, located in the central part of the channel, form one T6(2) tape, and two neighboring six-membered rings of water molecules share one side (the O1W···O3Wⁱ side; see Fig. 4). Two different six-membered rings, linked by one side, form the nother T6(2) tapes. One of these six-membered rings is formed by the O1W, O2W, O3W, O4W and O5W water molecules, as well as by the disordered carboxyl group of the N-phthaloyl-β-alaninate anion either via atom O5 or via both atom O5A and atom O6A. The third cyclic hexamer involves the O2W, O4W, O5W and O6W water molecules, carbonyl atom O4 of the brucinium cation, and either atom O6A or both atom O5 and atom O6 of the disordered carboxyl groups of the anions. [PLEASE CHECK CAREFULLY; text has been altered.]

The resulting 3T6(2) tape is linked to atom O7 of the phthaloyl group of the N-phthaloyl-β-alaninate anion. The three cyclic hexamers of the 3T6(2) tape exhibit a more or less deformed boat conformation. The average O···O distance in the 3T6(2) tape is 2.79 Å, similar to that found in ice I_h (2.759 Å at 143 K; Eisenberg & Kauzmann, 1969) and in liquid water (2.85 Å; Narten et al., 1982). The water-molecule tape remains stable at room temperature. Thermogravimetric analysis shows that the crystals of (2) lose ca 13.5% of their weight, in one step, near 373 K, which seems to correspond to complete loss of the water of crystallization.

As mentioned above, the columnar self-assembly of strychninium cations in (1) is similar to that in (-)-strychninium (+)-neopentyl phthalate chloroform solvate (Yuan et al., 1994). It is noteworthy that the columnar self-assembly of strychninium cations in (1) is also similar to the self-assembly of brucinium cations in brucinium N-phthaloyl-L-α-alaninate sesquihydrate (Bialonska & Ciunik, 2004). The similarity of the crystal structures of (2) and brucinium N-phthaloyl-L-α-alaninate sesquihydrate is revealed in the π–π stacking interactions.

In both of these crystals, the brucine arene rings, and the phthaloyl groups of the N-phthaloyl-β- or N-phthaloyl-L-α-alaninate anions, participate in π–π interactions. Various brucine and strychnine self-assemblies in the structures under investigation are due to the presence of two methoxy groups linked to the arene ring of brucine. Comparison of the crystal structures of the strychninium and brucinium salts with N-phthaloyl-D– and N-phthaloyl-L-α-alanine, as well as that with N-phthaloyl-β-alanine, shows that the presence of the two methoxy groups in brucine molecules is responsible for the tendency of brucine to exhibit stacking interactions with the phthaloyl group of the α- or β-alanine derivative. The π–π stacking, involving brucine arene rings and guest anions, is also observed in crystals of other brucinium salt (Kuwata et al., 1993). This tendency to form stacks has not been observed in strychnine, which has no methoxy groups.

In summary, comparison of the crystal structures of (1) and (2) has allowed us to discover one of the differences between these alkaloids in molecular recognition. Unlike strychninium cations, brucinium cations display a greater tendency to stacking interactions with cocrystallizing guests.

S2. Experimental

Crystals of (1) and (2) were obtained from ethanol solutions containing equimolar amount of the alkaloid (commercially available) and N-phthaloyl-β-alanine (Wróbel, 1983). The crystallizations were performed at room temperature by slow evaporation of the solvent.

S3. Refinement

In (2), the carboxyl group was found to be disordered over two positions, viz. sites C24, O5 and O6, and C24A, O5A and O6A, with occupancy factors of 0.67 and 1/3, respectively. The O6W water molecule also has partial occupancy (0.67). All the occupancy factors for the disordered carboxyl group of the N-phthaloyl-β-alaninate anion and the O6W water molecule were initially refined and their occupancy parameters were then fixed prior to the final refinements. In both compounds, all H atoms bonded to C and N atoms were treated as riding atoms, with C—H distances of 0.95–1.00 Å and N—H distances of 0.93 Å. The remained H atoms were located in difference maps and then refined with isotropic displacement parameters before being fixed prior to the final cycles of refinement. Friedel pairs were merged before the final refinement. The absolute configurations of (1) and (2) were chosen on the basis of the known absolute configurations of strychnine (Robertson & Beevers, 1951) and brucine (Toda et al., 1985), respectively.

Computing details

For both compounds, 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, 1990); 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. The molecular configuration and atom-numbering scheme in the crystal structure of (a) (1) and (b) (2). Non-H atoms are shown as 30% probability displacement ellipsoids.
	Fig. 2. The packing of (1). N-phthaloyl-β-alaninate anions and N-phthaloyl-β-alanine molecules (grey) form a three-dimensional network, with channels occupied by columns of strychnine cations extending along the [100] direction. For clarity, H atoms have been omitted.
	Fig. 3. The packing of (2), showing the columnar packing of the brucinium cations. Channels, extending along the [010] direction, between consecutive brucine columns are occupied by water molecules.
	Fig. 4. The 3T6(2) tape in the crystal of (2). [Symmetry codes: (i) −x + 1, y + 1/2, −z + 1, (ii) x + 1, y, z, (iii) x, y − 1, z, (iv) x + 1, y − 1, z.] (See also Table 1.)

(1) strychninium N-phthaloyl-β-alaninate N-phthaloyl-β-alanine

Crystal data

C21H23N2O2^+·C11H8NO4^−·C11H9NO4	F(000) = 1624
Mr = 772.79	Dx = 1.419 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1032 reflections
a = 7.788 (2) Å	θ = 3.4–28.6°
b = 16.596 (3) Å	µ = 0.10 mm^−1
c = 27.986 (3) Å	T = 100 K
V = 3617.2 (12) Å^3	Block, colourless
Z = 4	0.30 × 0.30 × 0.30 mm

Data collection

Kuma KM-4 CCD diffractometer	3791 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 27.5°, θmin = 3.4°
ω scans	h = −8→9
24819 measured reflections	k = −21→21
4630 independent reflections	l = −36→35

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)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0474P)^2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
4630 reflections	Δρmax = 0.19 e Å^−3
514 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Absolute structure: from known structure (Robertson & Beevers, 1951)
Primary atom site location: structure-invariant direct methods

