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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106021068/gg3018sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106021068/gg3018Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106021068/gg3018IIsup3.hkl
Contains datablock bdnbzac2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106021068/gg3018IIIsup4.hkl
Contains datablock bdnbzac3

CCDC references: 618614; 618615; 618616

Comment top

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 ππ 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 ππ 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).

Experimental top

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.

Refinement top

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 top

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 top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
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 top
Crystal data top
C23H27N2O4+·C7H3N2O6·CH4OF(000) = 1344
Mr = 638.62Dx = 1.495 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 16721 reflections
a = 11.8539 (18) Åθ = 3.4–28.6°
b = 12.2726 (18) ŵ = 0.12 mm1
c = 19.498 (3) ÅT = 100 K
V = 2836.5 (7) Å3Block, orange
Z = 40.30 × 0.30 × 0.25 mm
Data collection top
Kuma KM-4 CCD
diffractometer
2929 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.077
Graphite monochromatorθmax = 27.0°, θmin = 3.4°
ω scanh = 1515
18431 measured reflectionsk = 1115
3470 independent reflectionsl = 2424
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0408P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3470 reflectionsΔρmax = 0.21 e Å3
415 parametersΔρmin = 0.26 e Å3
0 restraintsAbsolute structure: from known structure (Toda et al., 1985)
Primary atom site location: structure-invariant direct methods
Crystal data top
C23H27N2O4+·C7H3N2O6·CH4OV = 2836.5 (7) Å3
Mr = 638.62Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 11.8539 (18) ŵ = 0.12 mm1
b = 12.2726 (18) ÅT = 100 K
c = 19.498 (3) Å0.30 × 0.30 × 0.25 mm
Data collection top
Kuma KM-4 CCD
diffractometer
2929 reflections with I > 2σ(I)
18431 measured reflectionsRint = 0.077
3470 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 1.08Δρmax = 0.21 e Å3
3470 reflectionsΔρmin = 0.26 e Å3
415 parametersAbsolute structure: from known structure (Toda et al., 1985)
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.70343 (19)0.65878 (17)0.64497 (11)0.0197 (5)
O20.6168 (2)0.06246 (16)0.88547 (10)0.0172 (5)
O30.6216 (2)0.04939 (16)0.77389 (11)0.0169 (5)
O40.6754 (2)0.46747 (18)0.85395 (11)0.0234 (6)
N10.6411 (2)0.3996 (2)0.74707 (13)0.0139 (6)
N20.6496 (2)0.3217 (2)0.51487 (13)0.0165 (6)
H2A0.64130.26480.48370.020*
C10.6290 (3)0.2359 (2)0.82499 (16)0.0143 (7)
H10.62760.27740.86610.017*
C20.6231 (3)0.1232 (2)0.82643 (16)0.0143 (7)
C30.6255 (3)0.0615 (2)0.76533 (16)0.0135 (7)
C40.6314 (3)0.1134 (2)0.70204 (17)0.0150 (7)
H40.63090.07230.66070.018*
C50.6381 (3)0.2280 (2)0.70039 (16)0.0125 (7)
C60.6371 (3)0.2866 (2)0.76074 (17)0.0140 (7)
C70.6319 (3)0.3032 (2)0.63931 (16)0.0122 (7)
C80.6540 (3)0.4174 (2)0.67188 (16)0.0130 (7)
H80.59500.46960.65580.016*
C90.6732 (3)0.4809 (3)0.79172 (17)0.0175 (7)
C100.6985 (3)0.5895 (3)0.75810 (17)0.0200 (8)
H10A0.74290.63390.79070.024*
H10B0.62600.62770.75040.024*
C110.7635 (3)0.5855 (2)0.68877 (16)0.0167 (7)
H110.84160.61400.69600.020*
C120.7574 (3)0.6821 (3)0.58034 (17)0.0231 (8)
H12A0.84030.68080.58640.028*
H12B0.73560.75600.56490.028*
C130.7241 (3)0.5999 (3)0.52651 (17)0.0196 (8)
H130.68270.62420.48770.023*
C140.7503 (3)0.4948 (3)0.53123 (16)0.0157 (7)
C150.7120 (3)0.4132 (3)0.47916 (17)0.0189 (8)
H15A0.77800.38350.45430.023*
H15B0.66170.44880.44540.023*
C160.5337 (3)0.3567 (3)0.53735 (17)0.0179 (8)
H16A0.47620.33500.50310.022*
H16B0.53040.43660.54370.022*
C170.5145 (3)0.2983 (2)0.60473 (16)0.0160 (7)
H17A0.49040.22210.59720.019*
H17B0.45700.33620.63280.019*
C180.7704 (3)0.4686 (2)0.66240 (15)0.0138 (7)
H180.82140.42940.69500.017*
C190.8199 (3)0.4483 (2)0.59055 (16)0.0151 (7)
H190.89750.48020.58860.018*
C200.8286 (3)0.3247 (3)0.58257 (17)0.0167 (7)
H20A0.87120.30670.54040.020*
H20B0.86940.29330.62220.020*
C210.7109 (3)0.2768 (3)0.57848 (16)0.0148 (7)
H210.71730.19590.57400.018*
C220.6187 (3)0.1216 (3)0.94913 (16)0.0243 (8)
H22A0.61340.07020.98750.036*
H22B0.55480.17210.95070.036*
H22C0.68940.16270.95260.036*
C230.6214 (3)0.1137 (3)0.71266 (16)0.0189 (7)
H23A0.61870.19110.72480.028*
H23B0.69020.09890.68640.028*
H23C0.55530.09500.68490.028*
O50.6330 (2)0.13978 (19)0.44295 (11)0.0272 (6)
O60.6202 (2)0.25299 (17)0.35335 (12)0.0269 (6)
O70.6021 (2)0.25284 (18)0.39993 (12)0.0272 (6)
O80.6009 (2)0.31690 (18)0.29559 (12)0.0223 (6)
O90.5820 (3)0.0679 (2)0.10499 (13)0.0380 (8)
O100.5987 (2)0.10632 (19)0.12238 (12)0.0264 (6)
N30.6006 (2)0.2413 (2)0.33703 (15)0.0200 (7)
N40.5904 (2)0.0121 (2)0.14286 (14)0.0215 (7)
C240.6242 (3)0.1604 (3)0.37881 (17)0.0207 (8)
C250.6139 (3)0.0630 (3)0.33135 (17)0.0167 (7)
C260.6137 (3)0.0433 (3)0.35618 (16)0.0168 (7)
H260.62340.05710.40380.020*
C270.5991 (3)0.1288 (3)0.31054 (17)0.0165 (7)
C280.5873 (3)0.1134 (3)0.24020 (17)0.0171 (7)
H280.57590.17250.20960.021*
C290.5931 (3)0.0071 (3)0.21761 (16)0.0166 (7)
C300.6059 (3)0.0813 (3)0.26106 (16)0.0155 (7)
H300.60900.15320.24320.019*
O310.6434 (2)0.0262 (2)0.53875 (14)0.0352 (7)
