Isomorphous brucinium 4-nitro­benzoate methanol solvate and brucinium 4-nitro­benzoate dihydrate

In isomorphous crystals of brucinium 4-nitro­benzoate methanol solvate, C₂₃H₂₇N₂O₄⁺·C₇H₄NO₄^-·CH₃OH, and brucinium 4-nitro­benzoate dihydrate, C₂₃H₂₇N₂O₄⁺·C₇H₄NO₄^-·2H₂O, the brucinium cations form reverse corrugated layers, in which the amine N and amide O atoms of the brucinium cations are located in the grooves and at convex points of the layer surface, respectively. Similarly, as observed for the commonly occurring corrugated brucinium layers, the amide O atoms of the cations are involved in hydrogen bonds in which solvent mol­ecules are the donors.

S1. Comment

Brucine is a common resolving agent used for separation of racemic acids by fractional crystallization of brucinium diastereomeric salts (Jacques et al., 1991). In many crystals of brucinium salts, the cations form corrugated layers separated by guest anions and solvent molecules. A common feature of these layers is that the amine N and the amide O atoms of brucine molecules are located at convex and concave points of the corrugated layer surface. The amide O atoms are involved in hydrogen bonds in which solvent molecules are usually the donors (Bialonska & Ciunik, 2006).

Crystallization and recrystallization of the brucinium salt of 3,5-dinitrobenzoic acid led to the formation of various pseudopolymorphic crystals of brucinium salts. Isomorphous crystals of brucinium 4-nitrobenzoate methanol solvate, (I), and brucinium 4-nitrobenzoate dihydrate, (II), were obtained from methanol solution.

In (I) and (II), the brucinium cation and the 4-nitrobenzoate anion are linked to each other by ionic hydrogen bonds. In the ionic N—H⁺···O^- hydrogen bond, the protonated amine N2 atom of the brucinium cation and atom O5 of the deprotonated carboxyl group of the 4-nitrobenzoate anion are the donor and acceptor, respectively (Fig. 1, and Tables 1 and 2). The amide O4 atom of the brucinium cation accepts an O—H···O hydrogen bond from the methanol atom O31 or the water O2W molecule in (I) and (II), respectively. In (II), the O2W molecule is also a donor to the water atom O1W. Atom O1W in turn is a donor to atom O1 of the cation at (-x, y + 1/2, -z + 1) and to atom O6 of the anion at (-x, y + 1/2, -z) (Table 2).

In (I) and (II), the cations form corrugated layers (Fig. 2a). However, compared with the usual brucinium corrugated layers (Fig. 2b), the layers in (I) and (II) reveal a reverse corrugation. This means that the amine N2 and amide O4 atoms of the cations, which are located at convex points and in grooves, respectively, of a surface of the usual corrugated layers, are found in grooves and at convex points of the layer surface in (I) and (II). The reverse corrugated layers in (I) and (II) are stabilized by C—H···O and C—H···π hydrogen bonds. Among them, the shortest intermolecular contacts between brucinium cations are found for C17—H17A···O2(1 - x, -1/2 + y, -z) and C15—H15A···Cp1 (-x, -1/2 + y, -z) hydrogen bonds (Cp1 is the centroid of the C1–C6 arene ring).

Related literature

For related literature, see: Bialonska & Ciunik (2006); Jacques et al. (1991); Toda et al. (1985).

S2. Experimental

Crystals of (I) were grown from a methanol solution containing an equimolar amount of brucine (commercially available) and 4-nitrobenzoic acid. Crystals of (II) were obtained from a sample containing crystals of (I) dissolved in methanol solution by heating. The crystallization and recrystallization were performed at room temperature by slow evaporation of solvent.

S3. Refinement

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) and (II) 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) compound (I) and (b) compound (II). Non-H atoms are shown as 30% probability displacement ellipsoids.

Fig. 2. (a) The packing in (II), where brucinium cations (open bonds) form reverse corrugated layers. (b) The packing in brucinium 4-nitrobenzoate 2.6 hydrate (see supplementary materials), where brucinium cations form common corrugated layers separated by anion/water sheets. Water molecules and 4-nitrobenzoate anions with occupancy equal to 0.4 have been omitted. Crystals of brucinium 4-nitrobenzoate 2.6 hydrate were grown from ethanol solution. For clarity, H atoms have been omitted.

(I) brucinium 4-nitrobenzoate methanol solvate

Crystal data

C23H27N2O4^+·C7H4NO4^−·CH4O	F(000) = 628
Mr = 593.62	Dx = 1.441 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5682 reflections
a = 9.830 (2) Å	θ = 3.5–28.1°
b = 12.364 (3) Å	µ = 0.11 mm^−1
c = 11.560 (3) Å	T = 100 K
β = 103.09 (3)°	Block, yellow
V = 1368.5 (6) Å^3	0.25 × 0.25 × 0.20 mm
Z = 2

Data collection

Kuma KM-4-CCD diffractometer	2492 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 27.0°, θmin = 3.5°
ω scans	h = −12→12
9166 measured reflections	k = −12→15
3078 independent reflections	l = −14→13

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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0734P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.004
3078 reflections	Δρmax = 0.26 e Å^−3
388 parameters	Δρmin = −0.30 e Å^−3
1 restraint	Absolute 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	0.1281 (3)	0.3471 (2)	0.4813 (2)	0.0262 (6)
O2	0.3574 (3)	0.8443 (2)	0.0189 (2)	0.0258 (6)
O3	0.3296 (3)	0.7037 (2)	−0.1462 (2)	0.0263 (6)
O4	0.2505 (3)	0.7043 (2)	0.4065 (3)	0.0295 (7)
N1	0.2673 (3)	0.5555 (3)	0.2921 (3)	0.0221 (7)
N2	0.1864 (3)	0.2286 (3)	0.0918 (3)	0.0240 (7)
H2	0.1901	0.1953	0.0204	0.029*
C1	0.3178 (4)	0.7131 (3)	0.1665 (4)	0.0233 (8)
H1	0.3296	0.7652	0.2284	0.028*
C2	0.3311 (4)	0.7409 (3)	0.0532 (4)	0.0234 (8)
C3	0.3135 (4)	0.6634 (3)	−0.0380 (3)	0.0214 (8)
C4	0.2850 (4)	0.5562 (3)	−0.0174 (4)	0.0222 (8)
H4	0.2759	0.5035	−0.0785	0.027*
C5	0.2700 (4)	0.5282 (3)	0.0963 (4)	0.0207 (8)