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
O1	0.3783 (3)	0.32529 (12)	0.37423 (7)	0.0293 (5)
O2	0.3111 (3)	0.15709 (11)	0.50709 (7)	0.0289 (5)
N1	0.3642 (3)	0.29172 (13)	0.50803 (8)	0.0193 (5)
N2	0.3702 (3)	0.56469 (14)	0.47815 (9)	0.0252 (6)
H2A	0.3665	0.6151	0.4927	0.030*
C1	0.2907 (4)	0.25233 (19)	0.59324 (11)	0.0267 (7)
H1	0.3022	0.1959	0.5883	0.032*
C2	0.2442 (4)	0.2838 (2)	0.63744 (11)	0.0329 (8)
H2	0.2222	0.2481	0.6633	0.040*
C3	0.2293 (4)	0.3662 (2)	0.64466 (11)	0.0329 (8)
H3	0.1969	0.3859	0.6752	0.040*
C4	0.2608 (4)	0.42001 (18)	0.60799 (10)	0.0270 (7)
H4	0.2519	0.4764	0.6132	0.032*
C5	0.3057 (4)	0.39010 (17)	0.56341 (10)	0.0214 (6)
C6	0.3199 (3)	0.30743 (17)	0.55636 (10)	0.0213 (6)
C7	0.3595 (3)	0.43601 (16)	0.51923 (10)	0.0195 (6)
C8	0.3635 (4)	0.36828 (15)	0.48046 (10)	0.0188 (6)
H8	0.4717	0.3726	0.4614	0.023*
C9	0.3309 (4)	0.22053 (17)	0.48519 (11)	0.0229 (6)
C10	0.3233 (4)	0.22344 (17)	0.43127 (10)	0.0265 (7)
H10A	0.2529	0.1774	0.4203	0.032*
H10B	0.4411	0.2151	0.4189	0.032*
C11	0.2511 (4)	0.30048 (17)	0.40814 (10)	0.0240 (6)
H11	0.1432	0.2866	0.3906	0.029*
C12	0.3248 (5)	0.3893 (2)	0.34349 (11)	0.0362 (8)
H12A	0.2006	0.3837	0.3367	0.043*
H12B	0.3873	0.3854	0.3128	0.043*
C13	0.3577 (4)	0.47018 (19)	0.36539 (11)	0.0327 (8)
H13	0.4398	0.5045	0.3507	0.039*
C14	0.2776 (4)	0.49635 (19)	0.40438 (11)	0.0288 (7)
C15	0.3210 (4)	0.57573 (18)	0.42658 (11)	0.0331 (8)
H15A	0.2208	0.6122	0.4244	0.040*
H15B	0.4176	0.6008	0.4090	0.040*
C16	0.5502 (4)	0.53222 (17)	0.48403 (11)	0.0245 (7)
H16A	0.6326	0.5763	0.4906	0.029*
H16B	0.5875	0.5029	0.4550	0.029*
C17	0.5368 (4)	0.47578 (17)	0.52624 (10)	0.0224 (6)
H17A	0.5419	0.5058	0.5568	0.027*
H17B	0.6297	0.4351	0.5257	0.027*
C18	0.2089 (4)	0.36334 (16)	0.44656 (10)	0.0215 (6)
H18	0.1137	0.3394	0.4659	0.026*
C19	0.1444 (4)	0.44609 (17)	0.43085 (10)	0.0254 (7)
H19	0.0418	0.4388	0.4098	0.030*
C20	0.0889 (4)	0.49094 (17)	0.47634 (11)	0.0266 (7)
H20A	0.0296	0.5417	0.4678	0.032*
H20B	0.0088	0.4572	0.4951	0.032*
C21	0.2481 (4)	0.50923 (17)	0.50560 (10)	0.0239 (6)
H21	0.2121	0.5372	0.5356	0.029*
O3	0.3892 (3)	0.70460 (12)	0.52130 (8)	0.0350 (5)
O4	0.3578 (3)	0.64022 (13)	0.59074 (8)	0.0391 (6)
O5	0.5829 (3)	0.81687 (13)	0.72577 (8)	0.0403 (6)
O6	0.2279 (3)	0.94199 (14)	0.61885 (8)	0.0411 (6)
N3	0.4002 (3)	0.86166 (14)	0.66610 (9)	0.0291 (6)
C22	0.3893 (4)	0.70134 (18)	0.56728 (12)	0.0293 (7)
C23	0.4366 (4)	0.77910 (18)	0.59289 (11)	0.0333 (8)
H23A	0.5632	0.7830	0.5952	0.040*
H23B	0.3955	0.8255	0.5738	0.040*
C24	0.3606 (5)	0.78410 (18)	0.64259 (11)	0.0331 (8)
H24A	0.2344	0.7775	0.6405	0.040*
H24B	0.4064	0.7394	0.6623	0.040*
C25	0.5038 (4)	0.8704 (2)	0.70667 (11)	0.0317 (7)
C26	0.4900 (4)	0.95727 (18)	0.72022 (11)	0.0286 (7)
C27	0.5608 (4)	0.9993 (2)	0.75846 (11)	0.0355 (8)
H27	0.6354	0.9737	0.7806	0.043*
C28	0.5174 (4)	1.0810 (2)	0.76288 (12)	0.0379 (8)
H28	0.5641	1.1114	0.7885	0.046*
C29	0.4090 (5)	1.1179 (2)	0.73103 (12)	0.0379 (8)
H29	0.3815	1.1732	0.7351	0.045*
C30	0.3377 (4)	1.07511 (19)	0.69232 (11)	0.0325 (7)
H30	0.2623	1.1003	0.6702	0.039*
C31	0.3823 (4)	0.99526 (18)	0.68801 (10)	0.0275 (7)
C32	0.3234 (4)	0.93388 (18)	0.65275 (11)	0.0292 (7)
O3A	0.3794 (4)	0.76255 (13)	0.40666 (9)	0.0478 (7)
O4A	0.4184 (3)	0.83651 (13)	0.47276 (8)	0.0406 (6)
H4A	0.4078	0.7917	0.4864	0.061*
O5A	0.1516 (3)	1.06452 (13)	0.36571 (8)	0.0374 (6)
O6A	0.5389 (3)	0.92779 (13)	0.27318 (9)	0.0407 (6)
N3A	0.3374 (3)	0.97864 (14)	0.32570 (9)	0.0288 (6)
C22A	0.4027 (4)	0.82693 (19)	0.42625 (12)	0.0336 (8)
C23A	0.4205 (4)	0.90450 (18)	0.39852 (11)	0.0332 (8)
H23C	0.5418	0.9113	0.3887	0.040*
H23D	0.3897	0.9503	0.4195	0.040*
C24A	0.3066 (4)	0.90611 (18)	0.35423 (11)	0.0323 (8)
H24C	0.3300	0.8578	0.3345	0.039*
H24D	0.1846	0.9044	0.3641	0.039*
C25A	0.2548 (4)	1.05245 (19)	0.33398 (11)	0.0298 (7)
C26A	0.3204 (4)	1.10923 (18)	0.29698 (10)	0.0282 (7)
C27A	0.2864 (4)	1.18908 (19)	0.28906 (11)	0.0337 (8)
H27A	0.2048	1.2173	0.3080	0.040*
C28A	0.3753 (5)	1.2276 (2)	0.25239 (11)	0.0379 (8)
H28A	0.3539	1.2830	0.2462	0.046*
C29A	0.4937 (5)	1.1869 (2)	0.22495 (12)	0.0390 (8)
H29A	0.5530	1.2148	0.2004	0.047*
C30A	0.5283 (4)	1.1053 (2)	0.23252 (11)	0.0344 (8)
H30A	0.6101	1.0771	0.2137	0.041*
C31A	0.4381 (4)	1.06739 (18)	0.26864 (11)	0.0269 (7)
C32A	0.4500 (4)	0.98314 (19)	0.28745 (11)	0.0304 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0279 (12)	0.0368 (12)	0.0233 (11)	−0.0023 (10)	0.0022 (9)	−0.0005 (9)
O2	0.0277 (12)	0.0190 (11)	0.0400 (13)	−0.0002 (9)	−0.0083 (10)	0.0023 (10)
N1	0.0197 (12)	0.0184 (12)	0.0197 (12)	−0.0005 (10)	0.0008 (10)	−0.0016 (10)
N2	0.0257 (13)	0.0177 (12)	0.0322 (14)	0.0011 (11)	−0.0029 (11)	−0.0012 (11)
C1	0.0208 (16)	0.0277 (16)	0.0316 (17)	−0.0023 (13)	−0.0044 (13)	0.0057 (14)
C2	0.0234 (17)	0.049 (2)	0.0259 (17)	−0.0006 (15)	0.0017 (13)	0.0084 (15)
C3	0.0263 (17)	0.047 (2)	0.0259 (17)	0.0008 (15)	0.0005 (14)	−0.0042 (15)
C4	0.0255 (16)	0.0285 (17)	0.0271 (16)	0.0032 (14)	−0.0007 (13)	−0.0052 (13)
C5	0.0171 (14)	0.0233 (15)	0.0238 (15)	0.0026 (12)	−0.0002 (12)	−0.0005 (12)
C6	0.0120 (13)	0.0275 (16)	0.0245 (15)	0.0001 (12)	−0.0008 (11)	−0.0005 (13)
C7	0.0157 (14)	0.0217 (14)	0.0211 (14)	0.0014 (12)	0.0009 (11)	−0.0023 (12)
C8	0.0185 (15)	0.0142 (13)	0.0237 (15)	−0.0022 (11)	0.0006 (12)	0.0025 (11)
C9	0.0113 (14)	0.0219 (15)	0.0356 (17)	0.0007 (12)	−0.0010 (12)	−0.0013 (13)
C10	0.0256 (16)	0.0240 (16)	0.0300 (17)	−0.0025 (13)	0.0022 (13)	−0.0062 (13)
C11	0.0195 (14)	0.0300 (16)	0.0225 (15)	−0.0054 (13)	−0.0011 (12)	−0.0038 (12)
C12	0.040 (2)	0.045 (2)	0.0238 (17)	−0.0053 (17)	−0.0006 (15)	0.0038 (15)
C13	0.0396 (19)	0.0365 (18)	0.0219 (16)	−0.0064 (15)	−0.0080 (15)	0.0099 (14)
C14	0.0279 (17)	0.0290 (16)	0.0294 (17)	−0.0002 (14)	−0.0107 (14)	0.0067 (14)
C15	0.0343 (18)	0.0283 (17)	0.0367 (18)	−0.0010 (15)	−0.0067 (15)	0.0098 (14)
C16	0.0194 (15)	0.0234 (15)	0.0308 (17)	−0.0011 (12)	−0.0030 (13)	−0.0002 (13)
C17	0.0229 (15)	0.0191 (14)	0.0251 (16)	−0.0025 (12)	−0.0007 (12)	−0.0036 (12)
C18	0.0171 (14)	0.0227 (15)	0.0248 (15)	−0.0036 (12)	−0.0040 (12)	0.0010 (12)
C19	0.0208 (15)	0.0274 (16)	0.0280 (16)	−0.0002 (13)	−0.0056 (13)	0.0024 (13)
C20	0.0207 (15)	0.0224 (15)	0.0367 (17)	0.0042 (13)	−0.0040 (13)	0.0001 (14)
C21	0.0223 (15)	0.0189 (14)	0.0305 (16)	0.0016 (12)	0.0008 (13)	0.0007 (12)
O3	0.0494 (15)	0.0209 (11)	0.0346 (13)	−0.0016 (10)	0.0034 (11)	−0.0010 (10)
O4	0.0521 (15)	0.0233 (12)	0.0418 (14)	−0.0072 (11)	0.0066 (12)	−0.0008 (10)
O5	0.0401 (14)	0.0355 (13)	0.0453 (14)	0.0070 (11)	−0.0102 (11)	0.0063 (11)
O6	0.0483 (15)	0.0411 (14)	0.0338 (13)	0.0090 (12)	−0.0107 (11)	−0.0028 (11)
N3	0.0332 (15)	0.0252 (13)	0.0287 (14)	−0.0007 (12)	−0.0041 (12)	0.0006 (11)
C22	0.0262 (17)	0.0223 (16)	0.040 (2)	−0.0009 (14)	0.0047 (15)	0.0003 (14)
C23	0.0344 (19)	0.0231 (17)	0.042 (2)	−0.0045 (14)	0.0080 (16)	−0.0025 (15)
C24	0.042 (2)	0.0250 (16)	0.0324 (18)	−0.0037 (15)	0.0007 (15)	−0.0005 (14)
C25	0.0266 (17)	0.0365 (19)	0.0321 (18)	−0.0014 (15)	0.0005 (14)	0.0024 (15)
C26	0.0256 (16)	0.0310 (17)	0.0292 (17)	−0.0032 (14)	0.0045 (13)	−0.0019 (14)
C27	0.0306 (19)	0.045 (2)	0.0307 (18)	−0.0045 (15)	0.0003 (15)	−0.0040 (16)
C28	0.0334 (19)	0.047 (2)	0.0337 (19)	−0.0083 (16)	0.0074 (16)	−0.0125 (17)
C29	0.042 (2)	0.0277 (17)	0.044 (2)	−0.0086 (16)	0.0165 (17)	−0.0042 (16)
C30	0.0351 (18)	0.0312 (17)	0.0312 (17)	−0.0001 (15)	0.0090 (14)	0.0015 (14)
C31	0.0280 (17)	0.0280 (16)	0.0266 (16)	−0.0027 (14)	0.0049 (13)	0.0011 (14)
C32	0.0303 (17)	0.0322 (18)	0.0252 (16)	0.0026 (15)	0.0033 (14)	0.0029 (14)
O3A	0.0676 (18)	0.0251 (13)	0.0507 (15)	−0.0073 (13)	−0.0089 (14)	−0.0013 (11)
O4A	0.0607 (16)	0.0231 (12)	0.0379 (14)	−0.0033 (11)	0.0003 (12)	0.0033 (10)
O5A	0.0362 (13)	0.0411 (14)	0.0348 (13)	0.0009 (11)	0.0070 (11)	−0.0049 (11)
O6A	0.0384 (14)	0.0376 (13)	0.0462 (14)	0.0072 (11)	0.0045 (11)	−0.0091 (11)
N3A	0.0303 (15)	0.0278 (14)	0.0283 (14)	−0.0011 (11)	0.0001 (11)	−0.0004 (11)
C22A	0.0319 (19)	0.0249 (17)	0.044 (2)	−0.0026 (15)	−0.0004 (16)	0.0018 (16)
C23A	0.0330 (18)	0.0263 (17)	0.0404 (19)	−0.0038 (15)	−0.0054 (15)	0.0015 (15)
C24A	0.0377 (19)	0.0249 (17)	0.0344 (18)	−0.0062 (15)	0.0008 (15)	−0.0004 (14)
C25A	0.0290 (17)	0.0328 (17)	0.0275 (17)	−0.0037 (15)	−0.0037 (14)	−0.0074 (14)
C26A	0.0283 (17)	0.0304 (17)	0.0260 (16)	−0.0049 (14)	−0.0018 (14)	−0.0049 (14)
C27A	0.0375 (19)	0.0317 (18)	0.0318 (18)	0.0028 (15)	−0.0073 (15)	−0.0035 (14)
C28A	0.048 (2)	0.0299 (18)	0.0364 (19)	−0.0077 (16)	−0.0107 (17)	0.0023 (15)
C29A	0.038 (2)	0.046 (2)	0.0329 (19)	−0.0124 (17)	−0.0054 (16)	0.0047 (17)
C30A	0.0301 (18)	0.047 (2)	0.0263 (17)	−0.0058 (16)	−0.0035 (14)	−0.0034 (16)
C31A	0.0263 (16)	0.0312 (16)	0.0232 (15)	−0.0035 (13)	−0.0008 (13)	−0.0052 (13)
C32A	0.0309 (18)	0.0331 (18)	0.0273 (17)	−0.0022 (15)	−0.0031 (14)	−0.0056 (14)