H310.62600.02640.51440.053*
C310.5343 (3)0.0710 (4)0.5387 (2)0.0411 (11)
H31A0.51360.09180.49180.062*
H31B0.48050.01690.55590.062*
H31C0.53270.13560.56820.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0288 (14)0.0142 (12)0.0160 (12)0.0019 (10)0.0026 (11)0.0032 (10)
O20.0259 (13)0.0162 (11)0.0095 (11)0.0013 (10)0.0005 (11)0.0012 (9)
O30.0240 (13)0.0110 (11)0.0156 (11)0.0009 (10)0.0005 (11)0.0012 (9)
O40.0382 (16)0.0206 (13)0.0113 (13)0.0062 (11)0.0015 (11)0.0018 (10)
N10.0173 (15)0.0131 (13)0.0112 (13)0.0004 (11)0.0014 (12)0.0002 (11)
N20.0273 (17)0.0115 (13)0.0107 (14)0.0013 (12)0.0006 (12)0.0035 (11)
C10.0149 (17)0.0165 (16)0.0115 (16)0.0003 (14)0.0010 (15)0.0010 (13)
C20.0149 (17)0.0165 (16)0.0114 (15)0.0016 (14)0.0001 (15)0.0028 (13)
C30.0114 (16)0.0135 (16)0.0157 (16)0.0003 (13)0.0008 (15)0.0002 (13)
C40.0136 (17)0.0143 (16)0.0172 (16)0.0031 (14)0.0014 (15)0.0035 (14)
C50.0115 (17)0.0152 (15)0.0107 (16)0.0011 (13)0.0018 (14)0.0009 (13)
C60.0132 (17)0.0120 (15)0.0167 (17)0.0007 (13)0.0009 (15)0.0008 (13)
C70.0135 (17)0.0102 (14)0.0129 (16)0.0007 (13)0.0005 (14)0.0006 (13)
C80.0166 (17)0.0121 (16)0.0103 (15)0.0021 (13)0.0007 (14)0.0008 (13)
C90.0176 (17)0.0180 (18)0.0171 (18)0.0010 (14)0.0017 (15)0.0024 (15)
C100.028 (2)0.0155 (18)0.0168 (18)0.0058 (14)0.0025 (16)0.0029 (15)
C110.0226 (19)0.0121 (16)0.0153 (17)0.0020 (14)0.0006 (15)0.0001 (14)
C120.034 (2)0.0148 (17)0.0206 (19)0.0019 (16)0.0043 (17)0.0032 (15)
C130.028 (2)0.0166 (18)0.0142 (17)0.0021 (15)0.0018 (16)0.0045 (15)
C140.0158 (17)0.0196 (17)0.0117 (16)0.0027 (14)0.0007 (15)0.0005 (14)
C150.027 (2)0.0143 (17)0.0154 (18)0.0007 (15)0.0011 (16)0.0046 (14)
C160.0202 (19)0.0159 (17)0.0177 (18)0.0001 (14)0.0001 (15)0.0034 (14)
C170.0189 (18)0.0149 (17)0.0141 (17)0.0032 (14)0.0028 (15)0.0004 (14)
C180.0159 (17)0.0132 (16)0.0123 (17)0.0016 (13)0.0006 (14)0.0005 (13)
C190.0155 (17)0.0156 (16)0.0143 (17)0.0013 (13)0.0023 (14)0.0020 (14)
C200.0153 (17)0.0198 (17)0.0151 (17)0.0040 (14)0.0024 (14)0.0026 (15)
C210.0200 (18)0.0111 (16)0.0133 (17)0.0039 (13)0.0011 (15)0.0001 (14)
C220.037 (2)0.0241 (19)0.0118 (17)0.0066 (17)0.0001 (17)0.0001 (14)
C230.027 (2)0.0125 (16)0.0169 (17)0.0001 (15)0.0016 (16)0.0006 (14)
O50.0479 (18)0.0197 (12)0.0139 (12)0.0021 (12)0.0021 (12)0.0034 (10)
O60.0403 (17)0.0165 (12)0.0238 (14)0.0026 (12)0.0023 (13)0.0003 (11)
O70.0410 (17)0.0202 (13)0.0206 (14)0.0004 (12)0.0037 (13)0.0033 (11)
O80.0250 (14)0.0155 (12)0.0264 (13)0.0014 (10)0.0027 (11)0.0082 (11)
O90.068 (2)0.0301 (15)0.0164 (13)0.0147 (14)0.0023 (14)0.0071 (12)
O100.0353 (16)0.0251 (13)0.0187 (13)0.0000 (12)0.0043 (12)0.0051 (11)
N30.0168 (15)0.0191 (15)0.0242 (17)0.0022 (12)0.0010 (14)0.0008 (13)
N40.0201 (16)0.0297 (17)0.0146 (15)0.0011 (13)0.0016 (13)0.0018 (14)
C240.0203 (19)0.0219 (18)0.0198 (19)0.0003 (16)0.0031 (16)0.0035 (15)
C250.0140 (17)0.0182 (16)0.0179 (17)0.0001 (14)0.0021 (15)0.0025 (14)
C260.0151 (17)0.0217 (17)0.0136 (16)0.0009 (15)0.0010 (16)0.0003 (14)
C270.0143 (17)0.0153 (16)0.0201 (18)0.0005 (13)0.0019 (15)0.0015 (14)
C280.0145 (17)0.0180 (17)0.0190 (17)0.0006 (14)0.0002 (15)0.0067 (15)
C290.0155 (17)0.0223 (18)0.0120 (16)0.0003 (14)0.0020 (14)0.0002 (14)
C300.0135 (17)0.0164 (17)0.0164 (17)0.0011 (14)0.0016 (15)0.0005 (14)
O310.0333 (16)0.0379 (15)0.0343 (15)0.0021 (13)0.0027 (13)0.0111 (13)
C310.032 (3)0.066 (3)0.025 (2)0.008 (2)0.005 (2)0.003 (2)
Geometric parameters (Å, º) top
O1—C111.430 (4)C16—C171.513 (4)
O1—C121.442 (4)C16—H16A0.9900
O2—C21.374 (4)C16—H16B0.9900
O2—C221.438 (4)C17—H17A0.9900
O3—C31.372 (4)C17—H17B0.9900
O3—C231.431 (4)C18—C191.539 (4)
O4—C91.225 (4)C18—H181.0000
N1—C91.378 (4)C19—C201.530 (4)
N1—C61.413 (4)C19—H191.0000
N1—C81.490 (4)C20—C211.516 (4)
N2—C161.505 (4)C20—H20A0.9900
N2—C151.515 (4)C20—H20B0.9900
N2—C211.540 (4)C21—H211.0000
N2—H2A0.9300C22—H22A0.9800
C1—C21.385 (4)C22—H22B0.9800
C1—C61.402 (4)C22—H22C0.9800
C1—H10.9500C23—H23A0.9800
C2—C31.412 (4)C23—H23B0.9800
C3—C41.390 (4)C23—H23C0.9800
C4—C51.409 (4)O5—C241.280 (4)
C4—H40.9500O6—C241.241 (4)
C5—C61.379 (4)O7—N31.235 (3)
C5—C71.509 (4)O8—N31.230 (3)
C7—C211.546 (4)O9—N41.232 (4)
C7—C171.547 (4)O10—N41.227 (4)
C7—C81.561 (4)N3—C271.474 (4)
C8—C181.528 (4)N4—C291.477 (4)
C8—H81.0000C24—C251.517 (4)
C9—C101.514 (4)C25—C261.391 (4)
C10—C111.557 (4)C25—C301.392 (4)
C10—H10A0.9900C26—C271.387 (4)
C10—H10B0.9900C26—H260.9500
C11—C181.526 (4)C27—C281.392 (4)
C11—H111.0000C28—C291.378 (5)
C12—C131.508 (4)C28—H280.9500
C12—H12A0.9900C29—C301.384 (4)
C12—H12B0.9900C30—H300.9500
C13—C141.331 (5)O31—C311.406 (5)
C13—H130.9500O31—H310.8274
C14—C151.496 (4)C31—H31A0.9800
C14—C191.530 (4)C31—H31B0.9800
C15—H15A0.9900C31—H31C0.9800
C15—H15B0.9900
C11—O1—C12115.2 (3)C17—C16—H16B110.8
C2—O2—C22116.7 (2)H16A—C16—H16B108.9
C3—O3—C23116.5 (2)C16—C17—C7103.0 (3)
C9—N1—C6126.9 (3)C16—C17—H17A111.2
C9—N1—C8119.2 (3)C7—C17—H17A111.2
C6—N1—C8109.4 (2)C16—C17—H17B111.2
C16—N2—C15111.6 (2)C7—C17—H17B111.2
C16—N2—C21107.4 (2)H17A—C17—H17B109.1
C15—N2—C21113.9 (3)C11—C18—C8107.3 (3)
C16—N2—H2A107.9C11—C18—C19118.6 (3)
C15—N2—H2A107.9C8—C18—C19112.8 (3)
C21—N2—H2A107.9C11—C18—H18105.7
C2—C1—C6117.7 (3)C8—C18—H18105.7
C2—C1—H1121.1C19—C18—H18105.7
C6—C1—H1121.1C20—C19—C14109.2 (3)
O2—C2—C1124.2 (3)C20—C19—C18106.2 (3)
O2—C2—C3114.6 (2)C14—C19—C18115.0 (3)
C1—C2—C3121.2 (3)C20—C19—H19108.8