C6	0.2862 (4)	0.6046 (3)	0.1856 (3)	0.0199 (8)
C7	0.2507 (4)	0.4163 (3)	0.1436 (3)	0.0219 (8)
C8	0.2232 (4)	0.4404 (3)	0.2678 (3)	0.0215 (8)
H8	0.2835	0.3925	0.3280	0.026*
C9	0.2339 (4)	0.6063 (3)	0.3873 (4)	0.0255 (9)
C10	0.1798 (4)	0.5323 (3)	0.4707 (4)	0.0252 (9)
H10A	0.1337	0.5776	0.5212	0.030*
H10B	0.2611	0.4972	0.5236	0.030*
C11	0.0765 (4)	0.4428 (3)	0.4146 (3)	0.0239 (8)
H11	−0.0188	0.4605	0.4263	0.029*
C12	0.0391 (4)	0.2538 (3)	0.4566 (4)	0.0279 (9)
H12A	−0.0597	0.2774	0.4361	0.033*
H12B	0.0527	0.2081	0.5286	0.033*
C13	0.0695 (4)	0.1884 (3)	0.3560 (4)	0.0264 (9)
H13	0.1031	0.1166	0.3712	0.032*
C14	0.0509 (4)	0.2277 (3)	0.2459 (4)	0.0244 (9)
C15	0.0898 (4)	0.1634 (3)	0.1486 (4)	0.0277 (9)
H15A	0.0046	0.1443	0.0882	0.033*
H15B	0.1365	0.0956	0.1814	0.033*
C16	0.3320 (4)	0.2315 (3)	0.1674 (4)	0.0247 (9)
H16A	0.3918	0.1771	0.1402	0.030*
H16B	0.3319	0.2172	0.2516	0.030*
C17	0.3832 (4)	0.3457 (3)	0.1519 (4)	0.0230 (8)
H17A	0.4188	0.3516	0.0785	0.028*
H17B	0.4581	0.3672	0.2207	0.028*
C18	0.0716 (4)	0.4337 (3)	0.2817 (3)	0.0223 (8)
H18	0.0250	0.5013	0.2450	0.027*
C19	−0.0100 (4)	0.3398 (3)	0.2109 (3)	0.0230 (8)
H19	−0.1085	0.3417	0.2204	0.028*
C20	−0.0093 (4)	0.3617 (3)	0.0801 (3)	0.0232 (8)
H20A	−0.0740	0.3114	0.0280	0.028*
H20B	−0.0405	0.4366	0.0585	0.028*
C21	0.1376 (4)	0.3457 (3)	0.0639 (4)	0.0222 (8)
H21	0.1382	0.3610	−0.0209	0.027*
C22	0.3869 (5)	0.9245 (3)	0.1103 (4)	0.0303 (9)
H22A	0.4039	0.9942	0.0758	0.045*
H22B	0.4700	0.9032	0.1703	0.045*
H22C	0.3071	0.9311	0.1476	0.045*
C23	0.3040 (5)	0.6289 (3)	−0.2437 (4)	0.0299 (10)
H23A	0.3184	0.6653	−0.3152	0.045*
H23B	0.2076	0.6026	−0.2576	0.045*
H23C	0.3685	0.5677	−0.2248	0.045*
O5	0.2011 (3)	0.1332 (2)	−0.1007 (3)	0.0325 (7)
O6	0.2924 (3)	0.2916 (2)	−0.1420 (3)	0.0330 (7)
O7	0.4683 (3)	−0.1051 (2)	−0.5409 (3)	0.0359 (7)
O8	0.4533 (4)	0.0489 (2)	−0.6329 (3)	0.0369 (8)
N3	0.4396 (4)	−0.0082 (3)	−0.5480 (3)	0.0271 (8)
C24	0.2648 (4)	0.1948 (3)	−0.1619 (4)	0.0271 (9)
C25	0.3077 (4)	0.1406 (3)	−0.2650 (4)	0.0239 (8)
C26	0.3005 (4)	0.0278 (3)	−0.2780 (4)	0.0267 (9)
H26	0.2672	−0.0151	−0.2221	0.032*
C27	0.3418 (4)	−0.0209 (3)	−0.3723 (4)	0.0246 (9)
H27	0.3370	−0.0972	−0.3822	0.029*
C28	0.3902 (4)	0.0437 (3)	−0.4513 (4)	0.0216 (8)
C29	0.3975 (4)	0.1551 (3)	−0.4414 (4)	0.0257 (9)
H29	0.4301	0.1976	−0.4980	0.031*
C30	0.3559 (4)	0.2032 (3)	−0.3468 (3)	0.0253 (9)
H30	0.3604	0.2796	−0.3379	0.030*
O31	0.1507 (3)	0.9138 (3)	0.3399 (3)	0.0442 (9)
H31	0.1841	0.8536	0.3545	0.066*
C31	0.0203 (5)	0.8840 (4)	0.2673 (4)	0.0367 (11)
H31A	−0.0219	0.9436	0.2149	0.055*
H31B	0.0313	0.8215	0.2220	0.055*
H31C	−0.0463	0.8613	0.3108	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0237 (15)	0.0221 (14)	0.0312 (15)	−0.0033 (12)	0.0023 (11)	0.0018 (12)
O2	0.0302 (16)	0.0154 (13)	0.0328 (16)	−0.0027 (12)	0.0093 (12)	−0.0036 (12)
O3	0.0316 (16)	0.0220 (14)	0.0260 (15)	−0.0025 (12)	0.0081 (12)	−0.0031 (12)
O4	0.0325 (16)	0.0190 (14)	0.0373 (17)	−0.0022 (12)	0.0084 (13)	−0.0042 (13)
N1	0.0207 (17)	0.0161 (16)	0.0293 (18)	−0.0024 (12)	0.0051 (13)	−0.0048 (13)
N2	0.0250 (18)	0.0193 (18)	0.0289 (18)	−0.0011 (13)	0.0086 (14)	−0.0041 (14)
C1	0.0176 (19)	0.020 (2)	0.032 (2)	0.0014 (15)	0.0049 (15)	−0.0040 (17)
C2	0.0180 (19)	0.0186 (19)	0.033 (2)	−0.0009 (16)	0.0044 (16)	0.0003 (17)
C3	0.019 (2)	0.0215 (19)	0.024 (2)	0.0031 (15)	0.0058 (15)	−0.0011 (16)
C4	0.0173 (19)	0.021 (2)	0.028 (2)	−0.0018 (15)	0.0065 (15)	−0.0055 (16)
C5	0.0161 (19)	0.0169 (19)	0.029 (2)	−0.0007 (15)	0.0051 (15)	−0.0020 (16)
C6	0.0179 (19)	0.0185 (19)	0.023 (2)	0.0001 (15)	0.0047 (15)	0.0004 (16)
C7	0.020 (2)	0.0156 (18)	0.030 (2)	−0.0002 (15)	0.0067 (15)	−0.0038 (16)
C8	0.025 (2)	0.0134 (19)	0.027 (2)	−0.0025 (15)	0.0076 (16)	−0.0036 (16)
C9	0.021 (2)	0.024 (2)	0.030 (2)	0.0000 (16)	0.0033 (16)	0.0000 (17)
C10	0.028 (2)	0.020 (2)	0.030 (2)	0.0011 (17)	0.0122 (17)	−0.0007 (17)
C11	0.020 (2)	0.020 (2)	0.031 (2)	0.0030 (15)	0.0033 (15)	−0.0035 (17)
C12	0.026 (2)	0.025 (2)	0.033 (2)	−0.0056 (17)	0.0081 (17)	−0.0002 (18)
C13	0.024 (2)	0.018 (2)	0.037 (2)	−0.0021 (16)	0.0063 (17)	−0.0007 (17)
C14	0.0179 (19)	0.023 (2)	0.034 (2)	−0.0019 (15)	0.0080 (16)	−0.0017 (17)
C15	0.029 (2)	0.018 (2)	0.039 (2)	−0.0049 (16)	0.0128 (18)	−0.0048 (17)
C16	0.019 (2)	0.019 (2)	0.036 (2)	0.0020 (15)	0.0057 (16)	−0.0007 (17)
C17	0.0162 (19)	0.022 (2)	0.031 (2)	0.0008 (16)	0.0076 (15)	−0.0012 (17)
C18	0.018 (2)	0.0136 (18)	0.035 (2)	−0.0032 (15)	0.0051 (16)	−0.0031 (17)
C19	0.0171 (19)	0.0189 (19)	0.034 (2)	−0.0019 (15)	0.0067 (15)	−0.0018 (17)
C20	0.0203 (19)	0.020 (2)	0.028 (2)	−0.0023 (15)	0.0028 (15)	−0.0053 (16)
C21	0.025 (2)	0.0134 (18)	0.028 (2)	−0.0030 (15)	0.0044 (15)	−0.0022 (16)
C22	0.034 (2)	0.020 (2)	0.038 (2)	−0.0065 (18)	0.0098 (18)	−0.0081 (18)
C23	0.032 (2)	0.027 (2)	0.029 (2)	0.0009 (18)	0.0049 (18)	−0.0082 (18)
O5	0.0394 (18)	0.0254 (16)	0.0356 (17)	−0.0058 (13)	0.0148 (14)	−0.0050 (13)
O6	0.0401 (18)	0.0213 (16)	0.0402 (18)	−0.0050 (13)	0.0145 (14)	−0.0069 (13)
O7	0.0386 (18)	0.0244 (17)	0.047 (2)	0.0056 (13)	0.0151 (14)	−0.0010 (14)
O8	0.047 (2)	0.0300 (17)	0.0385 (18)	−0.0024 (14)	0.0198 (15)	−0.0014 (14)
N3	0.0301 (19)	0.0197 (19)	0.033 (2)	−0.0020 (15)	0.0109 (15)	−0.0037 (15)
C24	0.022 (2)	0.026 (2)	0.034 (2)	−0.0021 (17)	0.0073 (17)	−0.0042 (19)
C25	0.023 (2)	0.023 (2)	0.026 (2)	−0.0002 (16)	0.0053 (15)	−0.0016 (16)
C26	0.024 (2)	0.027 (2)	0.029 (2)	−0.0035 (17)	0.0071 (17)	0.0012 (17)
C27	0.024 (2)	0.018 (2)	0.033 (2)	0.0012 (16)	0.0090 (17)	−0.0017 (17)
C28	0.021 (2)	0.0191 (19)	0.026 (2)	−0.0025 (15)	0.0092 (16)	−0.0045 (16)
C29	0.027 (2)	0.022 (2)	0.028 (2)	−0.0039 (16)	0.0061 (17)	−0.0007 (17)
C30	0.028 (2)	0.0172 (19)	0.031 (2)	0.0001 (16)	0.0071 (17)	−0.0004 (17)
O31	0.0379 (19)	0.0251 (17)	0.062 (2)	−0.0018 (14)	−0.0056 (16)	−0.0074 (16)
C31	0.033 (2)	0.032 (2)	0.042 (3)	−0.0059 (19)	0.0015 (19)	0.001 (2)