Geometric parameters (Å, º)

O1—C12	1.429 (4)	C21—H21	1.0000
O1—C11	1.432 (3)	O3—C22	1.288 (4)
O2—C9	1.228 (3)	O4—C22	1.233 (4)
N1—C9	1.368 (3)	O5—C25	1.206 (4)
N1—C6	1.420 (3)	O6—C32	1.213 (4)
N1—C8	1.487 (3)	N3—C32	1.391 (4)
N2—C15	1.504 (4)	N3—C25	1.401 (4)
N2—C16	1.511 (4)	N3—C24	1.478 (4)
N2—C21	1.530 (4)	C22—C23	1.522 (4)
N2—H2A	0.9300	C23—C24	1.514 (4)
C1—C2	1.391 (4)	C23—H23A	0.9900
C1—C6	1.397 (4)	C23—H23B	0.9900
C1—H1	0.9500	C24—H24A	0.9900
C2—C3	1.388 (4)	C24—H24B	0.9900
C2—H2	0.9500	C25—C26	1.495 (4)
C3—C4	1.382 (4)	C26—C31	1.383 (4)
C3—H3	0.9500	C26—C27	1.391 (4)
C4—C5	1.388 (4)	C27—C28	1.403 (5)
C4—H4	0.9500	C27—H27	0.9500
C5—C6	1.390 (4)	C28—C29	1.372 (5)
C5—C7	1.512 (4)	C28—H28	0.9500
C7—C21	1.541 (4)	C29—C30	1.409 (5)
C7—C17	1.543 (4)	C29—H29	0.9500
C7—C8	1.563 (4)	C30—C31	1.375 (4)
C8—C18	1.535 (4)	C30—H30	0.9500
C8—H8	1.0000	C31—C32	1.490 (4)
C9—C10	1.511 (4)	O3A—C22A	1.214 (4)
C10—C11	1.540 (4)	O4A—C22A	1.317 (4)
C10—H10A	0.9900	O4A—H4A	0.8400
C10—H10B	0.9900	O5A—C25A	1.214 (4)
C11—C18	1.534 (4)	O6A—C32A	1.218 (4)
C11—H11	1.0000	N3A—C32A	1.386 (4)
C12—C13	1.498 (4)	N3A—C25A	1.403 (4)
C12—H12A	0.9900	N3A—C24A	1.464 (4)
C12—H12B	0.9900	C22A—C23A	1.510 (4)
C13—C14	1.330 (4)	C23A—C24A	1.524 (4)
C13—H13	0.9500	C23A—H23C	0.9900
C14—C15	1.495 (4)	C23A—H23D	0.9900
C14—C19	1.523 (4)	C24A—H24C	0.9900
C15—H15A	0.9900	C24A—H24D	0.9900
C15—H15B	0.9900	C25A—C26A	1.491 (4)
C16—C17	1.511 (4)	C26A—C27A	1.370 (4)
C16—H16A	0.9900	C26A—C31A	1.397 (4)
C16—H16B	0.9900	C27A—C28A	1.394 (4)
C17—H17A	0.9900	C27A—H27A	0.9500
C17—H17B	0.9900	C28A—C29A	1.377 (5)
C18—C19	1.527 (4)	C28A—H28A	0.9500
C18—H18	1.0000	C29A—C30A	1.397 (5)
C19—C20	1.537 (4)	C29A—H29A	0.9500
C19—H19	1.0000	C30A—C31A	1.382 (4)
C20—C21	1.516 (4)	C30A—H30A	0.9500
C20—H20A	0.9900	C31A—C32A	1.497 (4)
C20—H20B	0.9900
C12—O1—C11	114.3 (2)	C21—C20—C19	108.3 (2)
C9—N1—C6	123.9 (2)	C21—C20—H20A	110.0
C9—N1—C8	119.7 (2)	C19—C20—H20A	110.0
C6—N1—C8	109.7 (2)	C21—C20—H20B	110.0
C15—N2—C16	112.6 (2)	C19—C20—H20B	110.0
C15—N2—C21	113.4 (2)	H20A—C20—H20B	108.4
C16—N2—C21	107.9 (2)	C20—C21—N2	110.9 (2)
C15—N2—H2A	107.6	C20—C21—C7	115.8 (2)
C16—N2—H2A	107.6	N2—C21—C7	104.4 (2)
C21—N2—H2A	107.6	C20—C21—H21	108.5
C2—C1—C6	117.0 (3)	N2—C21—H21	108.5
C2—C1—H1	121.5	C7—C21—H21	108.5
C6—C1—H1	121.5	C32—N3—C25	112.1 (2)
C3—C2—C1	121.4 (3)	C32—N3—C24	122.8 (3)
C3—C2—H2	119.3	C25—N3—C24	124.8 (3)
C1—C2—H2	119.3	O4—C22—O3	124.5 (3)
C4—C3—C2	120.9 (3)	O4—C22—C23	119.7 (3)
C4—C3—H3	119.5	O3—C22—C23	115.8 (3)
C2—C3—H3	119.5	C24—C23—C22	112.6 (2)
C3—C4—C5	118.8 (3)	C24—C23—H23A	109.1
C3—C4—H4	120.6	C22—C23—H23A	109.1
C5—C4—H4	120.6	C24—C23—H23B	109.1
C4—C5—C6	120.0 (3)	C22—C23—H23B	109.1
C4—C5—C7	128.7 (3)	H23A—C23—H23B	107.8
C6—C5—C7	111.1 (2)	N3—C24—C23	112.0 (2)
C5—C6—C1	121.9 (3)	N3—C24—H24A	109.2
C5—C6—N1	109.6 (2)	C23—C24—H24A	109.2
C1—C6—N1	128.5 (3)	N3—C24—H24B	109.2
C5—C7—C21	116.4 (2)	C23—C24—H24B	109.2
C5—C7—C17	111.1 (2)	H24A—C24—H24B	107.9
C21—C7—C17	101.4 (2)	O5—C25—N3	125.3 (3)
C5—C7—C8	102.2 (2)	O5—C25—C26	129.4 (3)
C21—C7—C8	114.0 (2)	N3—C25—C26	105.3 (3)
C17—C7—C8	112.2 (2)	C31—C26—C27	120.9 (3)
N1—C8—C18	106.1 (2)	C31—C26—C25	108.5 (3)
N1—C8—C7	104.8 (2)	C27—C26—C25	130.5 (3)
C18—C8—C7	116.9 (2)	C26—C27—C28	117.1 (3)
N1—C8—H8	109.6	C26—C27—H27	121.4
C18—C8—H8	109.6	C28—C27—H27	121.4
C7—C8—H8	109.6	C29—C28—C27	121.5 (3)
O2—C9—N1	122.1 (3)	C29—C28—H28	119.2
O2—C9—C10	121.4 (3)	C27—C28—H28	119.2
N1—C9—C10	116.5 (2)	C28—C29—C30	121.1 (3)
C9—C10—C11	117.4 (2)	C28—C29—H29	119.5
C9—C10—H10A	107.9	C30—C29—H29	119.5
C11—C10—H10A	107.9	C31—C30—C29	117.0 (3)
C9—C10—H10B	107.9	C31—C30—H30	121.5
C11—C10—H10B	107.9	C29—C30—H30	121.5
H10A—C10—H10B	107.2	C30—C31—C26	122.3 (3)
O1—C11—C18	114.7 (2)	C30—C31—C32	129.7 (3)
O1—C11—C10	105.3 (2)	C26—C31—C32	107.8 (3)
C18—C11—C10	110.4 (2)	O6—C32—N3	124.7 (3)
O1—C11—H11	108.8	O6—C32—C31	129.1 (3)
C18—C11—H11	108.8	N3—C32—C31	106.2 (3)
C10—C11—H11	108.8	C22A—O4A—H4A	109.5
O1—C12—C13	111.7 (2)	C32A—N3A—C25A	111.8 (2)
O1—C12—H12A	109.3	C32A—N3A—C24A	124.7 (3)
C13—C12—H12A	109.3	C25A—N3A—C24A	123.6 (3)
O1—C12—H12B	109.3	O3A—C22A—O4A	124.5 (3)
C13—C12—H12B	109.3	O3A—C22A—C23A	122.1 (3)
H12A—C12—H12B	107.9	O4A—C22A—C23A	113.4 (3)
C14—C13—C12	123.2 (3)	C22A—C23A—C24A	112.3 (3)
C14—C13—H13	118.4	C22A—C23A—H23C	109.1
C12—C13—H13	118.4	C24A—C23A—H23C	109.1
C13—C14—C15	121.5 (3)	C22A—C23A—H23D	109.1
C13—C14—C19	122.7 (3)	C24A—C23A—H23D	109.1
C15—C14—C19	115.7 (3)	H23C—C23A—H23D	107.9
C14—C15—N2	110.4 (2)	N3A—C24A—C23A	111.3 (2)
C14—C15—H15A	109.6	N3A—C24A—H24C	109.4
N2—C15—H15A	109.6	C23A—C24A—H24C	109.4
C14—C15—H15B	109.6	N3A—C24A—H24D	109.4
N2—C15—H15B	109.6	C23A—C24A—H24D	109.4
H15A—C15—H15B	108.1	H24C—C24A—H24D	108.0
N2—C16—C17	104.0 (2)	O5A—C25A—N3A	124.6 (3)
N2—C16—H16A	111.0	O5A—C25A—C26A	129.1 (3)