O3—C3—C4124.3 (3)C14—C19—H19108.8
O3—C3—C2115.4 (3)C18—C19—H19108.8
C4—C3—C2120.3 (3)C21—C20—C19109.1 (3)
C3—C4—C5118.7 (3)C21—C20—H20A109.9
C3—C4—H4120.7C19—C20—H20A109.9
C5—C4—H4120.7C21—C20—H20B109.9
C6—C5—C4120.1 (3)C19—C20—H20B109.9
C6—C5—C7110.7 (3)H20A—C20—H20B108.3
C4—C5—C7128.7 (3)C20—C21—N2109.8 (2)
C5—C6—C1122.1 (3)C20—C21—C7115.9 (3)
C5—C6—N1110.5 (3)N2—C21—C7104.9 (2)
C1—C6—N1127.3 (3)C20—C21—H21108.7
C5—C7—C21116.6 (2)N2—C21—H21108.7
C5—C7—C17111.4 (3)C7—C21—H21108.7
C21—C7—C17101.7 (2)O2—C22—H22A109.5
C5—C7—C8102.7 (2)O2—C22—H22B109.5
C21—C7—C8113.5 (3)H22A—C22—H22B109.5
C17—C7—C8111.3 (2)O2—C22—H22C109.5
N1—C8—C18105.8 (2)H22A—C22—H22C109.5
N1—C8—C7104.6 (2)H22B—C22—H22C109.5
C18—C8—C7118.2 (3)O3—C23—H23A109.5
N1—C8—H8109.3O3—C23—H23B109.5
C18—C8—H8109.3H23A—C23—H23B109.5
C7—C8—H8109.3O3—C23—H23C109.5
O4—C9—N1122.3 (3)H23A—C23—H23C109.5
O4—C9—C10122.9 (3)H23B—C23—H23C109.5
N1—C9—C10114.7 (3)O8—N3—O7124.4 (3)
C9—C10—C11116.5 (3)O8—N3—C27118.4 (3)
C9—C10—H10A108.2O7—N3—C27117.1 (3)
C11—C10—H10A108.2O10—N4—O9124.2 (3)
C9—C10—H10B108.2O10—N4—C29118.0 (3)
C11—C10—H10B108.2O9—N4—C29117.8 (3)
H10A—C10—H10B107.3O6—C24—O5125.1 (3)
O1—C11—C18114.6 (3)O6—C24—C25118.3 (3)
O1—C11—C10104.6 (3)O5—C24—C25116.6 (3)
C18—C11—C10110.4 (2)C26—C25—C30119.6 (3)
O1—C11—H11109.0C26—C25—C24121.8 (3)
C18—C11—H11109.0C30—C25—C24118.6 (3)
C10—C11—H11109.0C27—C26—C25119.1 (3)
O1—C12—C13111.1 (3)C27—C26—H26120.4
O1—C12—H12A109.4C25—C26—H26120.4
C13—C12—H12A109.4C26—C27—C28122.8 (3)
O1—C12—H12B109.4C26—C27—N3118.9 (3)
C13—C12—H12B109.4C28—C27—N3118.3 (3)
H12A—C12—H12B108.0C29—C28—C27116.0 (3)
C14—C13—C12122.6 (3)C29—C28—H28122.0
C14—C13—H13118.7C27—C28—H28122.0
C12—C13—H13118.7C28—C29—C30123.5 (3)
C13—C14—C15122.1 (3)C28—C29—N4117.7 (3)
C13—C14—C19122.6 (3)C30—C29—N4118.8 (3)
C15—C14—C19115.3 (3)C29—C30—C25118.9 (3)
C14—C15—N2109.4 (3)C29—C30—H30120.5
C14—C15—H15A109.8C25—C30—H30120.5
N2—C15—H15A109.8C31—O31—H3194.3
C14—C15—H15B109.8O31—C31—H31A109.5
N2—C15—H15B109.8O31—C31—H31B109.5
H15A—C15—H15B108.2H31A—C31—H31B109.5
N2—C16—C17104.8 (3)O31—C31—H31C109.5
N2—C16—H16A110.8H31A—C31—H31C109.5
C17—C16—H16A110.8H31B—C31—H31C109.5
N2—C16—H16B110.8
C22—O2—C2—C11.2 (5)C21—N2—C16—C1718.7 (3)
C22—O2—C2—C3177.6 (3)N2—C16—C17—C738.2 (3)
C6—C1—C2—O2178.9 (3)C5—C7—C17—C16167.4 (2)
C6—C1—C2—C30.2 (5)C21—C7—C17—C1642.5 (3)
C23—O3—C3—C41.3 (5)C8—C7—C17—C1678.7 (3)
C23—O3—C3—C2178.7 (3)O1—C11—C18—C873.8 (3)
O2—C2—C3—O30.2 (4)C10—C11—C18—C844.1 (3)
C1—C2—C3—O3178.6 (3)O1—C11—C18—C1955.5 (4)
O2—C2—C3—C4179.7 (3)C10—C11—C18—C19173.3 (3)
C1—C2—C3—C41.4 (5)N1—C8—C18—C1172.2 (3)
O3—C3—C4—C5178.3 (3)C7—C8—C18—C11171.1 (3)
C2—C3—C4—C51.8 (5)N1—C8—C18—C19155.3 (2)
C3—C4—C5—C60.9 (5)C7—C8—C18—C1938.6 (4)
C3—C4—C5—C7172.3 (3)C13—C14—C19—C20176.7 (3)
C4—C5—C6—C10.4 (5)C15—C14—C19—C202.4 (4)
C7—C5—C6—C1172.5 (3)C13—C14—C19—C1857.4 (4)
C4—C5—C6—N1178.2 (3)C15—C14—C19—C18121.6 (3)
C7—C5—C6—N15.4 (4)C11—C18—C19—C20173.4 (3)
C2—C1—C6—C50.7 (5)C8—C18—C19—C2060.0 (3)
C2—C1—C6—N1178.2 (3)C11—C18—C19—C1465.7 (4)
C9—N1—C6—C5160.1 (3)C8—C18—C19—C1460.9 (3)
C8—N1—C6—C54.4 (4)C14—C19—C20—C2156.0 (3)
C9—N1—C6—C122.2 (5)C18—C19—C20—C2168.6 (3)
C8—N1—C6—C1177.9 (3)C19—C20—C21—N262.1 (3)
C6—C5—C7—C21136.8 (3)C19—C20—C21—C756.4 (4)
C4—C5—C7—C2151.1 (5)C16—N2—C21—C20133.1 (3)
C6—C5—C7—C17107.1 (3)C15—N2—C21—C209.0 (3)
C4—C5—C7—C1765.0 (4)C16—N2—C21—C77.9 (3)
C6—C5—C7—C812.1 (3)C15—N2—C21—C7116.2 (3)
C4—C5—C7—C8175.8 (3)C5—C7—C21—C2086.8 (3)
C9—N1—C8—C1844.0 (3)C17—C7—C21—C20151.9 (3)
C6—N1—C8—C18113.8 (3)C8—C7—C21—C2032.3 (4)
C9—N1—C8—C7169.6 (3)C5—C7—C21—N2152.0 (3)
C6—N1—C8—C711.7 (3)C17—C7—C21—N230.6 (3)
C5—C7—C8—N113.9 (3)C8—C7—C21—N289.0 (3)
C21—C7—C8—N1140.6 (3)O6—C24—C25—C26177.7 (3)
C17—C7—C8—N1105.4 (3)O5—C24—C25—C260.2 (5)
C5—C7—C8—C18103.4 (3)O6—C24—C25—C303.0 (5)
C21—C7—C8—C1823.3 (4)O5—C24—C25—C30179.0 (3)
C17—C7—C8—C18137.3 (3)C30—C25—C26—C273.5 (5)
C6—N1—C9—O418.9 (5)C24—C25—C26—C27177.2 (3)
C8—N1—C9—O4172.5 (3)C25—C26—C27—C281.6 (5)
C6—N1—C9—C10164.7 (3)C25—C26—C27—N3179.1 (3)
C8—N1—C9—C1011.1 (4)O8—N3—C27—C26171.6 (3)
O4—C9—C10—C11143.4 (3)O7—N3—C27—C268.0 (5)
N1—C9—C10—C1140.2 (4)O8—N3—C27—C286.0 (4)
C12—O1—C11—C1867.9 (4)O7—N3—C27—C28174.4 (3)
C12—O1—C11—C10171.0 (2)C26—C27—C28—C291.2 (5)
C9—C10—C11—O1133.9 (3)N3—C27—C28—C29176.3 (3)
C9—C10—C11—C1810.1 (4)C27—C28—C29—C302.3 (5)
C11—O1—C12—C1388.1 (3)C27—C28—C29—N4175.1 (3)
O1—C12—C13—C1464.1 (4)O10—N4—C29—C28178.0 (3)
C12—C13—C14—C15177.0 (3)O9—N4—C29—C280.7 (5)
C12—C13—C14—C192.0 (5)O10—N4—C29—C300.5 (4)
C13—C14—C15—N2125.1 (3)O9—N4—C29—C30178.2 (3)
C19—C14—C15—N253.9 (4)C28—C29—C30—C250.4 (5)
C16—N2—C15—C1474.5 (3)N4—C29—C30—C25177.0 (3)
C21—N2—C15—C1447.3 (3)C26—C25—C30—C292.6 (5)
C15—N2—C16—C17144.2 (3)C24—C25—C30—C29178.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.931.732.643 (3)166
O31—H31···O50.831.972.766 (3)161.1
(II) brucinim 3,5-dintrobenzoate dimethanol solvate top
Crystal data top
C23H27N2O4+·C7H3N2O6·2CH4OF(000) = 1416
Mr = 670.66Dx = 1.481 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 17566 reflections
a = 7.1733 (18) Åθ = 3.4–28.5°
b = 19.100 (2) ŵ = 0.11 mm1
c = 21.955 (2) ÅT = 100 K
V = 3008.0 (9) Å3Block, orange
Z = 40.30 × 0.30 × 0.30 mm
Data collection top
Kuma KM-4 CCD
diffractometer
3407 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.085