Geometric parameters (Å, º)

O1—C12	1.438 (5)	C15—H15B	0.9900
O1—C11	1.441 (5)	C16—C17	1.523 (5)
O2—C2	1.381 (5)	C16—H16A	0.9900
O2—C22	1.431 (5)	C16—H16B	0.9900
O3—C3	1.388 (5)	C17—H17A	0.9900
O3—C23	1.436 (5)	C17—H17B	0.9900
O4—C9	1.236 (5)	C18—C19	1.537 (5)
N1—C9	1.370 (5)	C18—H18	1.0000
N1—C6	1.423 (5)	C19—C20	1.538 (6)
N1—C8	1.495 (5)	C19—H19	1.0000
N2—C16	1.498 (5)	C20—C21	1.510 (5)
N2—C15	1.505 (5)	C20—H20A	0.9900
N2—C21	1.536 (5)	C20—H20B	0.9900
N2—H2	0.9300	C21—H21	1.0000
C1—C2	1.388 (6)	C22—H22A	0.9800
C1—C6	1.406 (5)	C22—H22B	0.9800
C1—H1	0.9500	C22—H22C	0.9800
C2—C3	1.405 (6)	C23—H23A	0.9800
C3—C4	1.387 (5)	C23—H23B	0.9800
C4—C5	1.399 (6)	C23—H23C	0.9800
C4—H4	0.9500	O5—C24	1.294 (5)
C5—C6	1.381 (5)	O6—C24	1.237 (5)
C5—C7	1.515 (5)	O7—N3	1.229 (4)
C7—C21	1.544 (5)	O8—N3	1.240 (4)
C7—C8	1.549 (5)	N3—C28	1.463 (5)
C7—C17	1.553 (5)	C24—C25	1.509 (6)
C8—C18	1.538 (5)	C25—C30	1.385 (6)
C8—H8	1.0000	C25—C26	1.402 (6)
C9—C10	1.511 (6)	C26—C27	1.384 (6)
C10—C11	1.542 (5)	C26—H26	0.9500
C10—H10A	0.9900	C27—C28	1.377 (6)
C10—H10B	0.9900	C27—H27	0.9500
C11—C18	1.530 (6)	C28—C29	1.382 (5)
C11—H11	1.0000	C29—C30	1.385 (5)
C12—C13	1.501 (6)	C29—H29	0.9500
C12—H12A	0.9900	C30—H30	0.9500
C12—H12B	0.9900	O31—C31	1.413 (5)
C13—C14	1.336 (6)	O31—H31	0.8164
C13—H13	0.9500	C31—H31A	0.9839
C14—C15	1.496 (5)	C31—H31B	0.9528
C14—C19	1.527 (5)	C31—H31C	0.9541
C15—H15A	0.9900
C12—O1—C11	115.3 (3)	C17—C16—H16A	110.8
C2—O2—C22	116.7 (3)	N2—C16—H16B	110.8
C3—O3—C23	116.1 (3)	C17—C16—H16B	110.8
C9—N1—C6	127.0 (3)	H16A—C16—H16B	108.9
C9—N1—C8	118.4 (3)	C16—C17—C7	103.5 (3)
C6—N1—C8	109.4 (3)	C16—C17—H17A	111.1
C16—N2—C15	111.8 (3)	C7—C17—H17A	111.1
C16—N2—C21	108.2 (3)	C16—C17—H17B	111.1
C15—N2—C21	113.4 (3)	C7—C17—H17B	111.1
C16—N2—H2	107.7	H17A—C17—H17B	109.0
C15—N2—H2	107.7	C11—C18—C8	106.9 (3)
C21—N2—H2	107.7	C11—C18—C19	119.0 (3)
C2—C1—C6	117.1 (4)	C8—C18—C19	112.7 (3)
C2—C1—H1	121.5	C11—C18—H18	105.8
C6—C1—H1	121.5	C8—C18—H18	105.8
O2—C2—C1	124.3 (3)	C19—C18—H18	105.8
O2—C2—C3	114.5 (3)	C14—C19—C18	114.7 (3)
C1—C2—C3	121.1 (4)	C14—C19—C20	109.4 (3)
C4—C3—O3	124.5 (3)	C18—C19—C20	105.8 (3)
C4—C3—C2	121.2 (4)	C14—C19—H19	108.9
O3—C3—C2	114.3 (3)	C18—C19—H19	108.9
C3—C4—C5	117.8 (4)	C20—C19—H19	108.9
C3—C4—H4	121.1	C21—C20—C19	108.4 (3)
C5—C4—H4	121.1	C21—C20—H20A	110.0
C6—C5—C4	120.9 (4)	C19—C20—H20A	110.0
C6—C5—C7	111.0 (3)	C21—C20—H20B	110.0
C4—C5—C7	127.8 (3)	C19—C20—H20B	110.0
C5—C6—C1	121.8 (4)	H20A—C20—H20B	108.4
C5—C6—N1	109.8 (3)	C20—C21—N2	111.1 (3)
C1—C6—N1	128.4 (3)	C20—C21—C7	115.6 (3)
C5—C7—C21	115.7 (3)	N2—C21—C7	105.0 (3)
C5—C7—C8	102.7 (3)	C20—C21—H21	108.3
C21—C7—C8	114.1 (3)	N2—C21—H21	108.3
C5—C7—C17	111.4 (3)	C7—C21—H21	108.3
C21—C7—C17	101.5 (3)	O2—C22—H22A	109.5
C8—C7—C17	111.8 (3)	O2—C22—H22B	109.5
N1—C8—C18	106.1 (3)	H22A—C22—H22B	109.5
N1—C8—C7	104.7 (3)	O2—C22—H22C	109.5
C18—C8—C7	117.6 (3)	H22A—C22—H22C	109.5
N1—C8—H8	109.3	H22B—C22—H22C	109.5
C18—C8—H8	109.3	O3—C23—H23A	109.5
C7—C8—H8	109.3	O3—C23—H23B	109.5
O4—C9—N1	123.3 (4)	H23A—C23—H23B	109.5
O4—C9—C10	122.0 (4)	O3—C23—H23C	109.5
N1—C9—C10	114.7 (3)	H23A—C23—H23C	109.5
C9—C10—C11	117.4 (3)	H23B—C23—H23C	109.5
C9—C10—H10A	108.0	O7—N3—O8	122.9 (4)
C11—C10—H10A	108.0	O7—N3—C28	119.2 (4)
C9—C10—H10B	108.0	O8—N3—C28	118.0 (3)
C11—C10—H10B	108.0	O6—C24—O5	125.5 (4)
H10A—C10—H10B	107.2	O6—C24—C25	119.2 (4)
O1—C11—C18	113.8 (3)	O5—C24—C25	115.2 (4)
O1—C11—C10	104.2 (3)	C30—C25—C26	120.0 (4)
C18—C11—C10	110.1 (3)	C30—C25—C24	119.3 (4)
O1—C11—H11	109.5	C26—C25—C24	120.7 (4)
C18—C11—H11	109.5	C27—C26—C25	120.0 (4)
C10—C11—H11	109.5	C27—C26—H26	120.0
O1—C12—C13	111.5 (3)	C25—C26—H26	120.0
O1—C12—H12A	109.3	C28—C27—C26	118.4 (4)
C13—C12—H12A	109.3	C28—C27—H27	120.8
O1—C12—H12B	109.3	C26—C27—H27	120.8
C13—C12—H12B	109.3	C27—C28—C29	122.8 (4)
H12A—C12—H12B	108.0	C27—C28—N3	118.4 (3)
C14—C13—C12	122.3 (4)	C29—C28—N3	118.7 (4)
C14—C13—H13	118.9	C28—C29—C30	118.3 (4)
C12—C13—H13	118.9	C28—C29—H29	120.8
C13—C14—C15	121.3 (4)	C30—C29—H29	120.8
C13—C14—C19	122.9 (4)	C25—C30—C29	120.4 (4)
C15—C14—C19	115.8 (3)	C25—C30—H30	119.8
C14—C15—N2	109.7 (3)	C29—C30—H30	119.8
C14—C15—H15A	109.7	C31—O31—H31	98.8
N2—C15—H15A	109.7	O31—C31—H31A	111.7
C14—C15—H15B	109.7	O31—C31—H31B	109.8
N2—C15—H15B	109.7	H31A—C31—H31B	110.8
H15A—C15—H15B	108.2	O31—C31—H31C	113.7
N2—C16—C17	104.5 (3)	H31A—C31—H31C	107.5
N2—C16—H16A	110.8	H31B—C31—H31C	103.1
C22—O2—C2—C1	6.7 (5)	C16—N2—C15—C14	76.5 (4)
C22—O2—C2—C3	−175.3 (3)	C21—N2—C15—C14	−46.2 (4)
C6—C1—C2—O2	177.9 (3)	C15—N2—C16—C17	−142.5 (3)
C6—C1—C2—C3	0.0 (5)	C21—N2—C16—C17	−16.8 (4)
C23—O3—C3—C4	4.8 (5)	N2—C16—C17—C7	36.4 (4)
C23—O3—C3—C2	−176.3 (3)	C5—C7—C17—C16	−165.2 (3)
O2—C2—C3—C4	−179.4 (3)	C21—C7—C17—C16	−41.5 (4)
C1—C2—C3—C4	−1.3 (6)	C8—C7—C17—C16	80.5 (4)
O2—C2—C3—O3	1.7 (5)	O1—C11—C18—C8	−73.5 (4)
C1—C2—C3—O3	179.8 (3)	C10—C11—C18—C8	43.1 (4)
O3—C3—C4—C5	−179.2 (3)	O1—C11—C18—C19	55.5 (4)
C2—C3—C4—C5	2.0 (5)	C10—C11—C18—C19	172.1 (3)
C3—C4—C5—C6	−1.5 (5)	N1—C8—C18—C11	−72.1 (4)
C3—C4—C5—C7	−174.5 (4)	C7—C8—C18—C11	171.1 (3)
C4—C5—C6—C1	0.2 (6)	N1—C8—C18—C19	155.4 (3)
C7—C5—C6—C1	174.4 (3)	C7—C8—C18—C19	38.6 (5)
C4—C5—C6—N1	−179.4 (3)	C13—C14—C19—C18	58.1 (5)
C7—C5—C6—N1	−5.2 (4)	C15—C14—C19—C18	−121.6 (4)
C2—C1—C6—C5	0.5 (5)	C13—C14—C19—C20	176.9 (4)
C2—C1—C6—N1	180.0 (4)	C15—C14—C19—C20	−2.9 (4)
C9—N1—C6—C5	−159.0 (4)	C11—C18—C19—C14	−66.0 (4)
C8—N1—C6—C5	−5.2 (4)	C8—C18—C19—C14	60.3 (4)
C9—N1—C6—C1	21.5 (6)	C11—C18—C19—C20	173.3 (3)
C8—N1—C6—C1	175.2 (4)	C8—C18—C19—C20	−60.4 (4)
C6—C5—C7—C21	137.8 (3)	C14—C19—C20—C21	−54.6 (4)
C4—C5—C7—C21	−48.6 (5)	C18—C19—C20—C21	69.6 (4)
C6—C5—C7—C8	12.8 (4)	C19—C20—C21—N2	62.0 (4)
C4—C5—C7—C8	−173.6 (4)	C19—C20—C21—C7	−57.5 (4)
C6—C5—C7—C17	−107.0 (4)	C16—N2—C21—C20	−134.9 (3)
C4—C5—C7—C17	66.6 (5)	C15—N2—C21—C20	−10.2 (4)
C9—N1—C8—C18	44.1 (4)	C16—N2—C21—C7	−9.3 (4)
C6—N1—C8—C18	−112.2 (3)	C15—N2—C21—C7	115.4 (3)
C9—N1—C8—C7	169.3 (3)	C5—C7—C21—C20	−85.7 (4)
C6—N1—C8—C7	13.0 (4)	C8—C7—C21—C20	33.2 (5)
C5—C7—C8—N1	−14.9 (4)	C17—C7—C21—C20	153.7 (3)
C21—C7—C8—N1	−140.9 (3)	C5—C7—C21—N2	151.6 (3)
C17—C7—C8—N1	104.6 (3)	C8—C7—C21—N2	−89.6 (4)
C5—C7—C8—C18	102.6 (4)	C17—C7—C21—N2	30.9 (4)
C21—C7—C8—C18	−23.4 (5)	O6—C24—C25—C30	−10.6 (6)
C17—C7—C8—C18	−137.9 (3)	O5—C24—C25—C30	169.7 (4)
C6—N1—C9—O4	−19.4 (6)	O6—C24—C25—C26	168.8 (4)
C8—N1—C9—O4	−171.0 (4)	O5—C24—C25—C26	−10.9 (6)
C6—N1—C9—C10	162.9 (4)	C30—C25—C26—C27	0.2 (6)
C8—N1—C9—C10	11.2 (5)	C24—C25—C26—C27	−179.2 (4)
O4—C9—C10—C11	140.7 (4)	C25—C26—C27—C28	0.3 (6)
N1—C9—C10—C11	−41.5 (5)	C26—C27—C28—C29	−0.9 (6)
C12—O1—C11—C18	−67.9 (4)	C26—C27—C28—N3	177.4 (4)
C12—O1—C11—C10	172.2 (3)	O7—N3—C28—C27	−17.3 (6)
C9—C10—C11—O1	133.6 (3)	O8—N3—C28—C27	164.2 (4)
C9—C10—C11—C18	11.2 (5)	O7—N3—C28—C29	161.0 (4)
C11—O1—C12—C13	88.5 (4)	O8—N3—C28—C29	−17.4 (6)
O1—C12—C13—C14	−63.3 (5)	C27—C28—C29—C30	0.9 (6)
C12—C13—C14—C15	176.3 (4)	N3—C28—C29—C30	−177.4 (3)
C12—C13—C14—C19	−3.4 (6)	C26—C25—C30—C29	−0.2 (6)
C13—C14—C15—N2	−125.9 (4)	C24—C25—C30—C29	179.2 (4)
C19—C14—C15—N2	53.8 (4)	C28—C29—C30—C25	−0.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.93	1.62	2.552 (4)	177
O31—H31···O4	0.82	2.00	2.815 (4)	172

(II) brucinium 4-nitrobenzoate dihydrate

Crystal data

C23H27N2O4^+·C7H4NO4^−·2H2O	F(000) = 632
Mr = 597.61	Dx = 1.449 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7856 reflections
a = 10.085 (2) Å	θ = 3.6–27.0°
b = 12.338 (3) Å	µ = 0.11 mm^−1
c = 11.615 (3) Å	T = 100 K
β = 108.61 (3)°	Block, yellow
V = 1369.7 (6) Å^3	0.30 × 0.30 × 0.30 mm
Z = 2

Data collection

Kuma KM-4-CCD diffractometer	2925 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 27.0°, θmin = 3.6°
ω scans	h = −11→12
9184 measured reflections	k = −15→14
3110 independent reflections	l = −14→14