C17—C16—H16A	111.0	N3A—C25A—C26A	106.3 (3)
N2—C16—H16B	111.0	C27A—C26A—C31A	121.1 (3)
C17—C16—H16B	111.0	C27A—C26A—C25A	131.1 (3)
H16A—C16—H16B	109.0	C31A—C26A—C25A	107.8 (3)
C16—C17—C7	103.2 (2)	C26A—C27A—C28A	117.8 (3)
C16—C17—H17A	111.1	C26A—C27A—H27A	121.1
C7—C17—H17A	111.1	C28A—C27A—H27A	121.1
C16—C17—H17B	111.1	C29A—C28A—C27A	121.2 (3)
C7—C17—H17B	111.1	C29A—C28A—H28A	119.4
H17A—C17—H17B	109.1	C27A—C28A—H28A	119.4
C19—C18—C11	118.7 (2)	C28A—C29A—C30A	121.4 (3)
C19—C18—C8	112.8 (2)	C28A—C29A—H29A	119.3
C11—C18—C8	107.6 (2)	C30A—C29A—H29A	119.3
C19—C18—H18	105.6	C31A—C30A—C29A	117.0 (3)
C11—C18—H18	105.6	C31A—C30A—H30A	121.5
C8—C18—H18	105.6	C29A—C30A—H30A	121.5
C14—C19—C18	114.1 (2)	C30A—C31A—C26A	121.5 (3)
C14—C19—C20	109.2 (2)	C30A—C31A—C32A	130.6 (3)
C18—C19—C20	106.8 (2)	C26A—C31A—C32A	107.8 (3)
C14—C19—H19	108.9	O6A—C32A—N3A	124.9 (3)
C18—C19—H19	108.9	O6A—C32A—C31A	128.6 (3)
C20—C19—H19	108.9	N3A—C32A—C31A	106.4 (3)
C6—C1—C2—C3	−0.7 (5)	C15—N2—C21—C20	−10.3 (3)
C1—C2—C3—C4	−0.2 (5)	C16—N2—C21—C20	−135.7 (2)
C2—C3—C4—C5	0.9 (5)	C15—N2—C21—C7	115.2 (2)
C3—C4—C5—C6	−0.6 (4)	C16—N2—C21—C7	−10.2 (3)
C3—C4—C5—C7	−174.7 (3)	C5—C7—C21—C20	−84.3 (3)
C4—C5—C6—C1	−0.3 (4)	C17—C7—C21—C20	155.0 (2)
C7—C5—C6—C1	174.8 (3)	C8—C7—C21—C20	34.2 (3)
C4—C5—C6—N1	179.1 (3)	C5—C7—C21—N2	153.3 (2)
C7—C5—C6—N1	−5.9 (3)	C17—C7—C21—N2	32.7 (3)
C2—C1—C6—C5	0.9 (4)	C8—C7—C21—N2	−88.1 (3)
C2—C1—C6—N1	−178.3 (3)	O4—C22—C23—C24	−27.3 (4)
C9—N1—C6—C5	−156.3 (3)	O3—C22—C23—C24	154.1 (3)
C8—N1—C6—C5	−5.5 (3)	C32—N3—C24—C23	72.5 (4)
C9—N1—C6—C1	23.0 (4)	C25—N3—C24—C23	−114.1 (3)
C8—N1—C6—C1	173.8 (3)	C22—C23—C24—N3	−177.1 (3)
C4—C5—C7—C21	−46.8 (4)	C32—N3—C25—O5	179.1 (3)
C6—C5—C7—C21	138.7 (3)	C24—N3—C25—O5	5.1 (5)
C4—C5—C7—C17	68.5 (4)	C32—N3—C25—C26	0.2 (3)
C6—C5—C7—C17	−106.0 (3)	C24—N3—C25—C26	−173.8 (3)
C4—C5—C7—C8	−171.6 (3)	O5—C25—C26—C31	−179.0 (3)
C6—C5—C7—C8	13.9 (3)	N3—C25—C26—C31	−0.1 (3)
C9—N1—C8—C18	41.9 (3)	O5—C25—C26—C27	−1.3 (6)
C6—N1—C8—C18	−110.3 (2)	N3—C25—C26—C27	177.6 (3)
C9—N1—C8—C7	166.2 (2)	C31—C26—C27—C28	0.4 (5)
C6—N1—C8—C7	13.9 (3)	C25—C26—C27—C28	−177.1 (3)
C5—C7—C8—N1	−16.1 (3)	C26—C27—C28—C29	0.3 (5)
C21—C7—C8—N1	−142.5 (2)	C27—C28—C29—C30	−0.4 (5)
C17—C7—C8—N1	102.9 (3)	C28—C29—C30—C31	−0.2 (5)
C5—C7—C8—C18	101.0 (3)	C29—C30—C31—C26	0.9 (5)
C21—C7—C8—C18	−25.4 (3)	C29—C30—C31—C32	177.1 (3)
C17—C7—C8—C18	−140.0 (2)	C27—C26—C31—C30	−1.0 (5)
C6—N1—C9—O2	−23.6 (4)	C25—C26—C31—C30	177.0 (3)
C8—N1—C9—O2	−171.7 (3)	C27—C26—C31—C32	−177.9 (3)
C6—N1—C9—C10	157.6 (3)	C25—C26—C31—C32	0.1 (3)
C8—N1—C9—C10	9.5 (4)	C25—N3—C32—O6	−179.9 (3)
O2—C9—C10—C11	147.1 (3)	C24—N3—C32—O6	−5.8 (5)
N1—C9—C10—C11	−34.2 (4)	C25—N3—C32—C31	−0.1 (3)
C12—O1—C11—C18	−67.5 (3)	C24—N3—C32—C31	174.0 (3)
C12—O1—C11—C10	171.0 (2)	C30—C31—C32—O6	3.2 (6)
C9—C10—C11—O1	127.6 (3)	C26—C31—C32—O6	179.8 (3)
C9—C10—C11—C18	3.3 (4)	C30—C31—C32—N3	−176.5 (3)
C11—O1—C12—C13	86.8 (3)	C26—C31—C32—N3	0.0 (3)
O1—C12—C13—C14	−65.9 (4)	O3A—C22A—C23A—C24A	35.2 (5)
C12—C13—C14—C15	176.7 (3)	O4A—C22A—C23A—C24A	−146.1 (3)
C12—C13—C14—C19	0.3 (5)	C32A—N3A—C24A—C23A	94.1 (3)
C13—C14—C15—N2	−123.9 (3)	C25A—N3A—C24A—C23A	−86.1 (4)
C19—C14—C15—N2	52.7 (4)	C22A—C23A—C24A—N3A	−174.9 (3)
C16—N2—C15—C14	77.1 (3)	C32A—N3A—C25A—O5A	−179.2 (3)
C21—N2—C15—C14	−45.7 (3)	C24A—N3A—C25A—O5A	1.0 (5)
C15—N2—C16—C17	−142.9 (2)	C32A—N3A—C25A—C26A	0.6 (3)
C21—N2—C16—C17	−17.1 (3)	C24A—N3A—C25A—C26A	−179.3 (3)
N2—C16—C17—C7	37.8 (3)	O5A—C25A—C26A—C27A	1.4 (6)
C5—C7—C17—C16	−168.1 (2)	N3A—C25A—C26A—C27A	−178.4 (3)
C21—C7—C17—C16	−43.8 (3)	O5A—C25A—C26A—C31A	179.6 (3)
C8—C7—C17—C16	78.2 (3)	N3A—C25A—C26A—C31A	−0.1 (3)
O1—C11—C18—C19	58.0 (3)	C31A—C26A—C27A—C28A	−1.2 (5)
C10—C11—C18—C19	176.8 (2)	C25A—C26A—C27A—C28A	176.9 (3)
O1—C11—C18—C8	−71.6 (3)	C26A—C27A—C28A—C29A	0.0 (5)
C10—C11—C18—C8	47.2 (3)	C27A—C28A—C29A—C30A	0.5 (5)
N1—C8—C18—C19	156.4 (2)	C28A—C29A—C30A—C31A	0.2 (5)
C7—C8—C18—C19	40.1 (3)	C29A—C30A—C31A—C26A	−1.4 (4)
N1—C8—C18—C11	−70.7 (3)	C29A—C30A—C31A—C32A	−176.6 (3)
C7—C8—C18—C11	172.9 (2)	C27A—C26A—C31A—C30A	1.9 (5)
C13—C14—C19—C18	55.8 (4)	C25A—C26A—C31A—C30A	−176.5 (3)
C15—C14—C19—C18	−120.8 (3)	C27A—C26A—C31A—C32A	178.1 (3)
C13—C14—C19—C20	175.2 (3)	C25A—C26A—C31A—C32A	−0.4 (3)
C15—C14—C19—C20	−1.3 (3)	C25A—N3A—C32A—O6A	179.1 (3)
C11—C18—C19—C14	−67.2 (3)	C24A—N3A—C32A—O6A	−1.0 (5)
C8—C18—C19—C14	60.0 (3)	C25A—N3A—C32A—C31A	−0.8 (3)
C11—C18—C19—C20	172.0 (2)	C24A—N3A—C32A—C31A	179.1 (3)
C8—C18—C19—C20	−60.8 (3)	C30A—C31A—C32A—O6A	−3.5 (5)
C14—C19—C20—C21	−55.5 (3)	C26A—C31A—C32A—O6A	−179.2 (3)
C18—C19—C20—C21	68.3 (3)	C30A—C31A—C32A—N3A	176.4 (3)
C19—C20—C21—N2	62.4 (3)	C26A—C31A—C32A—N3A	0.7 (3)
C19—C20—C21—C7	−56.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.93	1.70	2.621 (3)	172
O4A—H4A···O3	0.84	1.75	2.586 (3)	173