Graphite monochromatorθmax = 27.0°, θmin = 3.4°
ω scanh = 69
20084 measured reflectionsk = 2424
3707 independent reflectionsl = 2827
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.124 w = 1/[σ2(Fo2) + (0.079P)2 + 0.1302P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3707 reflectionsΔρmax = 0.31 e Å3
433 parametersΔρmin = 0.44 e Å3
0 restraintsAbsolute structure: from known structure (Toda et al., 1985)
Primary atom site location: structure-invariant direct methods
Crystal data top
C23H27N2O4+·C7H3N2O6·2CH4OV = 3008.0 (9) Å3
Mr = 670.66Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.1733 (18) ŵ = 0.11 mm1
b = 19.100 (2) ÅT = 100 K
c = 21.955 (2) Å0.30 × 0.30 × 0.30 mm
Data collection top
Kuma KM-4 CCD
diffractometer
3407 reflections with I > 2σ(I)
20084 measured reflectionsRint = 0.085
3707 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.124H-atom parameters constrained
S = 1.10Δρmax = 0.31 e Å3
3707 reflectionsΔρmin = 0.44 e Å3
433 parametersAbsolute structure: from known structure (Toda et al., 1985)
Special details top

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 (Å2) top
xyzUiso*/Ueq
O11.0572 (3)0.65185 (11)0.17580 (9)0.0174 (4)
O20.9188 (3)0.88938 (10)0.50934 (10)0.0215 (5)
O30.9007 (3)0.77357 (10)0.56931 (9)0.0199 (5)
O41.0757 (3)0.85828 (10)0.29024 (10)0.0230 (5)
N10.9553 (3)0.75288 (12)0.31800 (10)0.0143 (5)
N20.8798 (4)0.51620 (12)0.35694 (11)0.0152 (5)
H2A0.84720.48470.38740.018*
C10.9339 (4)0.83051 (15)0.41128 (13)0.0152 (6)
H10.94270.87320.38930.018*
C20.9190 (4)0.83002 (14)0.47436 (13)0.0161 (6)
C30.9068 (4)0.76672 (14)0.50706 (13)0.0159 (6)
C40.9011 (4)0.70343 (15)0.47599 (13)0.0153 (6)
H40.88770.66070.49770.018*
C50.9151 (4)0.70330 (14)0.41288 (13)0.0138 (6)
C60.9353 (4)0.76587 (14)0.38134 (13)0.0141 (6)
C70.8940 (4)0.64324 (14)0.36868 (12)0.0128 (5)
C80.9576 (4)0.67609 (13)0.30707 (13)0.0131 (6)
H80.86460.66430.27470.016*
C91.0462 (4)0.79642 (15)0.27851 (13)0.0157 (6)
C101.1084 (5)0.76430 (15)0.21877 (14)0.0209 (6)
H10A1.21300.79270.20280.025*
H10B1.00420.76850.18940.025*
C111.1709 (4)0.68714 (14)0.22002 (13)0.0167 (6)
H111.30420.68430.20700.020*
C121.1148 (5)0.58159 (15)0.16231 (13)0.0196 (6)
H12A1.25260.57910.16380.024*
H12B1.07530.56960.12040.024*
C131.0346 (4)0.52852 (15)0.20610 (13)0.0175 (6)
H130.95230.49390.19060.021*
C141.0735 (4)0.52800 (14)0.26530 (13)0.0149 (6)
C150.9839 (4)0.47655 (15)0.30807 (13)0.0171 (6)
H15A1.08060.44660.32690.021*
H15B0.89660.44610.28530.021*
C160.7035 (4)0.54867 (14)0.33266 (13)0.0158 (6)
H16A0.71120.55560.28800.019*
H16B0.59390.51910.34200.019*
C170.6920 (4)0.61773 (15)0.36530 (13)0.0152 (6)
H17A0.63900.61170.40660.018*
H17B0.61370.65130.34230.018*
C181.1534 (4)0.65789 (14)0.28435 (13)0.0150 (6)
H181.24150.68580.31000.018*
C191.2035 (4)0.58045 (15)0.29542 (13)0.0156 (6)
H191.33330.57190.28060.019*
C201.1988 (4)0.57021 (15)0.36486 (13)0.0155 (6)
H20A1.25080.52380.37560.019*
H20B1.27520.60670.38500.019*
C210.9976 (4)0.57533 (14)0.38630 (13)0.0142 (6)
H210.99420.56990.43160.017*
C220.9245 (5)0.95494 (16)0.47857 (15)0.0280 (8)
H22A0.92340.99300.50850.042*
H22B0.81560.95920.45190.042*
H22C1.03860.95780.45410.042*
C230.9282 (5)0.71057 (16)0.60352 (13)0.0203 (6)
H23A0.92140.72110.64710.030*
H23B1.05090.69090.59390.030*
H23C0.83110.67660.59290.030*
O50.7730 (4)0.43850 (12)0.45405 (10)0.0278 (6)
O60.6689 (3)0.35445 (12)0.39161 (10)0.0268 (5)
O70.8617 (3)0.38241 (13)0.66949 (11)0.0301 (6)
O80.8514 (3)0.27508 (13)0.70124 (10)0.0284 (5)
O90.7048 (4)0.09022 (12)0.55984 (11)0.0338 (6)
O100.6906 (4)0.11248 (12)0.46282 (10)0.0265 (5)
N30.8364 (4)0.31986 (14)0.66110 (12)0.0219 (6)
N40.7068 (4)0.13072 (13)0.51631 (12)0.0209 (6)
C240.7239 (4)0.37673 (16)0.44148 (14)0.0192 (6)
C250.7357 (4)0.32419 (15)0.49341 (14)0.0172 (6)
C260.7724 (4)0.34622 (16)0.55295 (14)0.0193 (6)
H260.78630.39460.56190.023*
C270.7883 (4)0.29647 (16)0.59913 (14)0.0192 (6)
C280.7665 (4)0.22497 (15)0.58912 (14)0.0180 (6)
H280.77640.19150.62100.022*
C290.7290 (4)0.20589 (15)0.52915 (14)0.0175 (6)
C300.7148 (4)0.25303 (16)0.48158 (13)0.0162 (6)
H300.69110.23710.44130.019*
O310.9094 (5)0.54181 (17)0.53661 (13)0.0535 (9)
H310.88060.51060.51220.080*
C310.9439 (8)0.5278 (2)0.5990 (2)0.0551 (12)
H31A1.05260.55470.61250.083*
H31B0.96830.47770.60440.083*
H31C0.83480.54130.62310.083*
O320.4010 (3)0.40865 (12)0.31333 (11)0.0279 (5)
H320.48370.39510.33650.042*
C320.4390 (6)0.3928 (2)0.25114 (15)0.0331 (8)
H32A0.33230.40660.22600.050*
H32B0.46080.34240.24680.050*
H32C0.55010.41850.23790.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0232 (11)0.0145 (10)0.0146 (10)0.0010 (9)0.0005 (9)0.0016 (8)
O20.0325 (13)0.0118 (10)0.0204 (10)0.0016 (9)0.0002 (10)0.0041 (8)
O30.0263 (12)0.0185 (10)0.0148 (10)0.0020 (9)0.0005 (9)0.0026 (8)
O40.0338 (13)0.0119 (10)0.0234 (11)0.0014 (10)0.0036 (10)0.0017 (8)
N10.0194 (12)0.0098 (11)0.0136 (11)0.0003 (10)0.0005 (10)0.0005 (9)
N20.0210 (13)0.0108 (11)0.0139 (12)0.0003 (10)0.0012 (10)0.0004 (9)
C10.0153 (14)0.0115 (13)0.0188 (14)0.0001 (11)0.0026 (11)0.0005 (11)
C20.0148 (14)0.0121 (13)0.0213 (15)0.0006 (11)0.0012 (12)0.0059 (11)
C30.0156 (14)0.0167 (15)0.0153 (13)0.0000 (11)0.0002 (11)0.0028 (11)
C40.0146 (13)0.0138 (13)0.0176 (14)0.0013 (11)0.0020 (11)0.0002 (11)
C50.0121 (13)0.0110 (13)0.0182 (14)0.0013 (11)0.0014 (11)0.0001 (11)
