Brucinium 3,5-dinitro­benzoate methanol solvate, methanol disolvate and trihydrate

Crystals of brucinium 3,5-dinitro­benzoate methanol solvate, C₂₃H₂₇N₂O₄⁺·C₇H₃N₂O₆⁻·CH₃OH, (I), brucinium 3,5-dinitro­benzoate methanol disolvate, C₂₃H₂₇N₂O₄⁺·C₇H₃N₂O₆⁻·2CH₃OH, (II), and brucinium 3,5-dinitro­benzoate trihydrate, C₂₃H₂₇N₂O₄⁺·C₇H₃N₂O₆⁻·3H₂O, (III), were obtained from methanol [for (I) and (II)] or ethanol solutions [for (III)]. The brucinium cations and 3,5-dinitro­benzoate anions are linked by ionic N—H⁺...O⁻ hydrogen bonds. In the crystals of (I), (II) and (III), the brucinium cations exhibit different modes of packing, viz. corrugated ribbons, pillars and corrugated monolayer sheets, respectively. While in (III), the amide O atom of the brucinium cation participates in O—H...O hydrogen bonds, in which water mol­ecules are the donors, in (I) and (II), the amide O atom of the brucinium cation is involved in weak C—H...O hydrogen bonds and other brucinium cations are the donors.

S1. Comment

Brucine is one of the most often used resolving agents for separation of racemic acids (Jacques et al., 1991). The racemic resolution by fractional crystallization of brucinium diastereomeric salts is usually performed from water, methanol or ethanol solution. In our recent paper, concerning common brucine corrugated monolayer sheets, we showed that, in such cases, the amide O atoms of brucine molecules or brucinium cations reveal a great tendency to participate in hydrogen bonds, in which solvent molecules, usually water molecules, are the donors (Bialonska & Ciunik, 2006). The crystallization of brucinium 3,5-dinitrobenzoate from methanol and ethanol solutions has been performed. Crystals of brucinium 3,5-dinitrobenzoate methanol solvate, (I), were grown from methanol solution. As a result of a recrystallization of (I) from methanol solution, crystals of brucinium 3,5-dinitrobenzoate dimethanol solvate, (II), were obtained. Crystals of brucinium 3,5-dinitrobenzoate trihydrate, (III), were grown from ethanol solution.

Selected views of (I)–(III) with the numbering schemes employed are presented in Fig. 1. The geometry of the brucinium cations in the crystal structures of (I)–(III) is comparable to that found in other related compounds (Cambridge Structural Database, Version 5.27 of November 2005; Allen, 2002). In each of (I)–(III), the protonated tertiary amine N2 atom of the brucinium cation and atom O5 of the deprotonated carboxyl group of the 3,5-dinitrobenzoate anion are linked by ionic N—H⁺···O⁻ hydrogen bonds (see also Tables 1–3).

In (I), the brucinium cations form corrugated ribbons stabilized by C—H···O and C—H···π hydrogen bonds and extended in the [010] direction (Fig. 2). The brucinium ribbons are separated by the anions, which together with brucinium cations form π–π interactions (Table 2). The methanol molecule is a donor of the hydrogen bond, with atom O5 of the carboxyl group of the anion as the acceptor (see Fig. 1a and Table 1).

In (II), the brucinium cations form pillars extending in the [100] direction (Fig. 3). The arene rings of the brucinium cations are directed inwards in the pillars, allowing the O atoms of methoxy groups to participate in C—H···O hydrogen bonds. The anions are located in the channels formed by the four neighboring brucinium pillars. The brucinium cations and 3,5-dinitrobenzoate anions are linked, as mentioned above, by N—H⁺···O⁻ hydrogen bonds, and also by C—H···O hydrogen bonds. Again, methanol molecules are donors of the hydrogen bonds, with atoms O5 and O6 of the carboxyl group of the anion as the acceptors (see Fig. 1b and Table 3).

Similar to (I), in the crystal structure of (III), brucinium cations form corrugated ribbons. However, in (III), the consecutive ribbons are directly linked by C—H···O and C—H···π hydrogen bonds, resulting in common brucinium corrugated monolayer sheets (Fig. 4). The neighboring brucinium corrugated sheets are separated by the anions and water molecules. As mentioned above, the cations and anions are linked by ionic N—H⁺···O⁻ hydrogen bonds. Water molecules O1W–O3W, linked by O—H···O hydrogen bonds, form discrete D3 chains (see Fig. 1c and Table 4) (Infantes & Motherwell, 2002). Additionally, the O1W water molecule is a donor of the hydrogen bonds in which the carboxyl O6 atom of the anion and the amide O4(−x, y + 1/2, −z + 1/2) atom of the cation are the acceptors (see Table 3). The O2W and O3W water molecules are donors of the hydrogen bonds in which the O9(x − 1/2, −y + 5/2, −z + 1) atom of a nitro group and the O5(x − 1/2, −y + 3/2, −z + 1) atom of a carboxyl group of the anions are the acceptors, respectively.

As described above, in (I) and (III), brucinium cations form similar corrugated ribbons. These results confirm our previous observations (Bialonska & Ciunik, 2006), namely that in the crystal structures in which the brucinium ribbons form corrugated monolayer sheets, similar to those observed in (III), the amide O4 atom of the brucinium cations reveals a tendency to participate in hydrogen bonds with solvent molecules as the donors. On the other hand, in the cases in which brucinium cations form separated corrugated ribbons, similar to those observed in (I), the amide O4 atom does not exhibit the same behavior. However, the separated ribbons give the brucinium cations an opportunity for interactions, such as π–π interactions, with the anions. The formation of brucinium monolayer sheets does not allow brucinium cations to form such types of interaction with cocrystallizing guests. The interactions, involving the amide O atom of the brucinium corrugated layers, are specific for solvent molecules. In a similar way, weak interactions, involving the arene rings of separated brucinium corrugated ribbons, seem to be specific for guest molecules/anions. Simultaneously, it seems that such weak connections between the cations and anions resulting in cationic/anionic sheets decrease the ability of amide O atoms of brucinium cations to participate in hydrogen bonds with solvent molecules. Moreover, in (I), amide atom O4 of the brucinium cations seems to reveal similar properties to those of O atoms of nitro groups protruding out of the cationic/anionic sheet, which, generally, do not reveal a tendency to participate in strong hydrogen bonds.

In summary, on the basis of the crystal structures described above, a different molecular recognition of 3,5-dinitrobenzoate anions by brucinium cations appears in various solutions (methanol or ethanol). Various packing of brucinium cations and their various interactions with cocrystallizing 3,5-dinitrobenzoate anions are observed in the crystals of (I)–(III).

S2. Experimental

Crystals of (I) and (III) were grown from methanol or ethanol solution, respectively, containing equimolar amounts of brucine and 3,5-dinitrobenzoic acid. Crystals of (II) were obtained as a result of recrystallization of (I) from methanol solution. The crystallizations were performed at room temperature by slow evaporation of the solvent.

S3. Refinement

In the crystals of (I) - (III), all H atoms bonded to C atoms were treated as riding atoms, with C—H distances of 0.95 − 1.00 Å. The remaining H atoms were located in difference maps and then refined with isotropic displacements parameters before being fixed prior to the final cycles of refinement. Friedel pairs were merged before the final refinement (MERG 4). The absolute configurations of (I) - (III) were chosen on the basis of the known absolute configuration of brucine [Toda et al., 1985].

Computing details

For all 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 structures of (a) (I), (b) (II) and (c) (III). Non-H atoms are shown as 30% probability displacement ellipsoids. Fig. 2. The packing of (I), showing the brucinium ribbons (solid lines) separated by the anions (open lines). Fig. 3. The packing of (II), showing the columnar packing of brucinium cations. Channels, formed between four neighboring columns, are occupied by the anions. Fig. 4. The packing of (III), showing common brucinium corrugated monolayer sheets, separated by the anions and water molecules.

(I) brucinium 3,5-dinitrobenzoate methanol solvate

Crystal data

C23H27N2O4^+·C7H3N2O6^−·CH4O	F(000) = 1344
Mr = 638.62	Dx = 1.495 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 16721 reflections
a = 11.8539 (18) Å	θ = 3.4–28.6°
b = 12.2726 (18) Å	µ = 0.12 mm^−1
c = 19.498 (3) Å	T = 100 K
V = 2836.5 (7) Å^3	Block, orange
Z = 4	0.30 × 0.30 × 0.25 mm