(2) brucinium N-phthaloyl-β-alaninate 5.67-hydrate

Crystal data

C23H27N2O4^+·C11H8NO4^−·5.67H2O	F(000) = 761.4
Mr = 715.80	Dx = 1.384 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 10253 reflections
a = 11.527 (2) Å	θ = 3.3–28.1°
b = 7.6690 (13) Å	µ = 0.11 mm^−1
c = 19.500 (3) Å	T = 100 K
β = 94.832 (14)°	Block, colourless
V = 1717.7 (5) Å^3	0.25 × 0.20 × 0.20 mm
Z = 2

Data collection

Kuma KM-4 CCD diffractometer	2391 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.114
Graphite monochromator	θmax = 27.0°, θmin = 3.3°
ω scans	h = −14→14
11409 measured reflections	k = −8→9
3937 independent reflections	l = −24→24

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)] = 0.078	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0298P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
3937 reflections	Δρmax = 0.24 e Å^−3
488 parameters	Δρmin = −0.28 e Å^−3
79 restraints	Absolute structure: from known structure (Toda et al., 1985)
Primary atom site location: structure-invariant direct methods

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	0.0742 (3)	0.6124 (6)	−0.01214 (19)	0.0284 (11)
O2	−0.0728 (3)	0.3055 (6)	0.40005 (19)	0.0314 (12)
O3	0.1379 (3)	0.1972 (6)	0.4226 (2)	0.0313 (12)
O4	−0.1748 (3)	0.5548 (7)	0.1622 (2)	0.0388 (13)
N1	0.0046 (4)	0.4322 (7)	0.1598 (2)	0.0178 (12)
N2	0.3778 (4)	0.2693 (6)	0.1185 (2)	0.0222 (13)
H2	0.4429	0.2088	0.1373	0.027*
C1	−0.0499 (5)	0.3734 (9)	0.2804 (3)	0.0249 (16)
H1	−0.1275	0.4153	0.2725	0.030*
C2	−0.0079 (5)	0.3109 (9)	0.3443 (3)	0.0289 (17)
C3	0.1065 (5)	0.2499 (8)	0.3568 (3)	0.0234 (15)
C4	0.1802 (5)	0.2466 (8)	0.3036 (3)	0.0207 (15)
H4	0.2575	0.2033	0.3110	0.025*
C5	0.1372 (5)	0.3086 (8)	0.2392 (3)	0.0169 (14)
C6	0.0252 (5)	0.3727 (8)	0.2282 (3)	0.0183 (14)
C7	0.1977 (5)	0.3074 (8)	0.1728 (3)	0.0161 (13)
C8	0.1140 (4)	0.4221 (8)	0.1240 (3)	0.0176 (14)
H8	0.0978	0.3615	0.0788	0.021*
C9	−0.0818 (5)	0.5418 (9)	0.1349 (3)	0.0253 (16)
C10	−0.0612 (5)	0.6427 (9)	0.0701 (3)	0.0243 (15)
H10A	−0.1030	0.7551	0.0718	0.029*
H10B	−0.0981	0.5767	0.0304	0.029*
C11	0.0647 (4)	0.6829 (8)	0.0549 (3)	0.0211 (15)
H11	0.0747	0.8122	0.0529	0.025*
C12	0.1800 (5)	0.6603 (11)	−0.0429 (3)	0.041 (2)
H12A	0.2024	0.7806	−0.0290	0.050*
H12B	0.1655	0.6580	−0.0937	0.050*
C13	0.2782 (5)	0.5372 (10)	−0.0209 (3)	0.0352 (18)
H13	0.3106	0.4693	−0.0553	0.042*
C14	0.3219 (5)	0.5183 (9)	0.0436 (3)	0.0232 (15)
C15	0.4171 (5)	0.3882 (9)	0.0631 (3)	0.0271 (15)
H15A	0.4892	0.4499	0.0802	0.032*
H15B	0.4338	0.3187	0.0223	0.032*
C16	0.2905 (5)	0.1364 (8)	0.0893 (3)	0.0252 (15)
H16A	0.3288	0.0233	0.0816	0.030*
H16B	0.2510	0.1773	0.0452	0.030*
C17	0.2044 (5)	0.1196 (8)	0.1442 (3)	0.0204 (14)
H17A	0.2333	0.0369	0.1807	0.024*
H17B	0.1274	0.0798	0.1238	0.024*
C18	0.1501 (5)	0.6102 (8)	0.1117 (3)	0.0179 (14)
H18	0.1367	0.6764	0.1545	0.021*
C19	0.2817 (5)	0.6229 (9)	0.1026 (3)	0.0232 (15)
H19	0.3021	0.7481	0.0959	0.028*
C20	0.3452 (5)	0.5585 (8)	0.1711 (3)	0.0234 (15)
H20A	0.4296	0.5825	0.1715	0.028*
H20B	0.3149	0.6209	0.2103	0.028*
C21	0.3251 (5)	0.3661 (8)	0.1779 (3)	0.0184 (14)
H21	0.3644	0.3250	0.2227	0.022*
C22	−0.1865 (5)	0.3832 (10)	0.3923 (3)	0.0331 (18)
H22A	−0.2239	0.3705	0.4354	0.050*
H22B	−0.2337	0.3249	0.3550	0.050*
H22C	−0.1794	0.5073	0.3814	0.050*
C23	0.2581 (5)	0.1522 (10)	0.4395 (3)	0.0313 (17)
H23A	0.2694	0.1176	0.4879	0.047*
H23B	0.3073	0.2533	0.4316	0.047*
H23C	0.2795	0.0552	0.4103	0.047*
O5	0.5402 (5)	0.1069 (8)	0.1972 (3)	0.0226 (14)	0.67
O6	0.5212 (4)	−0.1184 (8)	0.1251 (3)	0.0250 (14)	0.67
C24	0.5718 (8)	−0.0377 (9)	0.1751 (4)	0.021 (2)	0.67
O5A	0.5877 (9)	0.1359 (15)	0.1593 (6)	0.017 (2)	0.33
O6A	0.4656 (9)	−0.0574 (17)	0.1982 (6)	0.028 (2)	0.33
C24A	0.5661 (12)	0.001 (2)	0.1923 (11)	0.021 (3)	0.33
O7	0.7790 (3)	−0.0955 (6)	0.40047 (19)	0.0322 (11)
O8	0.9803 (3)	−0.0818 (6)	0.2075 (2)	0.0276 (10)
N3	0.8564 (4)	−0.0694 (7)	0.2949 (2)	0.0205 (12)
C25	0.6772 (5)	−0.1144 (9)	0.2173 (3)	0.0304 (16)
H25A	0.7223	−0.1802	0.1879	0.036*
H25B	0.6492	−0.1956	0.2506	0.036*
C26	0.7566 (5)	0.0155 (9)	0.2571 (3)	0.0275 (16)
H26A	0.7852	0.1014	0.2245	0.033*
H26B	0.7114	0.0795	0.2900	0.033*
C27	0.8597 (5)	−0.1180 (9)	0.3644 (3)	0.0247 (15)
C28	0.9751 (5)	−0.2001 (8)	0.3818 (3)	0.0194 (14)
C29	1.0202 (5)	−0.2751 (9)	0.4417 (3)	0.0275 (16)
H29	0.9773	−0.2804	0.4812	0.033*
C30	1.1337 (5)	−0.3446 (9)	0.4422 (3)	0.0288 (16)
H30	1.1679	−0.4005	0.4825	0.035*
C31	1.1956 (5)	−0.3318 (8)	0.3844 (3)	0.0268 (16)
H31	1.2722	−0.3783	0.3859	0.032*
C32	1.1484 (5)	−0.2529 (8)	0.3248 (3)	0.0238 (15)
H32	1.1917	−0.2431	0.2856	0.029*
C33	1.0374 (5)	−0.1892 (8)	0.3237 (3)	0.0195 (14)
C34	0.9613 (5)	−0.1097 (8)	0.2666 (3)	0.0228 (15)
O1W	0.5430 (3)	0.3935 (7)	0.4523 (2)	0.0533 (14)
H11W	0.5467	0.2833	0.4533	0.080*
H12W	0.5046	0.4277	0.4855	0.080*
O2W	0.6318 (3)	0.4378 (6)	0.2309 (2)	0.0447 (13)
H21W	0.6695	0.4932	0.2027	0.067*
H22W	0.6114	0.3406	0.2140	0.067*
O3W	0.5550 (4)	0.0312 (7)	0.4341 (2)	0.0437 (13)
H31W	0.6238	−0.0040	0.4319	0.065*
H32W	0.5130	−0.0076	0.3998	0.065*
O4W	0.4280 (4)	−0.0782 (11)	0.3170 (3)	0.104 (3)
H41W	0.4260	−0.1899	0.3296	0.156*
H42W	0.4372	−0.0743	0.2742	0.156*
O5W	0.4836 (4)	0.5588 (8)	0.3270 (2)	0.077 (2)
H51W	0.5130	0.5238	0.3662	0.116*
H52W	0.5168	0.5105	0.2959	0.116*
O6W	0.6351 (5)	−0.3856 (10)	0.0668 (3)	0.047 (2)	0.67
H61W	0.5888	−0.3393	0.0914	0.071*	0.67
H62W	0.6983	−0.4024	0.0893	0.071*	0.67