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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0521P)^2 + 0.1159P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3110 reflections	Δρmax = 0.23 e Å^−3
388 parameters	Δρmin = −0.20 e Å^−3
1 restraint	Absolute 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	0.11911 (15)	0.35539 (12)	0.44381 (12)	0.0177 (3)
O2	0.36548 (15)	0.84592 (11)	0.00778 (12)	0.0163 (3)
O3	0.32463 (15)	0.70986 (12)	−0.16503 (12)	0.0176 (3)
O4	0.25676 (16)	0.70753 (12)	0.37666 (13)	0.0206 (3)
N1	0.27349 (17)	0.55629 (13)	0.26796 (14)	0.0128 (3)
N2	0.17895 (17)	0.23094 (13)	0.05939 (15)	0.0141 (3)
H2	0.1812	0.1962	−0.0110	0.017*
C1	0.3280 (2)	0.71275 (16)	0.14959 (18)	0.0137 (4)
H1	0.3451	0.7630	0.2146	0.016*
C2	0.3377 (2)	0.74346 (16)	0.03704 (18)	0.0140 (4)
C3	0.3124 (2)	0.66794 (16)	−0.05899 (17)	0.0137 (4)
C4	0.2807 (2)	0.56053 (16)	−0.04231 (17)	0.0130 (4)
H4	0.2670	0.5090	−0.1058	0.016*
C5	0.26952 (19)	0.53025 (16)	0.07075 (17)	0.0127 (4)
C6	0.29209 (19)	0.60531 (16)	0.16310 (17)	0.0122 (4)
C7	0.24892 (19)	0.41811 (16)	0.11471 (17)	0.0118 (4)
C8	0.2240 (2)	0.44285 (15)	0.23831 (16)	0.0115 (4)
H8	0.2821	0.3928	0.3024	0.014*
C9	0.2394 (2)	0.60976 (17)	0.35811 (17)	0.0148 (4)
C10	0.1816 (2)	0.53845 (17)	0.43710 (18)	0.0164 (4)
H10A	0.1368	0.5858	0.4829	0.020*
H10B	0.2611	0.5016	0.4972	0.020*
C11	0.0742 (2)	0.45114 (16)	0.37080 (17)	0.0146 (4)
H11	−0.0208	0.4726	0.3723	0.018*
C12	0.0257 (2)	0.26399 (17)	0.40795 (19)	0.0195 (4)
H12A	−0.0719	0.2904	0.3750	0.023*
H12B	0.0329	0.2188	0.4801	0.023*
C13	0.0595 (2)	0.19608 (18)	0.31369 (18)	0.0172 (4)
H13	0.0933	0.1243	0.3334	0.021*
C14	0.0429 (2)	0.23470 (16)	0.20289 (18)	0.0149 (4)
C15	0.0807 (2)	0.16860 (16)	0.10923 (18)	0.0162 (4)
H15A	−0.0053	0.1499	0.0422	0.019*
H15B	0.1259	0.1002	0.1464	0.019*
C16	0.3262 (2)	0.23310 (16)	0.14690 (19)	0.0170 (4)
H16A	0.3847	0.1771	0.1255	0.020*
H16B	0.3267	0.2205	0.2312	0.020*
C17	0.3792 (2)	0.34588 (16)	0.13331 (18)	0.0151 (4)
H17A	0.4132	0.3499	0.0623	0.018*
H17B	0.4558	0.3674	0.2071	0.018*
C18	0.0714 (2)	0.44026 (16)	0.23870 (17)	0.0127 (4)
H18	0.0277	0.5086	0.1975	0.015*
C19	−0.01409 (19)	0.34765 (16)	0.16197 (17)	0.0132 (4)
H19	−0.1124	0.3523	0.1637	0.016*
C20	−0.01399 (19)	0.36740 (17)	0.03092 (17)	0.0143 (4)
H20A	−0.0801	0.3171	−0.0255	0.017*
H20B	−0.0440	0.4426	0.0059	0.017*
C21	0.1334 (2)	0.34879 (15)	0.02627 (17)	0.0128 (4)
H21	0.1338	0.3631	−0.0584	0.015*
C22	0.4016 (2)	0.92377 (17)	0.10423 (19)	0.0190 (4)
H22A	0.4190	0.9942	0.0727	0.028*
H22B	0.4860	0.8999	0.1682	0.028*
H22C	0.3243	0.9306	0.1379	0.028*
C23	0.3030 (2)	0.63603 (17)	−0.26413 (18)	0.0176 (4)
H23A	0.3178	0.6737	−0.3333	0.026*
H23B	0.2071	0.6080	−0.2877	0.026*
H23C	0.3692	0.5757	−0.2394	0.026*
O5	0.20541 (17)	0.11227 (14)	−0.12251 (14)	0.0233 (3)
O6	0.28463 (18)	0.27240 (13)	−0.16032 (15)	0.0266 (4)
O7	0.47545 (18)	−0.10552 (13)	−0.55168 (15)	0.0278 (4)
O8	0.44703 (19)	0.04976 (14)	−0.64310 (15)	0.0275 (4)
N3	0.43946 (19)	−0.01034 (15)	−0.56068 (16)	0.0194 (4)
C24	0.2623 (2)	0.17384 (19)	−0.18006 (19)	0.0205 (4)
C25	0.3059 (2)	0.12344 (18)	−0.28173 (18)	0.0165 (4)
C26	0.3050 (2)	0.01188 (18)	−0.29745 (18)	0.0176 (4)
H26	0.2763	−0.0341	−0.2442	0.021*
C27	0.3460 (2)	−0.03304 (17)	−0.39057 (19)	0.0176 (4)
H27	0.3453	−0.1093	−0.4021	0.021*
C28	0.3881 (2)	0.03650 (17)	−0.46619 (18)	0.0155 (4)
C29	0.3901 (2)	0.14808 (17)	−0.45338 (18)	0.0175 (4)
H29	0.4187	0.1937	−0.5070	0.021*
C30	0.3491 (2)	0.19132 (18)	−0.35979 (18)	0.0185 (4)
H30	0.3503	0.2676	−0.3485	0.022*
O1W	−0.11300 (18)	0.91196 (15)	0.32066 (15)	0.0301 (4)
H11W	−0.1689	0.8676	0.2677	0.045*
H12W	−0.1172	0.8950	0.3930	0.045*
O2W	0.14850 (19)	0.92107 (15)	0.28352 (16)	0.0331 (4)
H21W	0.0679	0.9170	0.2975	0.050*
H22W	0.1893	0.8595	0.3133	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0213 (7)	0.0153 (7)	0.0164 (7)	−0.0035 (6)	0.0058 (6)	0.0005 (6)
O2	0.0209 (7)	0.0115 (7)	0.0179 (7)	−0.0026 (6)	0.0081 (6)	−0.0023 (6)
O3	0.0249 (8)	0.0154 (7)	0.0152 (7)	−0.0034 (6)	0.0100 (6)	−0.0014 (6)
O4	0.0304 (8)	0.0125 (7)	0.0217 (7)	−0.0020 (6)	0.0123 (6)	−0.0044 (6)
N1	0.0143 (8)	0.0110 (8)	0.0135 (8)	−0.0016 (6)	0.0050 (6)	−0.0011 (6)
N2	0.0163 (8)	0.0112 (8)	0.0156 (8)	−0.0009 (6)	0.0063 (6)	−0.0022 (6)
C1	0.0126 (9)	0.0135 (9)	0.0155 (9)	−0.0002 (7)	0.0053 (7)	−0.0037 (8)
C2	0.0129 (9)	0.0111 (9)	0.0184 (9)	0.0001 (7)	0.0057 (7)	−0.0005 (8)
C3	0.0137 (9)	0.0149 (10)	0.0137 (9)	−0.0005 (7)	0.0062 (7)	−0.0001 (8)
C4	0.0133 (9)	0.0126 (9)	0.0142 (9)	0.0001 (7)	0.0056 (7)	−0.0023 (7)
C5	0.0097 (8)	0.0122 (9)	0.0164 (9)	0.0005 (7)	0.0047 (7)	0.0002 (8)
C6	0.0092 (8)	0.0133 (9)	0.0141 (9)	−0.0002 (7)	0.0035 (7)	0.0010 (8)
C7	0.0118 (9)	0.0119 (9)	0.0124 (9)	−0.0006 (7)	0.0047 (7)	−0.0005 (7)
C8	0.0132 (9)	0.0096 (9)	0.0118 (9)	−0.0004 (7)	0.0041 (7)	−0.0006 (7)
C9	0.0137 (9)	0.0158 (10)	0.0140 (9)	0.0000 (7)	0.0030 (7)	−0.0015 (8)
C10	0.0195 (10)	0.0155 (10)	0.0157 (9)	−0.0016 (8)	0.0077 (8)	−0.0023 (8)
C11	0.0151 (9)	0.0158 (10)	0.0149 (9)	−0.0012 (8)	0.0075 (7)	−0.0020 (8)
C12	0.0254 (11)	0.0163 (10)	0.0193 (10)	−0.0077 (8)	0.0107 (9)	−0.0013 (8)
C13	0.0173 (10)	0.0142 (10)	0.0212 (10)	−0.0033 (8)	0.0076 (8)	−0.0003 (8)
C14	0.0137 (9)	0.0127 (9)	0.0190 (9)	−0.0034 (7)	0.0060 (7)	−0.0021 (8)
C15	0.0207 (10)	0.0130 (10)	0.0165 (9)	−0.0044 (8)	0.0082 (8)	−0.0014 (8)
C16	0.0145 (9)	0.0152 (10)	0.0206 (10)	0.0011 (8)	0.0046 (8)	−0.0016 (8)
C17	0.0139 (9)	0.0134 (9)	0.0191 (9)	0.0019 (7)	0.0066 (7)	−0.0014 (8)
C18	0.0109 (9)	0.0136 (9)	0.0140 (9)	0.0007 (7)	0.0044 (7)	−0.0017 (7)
C19	0.0109 (8)	0.0135 (9)	0.0151 (9)	−0.0003 (7)	0.0041 (7)	−0.0010 (7)
C20	0.0136 (9)	0.0145 (10)	0.0143 (9)	−0.0021 (7)	0.0036 (7)	−0.0016 (7)
C21	0.0144 (9)	0.0099 (9)	0.0139 (9)	−0.0016 (7)	0.0045 (7)	−0.0014 (7)
C22	0.0243 (11)	0.0113 (9)	0.0208 (10)	−0.0035 (8)	0.0065 (8)	−0.0036 (8)
C23	0.0214 (10)	0.0181 (10)	0.0154 (10)	−0.0002 (8)	0.0089 (8)	−0.0012 (8)
O5	0.0271 (8)	0.0256 (8)	0.0230 (7)	−0.0051 (7)	0.0159 (6)	−0.0053 (6)
O6	0.0366 (10)	0.0235 (9)	0.0239 (8)	−0.0050 (7)	0.0157 (7)	−0.0063 (7)
O7	0.0314 (9)	0.0198 (8)	0.0374 (9)	0.0048 (7)	0.0182 (7)	−0.0032 (7)
O8	0.0384 (9)	0.0255 (9)	0.0261 (8)	−0.0019 (7)	0.0207 (7)	−0.0010 (7)
N3	0.0186 (9)	0.0186 (9)	0.0239 (9)	−0.0020 (7)	0.0110 (7)	−0.0031 (7)
C24	0.0195 (10)	0.0261 (12)	0.0171 (10)	−0.0018 (9)	0.0077 (8)	−0.0042 (9)
C25	0.0129 (9)	0.0219 (11)	0.0142 (9)	−0.0024 (8)	0.0035 (7)	−0.0032 (8)
C26	0.0159 (10)	0.0211 (11)	0.0157 (10)	−0.0014 (8)	0.0048 (8)	0.0040 (8)
C27	0.0165 (10)	0.0144 (10)	0.0221 (10)	0.0004 (8)	0.0066 (8)	0.0003 (8)
C28	0.0128 (9)	0.0190 (10)	0.0146 (9)	0.0006 (8)	0.0043 (7)	−0.0017 (8)
C29	0.0190 (10)	0.0179 (10)	0.0169 (10)	−0.0012 (8)	0.0076 (8)	0.0007 (8)
C30	0.0185 (10)	0.0185 (11)	0.0184 (10)	−0.0025 (8)	0.0056 (8)	−0.0017 (8)
O1W	0.0395 (10)	0.0277 (9)	0.0270 (8)	0.0026 (8)	0.0159 (7)	0.0039 (7)
O2W	0.0344 (10)	0.0242 (9)	0.0434 (10)	0.0014 (7)	0.0161 (8)	0.0028 (8)

Geometric parameters (Å, º)