Data collection

Kuma KM-4 CCD diffractometer	2929 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.077
Graphite monochromator	θmax = 27.0°, θmin = 3.4°
ω scan	h = −15→15
18431 measured reflections	k = −11→15
3470 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)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0408P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3470 reflections	Δρmax = 0.21 e Å^−3
415 parameters	Δρmin = −0.26 e Å^−3
0 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
O1	0.70343 (19)	0.65878 (17)	0.64497 (11)	0.0197 (5)
O2	0.6168 (2)	0.06246 (16)	0.88547 (10)	0.0172 (5)
O3	0.6216 (2)	−0.04939 (16)	0.77389 (11)	0.0169 (5)
O4	0.6754 (2)	0.46747 (18)	0.85395 (11)	0.0234 (6)
N1	0.6411 (2)	0.3996 (2)	0.74707 (13)	0.0139 (6)
N2	0.6496 (2)	0.3217 (2)	0.51487 (13)	0.0165 (6)
H2A	0.6413	0.2648	0.4837	0.020*
C1	0.6290 (3)	0.2359 (2)	0.82499 (16)	0.0143 (7)
H1	0.6276	0.2774	0.8661	0.017*
C2	0.6231 (3)	0.1232 (2)	0.82643 (16)	0.0143 (7)
C3	0.6255 (3)	0.0615 (2)	0.76533 (16)	0.0135 (7)
C4	0.6314 (3)	0.1134 (2)	0.70204 (17)	0.0150 (7)
H4	0.6309	0.0723	0.6607	0.018*
C5	0.6381 (3)	0.2280 (2)	0.70039 (16)	0.0125 (7)
C6	0.6371 (3)	0.2866 (2)	0.76074 (17)	0.0140 (7)
C7	0.6319 (3)	0.3032 (2)	0.63931 (16)	0.0122 (7)
C8	0.6540 (3)	0.4174 (2)	0.67188 (16)	0.0130 (7)
H8	0.5950	0.4696	0.6558	0.016*
C9	0.6732 (3)	0.4809 (3)	0.79172 (17)	0.0175 (7)
C10	0.6985 (3)	0.5895 (3)	0.75810 (17)	0.0200 (8)
H10A	0.7429	0.6339	0.7907	0.024*
H10B	0.6260	0.6277	0.7504	0.024*
C11	0.7635 (3)	0.5855 (2)	0.68877 (16)	0.0167 (7)
H11	0.8416	0.6140	0.6960	0.020*
C12	0.7574 (3)	0.6821 (3)	0.58034 (17)	0.0231 (8)
H12A	0.8403	0.6808	0.5864	0.028*
H12B	0.7356	0.7560	0.5649	0.028*
C13	0.7241 (3)	0.5999 (3)	0.52651 (17)	0.0196 (8)
H13	0.6827	0.6242	0.4877	0.023*
C14	0.7503 (3)	0.4948 (3)	0.53123 (16)	0.0157 (7)
C15	0.7120 (3)	0.4132 (3)	0.47916 (17)	0.0189 (8)
H15A	0.7780	0.3835	0.4543	0.023*
H15B	0.6617	0.4488	0.4454	0.023*
C16	0.5337 (3)	0.3567 (3)	0.53735 (17)	0.0179 (8)
H16A	0.4762	0.3350	0.5031	0.022*
H16B	0.5304	0.4366	0.5437	0.022*
C17	0.5145 (3)	0.2983 (2)	0.60473 (16)	0.0160 (7)
H17A	0.4904	0.2221	0.5972	0.019*
H17B	0.4570	0.3362	0.6328	0.019*
C18	0.7704 (3)	0.4686 (2)	0.66240 (15)	0.0138 (7)
H18	0.8214	0.4294	0.6950	0.017*
C19	0.8199 (3)	0.4483 (2)	0.59055 (16)	0.0151 (7)
H19	0.8975	0.4802	0.5886	0.018*
C20	0.8286 (3)	0.3247 (3)	0.58257 (17)	0.0167 (7)
H20A	0.8712	0.3067	0.5404	0.020*
H20B	0.8694	0.2933	0.6222	0.020*
C21	0.7109 (3)	0.2768 (3)	0.57848 (16)	0.0148 (7)
H21	0.7173	0.1959	0.5740	0.018*
C22	0.6187 (3)	0.1216 (3)	0.94913 (16)	0.0243 (8)
H22A	0.6134	0.0702	0.9875	0.036*
H22B	0.5548	0.1721	0.9507	0.036*
H22C	0.6894	0.1627	0.9526	0.036*
C23	0.6214 (3)	−0.1137 (3)	0.71266 (16)	0.0189 (7)
H23A	0.6187	−0.1911	0.7248	0.028*
H23B	0.6902	−0.0989	0.6864	0.028*
H23C	0.5553	−0.0950	0.6849	0.028*
O5	0.6330 (2)	0.13978 (19)	0.44295 (11)	0.0272 (6)
O6	0.6202 (2)	0.25299 (17)	0.35335 (12)	0.0269 (6)
O7	0.6021 (2)	−0.25284 (18)	0.39993 (12)	0.0272 (6)
O8	0.6009 (2)	−0.31690 (18)	0.29559 (12)	0.0223 (6)
O9	0.5820 (3)	−0.0679 (2)	0.10499 (13)	0.0380 (8)
O10	0.5987 (2)	0.10632 (19)	0.12238 (12)	0.0264 (6)
N3	0.6006 (2)	−0.2413 (2)	0.33703 (15)	0.0200 (7)
N4	0.5904 (2)	0.0121 (2)	0.14286 (14)	0.0215 (7)
C24	0.6242 (3)	0.1604 (3)	0.37881 (17)	0.0207 (8)
C25	0.6139 (3)	0.0630 (3)	0.33135 (17)	0.0167 (7)
C26	0.6137 (3)	−0.0433 (3)	0.35618 (16)	0.0168 (7)
H26	0.6234	−0.0571	0.4038	0.020*
C27	0.5991 (3)	−0.1288 (3)	0.31054 (17)	0.0165 (7)
C28	0.5873 (3)	−0.1134 (3)	0.24020 (17)	0.0171 (7)
H28	0.5759	−0.1725	0.2096	0.021*
C29	0.5931 (3)	−0.0071 (3)	0.21761 (16)	0.0166 (7)
C30	0.6059 (3)	0.0813 (3)	0.26106 (16)	0.0155 (7)
H30	0.6090	0.1532	0.2432	0.019*
O31	0.6434 (2)	−0.0262 (2)	0.53875 (14)	0.0352 (7)
H31	0.6260	0.0264	0.5144	0.053*
C31	0.5343 (3)	−0.0710 (4)	0.5387 (2)	0.0411 (11)
H31A	0.5136	−0.0918	0.4918	0.062*
H31B	0.4805	−0.0169	0.5559	0.062*
H31C	0.5327	−0.1356	0.5682	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0288 (14)	0.0142 (12)	0.0160 (12)	0.0019 (10)	0.0026 (11)	0.0032 (10)
O2	0.0259 (13)	0.0162 (11)	0.0095 (11)	−0.0013 (10)	0.0005 (11)	0.0012 (9)
O3	0.0240 (13)	0.0110 (11)	0.0156 (11)	−0.0009 (10)	−0.0005 (11)	0.0012 (9)
O4	0.0382 (16)	0.0206 (13)	0.0113 (13)	−0.0062 (11)	0.0015 (11)	−0.0018 (10)
N1	0.0173 (15)	0.0131 (13)	0.0112 (13)	−0.0004 (11)	0.0014 (12)	0.0002 (11)
N2	0.0273 (17)	0.0115 (13)	0.0107 (14)	−0.0013 (12)	−0.0006 (12)	−0.0035 (11)
C1	0.0149 (17)	0.0165 (16)	0.0115 (16)	−0.0003 (14)	0.0010 (15)	−0.0010 (13)
C2	0.0149 (17)	0.0165 (16)	0.0114 (15)	−0.0016 (14)	0.0001 (15)	0.0028 (13)
C3	0.0114 (16)	0.0135 (16)	0.0157 (16)	−0.0003 (13)	−0.0008 (15)	−0.0002 (13)
C4	0.0136 (17)	0.0143 (16)	0.0172 (16)	−0.0031 (14)	0.0014 (15)	−0.0035 (14)
C5	0.0115 (17)	0.0152 (15)	0.0107 (16)	−0.0011 (13)	−0.0018 (14)	0.0009 (13)
C6	0.0132 (17)	0.0120 (15)	0.0167 (17)	0.0007 (13)	−0.0009 (15)	−0.0008 (13)
C7	0.0135 (17)	0.0102 (14)	0.0129 (16)	−0.0007 (13)	−0.0005 (14)	−0.0006 (13)
C8	0.0166 (17)	0.0121 (16)	0.0103 (15)	−0.0021 (13)	0.0007 (14)	−0.0008 (13)
C9	0.0176 (17)	0.0180 (18)	0.0171 (18)	−0.0010 (14)	0.0017 (15)	−0.0024 (15)
C10	0.028 (2)	0.0155 (18)	0.0168 (18)	−0.0058 (14)	0.0025 (16)	−0.0029 (15)
C11	0.0226 (19)	0.0121 (16)	0.0153 (17)	−0.0020 (14)	0.0006 (15)	−0.0001 (14)
C12	0.034 (2)	0.0148 (17)	0.0206 (19)	−0.0019 (16)	0.0043 (17)	0.0032 (15)
C13	0.028 (2)	0.0166 (18)	0.0142 (17)	−0.0021 (15)	0.0018 (16)	0.0045 (15)
C14	0.0158 (17)	0.0196 (17)	0.0117 (16)	−0.0027 (14)	0.0007 (15)	0.0005 (14)
C15	0.027 (2)	0.0143 (17)	0.0154 (18)	−0.0007 (15)	0.0011 (16)	0.0046 (14)
C16	0.0202 (19)	0.0159 (17)	0.0177 (18)	−0.0001 (14)	0.0001 (15)	−0.0034 (14)
C17	0.0189 (18)	0.0149 (17)	0.0141 (17)	−0.0032 (14)	−0.0028 (15)	0.0004 (14)
C18	0.0159 (17)	0.0132 (16)	0.0123 (17)	−0.0016 (13)	−0.0006 (14)	0.0005 (13)
C19	0.0155 (17)	0.0156 (16)	0.0143 (17)	−0.0013 (13)	0.0023 (14)	0.0020 (14)
C20	0.0153 (17)	0.0198 (17)	0.0151 (17)	0.0040 (14)	0.0024 (14)	0.0026 (15)
C21	0.0200 (18)	0.0111 (16)	0.0133 (17)	0.0039 (13)	0.0011 (15)	−0.0001 (14)
C22	0.037 (2)	0.0241 (19)	0.0118 (17)	−0.0066 (17)	−0.0001 (17)	−0.0001 (14)
C23	0.027 (2)	0.0125 (16)	0.0169 (17)	−0.0001 (15)	0.0016 (16)	−0.0006 (14)
O5	0.0479 (18)	0.0197 (12)	0.0139 (12)	−0.0021 (12)	−0.0021 (12)	−0.0034 (10)
O6	0.0403 (17)	0.0165 (12)	0.0238 (14)	−0.0026 (12)	0.0023 (13)	0.0003 (11)
O7	0.0410 (17)	0.0202 (13)	0.0206 (14)	−0.0004 (12)	−0.0037 (13)	0.0033 (11)
O8	0.0250 (14)	0.0155 (12)	0.0264 (13)	−0.0014 (10)	0.0027 (11)	−0.0082 (11)
O9	0.068 (2)	0.0301 (15)	0.0164 (13)	−0.0147 (14)	−0.0023 (14)	−0.0071 (12)
O10	0.0353 (16)	0.0251 (13)	0.0187 (13)	0.0000 (12)	0.0043 (12)	0.0051 (11)
N3	0.0168 (15)	0.0191 (15)	0.0242 (17)	−0.0022 (12)	0.0010 (14)	0.0008 (13)
N4	0.0201 (16)	0.0297 (17)	0.0146 (15)	−0.0011 (13)	0.0016 (13)	0.0018 (14)
C24	0.0203 (19)	0.0219 (18)	0.0198 (19)	0.0003 (16)	0.0031 (16)	−0.0035 (15)
C25	0.0140 (17)	0.0182 (16)	0.0179 (17)	0.0001 (14)	0.0021 (15)	−0.0025 (14)
C26	0.0151 (17)	0.0217 (17)	0.0136 (16)	0.0009 (15)	−0.0010 (16)	0.0003 (14)
C27	0.0143 (17)	0.0153 (16)	0.0201 (18)	0.0005 (13)	0.0019 (15)	0.0015 (14)
C28	0.0145 (17)	0.0180 (17)	0.0190 (17)	0.0006 (14)	0.0002 (15)	−0.0067 (15)
C29	0.0155 (17)	0.0223 (18)	0.0120 (16)	−0.0003 (14)	−0.0020 (14)	0.0002 (14)
C30	0.0135 (17)	0.0164 (17)	0.0164 (17)	0.0011 (14)	0.0016 (15)	0.0005 (14)
O31	0.0333 (16)	0.0379 (15)	0.0343 (15)	−0.0021 (13)	−0.0027 (13)	0.0111 (13)
C31	0.032 (3)	0.066 (3)	0.025 (2)	−0.008 (2)	0.005 (2)	0.003 (2)

Geometric parameters (Å, º)