C60.0152 (14)0.0112 (13)0.0161 (14)0.0007 (11)0.0002 (11)0.0004 (10)
C70.0134 (13)0.0119 (13)0.0130 (13)0.0009 (11)0.0003 (11)0.0008 (10)
C80.0157 (14)0.0086 (12)0.0151 (13)0.0011 (10)0.0000 (11)0.0019 (10)
C90.0172 (14)0.0150 (14)0.0148 (14)0.0001 (12)0.0021 (11)0.0026 (11)
C100.0279 (16)0.0169 (14)0.0178 (14)0.0022 (13)0.0027 (13)0.0022 (12)
C110.0180 (15)0.0156 (14)0.0164 (14)0.0041 (12)0.0031 (12)0.0014 (11)
C120.0307 (17)0.0137 (14)0.0145 (14)0.0007 (13)0.0036 (13)0.0015 (11)
C130.0203 (15)0.0157 (14)0.0164 (14)0.0002 (12)0.0017 (12)0.0014 (11)
C140.0157 (14)0.0106 (12)0.0183 (14)0.0036 (11)0.0010 (12)0.0022 (11)
C150.0219 (15)0.0136 (13)0.0157 (14)0.0014 (12)0.0002 (12)0.0026 (11)
C160.0158 (13)0.0141 (13)0.0174 (14)0.0023 (11)0.0008 (12)0.0006 (11)
C170.0147 (14)0.0146 (13)0.0162 (13)0.0004 (11)0.0046 (11)0.0004 (11)
C180.0163 (14)0.0136 (13)0.0151 (13)0.0018 (11)0.0015 (11)0.0012 (11)
C190.0139 (14)0.0146 (13)0.0183 (14)0.0024 (11)0.0009 (11)0.0005 (11)
C200.0169 (14)0.0140 (14)0.0154 (14)0.0013 (11)0.0027 (11)0.0008 (11)
C210.0194 (14)0.0106 (13)0.0127 (13)0.0036 (11)0.0007 (11)0.0007 (10)
C220.044 (2)0.0122 (14)0.0281 (17)0.0025 (14)0.0007 (16)0.0038 (13)
C230.0226 (16)0.0214 (15)0.0170 (15)0.0029 (13)0.0003 (12)0.0003 (12)
O50.0388 (14)0.0188 (11)0.0259 (12)0.0034 (10)0.0078 (11)0.0053 (9)
O60.0348 (14)0.0253 (12)0.0201 (11)0.0050 (11)0.0009 (10)0.0043 (9)
O70.0315 (13)0.0293 (13)0.0295 (13)0.0063 (11)0.0003 (11)0.0117 (10)
O80.0307 (13)0.0374 (14)0.0172 (11)0.0071 (11)0.0030 (10)0.0012 (10)
O90.0560 (17)0.0204 (12)0.0249 (12)0.0014 (12)0.0035 (12)0.0071 (10)
O100.0392 (14)0.0206 (11)0.0198 (11)0.0021 (11)0.0016 (10)0.0053 (9)
N30.0179 (13)0.0280 (14)0.0200 (13)0.0012 (11)0.0014 (11)0.0064 (11)
N40.0215 (13)0.0167 (13)0.0246 (14)0.0024 (11)0.0010 (11)0.0017 (11)
C240.0180 (14)0.0179 (14)0.0217 (15)0.0036 (12)0.0030 (12)0.0038 (12)
C250.0137 (14)0.0176 (14)0.0204 (14)0.0010 (11)0.0024 (12)0.0030 (12)
C260.0167 (15)0.0183 (14)0.0228 (15)0.0026 (12)0.0038 (12)0.0020 (12)
C270.0146 (14)0.0244 (15)0.0187 (15)0.0003 (12)0.0003 (12)0.0040 (12)
C280.0159 (14)0.0188 (14)0.0194 (15)0.0012 (11)0.0004 (12)0.0025 (12)
C290.0139 (13)0.0164 (14)0.0223 (15)0.0006 (12)0.0001 (12)0.0029 (12)
C300.0143 (13)0.0199 (14)0.0145 (13)0.0004 (12)0.0027 (11)0.0012 (12)
O310.077 (2)0.0492 (18)0.0341 (15)0.0061 (17)0.0064 (16)0.0027 (13)
C310.063 (3)0.050 (3)0.053 (3)0.001 (2)0.001 (3)0.002 (2)
O320.0258 (13)0.0313 (12)0.0265 (12)0.0050 (10)0.0008 (10)0.0014 (10)
C320.035 (2)0.042 (2)0.0218 (17)0.0049 (18)0.0031 (15)0.0020 (15)
Geometric parameters (Å, º) top
O1—C121.435 (3)C16—H16B0.9900
O1—C111.436 (3)C17—H17A0.9900
O2—C21.369 (3)C17—H17B0.9900
O2—C221.423 (4)C18—C191.541 (4)
O3—C31.374 (3)C18—H181.0000
O3—C231.432 (3)C19—C201.537 (4)
O4—C91.228 (3)C19—H191.0000
N1—C91.367 (4)C20—C211.521 (4)
N1—C61.420 (4)C20—H20A0.9900
N1—C81.486 (3)C20—H20B0.9900
N2—C161.506 (4)C21—H211.0000
N2—C151.511 (4)C22—H22A0.9800
N2—C211.551 (4)C22—H22B0.9800
N2—H2A0.9300C22—H22C0.9800
C1—C21.389 (4)C23—H23A0.9800
C1—C61.399 (4)C23—H23B0.9800
C1—H10.9500C23—H23C0.9800
C2—C31.409 (4)O5—C241.262 (4)
C3—C41.389 (4)O6—C241.239 (4)
C4—C51.389 (4)O7—N31.222 (3)
C4—H40.9500O8—N31.233 (3)
C5—C61.389 (4)O9—N41.229 (3)
C5—C71.510 (4)O10—N41.231 (3)
C7—C171.530 (4)N3—C271.473 (4)
C7—C211.544 (4)N4—C291.472 (4)
C7—C81.559 (4)C24—C251.521 (4)
C8—C181.531 (4)C25—C301.392 (4)
C8—H81.0000C25—C261.398 (4)
C9—C101.515 (4)C26—C271.394 (4)
C10—C111.541 (4)C26—H260.9500
C10—H10A0.9900C27—C281.392 (4)
C10—H10B0.9900C28—C291.392 (4)
C11—C181.524 (4)C28—H280.9500
C11—H111.0000C29—C301.383 (4)
C12—C131.511 (4)C30—H300.9500
C12—H12A0.9900O31—C311.417 (5)
C12—H12B0.9900O31—H310.8281
C13—C141.329 (4)C31—H31A0.9800
C13—H130.9500C31—H31B0.9800
C14—C151.504 (4)C31—H31C0.9800
C14—C191.520 (4)O32—C321.425 (4)
C15—H15A0.9900O32—H320.8233
C15—H15B0.9900C32—H32A0.9800
C16—C171.503 (4)C32—H32B0.9800
C16—H16A0.9900C32—H32C0.9800
C12—O1—C11114.5 (2)C16—C17—H17A110.9
C2—O2—C22117.5 (2)C7—C17—H17A110.9
C3—O3—C23115.9 (2)C16—C17—H17B110.9
C9—N1—C6124.3 (2)C7—C17—H17B110.9
C9—N1—C8119.5 (2)H17A—C17—H17B108.9
C6—N1—C8109.4 (2)C11—C18—C8107.1 (2)
C16—N2—C15111.7 (2)C11—C18—C19118.6 (2)
C16—N2—C21107.7 (2)C8—C18—C19112.4 (2)
C15—N2—C21113.0 (2)C11—C18—H18106.0
C16—N2—H2A108.1C8—C18—H18106.0
C15—N2—H2A108.1C19—C18—H18106.0
C21—N2—H2A108.1C14—C19—C20109.5 (2)
C2—C1—C6117.6 (3)C14—C19—C18114.9 (2)
C2—C1—H1121.2C20—C19—C18105.9 (2)
C6—C1—H1121.2C14—C19—H19108.8
O2—C2—C1123.6 (3)C20—C19—H19108.8
O2—C2—C3115.1 (2)C18—C19—H19108.8
C1—C2—C3121.2 (3)C21—C20—C19108.6 (2)
O3—C3—C4124.8 (3)C21—C20—H20A110.0
O3—C3—C2115.3 (2)C19—C20—H20A110.0
C4—C3—C2119.9 (3)C21—C20—H20B110.0
C3—C4—C5119.3 (3)C19—C20—H20B110.0
C3—C4—H4120.4H20A—C20—H20B108.3
C5—C4—H4120.4C20—C21—C7115.7 (2)
C6—C5—C4120.2 (3)C20—C21—N2110.0 (2)
C6—C5—C7110.1 (2)C7—C21—N2104.2 (2)
C4—C5—C7129.4 (3)C20—C21—H21108.9
C5—C6—C1121.6 (3)C7—C21—H21108.9
C5—C6—N1110.4 (2)N2—C21—H21108.9
C1—C6—N1128.0 (2)O2—C22—H22A109.5
C5—C7—C17111.6 (2)O2—C22—H22B109.5
C5—C7—C21115.4 (2)H22A—C22—H22B109.5
C17—C7—C21101.6 (2)O2—C22—H22C109.5
C5—C7—C8102.8 (2)H22A—C22—H22C109.5
C17—C7—C8111.3 (2)H22B—C22—H22C109.5
C21—C7—C8114.5 (2)O3—C23—H23A109.5
N1—C8—C18106.7 (2)O3—C23—H23B109.5
N1—C8—C7104.7 (2)H23A—C23—H23B109.5
C18—C8—C7117.4 (2)O3—C23—H23C109.5