O1—C11	1.440 (2)	C15—H15A	0.9900
O1—C12	1.443 (2)	C15—H15B	0.9900
O2—C2	1.361 (2)	C16—C17	1.517 (3)
O2—C22	1.432 (2)	C16—H16A	0.9900
O3—C3	1.377 (2)	C16—H16B	0.9900
O3—C23	1.429 (2)	C17—H17A	0.9900
O4—C9	1.228 (3)	C17—H17B	0.9900
N1—C9	1.371 (2)	C18—C19	1.534 (3)
N1—C6	1.425 (2)	C18—H18	1.0000
N1—C8	1.489 (2)	C19—C20	1.542 (3)
N2—C15	1.508 (3)	C19—H19	1.0000
N2—C16	1.509 (3)	C20—C21	1.522 (3)
N2—C21	1.536 (2)	C20—H20A	0.9900
N2—H2	0.9300	C20—H20B	0.9900
C1—C2	1.394 (3)	C21—H21	1.0000
C1—C6	1.396 (3)	C22—H22A	0.9800
C1—H1	0.9500	C22—H22B	0.9800
C2—C3	1.413 (3)	C22—H22C	0.9800
C3—C4	1.391 (3)	C23—H23A	0.9800
C4—C5	1.404 (3)	C23—H23B	0.9800
C4—H4	0.9500	C23—H23C	0.9800
C5—C6	1.380 (3)	O5—C24	1.264 (3)
C5—C7	1.512 (3)	O6—C24	1.245 (3)
C7—C21	1.543 (3)	O7—N3	1.224 (2)
C7—C17	1.545 (3)	O8—N3	1.232 (2)
C7—C8	1.565 (3)	N3—C28	1.473 (3)
C8—C18	1.540 (3)	C24—C25	1.518 (3)
C8—H8	1.0000	C25—C26	1.388 (3)
C9—C10	1.516 (3)	C25—C30	1.402 (3)
C10—C11	1.547 (3)	C26—C27	1.390 (3)
C10—H10A	0.9900	C26—H26	0.9500
C10—H10B	0.9900	C27—C28	1.387 (3)
C11—C18	1.531 (3)	C27—H27	0.9500
C11—H11	1.0000	C28—C29	1.384 (3)
C12—C13	1.502 (3)	C29—C30	1.387 (3)
C12—H12A	0.9900	C29—H29	0.9500
C12—H12B	0.9900	C30—H30	0.9500
C13—C14	1.332 (3)	O1W—H11W	0.8800
C13—H13	0.9500	O1W—H12W	0.8800
C14—C15	1.503 (3)	O2W—H21W	0.8800
C14—C19	1.524 (3)	O2W—H22W	0.8800
C11—O1—C12	114.68 (15)	N2—C16—C17	104.46 (16)
C2—O2—C22	116.67 (16)	N2—C16—H16A	110.9
C3—O3—C23	116.53 (15)	C17—C16—H16A	110.9
C9—N1—C6	125.60 (17)	N2—C16—H16B	110.9
C9—N1—C8	118.79 (16)	C17—C16—H16B	110.9
C6—N1—C8	109.09 (15)	H16A—C16—H16B	108.9
C15—N2—C16	112.12 (16)	C16—C17—C7	103.41 (16)
C15—N2—C21	113.47 (15)	C16—C17—H17A	111.1
C16—N2—C21	107.65 (15)	C7—C17—H17A	111.1
C15—N2—H2	107.8	C16—C17—H17B	111.1
C16—N2—H2	107.8	C7—C17—H17B	111.1
C21—N2—H2	107.8	H17A—C17—H17B	109.0
C2—C1—C6	117.50 (18)	C11—C18—C19	118.33 (16)
C2—C1—H1	121.3	C11—C18—C8	107.58 (15)
C6—C1—H1	121.3	C19—C18—C8	113.00 (15)
O2—C2—C1	124.62 (18)	C11—C18—H18	105.6
O2—C2—C3	114.53 (17)	C19—C18—H18	105.6
C1—C2—C3	120.80 (18)	C8—C18—H18	105.6
O3—C3—C4	124.92 (17)	C14—C19—C18	114.45 (16)
O3—C3—C2	114.41 (17)	C14—C19—C20	109.48 (16)
C4—C3—C2	120.66 (18)	C18—C19—C20	106.17 (16)
C3—C4—C5	118.32 (18)	C14—C19—H19	108.9
C3—C4—H4	120.8	C18—C19—H19	108.9
C5—C4—H4	120.8	C20—C19—H19	108.9
C6—C5—C4	120.39 (18)	C21—C20—C19	108.63 (16)
C6—C5—C7	110.98 (16)	C21—C20—H20A	110.0
C4—C5—C7	128.32 (17)	C19—C20—H20A	110.0
C5—C6—C1	122.29 (18)	C21—C20—H20B	110.0
C5—C6—N1	110.21 (17)	C19—C20—H20B	110.0
C1—C6—N1	127.49 (18)	H20A—C20—H20B	108.3
C5—C7—C21	116.00 (15)	C20—C21—N2	110.56 (15)
C5—C7—C17	111.89 (15)	C20—C21—C7	115.55 (16)
C21—C7—C17	101.60 (15)	N2—C21—C7	104.84 (14)
C5—C7—C8	102.18 (15)	C20—C21—H21	108.6
C21—C7—C8	114.26 (15)	N2—C21—H21	108.6
C17—C7—C8	111.27 (15)	C7—C21—H21	108.6
N1—C8—C18	106.28 (15)	O2—C22—H22A	109.5
N1—C8—C7	104.80 (15)	O2—C22—H22B	109.5
C18—C8—C7	116.86 (15)	H22A—C22—H22B	109.5
N1—C8—H8	109.5	O2—C22—H22C	109.5
C18—C8—H8	109.5	H22A—C22—H22C	109.5
C7—C8—H8	109.5	H22B—C22—H22C	109.5
O4—C9—N1	123.37 (19)	O3—C23—H23A	109.5
O4—C9—C10	121.66 (18)	O3—C23—H23B	109.5
N1—C9—C10	114.95 (17)	H23A—C23—H23B	109.5
C9—C10—C11	116.49 (16)	O3—C23—H23C	109.5
C9—C10—H10A	108.2	H23A—C23—H23C	109.5
C11—C10—H10A	108.2	H23B—C23—H23C	109.5
C9—C10—H10B	108.2	O7—N3—O8	123.61 (19)
C11—C10—H10B	108.2	O7—N3—C28	118.56 (18)
H10A—C10—H10B	107.3	O8—N3—C28	117.80 (17)
O1—C11—C18	114.83 (16)	O6—C24—O5	125.2 (2)
O1—C11—C10	103.87 (15)	O6—C24—C25	117.6 (2)
C18—C11—C10	110.25 (16)	O5—C24—C25	117.3 (2)
O1—C11—H11	109.2	C26—C25—C30	119.81 (19)
C18—C11—H11	109.2	C26—C25—C24	121.15 (19)
C10—C11—H11	109.2	C30—C25—C24	119.03 (19)
O1—C12—C13	111.54 (17)	C25—C26—C27	120.45 (19)
O1—C12—H12A	109.3	C25—C26—H26	119.8
C13—C12—H12A	109.3	C27—C26—H26	119.8
O1—C12—H12B	109.3	C28—C27—C26	118.2 (2)
C13—C12—H12B	109.3	C28—C27—H27	120.9
H12A—C12—H12B	108.0	C26—C27—H27	120.9
C14—C13—C12	121.13 (19)	C29—C28—C27	122.95 (19)
C14—C13—H13	119.4	C29—C28—N3	118.28 (18)
C12—C13—H13	119.4	C27—C28—N3	118.71 (19)
C13—C14—C15	121.50 (18)	C28—C29—C30	117.97 (19)
C13—C14—C19	123.16 (18)	C28—C29—H29	121.0
C15—C14—C19	115.33 (17)	C30—C29—H29	121.0
C14—C15—N2	110.54 (16)	C29—C30—C25	120.6 (2)
C14—C15—H15A	109.5	C29—C30—H30	119.7
N2—C15—H15A	109.5	C25—C30—H30	119.7
C14—C15—H15B	109.5	H11W—O1W—H12W	107.7
N2—C15—H15B	109.5	H21W—O2W—H22W	102.9
H15A—C15—H15B	108.1
C22—O2—C2—C1	7.0 (3)	C16—N2—C15—C14	76.2 (2)
C22—O2—C2—C3	−175.73 (17)	C21—N2—C15—C14	−46.0 (2)
C6—C1—C2—O2	176.96 (17)	C15—N2—C16—C17	−142.34 (16)
C6—C1—C2—C3	−0.2 (3)	C21—N2—C16—C17	−16.85 (19)
C23—O3—C3—C4	−0.1 (3)	N2—C16—C17—C7	36.98 (19)
C23—O3—C3—C2	178.69 (17)	C5—C7—C17—C16	−166.93 (16)
O2—C2—C3—O3	2.0 (2)	C21—C7—C17—C16	−42.54 (18)
C1—C2—C3—O3	179.47 (17)	C8—C7—C17—C16	79.47 (19)
O2—C2—C3—C4	−179.08 (17)	O1—C11—C18—C19	55.2 (2)
C1—C2—C3—C4	−1.6 (3)	C10—C11—C18—C19	172.13 (16)
O3—C3—C4—C5	−178.95 (17)	O1—C11—C18—C8	−74.3 (2)
C2—C3—C4—C5	2.3 (3)	C10—C11—C18—C8	42.6 (2)
C3—C4—C5—C6	−1.1 (3)	N1—C8—C18—C11	−71.10 (18)
C3—C4—C5—C7	−174.14 (18)	C7—C8—C18—C11	172.40 (16)
C4—C5—C6—C1	−0.7 (3)	N1—C8—C18—C19	156.43 (15)
C7—C5—C6—C1	173.41 (17)	C7—C8—C18—C19	39.9 (2)
C4—C5—C6—N1	179.38 (16)	C13—C14—C19—C18	58.8 (2)
C7—C5—C6—N1	−6.5 (2)	C15—C14—C19—C18	−120.85 (18)
C2—C1—C6—C5	1.4 (3)	C13—C14—C19—C20	177.78 (18)
C2—C1—C6—N1	−178.74 (17)	C15—C14—C19—C20	−1.8 (2)
C9—N1—C6—C5	−155.81 (18)	C11—C18—C19—C14	−67.0 (2)
C8—N1—C6—C5	−4.8 (2)	C8—C18—C19—C14	60.0 (2)
C9—N1—C6—C1	24.3 (3)	C11—C18—C19—C20	172.15 (16)
C8—N1—C6—C1	175.28 (18)	C8—C18—C19—C20	−60.9 (2)
C6—C5—C7—C21	139.16 (17)	C14—C19—C20—C21	−55.3 (2)
C4—C5—C7—C21	−47.3 (3)	C18—C19—C20—C21	68.71 (19)
C6—C5—C7—C17	−104.92 (18)	C19—C20—C21—N2	62.14 (19)
C4—C5—C7—C17	68.6 (3)	C19—C20—C21—C7	−56.7 (2)
C6—C5—C7—C8	14.21 (19)	C15—N2—C21—C20	−10.2 (2)
C4—C5—C7—C8	−172.26 (18)	C16—N2—C21—C20	−134.88 (16)
C9—N1—C8—C18	42.4 (2)	C15—N2—C21—C7	114.96 (17)
C6—N1—C8—C18	−110.91 (16)	C16—N2—C21—C7	−9.72 (19)
C9—N1—C8—C7	166.69 (16)	C5—C7—C21—C20	−84.8 (2)
C6—N1—C8—C7	13.43 (19)	C17—C7—C21—C20	153.68 (16)
C5—C7—C8—N1	−16.09 (17)	C8—C7—C21—C20	33.8 (2)
C21—C7—C8—N1	−142.19 (16)	C5—C7—C21—N2	153.29 (15)
C17—C7—C8—N1	103.47 (17)	C17—C7—C21—N2	31.71 (18)
C5—C7—C8—C18	101.22 (18)	C8—C7—C21—N2	−88.21 (18)
C21—C7—C8—C18	−24.9 (2)	O6—C24—C25—C26	169.8 (2)
C17—C7—C8—C18	−139.22 (17)	O5—C24—C25—C26	−10.5 (3)
C6—N1—C9—O4	−20.2 (3)	O6—C24—C25—C30	−9.4 (3)
C8—N1—C9—O4	−168.63 (18)	O5—C24—C25—C30	170.23 (19)
C6—N1—C9—C10	161.55 (17)	C30—C25—C26—C27	−0.4 (3)
C8—N1—C9—C10	13.1 (2)	C24—C25—C26—C27	−179.63 (18)
O4—C9—C10—C11	139.0 (2)	C25—C26—C27—C28	0.3 (3)
N1—C9—C10—C11	−42.6 (2)	C26—C27—C28—C29	−0.4 (3)
C12—O1—C11—C18	−66.1 (2)	C26—C27—C28—N3	176.51 (17)
C12—O1—C11—C10	173.46 (15)	O7—N3—C28—C29	159.61 (19)
C9—C10—C11—O1	135.19 (17)	O8—N3—C28—C29	−18.6 (3)
C9—C10—C11—C18	11.7 (2)	O7—N3—C28—C27	−17.5 (3)
C11—O1—C12—C13	88.4 (2)	O8—N3—C28—C27	164.33 (18)
O1—C12—C13—C14	−66.2 (3)	C27—C28—C29—C30	0.5 (3)
C12—C13—C14—C15	178.03 (18)	N3—C28—C29—C30	−176.39 (17)
C12—C13—C14—C19	−1.6 (3)	C28—C29—C30—C25	−0.6 (3)
C13—C14—C15—N2	−126.5 (2)	C26—C25—C30—C29	0.5 (3)
C19—C14—C15—N2	53.1 (2)	C24—C25—C30—C29	179.78 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.93	1.74	2.653 (2)	169
O2W—H22W···O4	0.88	2.05	2.924 (2)	172
O2W—H21W···O1W	0.88	1.93	2.807 (2)	177
O1W—H11W···O6^i	0.88	1.84	2.715 (3)	178
O1W—H12W···O1^ii	0.88	1.96	2.843 (2)	178