O1—C11	1.430 (4)	C16—C17	1.513 (4)
O1—C12	1.442 (4)	C16—H16A	0.9900
O2—C2	1.374 (4)	C16—H16B	0.9900
O2—C22	1.438 (4)	C17—H17A	0.9900
O3—C3	1.372 (4)	C17—H17B	0.9900
O3—C23	1.431 (4)	C18—C19	1.539 (4)
O4—C9	1.225 (4)	C18—H18	1.0000
N1—C9	1.378 (4)	C19—C20	1.530 (4)
N1—C6	1.413 (4)	C19—H19	1.0000
N1—C8	1.490 (4)	C20—C21	1.516 (4)
N2—C16	1.505 (4)	C20—H20A	0.9900
N2—C15	1.515 (4)	C20—H20B	0.9900
N2—C21	1.540 (4)	C21—H21	1.0000
N2—H2A	0.9300	C22—H22A	0.9800
C1—C2	1.385 (4)	C22—H22B	0.9800
C1—C6	1.402 (4)	C22—H22C	0.9800
C1—H1	0.9500	C23—H23A	0.9800
C2—C3	1.412 (4)	C23—H23B	0.9800
C3—C4	1.390 (4)	C23—H23C	0.9800
C4—C5	1.409 (4)	O5—C24	1.280 (4)
C4—H4	0.9500	O6—C24	1.241 (4)
C5—C6	1.379 (4)	O7—N3	1.235 (3)
C5—C7	1.509 (4)	O8—N3	1.230 (3)
C7—C21	1.546 (4)	O9—N4	1.232 (4)
C7—C17	1.547 (4)	O10—N4	1.227 (4)
C7—C8	1.561 (4)	N3—C27	1.474 (4)
C8—C18	1.528 (4)	N4—C29	1.477 (4)
C8—H8	1.0000	C24—C25	1.517 (4)
C9—C10	1.514 (4)	C25—C26	1.391 (4)
C10—C11	1.557 (4)	C25—C30	1.392 (4)
C10—H10A	0.9900	C26—C27	1.387 (4)
C10—H10B	0.9900	C26—H26	0.9500
C11—C18	1.526 (4)	C27—C28	1.392 (4)
C11—H11	1.0000	C28—C29	1.378 (5)
C12—C13	1.508 (4)	C28—H28	0.9500
C12—H12A	0.9900	C29—C30	1.384 (4)
C12—H12B	0.9900	C30—H30	0.9500
C13—C14	1.331 (5)	O31—C31	1.406 (5)
C13—H13	0.9500	O31—H31	0.8274
C14—C15	1.496 (4)	C31—H31A	0.9800
C14—C19	1.530 (4)	C31—H31B	0.9800
C15—H15A	0.9900	C31—H31C	0.9800
C15—H15B	0.9900
C11—O1—C12	115.2 (3)	C17—C16—H16B	110.8
C2—O2—C22	116.7 (2)	H16A—C16—H16B	108.9
C3—O3—C23	116.5 (2)	C16—C17—C7	103.0 (3)
C9—N1—C6	126.9 (3)	C16—C17—H17A	111.2
C9—N1—C8	119.2 (3)	C7—C17—H17A	111.2
C6—N1—C8	109.4 (2)	C16—C17—H17B	111.2
C16—N2—C15	111.6 (2)	C7—C17—H17B	111.2
C16—N2—C21	107.4 (2)	H17A—C17—H17B	109.1
C15—N2—C21	113.9 (3)	C11—C18—C8	107.3 (3)
C16—N2—H2A	107.9	C11—C18—C19	118.6 (3)
C15—N2—H2A	107.9	C8—C18—C19	112.8 (3)
C21—N2—H2A	107.9	C11—C18—H18	105.7
C2—C1—C6	117.7 (3)	C8—C18—H18	105.7
C2—C1—H1	121.1	C19—C18—H18	105.7
C6—C1—H1	121.1	C20—C19—C14	109.2 (3)
O2—C2—C1	124.2 (3)	C20—C19—C18	106.2 (3)
O2—C2—C3	114.6 (2)	C14—C19—C18	115.0 (3)
C1—C2—C3	121.2 (3)	C20—C19—H19	108.8
O3—C3—C4	124.3 (3)	C14—C19—H19	108.8
O3—C3—C2	115.4 (3)	C18—C19—H19	108.8
C4—C3—C2	120.3 (3)	C21—C20—C19	109.1 (3)
C3—C4—C5	118.7 (3)	C21—C20—H20A	109.9
C3—C4—H4	120.7	C19—C20—H20A	109.9
C5—C4—H4	120.7	C21—C20—H20B	109.9
C6—C5—C4	120.1 (3)	C19—C20—H20B	109.9
C6—C5—C7	110.7 (3)	H20A—C20—H20B	108.3
C4—C5—C7	128.7 (3)	C20—C21—N2	109.8 (2)
C5—C6—C1	122.1 (3)	C20—C21—C7	115.9 (3)
C5—C6—N1	110.5 (3)	N2—C21—C7	104.9 (2)
C1—C6—N1	127.3 (3)	C20—C21—H21	108.7
C5—C7—C21	116.6 (2)	N2—C21—H21	108.7
C5—C7—C17	111.4 (3)	C7—C21—H21	108.7
C21—C7—C17	101.7 (2)	O2—C22—H22A	109.5
C5—C7—C8	102.7 (2)	O2—C22—H22B	109.5
C21—C7—C8	113.5 (3)	H22A—C22—H22B	109.5
C17—C7—C8	111.3 (2)	O2—C22—H22C	109.5
N1—C8—C18	105.8 (2)	H22A—C22—H22C	109.5
N1—C8—C7	104.6 (2)	H22B—C22—H22C	109.5
C18—C8—C7	118.2 (3)	O3—C23—H23A	109.5
N1—C8—H8	109.3	O3—C23—H23B	109.5
C18—C8—H8	109.3	H23A—C23—H23B	109.5
C7—C8—H8	109.3	O3—C23—H23C	109.5
O4—C9—N1	122.3 (3)	H23A—C23—H23C	109.5
O4—C9—C10	122.9 (3)	H23B—C23—H23C	109.5
N1—C9—C10	114.7 (3)	O8—N3—O7	124.4 (3)
C9—C10—C11	116.5 (3)	O8—N3—C27	118.4 (3)
C9—C10—H10A	108.2	O7—N3—C27	117.1 (3)
C11—C10—H10A	108.2	O10—N4—O9	124.2 (3)
C9—C10—H10B	108.2	O10—N4—C29	118.0 (3)
C11—C10—H10B	108.2	O9—N4—C29	117.8 (3)
H10A—C10—H10B	107.3	O6—C24—O5	125.1 (3)
O1—C11—C18	114.6 (3)	O6—C24—C25	118.3 (3)
O1—C11—C10	104.6 (3)	O5—C24—C25	116.6 (3)
C18—C11—C10	110.4 (2)	C26—C25—C30	119.6 (3)
O1—C11—H11	109.0	C26—C25—C24	121.8 (3)
C18—C11—H11	109.0	C30—C25—C24	118.6 (3)
C10—C11—H11	109.0	C27—C26—C25	119.1 (3)
O1—C12—C13	111.1 (3)	C27—C26—H26	120.4
O1—C12—H12A	109.4	C25—C26—H26	120.4
C13—C12—H12A	109.4	C26—C27—C28	122.8 (3)
O1—C12—H12B	109.4	C26—C27—N3	118.9 (3)
C13—C12—H12B	109.4	C28—C27—N3	118.3 (3)
H12A—C12—H12B	108.0	C29—C28—C27	116.0 (3)
C14—C13—C12	122.6 (3)	C29—C28—H28	122.0
C14—C13—H13	118.7	C27—C28—H28	122.0
C12—C13—H13	118.7	C28—C29—C30	123.5 (3)
C13—C14—C15	122.1 (3)	C28—C29—N4	117.7 (3)
C13—C14—C19	122.6 (3)	C30—C29—N4	118.8 (3)
C15—C14—C19	115.3 (3)	C29—C30—C25	118.9 (3)
C14—C15—N2	109.4 (3)	C29—C30—H30	120.5
C14—C15—H15A	109.8	C25—C30—H30	120.5
N2—C15—H15A	109.8	C31—O31—H31	94.3
C14—C15—H15B	109.8	O31—C31—H31A	109.5
N2—C15—H15B	109.8	O31—C31—H31B	109.5
H15A—C15—H15B	108.2	H31A—C31—H31B	109.5
N2—C16—C17	104.8 (3)	O31—C31—H31C	109.5
N2—C16—H16A	110.8	H31A—C31—H31C	109.5
C17—C16—H16A	110.8	H31B—C31—H31C	109.5
N2—C16—H16B	110.8
C22—O2—C2—C1	−1.2 (5)	C21—N2—C16—C17	−18.7 (3)
C22—O2—C2—C3	177.6 (3)	N2—C16—C17—C7	38.2 (3)
C6—C1—C2—O2	178.9 (3)	C5—C7—C17—C16	−167.4 (2)
C6—C1—C2—C3	0.2 (5)	C21—C7—C17—C16	−42.5 (3)
C23—O3—C3—C4	−1.3 (5)	C8—C7—C17—C16	78.7 (3)
C23—O3—C3—C2	178.7 (3)	O1—C11—C18—C8	−73.8 (3)
O2—C2—C3—O3	−0.2 (4)	C10—C11—C18—C8	44.1 (3)
C1—C2—C3—O3	178.6 (3)	O1—C11—C18—C19	55.5 (4)
O2—C2—C3—C4	179.7 (3)	C10—C11—C18—C19	173.3 (3)
C1—C2—C3—C4	−1.4 (5)	N1—C8—C18—C11	−72.2 (3)
O3—C3—C4—C5	−178.3 (3)	C7—C8—C18—C11	171.1 (3)
C2—C3—C4—C5	1.8 (5)	N1—C8—C18—C19	155.3 (2)
C3—C4—C5—C6	−0.9 (5)	C7—C8—C18—C19	38.6 (4)
C3—C4—C5—C7	−172.3 (3)	C13—C14—C19—C20	176.7 (3)
C4—C5—C6—C1	−0.4 (5)	C15—C14—C19—C20	−2.4 (4)
C7—C5—C6—C1	172.5 (3)	C13—C14—C19—C18	57.4 (4)
C4—C5—C6—N1	−178.2 (3)	C15—C14—C19—C18	−121.6 (3)
C7—C5—C6—N1	−5.4 (4)	C11—C18—C19—C20	173.4 (3)
C2—C1—C6—C5	0.7 (5)	C8—C18—C19—C20	−60.0 (3)
C2—C1—C6—N1	178.2 (3)	C11—C18—C19—C14	−65.7 (4)
C9—N1—C6—C5	−160.1 (3)	C8—C18—C19—C14	60.9 (3)
C8—N1—C6—C5	−4.4 (4)	C14—C19—C20—C21	−56.0 (3)
C9—N1—C6—C1	22.2 (5)	C18—C19—C20—C21	68.6 (3)
C8—N1—C6—C1	177.9 (3)	C19—C20—C21—N2	62.1 (3)
C6—C5—C7—C21	136.8 (3)	C19—C20—C21—C7	−56.4 (4)
C4—C5—C7—C21	−51.1 (5)	C16—N2—C21—C20	−133.1 (3)
C6—C5—C7—C17	−107.1 (3)	C15—N2—C21—C20	−9.0 (3)
C4—C5—C7—C17	65.0 (4)	C16—N2—C21—C7	−7.9 (3)
C6—C5—C7—C8	12.1 (3)	C15—N2—C21—C7	116.2 (3)
C4—C5—C7—C8	−175.8 (3)	C5—C7—C21—C20	−86.8 (3)
C9—N1—C8—C18	44.0 (3)	C17—C7—C21—C20	151.9 (3)
C6—N1—C8—C18	−113.8 (3)	C8—C7—C21—C20	32.3 (4)
C9—N1—C8—C7	169.6 (3)	C5—C7—C21—N2	152.0 (3)
C6—N1—C8—C7	11.7 (3)	C17—C7—C21—N2	30.6 (3)
C5—C7—C8—N1	−13.9 (3)	C8—C7—C21—N2	−89.0 (3)
C21—C7—C8—N1	−140.6 (3)	O6—C24—C25—C26	−177.7 (3)
C17—C7—C8—N1	105.4 (3)	O5—C24—C25—C26	0.2 (5)
C5—C7—C8—C18	103.4 (3)	O6—C24—C25—C30	3.0 (5)
C21—C7—C8—C18	−23.3 (4)	O5—C24—C25—C30	−179.0 (3)
C17—C7—C8—C18	−137.3 (3)	C30—C25—C26—C27	−3.5 (5)
C6—N1—C9—O4	−18.9 (5)	C24—C25—C26—C27	177.2 (3)
C8—N1—C9—O4	−172.5 (3)	C25—C26—C27—C28	1.6 (5)
C6—N1—C9—C10	164.7 (3)	C25—C26—C27—N3	179.1 (3)
C8—N1—C9—C10	11.1 (4)	O8—N3—C27—C26	−171.6 (3)
O4—C9—C10—C11	143.4 (3)	O7—N3—C27—C26	8.0 (5)
N1—C9—C10—C11	−40.2 (4)	O8—N3—C27—C28	6.0 (4)
C12—O1—C11—C18	−67.9 (4)	O7—N3—C27—C28	−174.4 (3)
C12—O1—C11—C10	171.0 (2)	C26—C27—C28—C29	1.2 (5)
C9—C10—C11—O1	133.9 (3)	N3—C27—C28—C29	−176.3 (3)
C9—C10—C11—C18	10.1 (4)	C27—C28—C29—C30	−2.3 (5)
C11—O1—C12—C13	88.1 (3)	C27—C28—C29—N4	175.1 (3)
O1—C12—C13—C14	−64.1 (4)	O10—N4—C29—C28	−178.0 (3)
C12—C13—C14—C15	177.0 (3)	O9—N4—C29—C28	0.7 (5)
C12—C13—C14—C19	−2.0 (5)	O10—N4—C29—C30	−0.5 (4)
C13—C14—C15—N2	−125.1 (3)	O9—N4—C29—C30	178.2 (3)
C19—C14—C15—N2	53.9 (4)	C28—C29—C30—C25	0.4 (5)
C16—N2—C15—C14	74.5 (3)	N4—C29—C30—C25	−177.0 (3)
C21—N2—C15—C14	−47.3 (3)	C26—C25—C30—C29	2.6 (5)
C15—N2—C16—C17	−144.2 (3)	C24—C25—C30—C29	−178.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5	0.93	1.73	2.643 (3)	166
O31—H31···O5	0.83	1.97	2.766 (3)	161.1