N1—C8—H8109.3H23A—C23—H23C109.5
C18—C8—H8109.3H23B—C23—H23C109.5
C7—C8—H8109.3O7—N3—O8123.9 (3)
O4—C9—N1122.3 (3)O7—N3—C27118.1 (3)
O4—C9—C10121.4 (3)O8—N3—C27118.1 (3)
N1—C9—C10116.3 (2)O9—N4—O10124.2 (3)
C9—C10—C11117.2 (2)O9—N4—C29117.8 (3)
C9—C10—H10A108.0O10—N4—C29118.0 (2)
C11—C10—H10A108.0O6—C24—O5127.1 (3)
C9—C10—H10B108.0O6—C24—C25117.0 (3)
C11—C10—H10B108.0O5—C24—C25115.9 (3)
H10A—C10—H10B107.2C30—C25—C26119.2 (3)
O1—C11—C18114.1 (2)C30—C25—C24119.9 (3)
O1—C11—C10105.8 (2)C26—C25—C24120.8 (3)
C18—C11—C10110.1 (2)C27—C26—C25119.3 (3)
O1—C11—H11108.9C27—C26—H26120.3
C18—C11—H11108.9C25—C26—H26120.3
C10—C11—H11108.9C28—C27—C26123.0 (3)
O1—C12—C13112.7 (2)C28—C27—N3118.0 (3)
O1—C12—H12A109.0C26—C27—N3119.0 (3)
C13—C12—H12A109.0C27—C28—C29115.3 (3)
O1—C12—H12B109.0C27—C28—H28122.3
C13—C12—H12B109.0C29—C28—H28122.3
H12A—C12—H12B107.8C30—C29—C28123.9 (3)
C14—C13—C12123.2 (3)C30—C29—N4118.9 (3)
C14—C13—H13118.4C28—C29—N4117.2 (3)
C12—C13—H13118.4C29—C30—C25119.2 (3)
C13—C14—C15121.7 (3)C29—C30—H30120.4
C13—C14—C19123.3 (3)C25—C30—H30120.4
C15—C14—C19114.9 (2)C31—O31—H31122.2
C14—C15—N2109.1 (2)O31—C31—H31A109.5
C14—C15—H15A109.9O31—C31—H31B109.5
N2—C15—H15A109.9H31A—C31—H31B109.5
C14—C15—H15B109.9O31—C31—H31C109.5
N2—C15—H15B109.9H31A—C31—H31C109.5
H15A—C15—H15B108.3H31B—C31—H31C109.5
C17—C16—N2103.8 (2)C32—O32—H32112.8
C17—C16—H16A111.0O32—C32—H32A109.5
N2—C16—H16A111.0O32—C32—H32B109.5
C17—C16—H16B111.0H32A—C32—H32B109.5
N2—C16—H16B111.0O32—C32—H32C109.5
H16A—C16—H16B109.0H32A—C32—H32C109.5
C16—C17—C7104.5 (2)H32B—C32—H32C109.5
C22—O2—C2—C13.3 (4)C21—N2—C16—C1718.0 (3)
C22—O2—C2—C3177.9 (3)N2—C16—C17—C738.0 (3)
C6—C1—C2—O2179.0 (3)C5—C7—C17—C16166.4 (2)
C6—C1—C2—C30.3 (5)C21—C7—C17—C1643.0 (3)
C23—O3—C3—C413.0 (4)C8—C7—C17—C1679.3 (3)
C23—O3—C3—C2167.2 (3)O1—C11—C18—C868.9 (3)
O2—C2—C3—O31.4 (4)C10—C11—C18—C849.8 (3)
C1—C2—C3—O3177.3 (3)O1—C11—C18—C1959.5 (4)
O2—C2—C3—C4178.4 (3)C10—C11—C18—C19178.2 (2)
C1—C2—C3—C42.9 (5)N1—C8—C18—C1171.2 (3)
O3—C3—C4—C5177.7 (3)C7—C8—C18—C11171.9 (2)
C2—C3—C4—C52.6 (4)N1—C8—C18—C19156.9 (2)
C3—C4—C5—C60.2 (4)C7—C8—C18—C1940.0 (3)
C3—C4—C5—C7173.3 (3)C13—C14—C19—C20173.3 (3)
C4—C5—C6—C12.9 (4)C15—C14—C19—C204.1 (3)
C7—C5—C6—C1171.8 (3)C13—C14—C19—C1854.4 (4)
C4—C5—C6—N1177.3 (3)C15—C14—C19—C18123.1 (3)
C7—C5—C6—N17.9 (3)C11—C18—C19—C1466.9 (4)
C2—C1—C6—C52.6 (4)C8—C18—C19—C1459.0 (3)
C2—C1—C6—N1177.7 (3)C11—C18—C19—C20172.1 (2)
C9—N1—C6—C5153.5 (3)C8—C18—C19—C2062.0 (3)
C8—N1—C6—C52.9 (3)C14—C19—C20—C2155.0 (3)
C9—N1—C6—C126.7 (5)C18—C19—C20—C2169.4 (3)
C8—N1—C6—C1177.4 (3)C19—C20—C21—C755.6 (3)
C6—C5—C7—C17104.7 (3)C19—C20—C21—N262.1 (3)
C4—C5—C7—C1769.4 (4)C5—C7—C21—C2087.7 (3)
C6—C5—C7—C21140.0 (3)C17—C7—C21—C20151.5 (2)
C4—C5—C7—C2145.9 (4)C8—C7—C21—C2031.5 (3)
C6—C5—C7—C814.6 (3)C5—C7—C21—N2151.5 (2)
C4—C5—C7—C8171.3 (3)C17—C7—C21—N230.7 (3)
C9—N1—C8—C1839.0 (3)C8—C7—C21—N289.4 (3)
C6—N1—C8—C18113.2 (2)C16—N2—C21—C20132.9 (2)
C9—N1—C8—C7164.1 (2)C15—N2—C21—C209.0 (3)
C6—N1—C8—C711.8 (3)C16—N2—C21—C78.3 (3)
C5—C7—C8—N115.5 (3)C15—N2—C21—C7115.6 (2)
C17—C7—C8—N1104.1 (2)O6—C24—C25—C3010.2 (4)
C21—C7—C8—N1141.5 (2)O5—C24—C25—C30169.2 (3)
C5—C7—C8—C18102.5 (3)O6—C24—C25—C26171.5 (3)
C17—C7—C8—C18137.9 (2)O5—C24—C25—C269.0 (4)
C21—C7—C8—C1823.4 (3)C30—C25—C26—C270.3 (4)
C6—N1—C9—O419.7 (4)C24—C25—C26—C27177.9 (3)
C8—N1—C9—O4167.6 (3)C25—C26—C27—C281.0 (5)
C6—N1—C9—C10160.6 (3)C25—C26—C27—N3176.9 (3)
C8—N1—C9—C1012.7 (4)O7—N3—C27—C28177.6 (3)
O4—C9—C10—C11145.9 (3)O8—N3—C27—C281.3 (4)
N1—C9—C10—C1134.5 (4)O7—N3—C27—C260.4 (4)
C12—O1—C11—C1869.1 (3)O8—N3—C27—C26179.4 (3)
C12—O1—C11—C10169.8 (2)C26—C27—C28—C290.6 (5)
C9—C10—C11—O1124.4 (3)N3—C27—C28—C29177.3 (3)
C9—C10—C11—C180.8 (4)C27—C28—C29—C300.4 (5)
C11—O1—C12—C1386.0 (3)C27—C28—C29—N4179.4 (3)
O1—C12—C13—C1463.4 (4)O9—N4—C29—C30174.2 (3)
C12—C13—C14—C15177.0 (3)O10—N4—C29—C305.5 (4)
C12—C13—C14—C190.3 (5)O9—N4—C29—C286.8 (4)
C13—C14—C15—N2121.1 (3)O10—N4—C29—C28173.5 (3)
C19—C14—C15—N256.4 (3)C28—C29—C30—C251.1 (5)
C16—N2—C15—C1473.3 (3)N4—C29—C30—C25180.0 (3)
C21—N2—C15—C1448.4 (3)C26—C25—C30—C290.7 (4)
C15—N2—C16—C17142.6 (2)C24—C25—C30—C29178.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.931.792.708 (3)169
O31—H31···O50.832.032.852 (4)172.0
O32—H32···O60.821.962.778 (3)174.6
(III) brucinium 3,5-dinitrobenzoate trihydrate top
Crystal data top
C23H27N2O4+·C7H3N2O6·3H2OF(000) = 1392
Mr = 660.63Dx = 1.457 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 18822 reflections
a = 8.2499 (8) Åθ = 3.5–28.5°
b = 12.5379 (12) ŵ = 0.12 mm1
c = 29.109 (3) ÅT = 100 K
V = 3010.9 (5) Å3Block, yellow
Z = 40.30 × 0.25 × 0.25 mm
Data collection top
Kuma KM-4 CCD
diffractometer
3036 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.070
Graphite monochromatorθmax = 27.0°, θmin = 3.5°
ω scanh = 1010
20148 measured reflectionsk = 1610
3700 independent reflectionsl = 3637
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.127 w = 1/[σ2(Fo2) + (0.0633P)2 + 0.1372P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
3700 reflectionsΔρmax = 0.26 e Å3
424 parametersΔρmin = 0.25 e Å3
0 restraintsAbsolute structure: from known structure (Toda et al., 1985)
Primary atom site location: structure-invariant direct methods
Crystal data top
C23H27N2O4+·C7H3N2O6·3H2OV = 3010.9 (5) Å3
Mr = 660.63Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.2499 (8) ŵ = 0.12 mm1