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

(supplement) brucinium 4-nitrobenzoate 2.6 hydrate

Crystal data

C23H27N2O4·C7H4NO4·2.6(H2O)	F(000) = 1288
Mr = 608.42	Dx = 1.339 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 15622 reflections
a = 8.075 (2) Å	θ = 3.3–28.5°
b = 12.464 (2) Å	µ = 0.10 mm^−1
c = 29.994 (3) Å	T = 100 K
V = 3018.8 (9) Å^3	Needle, pale yellow
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Kuma KM-4 CCD diffractometer	2840 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.076
Graphite monochromator	θmax = 27.0°, θmin = 3.3°
ω scan	h = −10→10
20212 measured reflections	k = −12→15
3716 independent reflections	l = −38→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)] = 0.088	H-atom parameters constrained
wR(F^2) = 0.261	w = 1/[σ^2(Fo^2) + (0.1818P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3716 reflections	Δρmax = 1.09 e Å^−3
441 parameters	Δρmin = −0.29 e Å^−3
313 restraints	Absolute structure: Toda, F., Tanaka, K., Ueda, H. and Oshima, T. (1985). Isr. J. Chem., 25, 338-345.
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	0.2275 (5)	1.4548 (3)	0.69022 (13)	0.0327 (9)
O2	0.1926 (5)	0.8659 (3)	0.84444 (13)	0.0329 (9)
O3	0.2456 (5)	0.7573 (3)	0.77149 (14)	0.0332 (9)
O4	0.1630 (6)	1.2669 (3)	0.82322 (13)	0.0408 (11)
N1	0.1533 (6)	1.1969 (3)	0.75340 (15)	0.0263 (10)
N2	0.1899 (7)	1.1208 (4)	0.60388 (16)	0.0372 (12)
H2	0.1874	1.0651	0.5832	0.045*
C1	0.1701 (6)	1.0351 (4)	0.80468 (18)	0.0268 (11)
H1	0.1554	1.0749	0.8314	0.032*
C2	0.1931 (7)	0.9243 (4)	0.80566 (19)	0.0295 (12)
C3	0.2182 (7)	0.8656 (4)	0.7661 (2)	0.0300 (12)
C4	0.2163 (7)	0.9175 (4)	0.72538 (19)	0.0285 (12)
H4	0.2328	0.8783	0.6986	0.034*
C5	0.1896 (7)	1.0289 (4)	0.72404 (18)	0.0267 (11)
C6	0.1695 (7)	1.0860 (4)	0.76315 (18)	0.0254 (11)
C7	0.1664 (7)	1.1007 (4)	0.68419 (18)	0.0269 (12)
C8	0.1785 (7)	1.2158 (4)	0.70563 (17)	0.0253 (11)
H8	0.0886	1.2629	0.6937	0.030*
C9	0.1798 (7)	1.2785 (4)	0.78312 (19)	0.0293 (12)
C10	0.2289 (8)	1.3863 (4)	0.76371 (19)	0.0317 (13)
H10A	0.2983	1.4239	0.7860	0.038*
H10B	0.1268	1.4293	0.7598	0.038*
C11	0.3250 (7)	1.3865 (4)	0.71812 (18)	0.0276 (12)
H11	0.4365	1.4197	0.7226	0.033*
C12	0.3035 (8)	1.4834 (5)	0.6487 (2)	0.0375 (14)
H12A	0.4248	1.4890	0.6528	0.045*
H12B	0.2619	1.5544	0.6390	0.045*
C13	0.2671 (8)	1.4019 (5)	0.6132 (2)	0.0399 (15)
H13	0.2060	1.4234	0.5876	0.048*
C14	0.3181 (8)	1.2989 (5)	0.61632 (19)	0.0367 (14)
C15	0.2716 (9)	1.2150 (5)	0.58160 (19)	0.0393 (15)
H15A	0.1950	1.2469	0.5595	0.047*
H15B	0.3723	1.1908	0.5657	0.047*
C16	0.0149 (8)	1.1418 (5)	0.6178 (2)	0.0376 (14)
H16A	−0.0639	1.1139	0.5954	0.045*
H16B	−0.0045	1.2196	0.6218	0.045*
C17	−0.0046 (8)	1.0832 (5)	0.66144 (17)	0.0302 (13)
H17A	−0.0268	1.0060	0.6566	0.036*
H17B	−0.0953	1.1143	0.6795	0.036*
C18	0.3469 (7)	1.2714 (4)	0.70058 (19)	0.0296 (12)
H18	0.4229	1.2349	0.7221	0.036*
C19	0.4244 (8)	1.2567 (5)	0.6550 (2)	0.0351 (14)
H19	0.5339	1.2941	0.6545	0.042*
C20	0.4530 (7)	1.1354 (5)	0.6489 (2)	0.0333 (13)
H20A	0.5201	1.1223	0.6218	0.040*
H20B	0.5137	1.1062	0.6749	0.040*
C21	0.2858 (8)	1.0804 (5)	0.64459 (19)	0.0338 (14)
H21	0.3038	1.0013	0.6415	0.041*
C22	0.1904 (10)	0.9253 (6)	0.8856 (2)	0.0461 (16)
H22A	0.1892	0.8752	0.9108	0.069*
H22B	0.0912	0.9705	0.8867	0.069*
H22C	0.2894	0.9706	0.8874	0.069*
C23	0.2738 (9)	0.6963 (5)	0.7319 (2)	0.0407 (15)
H23A	0.2912	0.6209	0.7398	0.061*
H23B	0.3722	0.7239	0.7166	0.061*
H23C	0.1775	0.7024	0.7122	0.061*
O5	0.0696 (13)	1.0510 (6)	0.5067 (3)	0.0519 (18)	0.60
O6	0.1774 (10)	0.9369 (6)	0.5571 (2)	0.0397 (16)	0.60
O7	0.2321 (13)	0.5573 (8)	0.3909 (4)	0.037 (2)	0.60
O8	0.0255 (18)	0.6404 (11)	0.3547 (5)	0.039 (2)	0.60
N3	0.1281 (17)	0.6296 (9)	0.3854 (5)	0.0367 (19)	0.60
C24	0.125 (2)	0.9614 (9)	0.5189 (4)	0.047 (2)	0.60
C25	0.1165 (16)	0.8717 (9)	0.4830 (4)	0.0371 (18)	0.60
C26	0.2063 (14)	0.7755 (9)	0.4905 (4)	0.0410 (19)	0.60
H26	0.2650	0.7652	0.5176	0.049*	0.60
C27	0.2077 (15)	0.6980 (9)	0.4585 (3)	0.0407 (19)	0.60
H27	0.2719	0.6348	0.4624	0.049*	0.60
C28	0.1156 (15)	0.7123 (9)	0.4206 (4)	0.0304 (17)	0.60
C29	0.0241 (15)	0.8021 (11)	0.4131 (4)	0.0297 (19)	0.60
H29	−0.0414	0.8087	0.3870	0.036*	0.60
C30	0.0285 (16)	0.8841 (11)	0.4446 (4)	0.035 (2)	0.60
H30	−0.0301	0.9490	0.4392	0.042*	0.60
O5A	−0.0166 (19)	1.0242 (12)	0.5172 (5)	0.056 (3)*	0.40
O6A	0.2425 (19)	0.9878 (11)	0.5381 (4)	0.056 (3)*	0.40
O7A	0.193 (2)	0.5452 (14)	0.3921 (8)	0.037 (3)*	0.40
O8A	0.007 (3)	0.6225 (18)	0.3563 (8)	0.039 (3)*	0.40
N3A	0.106 (3)	0.6273 (14)	0.3878 (8)	0.037 (2)*	0.40
C24A	0.1177 (19)	0.9738 (17)	0.5137 (7)	0.045 (2)*	0.40
C25A	0.1415 (17)	0.8885 (9)	0.4777 (5)	0.039 (2)*	0.40
C26A	0.2734 (14)	0.8171 (9)	0.4756 (4)	0.038 (2)*	0.40
H26A	0.3645	0.8248	0.4954	0.046*	0.40
C27A	0.2721 (14)	0.7344 (8)	0.4445 (4)	0.033 (2)*	0.40
H27A	0.3622	0.6855	0.4431	0.039*	0.40
C28A	0.1388 (17)	0.7231 (11)	0.4156 (4)	0.032 (2)*	0.40
C29A	0.0069 (15)	0.7946 (15)	0.4177 (5)	0.032 (3)*	0.40
H29A	−0.0842	0.7869	0.3979	0.039*	0.40
C30A	0.0082 (15)	0.8773 (13)	0.4488 (6)	0.036 (3)*	0.40
H30A	−0.0819	0.9261	0.4502	0.043*	0.40
O1W	−0.1692 (15)	1.2066 (7)	0.5242 (2)	0.068 (3)	0.60
H11W	−0.2604	1.1679	0.5245	0.102*	0.60
H12W	−0.1247	1.2159	0.4974	0.102*	0.60
O2W	0.0336 (12)	1.3792 (7)	0.5055 (3)	0.063 (3)	0.60
H21W	0.1311	1.3834	0.4916	0.095*	0.60
H22W	−0.0076	1.3152	0.5102	0.095*	0.60
O3W	0.1396 (10)	0.7709 (8)	0.6240 (3)	0.056 (2)	0.60
H31W	0.1111	0.7724	0.5947	0.084*	0.60
H32W	0.0420	0.7650	0.6353	0.084*	0.60
O21W	0.056 (2)	1.4844 (12)	0.5020 (5)	0.069 (4)*	0.40
O31W	0.064 (2)	0.6852 (13)	0.6184 (5)	0.075 (4)*	0.40