(II) brucinim 3,5-dintrobenzoate dimethanol solvate

Crystal data

C23H27N2O4^+·C7H3N2O6^−·2CH4O	F(000) = 1416
Mr = 670.66	Dx = 1.481 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 17566 reflections
a = 7.1733 (18) Å	θ = 3.4–28.5°
b = 19.100 (2) Å	µ = 0.11 mm^−1
c = 21.955 (2) Å	T = 100 K
V = 3008.0 (9) Å^3	Block, orange
Z = 4	0.30 × 0.30 × 0.30 mm

Data collection

Kuma KM-4 CCD diffractometer	3407 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.085
Graphite monochromator	θmax = 27.0°, θmin = 3.4°
ω scan	h = −6→9
20084 measured reflections	k = −24→24
3707 independent reflections	l = −28→27

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)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.079P)^2 + 0.1302P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3707 reflections	Δρmax = 0.31 e Å^−3
433 parameters	Δρmin = −0.44 e Å^−3
0 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
O1	1.0572 (3)	0.65185 (11)	0.17580 (9)	0.0174 (4)
O2	0.9188 (3)	0.88938 (10)	0.50934 (10)	0.0215 (5)
O3	0.9007 (3)	0.77357 (10)	0.56931 (9)	0.0199 (5)
O4	1.0757 (3)	0.85828 (10)	0.29024 (10)	0.0230 (5)
N1	0.9553 (3)	0.75288 (12)	0.31800 (10)	0.0143 (5)
N2	0.8798 (4)	0.51620 (12)	0.35694 (11)	0.0152 (5)
H2A	0.8472	0.4847	0.3874	0.018*
C1	0.9339 (4)	0.83051 (15)	0.41128 (13)	0.0152 (6)
H1	0.9427	0.8732	0.3893	0.018*
C2	0.9190 (4)	0.83002 (14)	0.47436 (13)	0.0161 (6)
C3	0.9068 (4)	0.76672 (14)	0.50706 (13)	0.0159 (6)
C4	0.9011 (4)	0.70343 (15)	0.47599 (13)	0.0153 (6)
H4	0.8877	0.6607	0.4977	0.018*
C5	0.9151 (4)	0.70330 (14)	0.41288 (13)	0.0138 (6)
C6	0.9353 (4)	0.76587 (14)	0.38134 (13)	0.0141 (6)
C7	0.8940 (4)	0.64324 (14)	0.36868 (12)	0.0128 (5)
C8	0.9576 (4)	0.67609 (13)	0.30707 (13)	0.0131 (6)
H8	0.8646	0.6643	0.2747	0.016*
C9	1.0462 (4)	0.79642 (15)	0.27851 (13)	0.0157 (6)
C10	1.1084 (5)	0.76430 (15)	0.21877 (14)	0.0209 (6)
H10A	1.2130	0.7927	0.2028	0.025*
H10B	1.0042	0.7685	0.1894	0.025*
C11	1.1709 (4)	0.68714 (14)	0.22002 (13)	0.0167 (6)
H11	1.3042	0.6843	0.2070	0.020*
C12	1.1148 (5)	0.58159 (15)	0.16231 (13)	0.0196 (6)
H12A	1.2526	0.5791	0.1638	0.024*
H12B	1.0753	0.5696	0.1204	0.024*
C13	1.0346 (4)	0.52852 (15)	0.20610 (13)	0.0175 (6)
H13	0.9523	0.4939	0.1906	0.021*
C14	1.0735 (4)	0.52800 (14)	0.26530 (13)	0.0149 (6)
C15	0.9839 (4)	0.47655 (15)	0.30807 (13)	0.0171 (6)
H15A	1.0806	0.4466	0.3269	0.021*
H15B	0.8966	0.4461	0.2853	0.021*
C16	0.7035 (4)	0.54867 (14)	0.33266 (13)	0.0158 (6)
H16A	0.7112	0.5556	0.2880	0.019*
H16B	0.5939	0.5191	0.3420	0.019*
C17	0.6920 (4)	0.61773 (15)	0.36530 (13)	0.0152 (6)
H17A	0.6390	0.6117	0.4066	0.018*
H17B	0.6137	0.6513	0.3423	0.018*
C18	1.1534 (4)	0.65789 (14)	0.28435 (13)	0.0150 (6)
H18	1.2415	0.6858	0.3100	0.018*
C19	1.2035 (4)	0.58045 (15)	0.29542 (13)	0.0156 (6)
H19	1.3333	0.5719	0.2806	0.019*
C20	1.1988 (4)	0.57021 (15)	0.36486 (13)	0.0155 (6)
H20A	1.2508	0.5238	0.3756	0.019*
H20B	1.2752	0.6067	0.3850	0.019*
C21	0.9976 (4)	0.57533 (14)	0.38630 (13)	0.0142 (6)
H21	0.9942	0.5699	0.4316	0.017*
C22	0.9245 (5)	0.95494 (16)	0.47857 (15)	0.0280 (8)
H22A	0.9234	0.9930	0.5085	0.042*
H22B	0.8156	0.9592	0.4519	0.042*
H22C	1.0386	0.9578	0.4541	0.042*
C23	0.9282 (5)	0.71057 (16)	0.60352 (13)	0.0203 (6)
H23A	0.9214	0.7211	0.6471	0.030*
H23B	1.0509	0.6909	0.5939	0.030*
H23C	0.8311	0.6766	0.5929	0.030*
O5	0.7730 (4)	0.43850 (12)	0.45405 (10)	0.0278 (6)
O6	0.6689 (3)	0.35445 (12)	0.39161 (10)	0.0268 (5)
O7	0.8617 (3)	0.38241 (13)	0.66949 (11)	0.0301 (6)
O8	0.8514 (3)	0.27508 (13)	0.70124 (10)	0.0284 (5)
O9	0.7048 (4)	0.09022 (12)	0.55984 (11)	0.0338 (6)
O10	0.6906 (4)	0.11248 (12)	0.46282 (10)	0.0265 (5)
N3	0.8364 (4)	0.31986 (14)	0.66110 (12)	0.0219 (6)
N4	0.7068 (4)	0.13072 (13)	0.51631 (12)	0.0209 (6)
C24	0.7239 (4)	0.37673 (16)	0.44148 (14)	0.0192 (6)
C25	0.7357 (4)	0.32419 (15)	0.49341 (14)	0.0172 (6)
C26	0.7724 (4)	0.34622 (16)	0.55295 (14)	0.0193 (6)
H26	0.7863	0.3946	0.5619	0.023*
C27	0.7883 (4)	0.29647 (16)	0.59913 (14)	0.0192 (6)
C28	0.7665 (4)	0.22497 (15)	0.58912 (14)	0.0180 (6)
H28	0.7764	0.1915	0.6210	0.022*
C29	0.7290 (4)	0.20589 (15)	0.52915 (14)	0.0175 (6)
C30	0.7148 (4)	0.25303 (16)	0.48158 (13)	0.0162 (6)
H30	0.6911	0.2371	0.4413	0.019*
O31	0.9094 (5)	0.54181 (17)	0.53661 (13)	0.0535 (9)
H31	0.8806	0.5106	0.5122	0.080*
C31	0.9439 (8)	0.5278 (2)	0.5990 (2)	0.0551 (12)
H31A	1.0526	0.5547	0.6125	0.083*
H31B	0.9683	0.4777	0.6044	0.083*
H31C	0.8348	0.5413	0.6231	0.083*
O32	0.4010 (3)	0.40865 (12)	0.31333 (11)	0.0279 (5)
H32	0.4837	0.3951	0.3365	0.042*
C32	0.4390 (6)	0.3928 (2)	0.25114 (15)	0.0331 (8)
H32A	0.3323	0.4066	0.2260	0.050*
H32B	0.4608	0.3424	0.2468	0.050*
H32C	0.5501	0.4185	0.2379	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0232 (11)	0.0145 (10)	0.0146 (10)	−0.0010 (9)	−0.0005 (9)	−0.0016 (8)
O2	0.0325 (13)	0.0118 (10)	0.0204 (10)	0.0016 (9)	0.0002 (10)	−0.0041 (8)
O3	0.0263 (12)	0.0185 (10)	0.0148 (10)	0.0020 (9)	−0.0005 (9)	−0.0026 (8)
O4	0.0338 (13)	0.0119 (10)	0.0234 (11)	−0.0014 (10)	0.0036 (10)	0.0017 (8)
N1	0.0194 (12)	0.0098 (11)	0.0136 (11)	−0.0003 (10)	0.0005 (10)	0.0005 (9)
N2	0.0210 (13)	0.0108 (11)	0.0139 (12)	−0.0003 (10)	−0.0012 (10)	0.0004 (9)
C1	0.0153 (14)	0.0115 (13)	0.0188 (14)	0.0001 (11)	−0.0026 (11)	0.0005 (11)
C2	0.0148 (14)	0.0121 (13)	0.0213 (15)	0.0006 (11)	0.0012 (12)	−0.0059 (11)
C3	0.0156 (14)	0.0167 (15)	0.0153 (13)	0.0000 (11)	−0.0002 (11)	−0.0028 (11)
C4	0.0146 (13)	0.0138 (13)	0.0176 (14)	−0.0013 (11)	0.0020 (11)	−0.0002 (11)
C5	0.0121 (13)	0.0110 (13)	0.0182 (14)	0.0013 (11)	0.0014 (11)	−0.0001 (11)
C6	0.0152 (14)	0.0112 (13)	0.0161 (14)	0.0007 (11)	0.0002 (11)	−0.0004 (10)
C7	0.0134 (13)	0.0119 (13)	0.0130 (13)	0.0009 (11)	0.0003 (11)	0.0008 (10)
C8	0.0157 (14)	0.0086 (12)	0.0151 (13)	−0.0011 (10)	0.0000 (11)	0.0019 (10)
C9	0.0172 (14)	0.0150 (14)	0.0148 (14)	−0.0001 (12)	−0.0021 (11)	0.0026 (11)
C10	0.0279 (16)	0.0169 (14)	0.0178 (14)	−0.0022 (13)	0.0027 (13)	0.0022 (12)
C11	0.0180 (15)	0.0156 (14)	0.0164 (14)	−0.0041 (12)	0.0031 (12)	−0.0014 (11)
C12	0.0307 (17)	0.0137 (14)	0.0145 (14)	0.0007 (13)	0.0036 (13)	−0.0015 (11)
C13	0.0203 (15)	0.0157 (14)	0.0164 (14)	0.0002 (12)	0.0017 (12)	−0.0014 (11)
C14	0.0157 (14)	0.0106 (12)	0.0183 (14)	0.0036 (11)	0.0010 (12)	−0.0022 (11)
C15	0.0219 (15)	0.0136 (13)	0.0157 (14)	0.0014 (12)	−0.0002 (12)	−0.0026 (11)
C16	0.0158 (13)	0.0141 (13)	0.0174 (14)	−0.0023 (11)	−0.0008 (12)	−0.0006 (11)
C17	0.0147 (14)	0.0146 (13)	0.0162 (13)	−0.0004 (11)	0.0046 (11)	−0.0004 (11)
C18	0.0163 (14)	0.0136 (13)	0.0151 (13)	−0.0018 (11)	0.0015 (11)	0.0012 (11)
C19	0.0139 (14)	0.0146 (13)	0.0183 (14)	0.0024 (11)	−0.0009 (11)	0.0005 (11)
C20	0.0169 (14)	0.0140 (14)	0.0154 (14)	0.0013 (11)	−0.0027 (11)	−0.0008 (11)
C21	0.0194 (14)	0.0106 (13)	0.0127 (13)	−0.0036 (11)	0.0007 (11)	0.0007 (10)
C22	0.044 (2)	0.0122 (14)	0.0281 (17)	0.0025 (14)	−0.0007 (16)	−0.0038 (13)
C23	0.0226 (16)	0.0214 (15)	0.0170 (15)	0.0029 (13)	0.0003 (12)	0.0003 (12)
O5	0.0388 (14)	0.0188 (11)	0.0259 (12)	−0.0034 (10)	0.0078 (11)	0.0053 (9)
O6	0.0348 (14)	0.0253 (12)	0.0201 (11)	0.0050 (11)	−0.0009 (10)	0.0043 (9)
O7	0.0315 (13)	0.0293 (13)	0.0295 (13)	−0.0063 (11)	0.0003 (11)	−0.0117 (10)
O8	0.0307 (13)	0.0374 (14)	0.0172 (11)	0.0071 (11)	−0.0030 (10)	−0.0012 (10)
O9	0.0560 (17)	0.0204 (12)	0.0249 (12)	−0.0014 (12)	−0.0035 (12)	0.0071 (10)
O10	0.0392 (14)	0.0206 (11)	0.0198 (11)	0.0021 (11)	0.0016 (10)	−0.0053 (9)
N3	0.0179 (13)	0.0280 (14)	0.0200 (13)	−0.0012 (11)	0.0014 (11)	−0.0064 (11)
N4	0.0215 (13)	0.0167 (13)	0.0246 (14)	0.0024 (11)	0.0010 (11)	0.0017 (11)
C24	0.0180 (14)	0.0179 (14)	0.0217 (15)	0.0036 (12)	0.0030 (12)	0.0038 (12)
C25	0.0137 (14)	0.0176 (14)	0.0204 (14)	0.0010 (11)	0.0024 (12)	0.0030 (12)
C26	0.0167 (15)	0.0183 (14)	0.0228 (15)	−0.0026 (12)	0.0038 (12)	−0.0020 (12)
C27	0.0146 (14)	0.0244 (15)	0.0187 (15)	0.0003 (12)	0.0003 (12)	−0.0040 (12)
C28	0.0159 (14)	0.0188 (14)	0.0194 (15)	0.0012 (11)	−0.0004 (12)	0.0025 (12)
C29	0.0139 (13)	0.0164 (14)	0.0223 (15)	0.0006 (12)	−0.0001 (12)	−0.0029 (12)
C30	0.0143 (13)	0.0199 (14)	0.0145 (13)	0.0004 (12)	0.0027 (11)	0.0012 (12)
O31	0.077 (2)	0.0492 (18)	0.0341 (15)	−0.0061 (17)	−0.0064 (16)	0.0027 (13)
C31	0.063 (3)	0.050 (3)	0.053 (3)	−0.001 (2)	−0.001 (3)	0.002 (2)
O32	0.0258 (13)	0.0313 (12)	0.0265 (12)	0.0050 (10)	−0.0008 (10)	−0.0014 (10)
C32	0.035 (2)	0.042 (2)	0.0218 (17)	0.0049 (18)	0.0031 (15)	0.0020 (15)