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.027 (2)	0.037 (3)	0.021 (2)	0.010 (2)	0.0062 (19)	0.007 (2)
O2	0.015 (2)	0.058 (3)	0.022 (2)	−0.004 (2)	0.0079 (19)	0.001 (2)
O3	0.031 (3)	0.044 (3)	0.020 (3)	−0.006 (2)	0.007 (2)	0.008 (2)
O4	0.016 (2)	0.074 (4)	0.028 (3)	0.004 (2)	0.006 (2)	−0.003 (2)
N1	0.016 (3)	0.022 (3)	0.015 (3)	0.003 (2)	0.003 (2)	−0.006 (2)
N2	0.019 (3)	0.025 (3)	0.022 (3)	0.015 (2)	0.002 (2)	0.001 (3)
C1	0.012 (3)	0.040 (4)	0.023 (3)	−0.003 (3)	0.004 (3)	−0.010 (3)
C2	0.018 (3)	0.048 (5)	0.022 (4)	−0.005 (3)	0.006 (3)	−0.002 (3)
C3	0.034 (4)	0.024 (4)	0.013 (3)	−0.012 (3)	0.008 (3)	−0.004 (3)
C4	0.019 (3)	0.019 (4)	0.024 (4)	−0.008 (3)	0.002 (3)	−0.003 (3)
C5	0.020 (3)	0.015 (3)	0.016 (3)	0.002 (3)	0.006 (3)	−0.006 (3)
C6	0.014 (3)	0.023 (4)	0.017 (3)	−0.009 (3)	−0.003 (3)	0.001 (3)
C7	0.021 (3)	0.012 (3)	0.016 (3)	0.003 (3)	0.006 (3)	−0.002 (3)
C8	0.013 (3)	0.020 (4)	0.021 (3)	0.005 (3)	0.006 (2)	−0.001 (3)
C9	0.027 (4)	0.027 (4)	0.021 (4)	−0.001 (3)	−0.005 (3)	−0.012 (3)
C10	0.024 (4)	0.023 (4)	0.026 (3)	0.013 (3)	−0.001 (3)	−0.001 (3)
C11	0.019 (3)	0.018 (4)	0.027 (4)	0.004 (3)	0.006 (3)	0.000 (3)
C12	0.029 (4)	0.059 (6)	0.037 (4)	0.013 (4)	0.006 (3)	0.016 (4)
C13	0.033 (4)	0.049 (5)	0.027 (4)	0.010 (4)	0.021 (3)	0.017 (4)
C14	0.027 (4)	0.025 (4)	0.019 (3)	−0.006 (3)	0.012 (3)	0.009 (3)
C15	0.022 (3)	0.036 (4)	0.025 (3)	0.006 (3)	0.013 (3)	0.015 (3)
C16	0.037 (4)	0.020 (4)	0.017 (3)	0.002 (3)	−0.007 (3)	−0.012 (3)
C17	0.021 (3)	0.021 (4)	0.019 (3)	0.014 (3)	0.000 (3)	−0.001 (3)
C18	0.023 (3)	0.008 (3)	0.022 (3)	0.004 (3)	−0.003 (3)	−0.003 (3)
C19	0.018 (3)	0.021 (4)	0.032 (4)	0.002 (3)	0.010 (3)	0.013 (3)
C20	0.019 (3)	0.026 (4)	0.025 (4)	−0.003 (3)	0.002 (3)	−0.002 (3)
C21	0.023 (3)	0.018 (4)	0.015 (3)	−0.002 (3)	0.007 (3)	−0.010 (3)
C22	0.022 (4)	0.054 (5)	0.025 (4)	−0.007 (4)	0.012 (3)	−0.006 (4)
C23	0.029 (4)	0.043 (5)	0.021 (4)	−0.006 (3)	0.003 (3)	0.005 (3)
O5	0.020 (3)	0.017 (3)	0.031 (3)	0.004 (3)	0.000 (3)	0.004 (3)
O6	0.020 (3)	0.028 (4)	0.028 (3)	0.002 (3)	0.003 (3)	0.000 (3)
C24	0.019 (4)	0.018 (4)	0.025 (4)	0.001 (3)	0.005 (3)	0.015 (4)
O5A	0.014 (5)	0.019 (5)	0.018 (5)	0.003 (4)	0.005 (4)	0.011 (5)
O6A	0.024 (4)	0.025 (5)	0.034 (5)	−0.001 (4)	0.000 (4)	0.009 (4)
C24A	0.018 (5)	0.019 (5)	0.025 (5)	0.000 (5)	0.002 (4)	0.006 (5)
O7	0.024 (2)	0.045 (3)	0.029 (2)	0.008 (2)	0.015 (2)	0.003 (2)
O8	0.029 (2)	0.031 (3)	0.023 (2)	−0.004 (2)	0.0042 (19)	0.002 (2)
N3	0.016 (3)	0.027 (3)	0.018 (3)	0.007 (2)	0.002 (2)	0.003 (2)
C25	0.020 (3)	0.023 (4)	0.046 (4)	−0.003 (3)	−0.012 (3)	0.010 (4)
C26	0.025 (4)	0.034 (4)	0.022 (4)	0.008 (3)	−0.004 (3)	0.003 (3)
C27	0.024 (3)	0.030 (4)	0.019 (3)	−0.001 (3)	−0.002 (3)	−0.005 (3)
C28	0.013 (3)	0.023 (4)	0.023 (4)	0.002 (3)	0.004 (3)	−0.003 (3)
C29	0.035 (4)	0.031 (4)	0.017 (4)	0.008 (3)	0.003 (3)	0.005 (3)
C30	0.031 (4)	0.032 (4)	0.022 (4)	0.011 (3)	−0.007 (3)	−0.003 (3)
C31	0.019 (3)	0.023 (4)	0.038 (4)	0.005 (3)	−0.001 (3)	−0.004 (3)
C32	0.018 (3)	0.034 (4)	0.019 (4)	−0.007 (3)	−0.002 (3)	−0.007 (3)
C33	0.022 (3)	0.025 (4)	0.013 (3)	−0.007 (3)	0.005 (3)	−0.010 (3)
C34	0.027 (3)	0.019 (4)	0.022 (4)	−0.013 (3)	0.000 (3)	−0.003 (3)
O1W	0.049 (3)	0.064 (4)	0.049 (3)	−0.003 (3)	0.020 (2)	−0.006 (3)
O2W	0.031 (3)	0.034 (3)	0.069 (3)	0.002 (2)	0.004 (2)	−0.018 (3)
O3W	0.033 (3)	0.064 (4)	0.035 (3)	0.007 (3)	0.006 (2)	−0.007 (3)
O4W	0.039 (3)	0.214 (8)	0.060 (4)	0.017 (5)	0.011 (3)	−0.050 (5)
O5W	0.053 (3)	0.155 (7)	0.024 (3)	−0.025 (4)	0.010 (2)	−0.005 (3)
O6W	0.037 (4)	0.054 (5)	0.050 (5)	−0.006 (4)	0.004 (3)	−0.017 (4)