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.032 (2)	0.0275 (19)	0.039 (2)	−0.0005 (17)	0.0026 (17)	0.0032 (17)
O2	0.036 (2)	0.029 (2)	0.033 (2)	−0.0003 (19)	0.0013 (18)	0.0016 (17)
O3	0.031 (2)	0.0206 (19)	0.048 (2)	0.0015 (16)	0.0074 (18)	−0.0023 (17)
O4	0.057 (3)	0.035 (2)	0.031 (2)	−0.012 (2)	0.017 (2)	−0.0082 (18)
N1	0.029 (2)	0.018 (2)	0.032 (2)	−0.0039 (19)	0.0020 (19)	−0.0039 (18)
N2	0.041 (3)	0.039 (3)	0.032 (3)	−0.001 (2)	0.002 (2)	−0.009 (2)
C1	0.023 (3)	0.025 (3)	0.032 (3)	−0.003 (2)	0.009 (2)	−0.013 (2)
C2	0.018 (3)	0.034 (3)	0.036 (3)	−0.003 (2)	0.004 (2)	−0.008 (2)
C3	0.023 (3)	0.024 (3)	0.043 (3)	0.002 (2)	0.004 (2)	−0.004 (2)
C4	0.028 (3)	0.021 (2)	0.036 (3)	−0.002 (2)	−0.003 (2)	−0.013 (2)
C5	0.021 (3)	0.028 (3)	0.031 (3)	0.001 (2)	−0.002 (2)	−0.011 (2)
C6	0.021 (3)	0.020 (2)	0.035 (3)	−0.004 (2)	0.000 (2)	−0.008 (2)
C7	0.029 (3)	0.021 (2)	0.030 (3)	−0.001 (2)	−0.004 (2)	−0.005 (2)
C8	0.021 (3)	0.025 (3)	0.030 (3)	−0.004 (2)	0.001 (2)	−0.005 (2)
C9	0.028 (3)	0.025 (3)	0.035 (3)	−0.001 (2)	0.003 (2)	−0.012 (2)
C10	0.037 (3)	0.023 (3)	0.035 (3)	0.000 (2)	0.003 (2)	−0.006 (2)
C11	0.029 (3)	0.024 (3)	0.030 (3)	−0.009 (2)	−0.004 (2)	−0.004 (2)
C12	0.042 (4)	0.031 (3)	0.040 (3)	−0.006 (3)	0.000 (3)	0.005 (3)
C13	0.039 (3)	0.046 (4)	0.034 (3)	−0.007 (3)	0.006 (3)	0.008 (3)
C14	0.035 (3)	0.041 (3)	0.035 (3)	−0.008 (3)	0.015 (3)	0.000 (3)
C15	0.047 (4)	0.045 (4)	0.027 (3)	−0.006 (3)	0.007 (3)	−0.002 (3)
C16	0.035 (3)	0.035 (3)	0.042 (4)	−0.006 (3)	−0.005 (3)	−0.012 (3)
C17	0.039 (3)	0.026 (3)	0.025 (3)	−0.005 (3)	0.000 (2)	−0.010 (2)
C18	0.030 (3)	0.022 (3)	0.036 (3)	−0.002 (2)	0.002 (2)	−0.003 (2)
C19	0.031 (3)	0.039 (3)	0.035 (3)	−0.008 (3)	0.003 (2)	−0.004 (3)
C20	0.033 (3)	0.037 (3)	0.030 (3)	0.001 (3)	0.012 (2)	−0.007 (3)
C21	0.036 (3)	0.037 (3)	0.028 (3)	−0.002 (3)	0.005 (2)	−0.011 (2)
C22	0.056 (4)	0.050 (4)	0.032 (3)	0.001 (3)	0.001 (3)	0.002 (3)
C23	0.045 (4)	0.029 (3)	0.048 (4)	0.002 (3)	0.002 (3)	−0.008 (3)
O5	0.064 (4)	0.039 (4)	0.052 (4)	−0.002 (4)	−0.003 (4)	−0.010 (3)
O6	0.050 (4)	0.035 (3)	0.034 (3)	−0.006 (3)	0.005 (3)	−0.007 (3)
O7	0.040 (5)	0.028 (4)	0.042 (3)	0.006 (4)	0.007 (4)	−0.005 (3)
O8	0.041 (4)	0.039 (5)	0.036 (4)	−0.009 (4)	−0.008 (3)	−0.008 (4)
N3	0.038 (4)	0.038 (3)	0.034 (3)	0.000 (3)	0.004 (3)	−0.006 (3)
C24	0.053 (4)	0.043 (4)	0.045 (4)	−0.002 (3)	−0.003 (3)	−0.005 (3)
C25	0.042 (3)	0.034 (3)	0.035 (3)	−0.001 (3)	0.003 (3)	−0.005 (3)
C26	0.039 (4)	0.041 (4)	0.043 (4)	0.007 (3)	−0.004 (3)	−0.006 (3)
C27	0.042 (4)	0.041 (4)	0.040 (4)	0.007 (3)	−0.003 (3)	−0.006 (3)
C28	0.033 (3)	0.032 (3)	0.027 (3)	−0.001 (3)	0.005 (3)	−0.007 (3)
C29	0.034 (4)	0.035 (4)	0.020 (3)	−0.001 (3)	0.000 (3)	−0.001 (3)
C30	0.044 (4)	0.030 (3)	0.032 (4)	0.003 (3)	0.008 (3)	0.002 (3)
O1W	0.108 (8)	0.065 (6)	0.032 (4)	0.004 (6)	−0.028 (5)	0.015 (4)
O2W	0.061 (6)	0.062 (6)	0.067 (6)	0.001 (5)	−0.031 (5)	0.018 (5)
O3W	0.033 (4)	0.079 (6)	0.057 (5)	0.008 (4)	0.006 (4)	−0.006 (5)

Geometric parameters (Å, º)