Geometric parameters (Å, º)

O1—C12	1.435 (3)	C16—H16B	0.9900
O1—C11	1.436 (3)	C17—H17A	0.9900
O2—C2	1.369 (3)	C17—H17B	0.9900
O2—C22	1.423 (4)	C18—C19	1.541 (4)
O3—C3	1.374 (3)	C18—H18	1.0000
O3—C23	1.432 (3)	C19—C20	1.537 (4)
O4—C9	1.228 (3)	C19—H19	1.0000
N1—C9	1.367 (4)	C20—C21	1.521 (4)
N1—C6	1.420 (4)	C20—H20A	0.9900
N1—C8	1.486 (3)	C20—H20B	0.9900
N2—C16	1.506 (4)	C21—H21	1.0000
N2—C15	1.511 (4)	C22—H22A	0.9800
N2—C21	1.551 (4)	C22—H22B	0.9800
N2—H2A	0.9300	C22—H22C	0.9800
C1—C2	1.389 (4)	C23—H23A	0.9800
C1—C6	1.399 (4)	C23—H23B	0.9800
C1—H1	0.9500	C23—H23C	0.9800
C2—C3	1.409 (4)	O5—C24	1.262 (4)
C3—C4	1.389 (4)	O6—C24	1.239 (4)
C4—C5	1.389 (4)	O7—N3	1.222 (3)
C4—H4	0.9500	O8—N3	1.233 (3)
C5—C6	1.389 (4)	O9—N4	1.229 (3)
C5—C7	1.510 (4)	O10—N4	1.231 (3)
C7—C17	1.530 (4)	N3—C27	1.473 (4)
C7—C21	1.544 (4)	N4—C29	1.472 (4)
C7—C8	1.559 (4)	C24—C25	1.521 (4)
C8—C18	1.531 (4)	C25—C30	1.392 (4)
C8—H8	1.0000	C25—C26	1.398 (4)
C9—C10	1.515 (4)	C26—C27	1.394 (4)
C10—C11	1.541 (4)	C26—H26	0.9500
C10—H10A	0.9900	C27—C28	1.392 (4)
C10—H10B	0.9900	C28—C29	1.392 (4)
C11—C18	1.524 (4)	C28—H28	0.9500
C11—H11	1.0000	C29—C30	1.383 (4)
C12—C13	1.511 (4)	C30—H30	0.9500
C12—H12A	0.9900	O31—C31	1.417 (5)
C12—H12B	0.9900	O31—H31	0.8281
C13—C14	1.329 (4)	C31—H31A	0.9800
C13—H13	0.9500	C31—H31B	0.9800
C14—C15	1.504 (4)	C31—H31C	0.9800
C14—C19	1.520 (4)	O32—C32	1.425 (4)
C15—H15A	0.9900	O32—H32	0.8233
C15—H15B	0.9900	C32—H32A	0.9800
C16—C17	1.503 (4)	C32—H32B	0.9800
C16—H16A	0.9900	C32—H32C	0.9800
C12—O1—C11	114.5 (2)	C16—C17—H17A	110.9
C2—O2—C22	117.5 (2)	C7—C17—H17A	110.9
C3—O3—C23	115.9 (2)	C16—C17—H17B	110.9
C9—N1—C6	124.3 (2)	C7—C17—H17B	110.9
C9—N1—C8	119.5 (2)	H17A—C17—H17B	108.9
C6—N1—C8	109.4 (2)	C11—C18—C8	107.1 (2)
C16—N2—C15	111.7 (2)	C11—C18—C19	118.6 (2)
C16—N2—C21	107.7 (2)	C8—C18—C19	112.4 (2)
C15—N2—C21	113.0 (2)	C11—C18—H18	106.0
C16—N2—H2A	108.1	C8—C18—H18	106.0
C15—N2—H2A	108.1	C19—C18—H18	106.0
C21—N2—H2A	108.1	C14—C19—C20	109.5 (2)
C2—C1—C6	117.6 (3)	C14—C19—C18	114.9 (2)
C2—C1—H1	121.2	C20—C19—C18	105.9 (2)
C6—C1—H1	121.2	C14—C19—H19	108.8
O2—C2—C1	123.6 (3)	C20—C19—H19	108.8
O2—C2—C3	115.1 (2)	C18—C19—H19	108.8
C1—C2—C3	121.2 (3)	C21—C20—C19	108.6 (2)
O3—C3—C4	124.8 (3)	C21—C20—H20A	110.0
O3—C3—C2	115.3 (2)	C19—C20—H20A	110.0
C4—C3—C2	119.9 (3)	C21—C20—H20B	110.0
C3—C4—C5	119.3 (3)	C19—C20—H20B	110.0
C3—C4—H4	120.4	H20A—C20—H20B	108.3
C5—C4—H4	120.4	C20—C21—C7	115.7 (2)
C6—C5—C4	120.2 (3)	C20—C21—N2	110.0 (2)
C6—C5—C7	110.1 (2)	C7—C21—N2	104.2 (2)
C4—C5—C7	129.4 (3)	C20—C21—H21	108.9
C5—C6—C1	121.6 (3)	C7—C21—H21	108.9
C5—C6—N1	110.4 (2)	N2—C21—H21	108.9
C1—C6—N1	128.0 (2)	O2—C22—H22A	109.5
C5—C7—C17	111.6 (2)	O2—C22—H22B	109.5
C5—C7—C21	115.4 (2)	H22A—C22—H22B	109.5
C17—C7—C21	101.6 (2)	O2—C22—H22C	109.5
C5—C7—C8	102.8 (2)	H22A—C22—H22C	109.5
C17—C7—C8	111.3 (2)	H22B—C22—H22C	109.5
C21—C7—C8	114.5 (2)	O3—C23—H23A	109.5
N1—C8—C18	106.7 (2)	O3—C23—H23B	109.5
N1—C8—C7	104.7 (2)	H23A—C23—H23B	109.5
C18—C8—C7	117.4 (2)	O3—C23—H23C	109.5
N1—C8—H8	109.3	H23A—C23—H23C	109.5
C18—C8—H8	109.3	H23B—C23—H23C	109.5
C7—C8—H8	109.3	O7—N3—O8	123.9 (3)
O4—C9—N1	122.3 (3)	O7—N3—C27	118.1 (3)
O4—C9—C10	121.4 (3)	O8—N3—C27	118.1 (3)
N1—C9—C10	116.3 (2)	O9—N4—O10	124.2 (3)
C9—C10—C11	117.2 (2)	O9—N4—C29	117.8 (3)
C9—C10—H10A	108.0	O10—N4—C29	118.0 (2)
C11—C10—H10A	108.0	O6—C24—O5	127.1 (3)
C9—C10—H10B	108.0	O6—C24—C25	117.0 (3)
C11—C10—H10B	108.0	O5—C24—C25	115.9 (3)
H10A—C10—H10B	107.2	C30—C25—C26	119.2 (3)
O1—C11—C18	114.1 (2)	C30—C25—C24	119.9 (3)
O1—C11—C10	105.8 (2)	C26—C25—C24	120.8 (3)
C18—C11—C10	110.1 (2)	C27—C26—C25	119.3 (3)
O1—C11—H11	108.9	C27—C26—H26	120.3
C18—C11—H11	108.9	C25—C26—H26	120.3
C10—C11—H11	108.9	C28—C27—C26	123.0 (3)
O1—C12—C13	112.7 (2)	C28—C27—N3	118.0 (3)
O1—C12—H12A	109.0	C26—C27—N3	119.0 (3)
C13—C12—H12A	109.0	C27—C28—C29	115.3 (3)