Geometric parameters (Å, º)

O1—C11	1.427 (6)	C19—H19	1.0000
O1—C12	1.450 (7)	C20—C21	1.501 (8)
O2—C2	1.371 (7)	C20—H20A	0.9900
O2—C22	1.436 (6)	C20—H20B	0.9900
O3—C3	1.365 (6)	C21—H21	1.0000
O3—C23	1.439 (6)	C22—H22A	0.9800
O4—C9	1.240 (6)	C22—H22B	0.9800
N1—C9	1.362 (7)	C22—H22C	0.9800
N1—C6	1.411 (6)	C23—H23A	0.9800
N1—C8	1.494 (6)	C23—H23B	0.9800
N2—C16	1.510 (7)	C23—H23C	0.9800
N2—C15	1.513 (7)	O5—C24	1.255 (5)
N2—C21	1.543 (6)	O6—C24	1.256 (5)
N2—H2	0.9300	C24—C25	1.527 (10)
C1—C2	1.384 (8)	O5A—C24A	1.256 (6)
C1—C6	1.391 (7)	O6A—C24A	1.255 (6)
C1—H1	0.9500	C24A—C25	1.598 (17)
C2—C3	1.401 (8)	O7—C27	1.224 (6)
C3—C4	1.395 (7)	O8—C34	1.209 (6)
C4—C5	1.394 (8)	N3—C27	1.404 (7)
C4—H4	0.9500	N3—C34	1.405 (7)
C5—C6	1.381 (7)	N3—C26	1.466 (7)
C5—C7	1.522 (7)	C25—C26	1.520 (8)
C7—C21	1.532 (7)	C25—H25A	0.9513
C7—C17	1.549 (8)	C25—H25B	0.9743
C7—C8	1.566 (7)	C26—H26A	0.9900
C8—C18	1.525 (8)	C26—H26B	0.9900
C8—H8	1.0000	C27—C28	1.485 (8)
C9—C10	1.519 (8)	C28—C29	1.366 (8)
C10—C11	1.536 (7)	C28—C33	1.393 (7)
C10—H10A	0.9900	C29—C30	1.411 (7)
C10—H10B	0.9900	C29—H29	0.9500
C11—C18	1.525 (7)	C30—C31	1.388 (8)
C11—H11	1.0000	C30—H30	0.9500
C12—C13	1.509 (9)	C31—C32	1.382 (8)
C12—H12A	0.9900	C31—H31	0.9500
C12—H12B	0.9900	C32—C33	1.368 (7)
C13—C14	1.323 (7)	C32—H32	0.9500
C13—H13	0.9500	C33—C34	1.490 (8)
C14—C19	1.507 (8)	O1W—H11W	0.8460
C14—C15	1.508 (8)	O1W—H12W	0.8563
C15—H15A	0.9900	O2W—H21W	0.8433
C15—H15B	0.9900	O2W—H22W	0.8402
C16—C17	1.525 (7)	O3W—H31W	0.8426
C16—H16A	0.9900	O3W—H32W	0.8455
C16—H16B	0.9900	O4W—H41W	0.8925
C17—H17A	0.9900	O4W—H42W	0.8503
C17—H17B	0.9900	O5W—H51W	0.8523
C18—C19	1.545 (7)	O5W—H52W	0.8323
C18—H18	1.0000	O6W—H61W	0.8277
C19—C20	1.548 (7)	O6W—H62W	0.8273
C11—O1—C12	114.5 (5)	C8—C18—C19	111.2 (5)
C2—O2—C22	117.3 (5)	C11—C18—H18	106.6
C3—O3—C23	117.4 (4)	C8—C18—H18	106.6
C9—N1—C6	126.6 (5)	C19—C18—H18	106.6
C9—N1—C8	119.1 (5)	C14—C19—C18	115.0 (5)
C6—N1—C8	110.1 (4)	C14—C19—C20	109.6 (5)
C16—N2—C15	111.6 (4)	C18—C19—C20	106.2 (4)
C16—N2—C21	108.5 (4)	C14—C19—H19	108.7
C15—N2—C21	114.0 (4)	C18—C19—H19	108.7
C16—N2—H2	107.5	C20—C19—H19	108.7
C15—N2—H2	107.5	C21—C20—C19	108.9 (5)
C21—N2—H2	107.5	C21—C20—H20A	109.9
C2—C1—C6	117.7 (5)	C19—C20—H20A	109.9
C2—C1—H1	121.1	C21—C20—H20B	109.9
C6—C1—H1	121.1	C19—C20—H20B	109.9
O2—C2—C1	123.4 (6)	H20A—C20—H20B	108.3
O2—C2—C3	114.9 (5)	C20—C21—C7	115.9 (5)
C1—C2—C3	121.7 (5)	C20—C21—N2	109.5 (5)
O3—C3—C4	124.3 (6)	C7—C21—N2	104.2 (4)
O3—C3—C2	115.6 (5)	C20—C21—H21	109.0
C4—C3—C2	120.0 (6)	C7—C21—H21	109.0
C5—C4—C3	118.1 (6)	N2—C21—H21	109.0
C5—C4—H4	121.0	O2—C22—H22A	109.5
C3—C4—H4	121.0	O2—C22—H22B	109.5
C6—C5—C4	121.2 (5)	H22A—C22—H22B	109.5
C6—C5—C7	111.1 (5)	O2—C22—H22C	109.5
C4—C5—C7	127.6 (5)	H22A—C22—H22C	109.5
C5—C6—C1	121.3 (5)	H22B—C22—H22C	109.5
C5—C6—N1	110.0 (5)	O3—C23—H23A	109.5
C1—C6—N1	128.7 (5)	O3—C23—H23B	109.5
C5—C7—C21	116.6 (4)	H23A—C23—H23B	109.5
C5—C7—C17	110.7 (5)	O3—C23—H23C	109.5
C21—C7—C17	102.7 (4)	H23A—C23—H23C	109.5
C5—C7—C8	102.1 (4)	H23B—C23—H23C	109.5
C21—C7—C8	114.4 (5)	O5—C24—O6	124.9 (8)
C17—C7—C8	110.5 (5)	O5—C24—C25	113.4 (6)
N1—C8—C18	106.0 (5)	O6—C24—C25	121.7 (6)
N1—C8—C7	104.3 (4)	O6A—C24A—O5A	124.4 (15)
C18—C8—C7	117.7 (4)	O6A—C24A—C25	119.9 (11)
N1—C8—H8	109.5	O5A—C24A—C25	115.1 (10)
C18—C8—H8	109.5	C27—N3—C34	111.6 (5)
C7—C8—H8	109.5	C27—N3—C26	124.0 (4)
O4—C9—N1	122.0 (6)	C34—N3—C26	124.4 (5)
O4—C9—C10	121.2 (6)	C26—C25—C24	116.1 (5)
N1—C9—C10	116.7 (5)	C26—C25—C24A	103.0 (9)
C9—C10—C11	118.7 (5)	C24—C25—C24A	16.6 (9)
C9—C10—H10A	107.6	C26—C25—H25A	108.7
C11—C10—H10A	107.6	C24—C25—H25A	109.2
C9—C10—H10B	107.6	C24A—C25—H25A	125.0
C11—C10—H10B	107.6	C26—C25—H25B	107.4
H10A—C10—H10B	107.1	C24—C25—H25B	108.1
O1—C11—C18	115.6 (4)	C24A—C25—H25B	104.7
O1—C11—C10	104.3 (4)	H25A—C25—H25B	107.0
C18—C11—C10	110.4 (5)	N3—C26—C25	112.2 (5)
O1—C11—H11	108.7	N3—C26—H26A	109.2
C18—C11—H11	108.7	C25—C26—H26A	109.2
C10—C11—H11	108.7	N3—C26—H26B	109.2
O1—C12—C13	111.1 (5)	C25—C26—H26B	109.2
O1—C12—H12A	109.4	H26A—C26—H26B	107.9
C13—C12—H12A	109.4	O7—C27—N3	123.9 (5)
O1—C12—H12B	109.4	O7—C27—C28	129.6 (6)
C13—C12—H12B	109.4	N3—C27—C28	106.5 (5)
H12A—C12—H12B	108.0	C29—C28—C33	122.4 (6)
C14—C13—C12	123.7 (6)	C29—C28—C27	130.0 (5)
C14—C13—H13	118.1	C33—C28—C27	107.6 (5)
C12—C13—H13	118.1	C28—C29—C30	116.8 (5)
C13—C14—C19	123.4 (6)	C28—C29—H29	121.6
C13—C14—C15	121.5 (6)	C30—C29—H29	121.6
C19—C14—C15	115.1 (5)	C31—C30—C29	120.5 (6)
C14—C15—N2	108.9 (4)	C31—C30—H30	119.8
C14—C15—H15A	109.9	C29—C30—H30	119.8
N2—C15—H15A	109.9	C32—C31—C30	121.5 (6)
C14—C15—H15B	109.9	C32—C31—H31	119.3
N2—C15—H15B	109.9	C30—C31—H31	119.3