O1—C11	1.430 (7)	C20—C21	1.520 (8)
O1—C12	1.434 (7)	C20—H20A	0.9900
O2—C2	1.372 (7)	C20—H20B	0.9900
O2—C22	1.441 (7)	C21—H21	1.0000
O3—C3	1.377 (7)	C22—H22A	0.9800
O3—C23	1.427 (7)	C22—H22B	0.9800
O4—C9	1.219 (7)	C22—H22C	0.9800
N1—C9	1.370 (7)	C23—H23A	0.9800
N1—C6	1.419 (7)	C23—H23B	0.9800
N1—C8	1.466 (7)	C23—H23C	0.9800
N2—C16	1.497 (8)	O5—C24	1.258 (6)
N2—C15	1.504 (8)	O6—C24	1.258 (6)
N2—C21	1.531 (8)	O7—N3	1.244 (5)
N2—H2	0.9300	O8—N3	1.245 (5)
C1—C2	1.395 (8)	N3—C28	1.479 (8)
C1—C6	1.397 (8)	C24—C25	1.553 (16)
C1—H1	0.9500	C25—C30	1.364 (14)
C2—C3	1.408 (8)	C25—C26	1.418 (16)
C3—C4	1.383 (8)	C26—C27	1.362 (15)
C4—C5	1.405 (7)	C26—H26	0.9500
C4—H4	0.9500	C27—C28	1.370 (15)
C5—C6	1.381 (7)	C27—H27	0.9500
C5—C7	1.505 (8)	C28—C29	1.359 (14)
C7—C21	1.551 (8)	C29—C30	1.391 (13)
C7—C17	1.556 (8)	C29—H29	0.9500
C7—C8	1.575 (7)	C30—H30	0.9500
C8—C18	1.534 (8)	O5A—C24A	1.258 (6)
C8—H8	1.0000	O6A—C24A	1.258 (6)
C9—C10	1.517 (8)	O7A—N3A	1.243 (5)
C10—C11	1.572 (8)	O8A—N3A	1.245 (5)
C10—H10A	0.9900	N3A—C28A	1.479 (9)
C10—H10B	0.9900	C24A—C25A	1.53 (2)
C11—C18	1.538 (7)	C25A—C26A	1.3900
C11—H11	1.0000	C25A—C30A	1.3900
C12—C13	1.500 (9)	C26A—C27A	1.3900
C12—H12A	0.9900	C26A—H26A	0.9500
C12—H12B	0.9900	C27A—C28A	1.3900
C13—C14	1.351 (9)	C27A—H27A	0.9500
C13—H13	0.9500	C28A—C29A	1.3900
C14—C15	1.523 (8)	C29A—C30A	1.3900
C14—C19	1.536 (9)	C29A—H29A	0.9500
C15—H15A	0.9900	C30A—H30A	0.9500
C15—H15B	0.9900	O1W—H11W	0.8803
C16—C17	1.506 (9)	O1W—H12W	0.8891
C16—H16A	0.9900	O2W—H21W	0.8930
C16—H16B	0.9900	O2W—H22W	0.8757
C17—H17A	0.9900	O3W—H31W	0.9080
C17—H17B	0.9900	O3W—H32W	0.8615
C18—C19	1.514 (8)	O21W—H21W	1.4303
C18—H18	1.0000	O31W—H31W	1.3522
C19—C20	1.541 (9)	O31W—H32W	1.1299
C19—H19	1.0000
C11—O1—C12	114.9 (5)	C19—C18—C11	118.0 (5)
C2—O2—C22	117.1 (4)	C8—C18—C11	106.6 (4)
C3—O3—C23	116.8 (5)	C19—C18—H18	105.9
C9—N1—C6	125.1 (5)	C8—C18—H18	105.9
C9—N1—C8	119.7 (4)	C11—C18—H18	105.9
C6—N1—C8	110.2 (4)	C18—C19—C14	114.2 (5)
C16—N2—C15	113.7 (5)	C18—C19—C20	106.7 (5)
C16—N2—C21	108.2 (5)	C14—C19—C20	109.3 (5)
C15—N2—C21	112.9 (5)	C18—C19—H19	108.8
C16—N2—H2	107.2	C14—C19—H19	108.8
C15—N2—H2	107.2	C20—C19—H19	108.8
C21—N2—H2	107.2	C21—C20—C19	108.6 (5)
C2—C1—C6	117.9 (5)	C21—C20—H20A	110.0
C2—C1—H1	121.0	C19—C20—H20A	110.0
C6—C1—H1	121.0	C21—C20—H20B	110.0
O2—C2—C1	122.9 (5)	C19—C20—H20B	110.0
O2—C2—C3	116.0 (5)	H20A—C20—H20B	108.3
C1—C2—C3	121.1 (5)	C20—C21—N2	111.7 (5)
O3—C3—C4	124.3 (5)	C20—C21—C7	114.4 (4)
O3—C3—C2	115.7 (5)	N2—C21—C7	104.0 (5)
C4—C3—C2	120.0 (5)	C20—C21—H21	108.9
C3—C4—C5	119.3 (5)	N2—C21—H21	108.9
C3—C4—H4	120.4	C7—C21—H21	108.9
C5—C4—H4	120.4	O2—C22—H22A	109.5
C6—C5—C4	120.2 (5)	O2—C22—H22B	109.5
C6—C5—C7	110.7 (4)	H22A—C22—H22B	109.5
C4—C5—C7	129.0 (5)	O2—C22—H22C	109.5
C5—C6—C1	121.5 (5)	H22A—C22—H22C	109.5
C5—C6—N1	109.7 (5)	H22B—C22—H22C	109.5
C1—C6—N1	128.7 (5)	O3—C23—H23A	109.5
C5—C7—C21	115.7 (5)	O3—C23—H23B	109.5
C5—C7—C17	112.0 (5)	H23A—C23—H23B	109.5
C21—C7—C17	101.1 (4)	O3—C23—H23C	109.5
C5—C7—C8	102.1 (4)	H23A—C23—H23C	109.5
C21—C7—C8	115.0 (4)	H23B—C23—H23C	109.5
C17—C7—C8	111.3 (4)	O7—N3—O8	128.8 (12)
N1—C8—C18	107.0 (4)	O7—N3—C28	117.1 (11)
N1—C8—C7	104.1 (4)	O8—N3—C28	114.0 (11)
C18—C8—C7	115.2 (4)	O5—C24—O6	126.9 (11)
N1—C8—H8	110.1	O5—C24—C25	114.9 (8)
C18—C8—H8	110.1	O6—C24—C25	118.1 (8)
C7—C8—H8	110.1	C30—C25—C26	119.7 (10)
O4—C9—N1	122.4 (5)	C30—C25—C24	121.8 (10)
O4—C9—C10	120.9 (5)	C26—C25—C24	118.5 (10)
N1—C9—C10	116.7 (5)	C27—C26—C25	119.5 (10)
C9—C10—C11	117.6 (4)	C27—C26—H26	120.2
C9—C10—H10A	107.9	C25—C26—H26	120.2
C11—C10—H10A	107.9	C28—C27—C26	119.2 (10)
C9—C10—H10B	107.9	C28—C27—H27	120.4
C11—C10—H10B	107.9	C26—C27—H27	120.4
H10A—C10—H10B	107.2	C29—C28—C27	122.6 (9)
O1—C11—C18	114.7 (4)	C29—C28—N3	119.6 (10)
O1—C11—C10	103.8 (4)	C27—C28—N3	117.7 (11)
C18—C11—C10	110.7 (4)	C28—C29—C30	118.7 (9)
O1—C11—H11	109.1	C28—C29—H29	120.7
C18—C11—H11	109.1	C30—C29—H29	120.7
C10—C11—H11	109.1	C25—C30—C29	120.2 (10)
O1—C12—C13	111.4 (5)	C25—C30—H30	119.9
O1—C12—H12A	109.4	C29—C30—H30	119.9
C13—C12—H12A	109.4	O7A—N3A—O8A	113.7 (18)
O1—C12—H12B	109.4	O7A—N3A—C28A	120.4 (18)
C13—C12—H12B	109.4	O8A—N3A—C28A	125.5 (18)
H12A—C12—H12B	108.0	O5A—C24A—O6A	124.9 (17)
C14—C13—C12	122.3 (6)	O5A—C24A—C25A	121.1 (13)
C14—C13—H13	118.9	O6A—C24A—C25A	114.0 (13)
C12—C13—H13	118.9	C26A—C25A—C30A	120.0
C13—C14—C15	122.0 (6)	C26A—C25A—C24A	125.1 (10)
C13—C14—C19	123.2 (6)	C30A—C25A—C24A	114.5 (10)
C15—C14—C19	114.8 (5)	C25A—C26A—C27A	120.0
N2—C15—C14	109.9 (5)	C25A—C26A—H26A	120.0
N2—C15—H15A	109.7	C27A—C26A—H26A	120.0
C14—C15—H15A	109.7	C28A—C27A—C26A	120.0
N2—C15—H15B	109.7	C28A—C27A—H27A	120.0
C14—C15—H15B	109.7	C26A—C27A—H27A	120.0
H15A—C15—H15B	108.2	C29A—C28A—C27A	120.0
N2—C16—C17	104.9 (5)	C29A—C28A—N3A	114.1 (12)
N2—C16—H16A	110.8	C27A—C28A—N3A	124.7 (12)
C17—C16—H16A	110.8	C28A—C29A—C30A	120.0
N2—C16—H16B	110.8	C28A—C29A—H29A	120.0
C17—C16—H16B	110.8	C30A—C29A—H29A	120.0
H16A—C16—H16B	108.8	C29A—C30A—C25A	120.0
C16—C17—C7	102.7 (5)	C29A—C30A—H30A	120.0
C16—C17—H17A	111.2	C25A—C30A—H30A	120.0
C7—C17—H17A	111.2	H11W—O1W—H12W	114.8
C16—C17—H17B	111.2	H21W—O2W—H22W	117.6
C7—C17—H17B	111.2	H31W—O3W—H32W	98.6
H17A—C17—H17B	109.1	H31W—O31W—H32W	64.7
C19—C18—C8	113.6 (5)
C22—O2—C2—C1	−8.5 (8)	C7—C8—C18—C19	41.2 (7)
C22—O2—C2—C3	171.5 (5)	N1—C8—C18—C11	−72.0 (5)
C6—C1—C2—O2	−178.7 (5)	C7—C8—C18—C11	172.8 (4)
C6—C1—C2—C3	1.3 (8)	O1—C11—C18—C19	58.0 (7)
C23—O3—C3—C4	0.1 (8)	C10—C11—C18—C19	175.0 (5)
C23—O3—C3—C2	−179.1 (5)	O1—C11—C18—C8	−71.2 (6)
O2—C2—C3—O3	−2.4 (7)	C10—C11—C18—C8	45.8 (6)
C1—C2—C3—O3	177.6 (5)	C8—C18—C19—C14	59.0 (7)
O2—C2—C3—C4	178.3 (5)	C11—C18—C19—C14	−66.8 (7)
C1—C2—C3—C4	−1.6 (9)	C8—C18—C19—C20	−61.8 (6)
O3—C3—C4—C5	−179.0 (5)	C11—C18—C19—C20	172.4 (5)
C2—C3—C4—C5	0.2 (8)	C13—C14—C19—C18	58.2 (8)
C3—C4—C5—C6	1.5 (8)	C15—C14—C19—C18	−121.0 (6)
C3—C4—C5—C7	−173.7 (5)	C13—C14—C19—C20	177.6 (6)
C4—C5—C6—C1	−1.9 (8)	C15—C14—C19—C20	−1.6 (7)
C7—C5—C6—C1	174.1 (5)	C18—C19—C20—C21	68.9 (6)
C4—C5—C6—N1	176.9 (5)	C14—C19—C20—C21	−55.1 (6)
C7—C5—C6—N1	−7.1 (6)	C19—C20—C21—N2	61.4 (6)
C2—C1—C6—C5	0.5 (8)	C19—C20—C21—C7	−56.4 (7)
C2—C1—C6—N1	−178.1 (5)	C16—N2—C21—C20	−134.7 (5)
C9—N1—C6—C5	−159.9 (5)	C15—N2—C21—C20	−7.9 (6)
C8—N1—C6—C5	−5.2 (6)	C16—N2—C21—C7	−10.8 (6)
C9—N1—C6—C1	18.8 (9)	C15—N2—C21—C7	115.9 (5)
C8—N1—C6—C1	173.5 (5)	C5—C7—C21—C20	−83.8 (6)
C6—C5—C7—C21	141.0 (5)	C17—C7—C21—C20	155.0 (5)
C4—C5—C7—C21	−43.5 (8)	C8—C7—C21—C20	35.0 (7)
C6—C5—C7—C17	−103.9 (5)	C5—C7—C21—N2	154.2 (4)
C4—C5—C7—C17	71.7 (7)	C17—C7—C21—N2	32.9 (5)
C6—C5—C7—C8	15.3 (6)	C8—C7—C21—N2	−87.1 (5)
C4—C5—C7—C8	−169.2 (6)	O5—C24—C25—C30	−11 (2)
C9—N1—C8—C18	48.2 (6)	O6—C24—C25—C30	165.0 (13)
C6—N1—C8—C18	−108.1 (5)	O5—C24—C25—C26	167.1 (13)
C9—N1—C8—C7	170.6 (5)	O6—C24—C25—C26	−16 (2)
C6—N1—C8—C7	14.4 (6)	C30—C25—C26—C27	2.1 (18)
C5—C7—C8—N1	−17.3 (5)	C24—C25—C26—C27	−176.5 (12)
C21—C7—C8—N1	−143.4 (5)	C25—C26—C27—C28	−3.2 (18)
C17—C7—C8—N1	102.4 (5)	C26—C27—C28—C29	1.1 (19)
C5—C7—C8—C18	99.6 (5)	C26—C27—C28—N3	176.4 (12)
C21—C7—C8—C18	−26.5 (7)	O7—N3—C28—C29	169.5 (13)
C17—C7—C8—C18	−140.7 (5)	O8—N3—C28—C29	−14 (2)
C6—N1—C9—O4	−26.5 (9)	O7—N3—C28—C27	−6 (2)
C8—N1—C9—O4	−178.9 (5)	O8—N3—C28—C27	171.1 (14)
C6—N1—C9—C10	154.5 (5)	C27—C28—C29—C30	2.1 (17)
C8—N1—C9—C10	2.0 (8)	N3—C28—C29—C30	−173.0 (13)
O4—C9—C10—C11	152.6 (6)	C26—C25—C30—C29	1.2 (18)
N1—C9—C10—C11	−28.4 (8)	C24—C25—C30—C29	179.8 (12)
C12—O1—C11—C18	−69.3 (6)	C28—C29—C30—C25	−3.3 (17)
C12—O1—C11—C10	169.8 (4)	O5A—C24A—C25A—C26A	−169.0 (17)
C9—C10—C11—O1	125.3 (5)	O6A—C24A—C25A—C26A	11 (3)
C9—C10—C11—C18	1.8 (7)	O5A—C24A—C25A—C30A	3 (3)
C11—O1—C12—C13	87.7 (6)	O6A—C24A—C25A—C30A	−176.0 (16)
O1—C12—C13—C14	−62.8 (8)	C30A—C25A—C26A—C27A	0.0
C12—C13—C14—C15	176.1 (5)	C24A—C25A—C26A—C27A	172.1 (17)
C12—C13—C14—C19	−2.9 (9)	C25A—C26A—C27A—C28A	0.0
C16—N2—C15—C14	75.5 (6)	C26A—C27A—C28A—C29A	0.0
C21—N2—C15—C14	−48.2 (7)	C26A—C27A—C28A—N3A	−167 (2)
C13—C14—C15—N2	−125.1 (6)	O7A—N3A—C28A—C29A	−161 (2)
C19—C14—C15—N2	54.1 (7)	O8A—N3A—C28A—C29A	26 (3)
C15—N2—C16—C17	−143.0 (5)	O7A—N3A—C28A—C27A	6 (4)
C21—N2—C16—C17	−16.8 (6)	O8A—N3A—C28A—C27A	−166 (2)
N2—C16—C17—C7	37.6 (5)	C27A—C28A—C29A—C30A	0.0
C5—C7—C17—C16	−167.4 (5)	N3A—C28A—C29A—C30A	168.1 (18)
C21—C7—C17—C16	−43.6 (5)	C28A—C29A—C30A—C25A	0.0
C8—C7—C17—C16	79.0 (5)	C26A—C25A—C30A—C29A	0.0
N1—C8—C18—C19	156.4 (5)	C24A—C25A—C30A—C29A	−172.9 (15)