O1—C12—H12B	109.0	C27—C28—H28	122.3
C13—C12—H12B	109.0	C29—C28—H28	122.3
H12A—C12—H12B	107.8	C30—C29—C28	123.9 (3)
C14—C13—C12	123.2 (3)	C30—C29—N4	118.9 (3)
C14—C13—H13	118.4	C28—C29—N4	117.2 (3)
C12—C13—H13	118.4	C29—C30—C25	119.2 (3)
C13—C14—C15	121.7 (3)	C29—C30—H30	120.4
C13—C14—C19	123.3 (3)	C25—C30—H30	120.4
C15—C14—C19	114.9 (2)	C31—O31—H31	122.2
C14—C15—N2	109.1 (2)	O31—C31—H31A	109.5
C14—C15—H15A	109.9	O31—C31—H31B	109.5
N2—C15—H15A	109.9	H31A—C31—H31B	109.5
C14—C15—H15B	109.9	O31—C31—H31C	109.5
N2—C15—H15B	109.9	H31A—C31—H31C	109.5
H15A—C15—H15B	108.3	H31B—C31—H31C	109.5
C17—C16—N2	103.8 (2)	C32—O32—H32	112.8
C17—C16—H16A	111.0	O32—C32—H32A	109.5
N2—C16—H16A	111.0	O32—C32—H32B	109.5
C17—C16—H16B	111.0	H32A—C32—H32B	109.5
N2—C16—H16B	111.0	O32—C32—H32C	109.5
H16A—C16—H16B	109.0	H32A—C32—H32C	109.5
C16—C17—C7	104.5 (2)	H32B—C32—H32C	109.5
C22—O2—C2—C1	3.3 (4)	C21—N2—C16—C17	−18.0 (3)
C22—O2—C2—C3	−177.9 (3)	N2—C16—C17—C7	38.0 (3)
C6—C1—C2—O2	179.0 (3)	C5—C7—C17—C16	−166.4 (2)
C6—C1—C2—C3	0.3 (5)	C21—C7—C17—C16	−43.0 (3)
C23—O3—C3—C4	13.0 (4)	C8—C7—C17—C16	79.3 (3)
C23—O3—C3—C2	−167.2 (3)	O1—C11—C18—C8	−68.9 (3)
O2—C2—C3—O3	−1.4 (4)	C10—C11—C18—C8	49.8 (3)
C1—C2—C3—O3	177.3 (3)	O1—C11—C18—C19	59.5 (4)
O2—C2—C3—C4	178.4 (3)	C10—C11—C18—C19	178.2 (2)
C1—C2—C3—C4	−2.9 (5)	N1—C8—C18—C11	−71.2 (3)
O3—C3—C4—C5	−177.7 (3)	C7—C8—C18—C11	171.9 (2)
C2—C3—C4—C5	2.6 (4)	N1—C8—C18—C19	156.9 (2)
C3—C4—C5—C6	0.2 (4)	C7—C8—C18—C19	40.0 (3)
C3—C4—C5—C7	−173.3 (3)	C13—C14—C19—C20	173.3 (3)
C4—C5—C6—C1	−2.9 (4)	C15—C14—C19—C20	−4.1 (3)
C7—C5—C6—C1	171.8 (3)	C13—C14—C19—C18	54.4 (4)
C4—C5—C6—N1	177.3 (3)	C15—C14—C19—C18	−123.1 (3)
C7—C5—C6—N1	−7.9 (3)	C11—C18—C19—C14	−66.9 (4)
C2—C1—C6—C5	2.6 (4)	C8—C18—C19—C14	59.0 (3)
C2—C1—C6—N1	−177.7 (3)	C11—C18—C19—C20	172.1 (2)
C9—N1—C6—C5	−153.5 (3)	C8—C18—C19—C20	−62.0 (3)
C8—N1—C6—C5	−2.9 (3)	C14—C19—C20—C21	−55.0 (3)
C9—N1—C6—C1	26.7 (5)	C18—C19—C20—C21	69.4 (3)
C8—N1—C6—C1	177.4 (3)	C19—C20—C21—C7	−55.6 (3)
C6—C5—C7—C17	−104.7 (3)	C19—C20—C21—N2	62.1 (3)
C4—C5—C7—C17	69.4 (4)	C5—C7—C21—C20	−87.7 (3)
C6—C5—C7—C21	140.0 (3)	C17—C7—C21—C20	151.5 (2)
C4—C5—C7—C21	−45.9 (4)	C8—C7—C21—C20	31.5 (3)
C6—C5—C7—C8	14.6 (3)	C5—C7—C21—N2	151.5 (2)
C4—C5—C7—C8	−171.3 (3)	C17—C7—C21—N2	30.7 (3)
C9—N1—C8—C18	39.0 (3)	C8—C7—C21—N2	−89.4 (3)
C6—N1—C8—C18	−113.2 (2)	C16—N2—C21—C20	−132.9 (2)
C9—N1—C8—C7	164.1 (2)	C15—N2—C21—C20	−9.0 (3)
C6—N1—C8—C7	11.8 (3)	C16—N2—C21—C7	−8.3 (3)
C5—C7—C8—N1	−15.5 (3)	C15—N2—C21—C7	115.6 (2)
C17—C7—C8—N1	104.1 (2)	O6—C24—C25—C30	10.2 (4)
C21—C7—C8—N1	−141.5 (2)	O5—C24—C25—C30	−169.2 (3)
C5—C7—C8—C18	102.5 (3)	O6—C24—C25—C26	−171.5 (3)
C17—C7—C8—C18	−137.9 (2)	O5—C24—C25—C26	9.0 (4)
C21—C7—C8—C18	−23.4 (3)	C30—C25—C26—C27	0.3 (4)
C6—N1—C9—O4	−19.7 (4)	C24—C25—C26—C27	−177.9 (3)
C8—N1—C9—O4	−167.6 (3)	C25—C26—C27—C28	−1.0 (5)
C6—N1—C9—C10	160.6 (3)	C25—C26—C27—N3	176.9 (3)
C8—N1—C9—C10	12.7 (4)	O7—N3—C27—C28	177.6 (3)
O4—C9—C10—C11	145.9 (3)	O8—N3—C27—C28	−1.3 (4)
N1—C9—C10—C11	−34.5 (4)	O7—N3—C27—C26	−0.4 (4)
C12—O1—C11—C18	−69.1 (3)	O8—N3—C27—C26	−179.4 (3)
C12—O1—C11—C10	169.8 (2)	C26—C27—C28—C29	0.6 (5)
C9—C10—C11—O1	124.4 (3)	N3—C27—C28—C29	−177.3 (3)
C9—C10—C11—C18	0.8 (4)	C27—C28—C29—C30	0.4 (5)
C11—O1—C12—C13	86.0 (3)	C27—C28—C29—N4	179.4 (3)
O1—C12—C13—C14	−63.4 (4)	O9—N4—C29—C30	−174.2 (3)
C12—C13—C14—C15	177.0 (3)	O10—N4—C29—C30	5.5 (4)
C12—C13—C14—C19	−0.3 (5)	O9—N4—C29—C28	6.8 (4)
C13—C14—C15—N2	−121.1 (3)	O10—N4—C29—C28	−173.5 (3)
C19—C14—C15—N2	56.4 (3)	C28—C29—C30—C25	−1.1 (5)
C16—N2—C15—C14	73.3 (3)	N4—C29—C30—C25	180.0 (3)
C21—N2—C15—C14	−48.4 (3)	C26—C25—C30—C29	0.7 (4)
C15—N2—C16—C17	−142.6 (2)	C24—C25—C30—C29	178.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5	0.93	1.79	2.708 (3)	169
O31—H31···O5	0.83	2.03	2.852 (4)	172.0
O32—H32···O6	0.82	1.96	2.778 (3)	174.6