b = 12.5379 (12) ÅT = 100 K
c = 29.109 (3) Å0.30 × 0.25 × 0.25 mm
Data collection top
Kuma KM-4 CCD
diffractometer
3036 reflections with I > 2σ(I)
20148 measured reflectionsRint = 0.070
3700 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.12Δρmax = 0.26 e Å3
3700 reflectionsΔρmin = 0.25 e Å3
424 parametersAbsolute structure: from known structure (Toda et al., 1985)
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.2421 (4)0.1057 (2)0.30492 (9)0.0244 (6)
O20.1616 (3)0.7046 (2)0.15824 (8)0.0226 (6)
O30.2230 (3)0.80417 (19)0.23312 (9)0.0240 (6)
O40.1418 (4)0.3017 (2)0.17173 (9)0.0262 (6)
N10.1561 (4)0.3657 (2)0.24474 (10)0.0191 (7)
N20.2622 (4)0.4249 (2)0.39789 (10)0.0229 (7)
H2A0.26770.47880.41980.028*
C10.1545 (5)0.5320 (3)0.19531 (13)0.0206 (8)
H10.13380.49540.16730.025*
C20.1729 (5)0.6411 (3)0.19625 (13)0.0214 (8)
C30.2077 (5)0.6958 (3)0.23710 (13)0.0207 (8)
C40.2201 (5)0.6397 (3)0.27808 (13)0.0207 (8)
H40.24110.67600.30610.025*
C50.2013 (5)0.5294 (3)0.27736 (13)0.0205 (8)
C60.1674 (5)0.4767 (3)0.23715 (13)0.0199 (8)
C70.1978 (5)0.4532 (3)0.31736 (13)0.0217 (8)
C80.2001 (4)0.3421 (3)0.29298 (13)0.0188 (8)
H80.11580.29490.30700.023*
C90.1685 (5)0.2871 (3)0.21266 (13)0.0235 (8)
C100.2141 (5)0.1777 (3)0.23102 (13)0.0218 (8)
H10A0.26610.13760.20570.026*
H10B0.11250.13990.23880.026*
C110.3270 (5)0.1714 (3)0.27315 (13)0.0231 (8)
H110.43110.13620.26420.028*
C120.3369 (6)0.0720 (3)0.34385 (13)0.0290 (9)
H12A0.45180.06450.33450.035*
H12B0.29830.00140.35440.035*
C130.3249 (5)0.1503 (3)0.38250 (14)0.0272 (9)
H130.27980.12750.41090.033*
C140.3752 (5)0.2506 (3)0.37851 (13)0.0229 (8)
C150.3517 (5)0.3296 (3)0.41672 (13)0.0242 (9)
H15A0.45810.35200.42910.029*
H15B0.28850.29670.44190.029*
C160.0860 (5)0.4013 (3)0.38941 (14)0.0254 (9)
H16A0.01890.42410.41580.030*
H16B0.06880.32410.38410.030*
C170.0442 (5)0.4650 (3)0.34686 (13)0.0224 (9)
H17A0.02320.54070.35450.027*
H17B0.05170.43500.33100.027*
C180.3614 (5)0.2834 (3)0.29142 (13)0.0209 (8)
H180.42720.31980.26720.025*
C190.4593 (5)0.2933 (3)0.33621 (12)0.0213 (8)
H190.56540.25570.33240.026*
C200.4908 (5)0.4135 (3)0.34217 (13)0.0238 (9)
H20A0.56950.42520.36740.029*
H20B0.53740.44320.31360.029*
C210.3336 (5)0.4687 (3)0.35314 (12)0.0210 (8)
H210.35460.54680.35690.025*
C220.1530 (6)0.6515 (3)0.11457 (13)0.0307 (10)
H22A0.14530.70460.09000.046*
H22B0.05720.60530.11380.046*
H22C0.25060.60820.11010.046*
C230.2505 (6)0.8623 (3)0.27477 (13)0.0267 (9)
H23A0.25990.93850.26780.040*
H23B0.35090.83730.28920.040*
H23C0.15940.85090.29580.040*
O50.2586 (4)0.5591 (2)0.46743 (9)0.0331 (7)
O60.2470 (4)0.6964 (2)0.41901 (9)0.0300 (7)
O70.0317 (4)0.6275 (2)0.62090 (10)0.0372 (8)
O80.0324 (4)0.7876 (2)0.64904 (9)0.0301 (7)
O90.3665 (4)1.0446 (2)0.49495 (10)0.0331 (7)
O100.2402 (4)1.0781 (2)0.55863 (9)0.0283 (6)
N30.0609 (4)0.7225 (3)0.61831 (11)0.0259 (8)
N40.2842 (4)1.0171 (3)0.52801 (11)0.0254 (8)
C240.2451 (5)0.6571 (3)0.45807 (13)0.0241 (9)
C250.2239 (5)0.7308 (3)0.49890 (12)0.0204 (8)
C260.1617 (5)0.6918 (3)0.53987 (13)0.0230 (8)
H260.13700.61820.54320.028*
C270.1364 (5)0.7621 (3)0.57567 (12)0.0227 (8)
C280.1747 (5)0.8689 (3)0.57281 (13)0.0237 (9)
H280.15690.91610.59780.028*
C290.2397 (5)0.9035 (3)0.53218 (13)0.0206 (8)
C300.2620 (5)0.8378 (3)0.49457 (13)0.0220 (8)
H300.30240.86540.46640.026*
O1W0.0585 (4)0.8771 (2)0.39960 (10)0.0369 (8)
H11W0.00080.85570.37630.055*
H12W0.12350.82310.40590.055*
O2W0.0600 (5)1.2431 (2)0.48415 (10)0.0455 (9)
H21W0.01961.28640.49200.068*
H22W0.02031.17870.48020.068*
O3W0.0134 (4)1.0232 (2)0.47067 (10)0.0331 (7)
H31W0.09270.99320.48650.050*
H32W0.00090.98230.44660.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0258 (15)0.0216 (13)0.0258 (14)0.0016 (12)0.0027 (12)0.0016 (11)
O20.0267 (15)0.0210 (13)0.0201 (14)0.0017 (12)0.0005 (12)0.0008 (11)
O30.0266 (16)0.0207 (13)0.0247 (14)0.0012 (12)0.0004 (12)0.0042 (11)
O40.0278 (15)0.0319 (15)0.0189 (14)0.0049 (13)0.0027 (12)0.0054 (12)
N10.0177 (16)0.0233 (16)0.0161 (16)0.0044 (14)0.0022 (13)0.0039 (13)
N20.0259 (18)0.0211 (15)0.0218 (16)0.0011 (15)0.0004 (14)0.0037 (14)
C10.017 (2)0.0263 (19)0.0180 (19)0.0004 (16)0.0006 (15)0.0061 (16)
C20.0179 (19)0.0264 (19)0.0198 (19)0.0019 (17)0.0002 (15)0.0020 (16)
C30.016 (2)0.0219 (19)0.024 (2)0.0000 (15)0.0044 (15)0.0042 (16)
C40.0181 (19)0.0225 (18)0.0216 (19)0.0027 (16)0.0013 (15)0.0051 (16)
C50.017 (2)0.0238 (19)0.021 (2)0.0022 (15)0.0005 (15)0.0043 (16)
C60.0140 (19)0.0219 (18)0.024 (2)0.0010 (15)0.0040 (15)0.0067 (16)
C70.019 (2)0.0217 (19)0.024 (2)0.0003 (16)0.0002 (15)0.0020 (16)
C80.0143 (19)0.0209 (18)0.0211 (19)0.0015 (15)0.0006 (15)0.0031 (16)
C90.020 (2)0.0244 (19)0.026 (2)0.0003 (17)0.0002 (16)0.0061 (17)
C100.026 (2)0.0202 (18)0.0193 (19)0.0014 (16)0.0029 (16)0.0037 (15)
C110.020 (2)0.0225 (19)0.027 (2)0.0008 (16)0.0030 (16)0.0032 (16)
C120.039 (3)0.0210 (19)0.027 (2)0.0032 (19)0.0071 (19)0.0011 (17)
C130.027 (2)0.031 (2)0.023 (2)0.0033 (19)0.0064 (17)0.0038 (18)
C140.019 (2)0.026 (2)0.024 (2)0.0017 (17)0.0019 (16)0.0003 (17)
C150.029 (2)0.0222 (19)0.022 (2)0.0027 (18)0.0005 (17)0.0020 (16)
C160.021 (2)0.029 (2)0.026 (2)0.0019 (17)0.0065 (16)0.0042 (18)
C170.019 (2)0.022 (2)0.026 (2)0.0002 (16)0.0032 (16)0.0030 (16)
C180.017 (2)0.0219 (18)0.024 (2)0.0002 (16)0.0008 (16)0.0026 (16)