H15A—C15—H15B	108.3	C33—C32—C31	118.1 (5)
N2—C16—C17	104.1 (4)	C33—C32—H32	121.0
N2—C16—H16A	110.9	C31—C32—H32	121.0
C17—C16—H16A	110.9	C32—C33—C28	120.8 (6)
N2—C16—H16B	110.9	C32—C33—C34	130.4 (5)
C17—C16—H16B	110.9	C28—C33—C34	108.8 (5)
H16A—C16—H16B	108.9	O8—C34—N3	124.5 (5)
C16—C17—C7	103.3 (5)	O8—C34—C33	130.0 (5)
C16—C17—H17A	111.1	N3—C34—C33	105.5 (5)
C7—C17—H17A	111.1	H11W—O1W—H12W	108.5
C16—C17—H17B	111.1	H21W—O2W—H22W	109.6
C7—C17—H17B	111.1	H31W—O3W—H32W	109.0
H17A—C17—H17B	109.1	H41W—O4W—H42W	108.2
C11—C18—C8	107.0 (4)	H51W—O5W—H52W	109.9
C11—C18—C19	118.3 (5)	H61W—O6W—H62W	110.0
C22—O2—C2—C1	−5.6 (9)	C10—C11—C18—C19	174.7 (5)
C22—O2—C2—C3	173.6 (5)	N1—C8—C18—C11	−72.3 (5)
C6—C1—C2—O2	179.6 (6)	C7—C8—C18—C11	171.5 (4)
C6—C1—C2—C3	0.5 (10)	N1—C8—C18—C19	157.2 (4)
C23—O3—C3—C4	6.6 (8)	C7—C8—C18—C19	41.0 (6)
C23—O3—C3—C2	−173.2 (6)	C13—C14—C19—C18	56.7 (8)
O2—C2—C3—O3	−1.2 (8)	C15—C14—C19—C18	−123.3 (5)
C1—C2—C3—O3	178.0 (6)	C13—C14—C19—C20	176.1 (6)
O2—C2—C3—C4	179.0 (5)	C15—C14—C19—C20	−3.9 (7)
C1—C2—C3—C4	−1.8 (10)	C11—C18—C19—C14	−64.9 (7)
O3—C3—C4—C5	−178.4 (5)	C8—C18—C19—C14	59.4 (6)
C2—C3—C4—C5	1.3 (9)	C11—C18—C19—C20	173.8 (5)
C3—C4—C5—C6	0.4 (9)	C8—C18—C19—C20	−61.9 (6)
C3—C4—C5—C7	−175.7 (6)	C14—C19—C20—C21	−55.5 (6)
C4—C5—C6—C1	−1.8 (9)	C18—C19—C20—C21	69.2 (6)
C7—C5—C6—C1	174.9 (6)	C19—C20—C21—C7	−55.2 (6)
C4—C5—C6—N1	178.0 (5)	C19—C20—C21—N2	62.3 (6)
C7—C5—C6—N1	−5.3 (7)	C5—C7—C21—C20	−87.0 (6)
C2—C1—C6—C5	1.3 (10)	C17—C7—C21—C20	151.8 (5)
C2—C1—C6—N1	−178.5 (6)	C8—C7—C21—C20	32.0 (7)
C9—N1—C6—C5	−162.0 (6)	C5—C7—C21—N2	152.6 (5)
C8—N1—C6—C5	−5.4 (7)	C17—C7—C21—N2	31.4 (5)
C9—N1—C6—C1	17.8 (10)	C8—C7—C21—N2	−88.4 (5)
C8—N1—C6—C1	174.4 (6)	C16—N2—C21—C20	−134.6 (5)
C6—C5—C7—C21	138.3 (5)	C15—N2—C21—C20	−9.6 (6)
C4—C5—C7—C21	−45.2 (8)	C16—N2—C21—C7	−9.9 (6)
C6—C5—C7—C17	−104.8 (6)	C15—N2—C21—C7	115.0 (5)
C4—C5—C7—C17	71.6 (7)	O5—C24—C25—C26	−24.8 (10)
C6—C5—C7—C8	12.9 (6)	O6—C24—C25—C26	157.8 (7)
C4—C5—C7—C8	−170.7 (6)	O5—C24—C25—C24A	15.4 (15)
C9—N1—C8—C18	46.9 (6)	O6—C24—C25—C24A	−162 (3)
C6—N1—C8—C18	−111.7 (5)	O6A—C24A—C25—C26	−134.7 (18)
C9—N1—C8—C7	171.8 (5)	O5A—C24A—C25—C26	54 (2)
C6—N1—C8—C7	13.2 (6)	O6A—C24A—C25—C24	82 (3)
C5—C7—C8—N1	−15.0 (6)	O5A—C24A—C25—C24	−89 (3)
C21—C7—C8—N1	−141.9 (4)	C27—N3—C26—C25	−95.4 (7)
C17—C7—C8—N1	102.7 (5)	C34—N3—C26—C25	85.6 (7)
C5—C7—C8—C18	102.1 (5)	C24—C25—C26—N3	−178.9 (6)
C21—C7—C8—C18	−24.9 (7)	C24A—C25—C26—N3	170.3 (7)
C17—C7—C8—C18	−140.2 (5)	C34—N3—C27—O7	179.6 (6)
C6—N1—C9—O4	−25.7 (9)	C26—N3—C27—O7	0.5 (10)
C8—N1—C9—O4	179.5 (5)	C34—N3—C27—C28	−1.4 (7)
C6—N1—C9—C10	156.7 (6)	C26—N3—C27—C28	179.6 (5)
C8—N1—C9—C10	2.0 (8)	O7—C27—C28—C29	1.7 (12)
O4—C9—C10—C11	155.4 (6)	N3—C27—C28—C29	−177.2 (6)
N1—C9—C10—C11	−27.0 (8)	O7—C27—C28—C33	−178.1 (7)
C12—O1—C11—C18	−68.6 (7)	N3—C27—C28—C33	2.9 (7)
C12—O1—C11—C10	170.0 (5)	C33—C28—C29—C30	−0.9 (10)
C9—C10—C11—O1	124.5 (6)	C27—C28—C29—C30	179.3 (6)
C9—C10—C11—C18	−0.4 (8)	C28—C29—C30—C31	1.5 (10)
C11—O1—C12—C13	86.0 (7)	C29—C30—C31—C32	−0.6 (10)
O1—C12—C13—C14	−62.7 (9)	C30—C31—C32—C33	−0.9 (9)
C12—C13—C14—C19	−2.4 (10)	C31—C32—C33—C28	1.5 (9)
C12—C13—C14—C15	177.6 (6)	C31—C32—C33—C34	−175.4 (6)
C13—C14—C15—N2	−125.1 (6)	C29—C28—C33—C32	−0.7 (10)
C19—C14—C15—N2	55.0 (7)	C27—C28—C33—C32	179.2 (6)
C16—N2—C15—C14	75.9 (6)	C29—C28—C33—C34	176.8 (6)
C21—N2—C15—C14	−47.4 (7)	C27—C28—C33—C34	−3.3 (7)
C15—N2—C16—C17	−142.4 (4)	C27—N3—C34—O8	179.6 (6)
C21—N2—C16—C17	−16.0 (6)	C26—N3—C34—O8	−1.3 (10)
N2—C16—C17—C7	35.6 (6)	C27—N3—C34—C33	−0.6 (7)
C5—C7—C17—C16	−167.1 (4)	C26—N3—C34—C33	178.5 (5)
C21—C7—C17—C16	−41.9 (5)	C32—C33—C34—O8	−0.5 (11)
C8—C7—C17—C16	80.5 (5)	C28—C33—C34—O8	−177.7 (6)
O1—C11—C18—C8	−69.8 (6)	C32—C33—C34—N3	179.7 (6)
C10—C11—C18—C8	48.3 (6)	C28—C33—C34—N3	2.5 (7)
O1—C11—C18—C19	56.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.93	1.74	2.632 (8)	161
N2—H2···O5A	0.93	1.78	2.685 (11)	164
N2—H2···O6A	0.93	2.37	3.074 (13)	133
O1W—H11W···O3W	0.85	1.97	2.806 (8)	168
O1W—H12W···O3W^i	0.86	1.93	2.779 (6)	169
O2W—H21W···O4^ii	0.84	2.08	2.840 (6)	151
O2W—H22W···O5A	0.84	1.90	2.729 (13)	167
O2W—H22W···O5	0.84	1.99	2.805 (8)	164
O3W—H31W···O7	0.84	2.06	2.886 (5)	166
O3W—H32W···O4W	0.85	1.90	2.738 (6)	174
O4W—H41W···O5W^iii	0.89	2.04	2.860 (11)	152
O4W—H42W···O6A	0.85	1.55	2.398 (13)	174
O4W—H42W···O5	0.85	2.43	3.107 (9)	137
O5W—H51W···O1W	0.85	1.96	2.786 (7)	163
O5W—H52W···O2W	0.83	1.99	2.800 (6)	164
O6W—H61W···O6	0.83	2.00	2.733 (9)	147
O6W—H62W···O4^iv	0.83	1.98	2.790 (7)	166

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y, z; (iii) x, y−1, z; (iv) x+1, y−1, z.