(III) brucinium 3,5-dinitrobenzoate trihydrate

Crystal data

C23H27N2O4^+·C7H3N2O6^−·3H2O	F(000) = 1392
Mr = 660.63	Dx = 1.457 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 18822 reflections
a = 8.2499 (8) Å	θ = 3.5–28.5°
b = 12.5379 (12) Å	µ = 0.12 mm^−1
c = 29.109 (3) Å	T = 100 K
V = 3010.9 (5) Å^3	Block, yellow
Z = 4	0.30 × 0.25 × 0.25 mm

Data collection

Kuma KM-4 CCD diffractometer	3036 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.070
Graphite monochromator	θmax = 27.0°, θmin = 3.5°
ω scan	h = −10→10
20148 measured reflections	k = −16→10
3700 independent reflections	l = −36→37

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)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0633P)^2 + 0.1372P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
3700 reflections	Δρmax = 0.26 e Å^−3
424 parameters	Δρmin = −0.25 e Å^−3
0 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
O1	0.2421 (4)	0.1057 (2)	0.30492 (9)	0.0244 (6)
O2	0.1616 (3)	0.7046 (2)	0.15824 (8)	0.0226 (6)
O3	0.2230 (3)	0.80417 (19)	0.23312 (9)	0.0240 (6)
O4	0.1418 (4)	0.3017 (2)	0.17173 (9)	0.0262 (6)
N1	0.1561 (4)	0.3657 (2)	0.24474 (10)	0.0191 (7)
N2	0.2622 (4)	0.4249 (2)	0.39789 (10)	0.0229 (7)
H2A	0.2677	0.4788	0.4198	0.028*
C1	0.1545 (5)	0.5320 (3)	0.19531 (13)	0.0206 (8)
H1	0.1338	0.4954	0.1673	0.025*
C2	0.1729 (5)	0.6411 (3)	0.19625 (13)	0.0214 (8)
C3	0.2077 (5)	0.6958 (3)	0.23710 (13)	0.0207 (8)
C4	0.2201 (5)	0.6397 (3)	0.27808 (13)	0.0207 (8)
H4	0.2411	0.6760	0.3061	0.025*
C5	0.2013 (5)	0.5294 (3)	0.27736 (13)	0.0205 (8)
C6	0.1674 (5)	0.4767 (3)	0.23715 (13)	0.0199 (8)
C7	0.1978 (5)	0.4532 (3)	0.31736 (13)	0.0217 (8)
C8	0.2001 (4)	0.3421 (3)	0.29298 (13)	0.0188 (8)
H8	0.1158	0.2949	0.3070	0.023*
C9	0.1685 (5)	0.2871 (3)	0.21266 (13)	0.0235 (8)
C10	0.2141 (5)	0.1777 (3)	0.23102 (13)	0.0218 (8)
H10A	0.2661	0.1376	0.2057	0.026*
H10B	0.1125	0.1399	0.2388	0.026*
C11	0.3270 (5)	0.1714 (3)	0.27315 (13)	0.0231 (8)
H11	0.4311	0.1362	0.2642	0.028*
C12	0.3369 (6)	0.0720 (3)	0.34385 (13)	0.0290 (9)
H12A	0.4518	0.0645	0.3345	0.035*
H12B	0.2983	0.0014	0.3544	0.035*
C13	0.3249 (5)	0.1503 (3)	0.38250 (14)	0.0272 (9)
H13	0.2798	0.1275	0.4109	0.033*
C14	0.3752 (5)	0.2506 (3)	0.37851 (13)	0.0229 (8)
C15	0.3517 (5)	0.3296 (3)	0.41672 (13)	0.0242 (9)
H15A	0.4581	0.3520	0.4291	0.029*
H15B	0.2885	0.2967	0.4419	0.029*
C16	0.0860 (5)	0.4013 (3)	0.38941 (14)	0.0254 (9)
H16A	0.0189	0.4241	0.4158	0.030*
H16B	0.0688	0.3241	0.3841	0.030*
C17	0.0442 (5)	0.4650 (3)	0.34686 (13)	0.0224 (9)
H17A	0.0232	0.5407	0.3545	0.027*
H17B	−0.0517	0.4350	0.3310	0.027*
C18	0.3614 (5)	0.2834 (3)	0.29142 (13)	0.0209 (8)
H18	0.4272	0.3198	0.2672	0.025*
C19	0.4593 (5)	0.2933 (3)	0.33621 (12)	0.0213 (8)
H19	0.5654	0.2557	0.3324	0.026*
C20	0.4908 (5)	0.4135 (3)	0.34217 (13)	0.0238 (9)
H20A	0.5695	0.4252	0.3674	0.029*
H20B	0.5374	0.4432	0.3136	0.029*
C21	0.3336 (5)	0.4687 (3)	0.35314 (12)	0.0210 (8)
H21	0.3546	0.5468	0.3569	0.025*
C22	0.1530 (6)	0.6515 (3)	0.11457 (13)	0.0307 (10)
H22A	0.1453	0.7046	0.0900	0.046*
H22B	0.0572	0.6053	0.1138	0.046*
H22C	0.2506	0.6082	0.1101	0.046*
C23	0.2505 (6)	0.8623 (3)	0.27477 (13)	0.0267 (9)
H23A	0.2599	0.9385	0.2678	0.040*
H23B	0.3509	0.8373	0.2892	0.040*
H23C	0.1594	0.8509	0.2958	0.040*
O5	0.2586 (4)	0.5591 (2)	0.46743 (9)	0.0331 (7)
O6	0.2470 (4)	0.6964 (2)	0.41901 (9)	0.0300 (7)
O7	0.0317 (4)	0.6275 (2)	0.62090 (10)	0.0372 (8)
O8	0.0324 (4)	0.7876 (2)	0.64904 (9)	0.0301 (7)
O9	0.3665 (4)	1.0446 (2)	0.49495 (10)	0.0331 (7)
O10	0.2402 (4)	1.0781 (2)	0.55863 (9)	0.0283 (6)
N3	0.0609 (4)	0.7225 (3)	0.61831 (11)	0.0259 (8)
N4	0.2842 (4)	1.0171 (3)	0.52801 (11)	0.0254 (8)
C24	0.2451 (5)	0.6571 (3)	0.45807 (13)	0.0241 (9)
C25	0.2239 (5)	0.7308 (3)	0.49890 (12)	0.0204 (8)
C26	0.1617 (5)	0.6918 (3)	0.53987 (13)	0.0230 (8)
H26	0.1370	0.6182	0.5432	0.028*
C27	0.1364 (5)	0.7621 (3)	0.57567 (12)	0.0227 (8)
C28	0.1747 (5)	0.8689 (3)	0.57281 (13)	0.0237 (9)
H28	0.1569	0.9161	0.5978	0.028*
C29	0.2397 (5)	0.9035 (3)	0.53218 (13)	0.0206 (8)
C30	0.2620 (5)	0.8378 (3)	0.49457 (13)	0.0220 (8)
H30	0.3024	0.8654	0.4664	0.026*
O1W	0.0585 (4)	0.8771 (2)	0.39960 (10)	0.0369 (8)
H11W	−0.0008	0.8557	0.3763	0.055*
H12W	0.1235	0.8231	0.4059	0.055*
O2W	0.0600 (5)	1.2431 (2)	0.48415 (10)	0.0455 (9)
H21W	−0.0196	1.2864	0.4920	0.068*
H22W	0.0203	1.1787	0.4802	0.068*
O3W	−0.0134 (4)	1.0232 (2)	0.47067 (10)	0.0331 (7)
H31W	−0.0927	0.9932	0.4865	0.050*
H32W	0.0009	0.9823	0.4466	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0258 (15)	0.0216 (13)	0.0258 (14)	−0.0016 (12)	−0.0027 (12)	0.0016 (11)
O2	0.0267 (15)	0.0210 (13)	0.0201 (14)	−0.0017 (12)	−0.0005 (12)	0.0008 (11)
O3	0.0266 (16)	0.0207 (13)	0.0247 (14)	−0.0012 (12)	−0.0004 (12)	−0.0042 (11)
O4	0.0278 (15)	0.0319 (15)	0.0189 (14)	0.0049 (13)	−0.0027 (12)	−0.0054 (12)
N1	0.0177 (16)	0.0233 (16)	0.0161 (16)	−0.0044 (14)	−0.0022 (13)	−0.0039 (13)
N2	0.0259 (18)	0.0211 (15)	0.0218 (16)	0.0011 (15)	−0.0004 (14)	−0.0037 (14)
C1	0.017 (2)	0.0263 (19)	0.0180 (19)	−0.0004 (16)	−0.0006 (15)	−0.0061 (16)
C2	0.0179 (19)	0.0264 (19)	0.0198 (19)	0.0019 (17)	0.0002 (15)	0.0020 (16)
C3	0.016 (2)	0.0219 (19)	0.024 (2)	0.0000 (15)	0.0044 (15)	−0.0042 (16)
C4	0.0181 (19)	0.0225 (18)	0.0216 (19)	0.0027 (16)	−0.0013 (15)	−0.0051 (16)
C5	0.017 (2)	0.0238 (19)	0.021 (2)	0.0022 (15)	−0.0005 (15)	−0.0043 (16)
C6	0.0140 (19)	0.0219 (18)	0.024 (2)	0.0010 (15)	0.0040 (15)	−0.0067 (16)
C7	0.019 (2)	0.0217 (19)	0.024 (2)	−0.0003 (16)	−0.0002 (15)	−0.0020 (16)
C8	0.0143 (19)	0.0209 (18)	0.0211 (19)	−0.0015 (15)	−0.0006 (15)	−0.0031 (16)
C9	0.020 (2)	0.0244 (19)	0.026 (2)	−0.0003 (17)	−0.0002 (16)	−0.0061 (17)
C10	0.026 (2)	0.0202 (18)	0.0193 (19)	−0.0014 (16)	0.0029 (16)	−0.0037 (15)
C11	0.020 (2)	0.0225 (19)	0.027 (2)	0.0008 (16)	0.0030 (16)	−0.0032 (16)
C12	0.039 (3)	0.0210 (19)	0.027 (2)	0.0032 (19)	−0.0071 (19)	0.0011 (17)
C13	0.027 (2)	0.031 (2)	0.023 (2)	0.0033 (19)	−0.0064 (17)	0.0038 (18)
C14	0.019 (2)	0.026 (2)	0.024 (2)	0.0017 (17)	−0.0019 (16)	−0.0003 (17)
C15	0.029 (2)	0.0222 (19)	0.022 (2)	0.0027 (18)	0.0005 (17)	0.0020 (16)
C16	0.021 (2)	0.029 (2)	0.026 (2)	−0.0019 (17)	0.0065 (16)	−0.0042 (18)
C17	0.019 (2)	0.022 (2)	0.026 (2)	0.0002 (16)	0.0032 (16)	−0.0030 (16)
C18	0.017 (2)	0.0219 (18)	0.024 (2)	−0.0002 (16)	−0.0008 (16)	−0.0026 (16)
C19	0.021 (2)	0.0235 (19)	0.020 (2)	0.0020 (17)	−0.0024 (16)	−0.0026 (16)
C20	0.023 (2)	0.027 (2)	0.021 (2)	−0.0037 (17)	0.0005 (16)	0.0000 (17)
C21	0.024 (2)	0.024 (2)	0.0150 (18)	−0.0040 (17)	−0.0008 (15)	0.0001 (15)
C22	0.043 (3)	0.027 (2)	0.021 (2)	0.001 (2)	−0.0042 (19)	0.0000 (17)
C23	0.032 (2)	0.0241 (19)	0.024 (2)	−0.0014 (19)	0.0004 (18)	−0.0075 (17)
O5	0.050 (2)	0.0256 (15)	0.0237 (14)	0.0027 (15)	0.0001 (14)	−0.0044 (12)
O6	0.0375 (17)	0.0337 (15)	0.0188 (14)	0.0017 (15)	0.0013 (13)	−0.0041 (12)
O7	0.047 (2)	0.0315 (17)	0.0330 (17)	−0.0118 (15)	0.0104 (15)	0.0004 (14)
O8	0.0311 (17)	0.0384 (16)	0.0208 (14)	0.0051 (14)	0.0005 (12)	−0.0047 (13)
O9	0.0340 (18)	0.0320 (16)	0.0334 (17)	−0.0075 (14)	0.0041 (14)	0.0006 (13)
O10	0.0261 (16)	0.0261 (14)	0.0328 (15)	0.0021 (13)	−0.0008 (13)	−0.0083 (13)
N3	0.0260 (19)	0.0275 (18)	0.0241 (18)	−0.0001 (16)	0.0022 (15)	−0.0021 (15)
N4	0.0246 (19)	0.0250 (17)	0.0266 (19)	−0.0006 (15)	−0.0059 (15)	−0.0005 (15)
C24	0.027 (2)	0.023 (2)	0.023 (2)	0.0018 (18)	0.0012 (17)	−0.0020 (16)
C25	0.019 (2)	0.026 (2)	0.0164 (18)	0.0010 (16)	−0.0045 (15)	−0.0025 (16)
C26	0.027 (2)	0.0165 (18)	0.026 (2)	0.0006 (17)	−0.0012 (17)	0.0005 (16)
C27	0.023 (2)	0.026 (2)	0.0195 (19)	0.0029 (17)	0.0005 (15)	−0.0022 (16)
C28	0.022 (2)	0.027 (2)	0.022 (2)	0.0020 (17)	−0.0028 (16)	−0.0040 (16)
C29	0.0184 (19)	0.0193 (18)	0.0241 (19)	0.0014 (16)	−0.0022 (16)	0.0003 (15)
C30	0.021 (2)	0.025 (2)	0.0205 (19)	0.0048 (17)	−0.0013 (16)	0.0019 (16)
O1W	0.0418 (19)	0.0364 (17)	0.0325 (17)	0.0067 (15)	−0.0125 (15)	−0.0053 (13)
O2W	0.058 (2)	0.0356 (17)	0.043 (2)	0.0018 (17)	0.0158 (17)	0.0051 (16)
O3W	0.0372 (18)	0.0313 (16)	0.0309 (16)	−0.0020 (14)	−0.0007 (14)	−0.0002 (13)

Geometric parameters (Å, º)

O1—C11	1.423 (5)	C16—C17	1.513 (5)
O1—C12	1.440 (5)	C16—H16A	0.9900
O2—C2	1.367 (4)	C16—H16B	0.9900
O2—C22	1.437 (4)	C17—H17A	0.9900
O3—C3	1.370 (4)	C17—H17B	0.9900
O3—C23	1.433 (4)	C18—C19	1.539 (5)
O4—C9	1.226 (5)	C18—H18	1.0000
N1—C9	1.361 (5)	C19—C20	1.538 (5)
N1—C6	1.413 (5)	C19—H19	1.0000
N1—C8	1.480 (5)	C20—C21	1.505 (6)
N2—C16	1.504 (5)	C20—H20A	0.9900
N2—C15	1.508 (5)	C20—H20B	0.9900
N2—C21	1.532 (5)	C21—H21	1.0000
N2—H2A	0.9300	C22—H22A	0.9800
C1—C2	1.376 (5)	C22—H22B	0.9800
C1—C6	1.405 (5)	C22—H22C	0.9800
C1—H1	0.9500	C23—H23A	0.9800
C2—C3	1.403 (5)	C23—H23B	0.9800
C3—C4	1.388 (5)	C23—H23C	0.9800
C4—C5	1.392 (5)	O5—C24	1.264 (5)
C4—H4	0.9500	O6—C24	1.239 (4)
C5—C6	1.373 (5)	O7—N3	1.217 (4)
C5—C7	1.507 (5)	O8—N3	1.234 (4)
C7—C17	1.538 (5)	O9—N4	1.227 (4)
C7—C21	1.542 (5)	O10—N4	1.229 (4)
C7—C8	1.563 (5)	N3—C27	1.475 (5)
C8—C18	1.522 (5)	N4—C29	1.476 (5)
C8—H8	1.0000	C24—C25	1.516 (5)
C9—C10	1.519 (5)	C25—C30	1.383 (5)
C10—C11	1.542 (6)	C25—C26	1.387 (5)
C10—H10A	0.9900	C26—C27	1.381 (5)
C10—H10B	0.9900	C26—H26	0.9500
C11—C18	1.529 (5)	C27—C28	1.377 (6)
C11—H11	1.0000	C28—C29	1.370 (5)
C12—C13	1.497 (6)	C28—H28	0.9500
C12—H12A	0.9900	C29—C30	1.383 (5)
C12—H12B	0.9900	C30—H30	0.9500
C13—C14	1.329 (5)	O1W—H11W	0.8799
C13—H13	0.9500	O1W—H12W	0.8832
C14—C15	1.502 (5)	O2W—H21W	0.8819
C14—C19	1.512 (5)	O2W—H22W	0.8788
C15—H15A	0.9900	O3W—H31W	0.8846
C15—H15B	0.9900	O3W—H32W	0.8749
C11—O1—C12	114.5 (3)	C17—C16—H16A	110.8
C2—O2—C22	116.7 (3)	N2—C16—H16B	110.8
C3—O3—C23	116.6 (3)	C17—C16—H16B	110.8
C9—N1—C6	126.9 (3)	H16A—C16—H16B	108.9
C9—N1—C8	119.2 (3)	C16—C17—C7	102.6 (3)
C6—N1—C8	109.2 (3)	C16—C17—H17A	111.2
C16—N2—C15	112.2 (3)	C7—C17—H17A	111.2
C16—N2—C21	107.6 (3)	C16—C17—H17B	111.2
C15—N2—C21	113.9 (3)	C7—C17—H17B	111.2
C16—N2—H2A	107.6	H17A—C17—H17B	109.2
C15—N2—H2A	107.6	C8—C18—C11	107.0 (3)
C21—N2—H2A	107.6	C8—C18—C19	113.3 (3)
C2—C1—C6	117.7 (3)	C11—C18—C19	117.8 (3)
C2—C1—H1	121.2	C8—C18—H18	106.0
C6—C1—H1	121.2	C11—C18—H18	106.0
O2—C2—C1	123.8 (3)	C19—C18—H18	106.0
O2—C2—C3	114.5 (3)	C14—C19—C20	109.4 (3)
C1—C2—C3	121.7 (4)	C14—C19—C18	114.8 (3)
O3—C3—C4	124.6 (3)	C20—C19—C18	105.3 (3)
O3—C3—C2	115.6 (3)	C14—C19—H19	109.0
C4—C3—C2	119.7 (3)	C20—C19—H19	109.0
C3—C4—C5	118.8 (3)	C18—C19—H19	109.0
C3—C4—H4	120.6	C21—C20—C19	109.2 (3)
C5—C4—H4	120.6	C21—C20—H20A	109.8
C6—C5—C4	120.9 (4)	C19—C20—H20A	109.8
C6—C5—C7	110.5 (3)	C21—C20—H20B	109.8
C4—C5—C7	128.4 (3)	C19—C20—H20B	109.8
C5—C6—C1	121.1 (3)	H20A—C20—H20B	108.3
C5—C6—N1	110.8 (3)	C20—C21—N2	110.3 (3)
C1—C6—N1	128.1 (3)	C20—C21—C7	115.1 (3)
C5—C7—C17	112.7 (3)	N2—C21—C7	104.5 (3)
C5—C7—C21	115.3 (3)	C20—C21—H21	108.9
C17—C7—C21	102.1 (3)	N2—C21—H21	108.9
C5—C7—C8	102.4 (3)	C7—C21—H21	108.9
C17—C7—C8	110.5 (3)	O2—C22—H22A	109.5
C21—C7—C8	114.2 (3)	O2—C22—H22B	109.5
N1—C8—C18	106.4 (3)	H22A—C22—H22B	109.5
N1—C8—C7	104.5 (3)	O2—C22—H22C	109.5
C18—C8—C7	117.1 (3)	H22A—C22—H22C	109.5
N1—C8—H8	109.5	H22B—C22—H22C	109.5
C18—C8—H8	109.5	O3—C23—H23A	109.5
C7—C8—H8	109.5	O3—C23—H23B	109.5
O4—C9—N1	123.1 (4)	H23A—C23—H23B	109.5
O4—C9—C10	121.4 (3)	O3—C23—H23C	109.5
N1—C9—C10	115.5 (3)	H23A—C23—H23C	109.5
C9—C10—C11	118.4 (3)	H23B—C23—H23C	109.5
C9—C10—H10A	107.7	O7—N3—O8	124.4 (3)
C11—C10—H10A	107.7	O7—N3—C27	117.8 (3)
C9—C10—H10B	107.7	O8—N3—C27	117.9 (3)
C11—C10—H10B	107.7	O9—N4—O10	123.9 (3)
H10A—C10—H10B	107.1	O9—N4—C29	118.2 (3)
O1—C11—C18	113.4 (3)	O10—N4—C29	117.9 (3)
O1—C11—C10	104.5 (3)	O6—C24—O5	125.7 (3)
C18—C11—C10	110.0 (3)	O6—C24—C25	118.6 (3)
O1—C11—H11	109.6	O5—C24—C25	115.7 (3)
C18—C11—H11	109.6	C30—C25—C26	120.3 (3)
C10—C11—H11	109.6	C30—C25—C24	119.6 (3)
O1—C12—C13	111.3 (3)	C26—C25—C24	120.1 (3)
O1—C12—H12A	109.4	C27—C26—C25	118.7 (3)
C13—C12—H12A	109.4	C27—C26—H26	120.7
O1—C12—H12B	109.4	C25—C26—H26	120.7
C13—C12—H12B	109.4	C28—C27—C26	122.7 (4)
H12A—C12—H12B	108.0	C28—C27—N3	118.4 (3)
C14—C13—C12	122.3 (4)	C26—C27—N3	118.9 (3)
C14—C13—H13	118.9	C29—C28—C27	116.8 (4)
C12—C13—H13	118.9	C29—C28—H28	121.6
C13—C14—C15	121.3 (4)	C27—C28—H28	121.6
C13—C14—C19	123.3 (4)	C28—C29—C30	123.1 (4)
C15—C14—C19	115.4 (3)	C28—C29—N4	118.3 (3)
C14—C15—N2	108.5 (3)	C30—C29—N4	118.5 (3)
C14—C15—H15A	110.0	C29—C30—C25	118.4 (4)
N2—C15—H15A	110.0	C29—C30—H30	120.8
C14—C15—H15B	110.0	C25—C30—H30	120.8
N2—C15—H15B	110.0	H11W—O1W—H12W	105.3
H15A—C15—H15B	108.4	H21W—O2W—H22W	108.8
N2—C16—C17	104.5 (3)	H31W—O3W—H32W	105.5
N2—C16—H16A	110.8
C22—O2—C2—C1	−9.0 (6)	C21—N2—C16—C17	−18.7 (4)
C22—O2—C2—C3	170.0 (4)	N2—C16—C17—C7	38.4 (4)
C6—C1—C2—O2	−179.3 (4)	C5—C7—C17—C16	−167.4 (3)
C6—C1—C2—C3	1.7 (6)	C21—C7—C17—C16	−43.1 (4)
C23—O3—C3—C4	−1.3 (6)	C8—C7—C17—C16	78.8 (4)
C23—O3—C3—C2	177.0 (3)	N1—C8—C18—C11	−72.5 (4)
O2—C2—C3—O3	0.8 (5)	C7—C8—C18—C11	171.1 (3)
C1—C2—C3—O3	179.9 (4)	N1—C8—C18—C19	155.9 (3)
O2—C2—C3—C4	179.2 (3)	C7—C8—C18—C19	39.6 (5)
C1—C2—C3—C4	−1.7 (6)	O1—C11—C18—C8	−71.0 (4)
O3—C3—C4—C5	179.8 (3)	C10—C11—C18—C8	45.5 (4)
C2—C3—C4—C5	1.5 (6)	O1—C11—C18—C19	57.9 (5)
C3—C4—C5—C6	−1.5 (6)	C10—C11—C18—C19	174.5 (3)
C3—C4—C5—C7	−175.2 (4)	C13—C14—C19—C20	176.5 (4)
C4—C5—C6—C1	1.6 (6)	C15—C14—C19—C20	−3.8 (5)
C7—C5—C6—C1	176.4 (4)	C13—C14—C19—C18	58.4 (5)
C4—C5—C6—N1	179.2 (4)	C15—C14—C19—C18	−121.9 (4)
C7—C5—C6—N1	−6.1 (4)	C8—C18—C19—C14	59.7 (4)
C2—C1—C6—C5	−1.7 (6)	C11—C18—C19—C14	−66.2 (5)
C2—C1—C6—N1	−178.8 (4)	C8—C18—C19—C20	−60.7 (4)
C9—N1—C6—C5	−160.6 (4)	C11—C18—C19—C20	173.3 (3)
C8—N1—C6—C5	−5.3 (4)	C14—C19—C20—C21	−54.6 (4)
C9—N1—C6—C1	16.8 (7)	C18—C19—C20—C21	69.3 (4)
C8—N1—C6—C1	172.1 (4)	C19—C20—C21—N2	60.6 (4)
C6—C5—C7—C17	−104.7 (4)	C19—C20—C21—C7	−57.3 (4)
C4—C5—C7—C17	69.6 (5)	C16—N2—C21—C20	−132.4 (3)
C6—C5—C7—C21	138.6 (3)	C15—N2—C21—C20	−7.4 (4)
C4—C5—C7—C21	−47.1 (6)	C16—N2—C21—C7	−8.2 (4)
C6—C5—C7—C8	14.0 (4)	C15—N2—C21—C7	116.9 (3)
C4—C5—C7—C8	−171.8 (4)	C5—C7—C21—C20	−85.1 (4)
C9—N1—C8—C18	46.7 (4)	C17—C7—C21—C20	152.4 (3)
C6—N1—C8—C18	−110.8 (3)	C8—C7—C21—C20	33.1 (5)
C9—N1—C8—C7	171.2 (3)	C5—C7—C21—N2	153.8 (3)
C6—N1—C8—C7	13.7 (4)	C17—C7—C21—N2	31.3 (3)
C5—C7—C8—N1	−16.2 (4)	C8—C7—C21—N2	−88.0 (4)
C17—C7—C8—N1	104.1 (3)	O6—C24—C25—C30	−22.0 (6)
C21—C7—C8—N1	−141.5 (3)	O5—C24—C25—C30	158.4 (4)
C5—C7—C8—C18	101.2 (4)	O6—C24—C25—C26	155.9 (4)
C17—C7—C8—C18	−138.5 (3)	O5—C24—C25—C26	−23.8 (6)
C21—C7—C8—C18	−24.1 (5)	C30—C25—C26—C27	1.0 (6)
C6—N1—C9—O4	−23.4 (6)	C24—C25—C26—C27	−176.8 (4)
C8—N1—C9—O4	−176.4 (4)	C25—C26—C27—C28	−1.9 (6)
C6—N1—C9—C10	158.1 (4)	C25—C26—C27—N3	176.3 (4)
C8—N1—C9—C10	5.1 (5)	O7—N3—C27—C28	−178.0 (4)
O4—C9—C10—C11	148.7 (4)	O8—N3—C27—C28	1.6 (5)
N1—C9—C10—C11	−32.7 (5)	O7—N3—C27—C26	3.7 (6)
C12—O1—C11—C18	−71.1 (4)	O8—N3—C27—C26	−176.7 (4)
C12—O1—C11—C10	169.1 (3)	C26—C27—C28—C29	0.3 (6)
C9—C10—C11—O1	126.8 (3)	N3—C27—C28—C29	−177.9 (4)
C9—C10—C11—C18	4.8 (5)	C27—C28—C29—C30	2.3 (6)
C11—O1—C12—C13	89.4 (4)	C27—C28—C29—N4	−179.3 (3)
O1—C12—C13—C14	−61.9 (5)	O9—N4—C29—C28	168.0 (4)
C12—C13—C14—C15	175.9 (4)	O10—N4—C29—C28	−10.0 (5)
C12—C13—C14—C19	−4.4 (6)	O9—N4—C29—C30	−13.5 (5)
C13—C14—C15—N2	−124.9 (4)	O10—N4—C29—C30	168.5 (3)
C19—C14—C15—N2	55.3 (4)	C28—C29—C30—C25	−3.2 (6)
C16—N2—C15—C14	73.7 (4)	N4—C29—C30—C25	178.4 (4)
C21—N2—C15—C14	−48.8 (4)	C26—C25—C30—C29	1.4 (6)
C15—N2—C16—C17	−144.8 (3)	C24—C25—C30—C29	179.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5	0.93	1.72	2.632 (4)	168
O1W—H11W···O4^i	0.88	1.94	2.817 (4)	175.4
O1W—H12W···O6	0.88	1.93	2.805 (4)	174.4
O2W—H21W···O9^ii	0.88	2.35	3.163 (4)	153.5
O2W—H22W···O3W	0.88	1.99	2.850 (4)	166.2
O3W—H31W···O5^iii	0.88	1.93	2.801 (4)	167.4
O3W—H32W···O1W	0.87	1.96	2.826 (4)	170.1

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x−1/2, −y+5/2, −z+1; (iii) x−1/2, −y+3/2, −z+1.