C190.021 (2)0.0235 (19)0.020 (2)0.0020 (17)0.0024 (16)0.0026 (16)
C200.023 (2)0.027 (2)0.021 (2)0.0037 (17)0.0005 (16)0.0000 (17)
C210.024 (2)0.024 (2)0.0150 (18)0.0040 (17)0.0008 (15)0.0001 (15)
C220.043 (3)0.027 (2)0.021 (2)0.001 (2)0.0042 (19)0.0000 (17)
C230.032 (2)0.0241 (19)0.024 (2)0.0014 (19)0.0004 (18)0.0075 (17)
O50.050 (2)0.0256 (15)0.0237 (14)0.0027 (15)0.0001 (14)0.0044 (12)
O60.0375 (17)0.0337 (15)0.0188 (14)0.0017 (15)0.0013 (13)0.0041 (12)
O70.047 (2)0.0315 (17)0.0330 (17)0.0118 (15)0.0104 (15)0.0004 (14)
O80.0311 (17)0.0384 (16)0.0208 (14)0.0051 (14)0.0005 (12)0.0047 (13)
O90.0340 (18)0.0320 (16)0.0334 (17)0.0075 (14)0.0041 (14)0.0006 (13)
O100.0261 (16)0.0261 (14)0.0328 (15)0.0021 (13)0.0008 (13)0.0083 (13)
N30.0260 (19)0.0275 (18)0.0241 (18)0.0001 (16)0.0022 (15)0.0021 (15)
N40.0246 (19)0.0250 (17)0.0266 (19)0.0006 (15)0.0059 (15)0.0005 (15)
C240.027 (2)0.023 (2)0.023 (2)0.0018 (18)0.0012 (17)0.0020 (16)
C250.019 (2)0.026 (2)0.0164 (18)0.0010 (16)0.0045 (15)0.0025 (16)
C260.027 (2)0.0165 (18)0.026 (2)0.0006 (17)0.0012 (17)0.0005 (16)
C270.023 (2)0.026 (2)0.0195 (19)0.0029 (17)0.0005 (15)0.0022 (16)
C280.022 (2)0.027 (2)0.022 (2)0.0020 (17)0.0028 (16)0.0040 (16)
C290.0184 (19)0.0193 (18)0.0241 (19)0.0014 (16)0.0022 (16)0.0003 (15)
C300.021 (2)0.025 (2)0.0205 (19)0.0048 (17)0.0013 (16)0.0019 (16)
O1W0.0418 (19)0.0364 (17)0.0325 (17)0.0067 (15)0.0125 (15)0.0053 (13)
O2W0.058 (2)0.0356 (17)0.043 (2)0.0018 (17)0.0158 (17)0.0051 (16)
O3W0.0372 (18)0.0313 (16)0.0309 (16)0.0020 (14)0.0007 (14)0.0002 (13)
Geometric parameters (Å, º) top
O1—C111.423 (5)C16—C171.513 (5)
O1—C121.440 (5)C16—H16A0.9900
O2—C21.367 (4)C16—H16B0.9900
O2—C221.437 (4)C17—H17A0.9900
O3—C31.370 (4)C17—H17B0.9900
O3—C231.433 (4)C18—C191.539 (5)
O4—C91.226 (5)C18—H181.0000
N1—C91.361 (5)C19—C201.538 (5)
N1—C61.413 (5)C19—H191.0000
N1—C81.480 (5)C20—C211.505 (6)
N2—C161.504 (5)C20—H20A0.9900
N2—C151.508 (5)C20—H20B0.9900
N2—C211.532 (5)C21—H211.0000
N2—H2A0.9300C22—H22A0.9800
C1—C21.376 (5)C22—H22B0.9800
C1—C61.405 (5)C22—H22C0.9800
C1—H10.9500C23—H23A0.9800
C2—C31.403 (5)C23—H23B0.9800
C3—C41.388 (5)C23—H23C0.9800
C4—C51.392 (5)O5—C241.264 (5)
C4—H40.9500O6—C241.239 (4)
C5—C61.373 (5)O7—N31.217 (4)
C5—C71.507 (5)O8—N31.234 (4)
C7—C171.538 (5)O9—N41.227 (4)
C7—C211.542 (5)O10—N41.229 (4)
C7—C81.563 (5)N3—C271.475 (5)
C8—C181.522 (5)N4—C291.476 (5)
C8—H81.0000C24—C251.516 (5)
C9—C101.519 (5)C25—C301.383 (5)
C10—C111.542 (6)C25—C261.387 (5)
C10—H10A0.9900C26—C271.381 (5)
C10—H10B0.9900C26—H260.9500
C11—C181.529 (5)C27—C281.377 (6)
C11—H111.0000C28—C291.370 (5)
C12—C131.497 (6)C28—H280.9500
C12—H12A0.9900C29—C301.383 (5)
C12—H12B0.9900C30—H300.9500
C13—C141.329 (5)O1W—H11W0.8799
C13—H130.9500O1W—H12W0.8832
C14—C151.502 (5)O2W—H21W0.8819
C14—C191.512 (5)O2W—H22W0.8788
C15—H15A0.9900O3W—H31W0.8846
C15—H15B0.9900O3W—H32W0.8749
C11—O1—C12114.5 (3)C17—C16—H16A110.8
C2—O2—C22116.7 (3)N2—C16—H16B110.8
C3—O3—C23116.6 (3)C17—C16—H16B110.8
C9—N1—C6126.9 (3)H16A—C16—H16B108.9
C9—N1—C8119.2 (3)C16—C17—C7102.6 (3)
C6—N1—C8109.2 (3)C16—C17—H17A111.2
C16—N2—C15112.2 (3)C7—C17—H17A111.2
C16—N2—C21107.6 (3)C16—C17—H17B111.2
C15—N2—C21113.9 (3)C7—C17—H17B111.2
C16—N2—H2A107.6H17A—C17—H17B109.2
C15—N2—H2A107.6C8—C18—C11107.0 (3)
C21—N2—H2A107.6C8—C18—C19113.3 (3)
C2—C1—C6117.7 (3)C11—C18—C19117.8 (3)
C2—C1—H1121.2C8—C18—H18106.0
C6—C1—H1121.2C11—C18—H18106.0
O2—C2—C1123.8 (3)C19—C18—H18106.0
O2—C2—C3114.5 (3)C14—C19—C20109.4 (3)
C1—C2—C3121.7 (4)C14—C19—C18114.8 (3)
O3—C3—C4124.6 (3)C20—C19—C18105.3 (3)
O3—C3—C2115.6 (3)C14—C19—H19109.0
C4—C3—C2119.7 (3)C20—C19—H19109.0
C3—C4—C5118.8 (3)C18—C19—H19109.0
C3—C4—H4120.6C21—C20—C19109.2 (3)
C5—C4—H4120.6C21—C20—H20A109.8
C6—C5—C4120.9 (4)C19—C20—H20A109.8
C6—C5—C7110.5 (3)C21—C20—H20B109.8
C4—C5—C7128.4 (3)C19—C20—H20B109.8
C5—C6—C1121.1 (3)H20A—C20—H20B108.3
C5—C6—N1110.8 (3)C20—C21—N2110.3 (3)
C1—C6—N1128.1 (3)C20—C21—C7115.1 (3)
C5—C7—C17112.7 (3)N2—C21—C7104.5 (3)
C5—C7—C21115.3 (3)C20—C21—H21108.9
C17—C7—C21102.1 (3)N2—C21—H21108.9
C5—C7—C8102.4 (3)C7—C21—H21108.9
C17—C7—C8110.5 (3)O2—C22—H22A109.5
C21—C7—C8114.2 (3)O2—C22—H22B109.5
N1—C8—C18106.4 (3)H22A—C22—H22B109.5
N1—C8—C7104.5 (3)O2—C22—H22C109.5
C18—C8—C7117.1 (3)H22A—C22—H22C109.5
N1—C8—H8109.5H22B—C22—H22C109.5
C18—C8—H8109.5O3—C23—H23A109.5
C7—C8—H8109.5O3—C23—H23B109.5
O4—C9—N1123.1 (4)H23A—C23—H23B109.5
O4—C9—C10121.4 (3)O3—C23—H23C109.5
N1—C9—C10115.5 (3)H23A—C23—H23C109.5
C9—C10—C11118.4 (3)H23B—C23—H23C109.5
C9—C10—H10A107.7O7—N3—O8124.4 (3)
C11—C10—H10A107.7O7—N3—C27117.8 (3)
C9—C10—H10B107.7O8—N3—C27117.9 (3)
C11—C10—H10B107.7O9—N4—O10123.9 (3)
H10A—C10—H10B107.1O9—N4—C29118.2 (3)
O1—C11—C18113.4 (3)O10—N4—C29117.9 (3)
O1—C11—C10104.5 (3)O6—C24—O5125.7 (3)
C18—C11—C10110.0 (3)O6—C24—C25118.6 (3)
O1—C11—H11109.6O5—C24—C25115.7 (3)
C18—C11—H11109.6C30—C25—C26120.3 (3)
C10—C11—H11109.6C30—C25—C24119.6 (3)
O1—C12—C13111.3 (3)C26—C25—C24120.1 (3)
O1—C12—H12A109.4C27—C26—C25118.7 (3)
C13—C12—H12A109.4C27—C26—H26120.7
O1—C12—H12B109.4C25—C26—H26120.7
C13—C12—H12B109.4C28—C27—C26122.7 (4)
H12A—C12—H12B108.0C28—C27—N3118.4 (3)
C14—C13—C12122.3 (4)C26—C27—N3118.9 (3)
C14—C13—H13118.9C29—C28—C27116.8 (4)
C12—C13—H13118.9C29—C28—H28121.6
C13—C14—C15121.3 (4)C27—C28—H28121.6
C13—C14—C19123.3 (4)C28—C29—C30123.1 (4)
C15—C14—C19115.4 (3)C28—C29—N4118.3 (3)
C14—C15—N2108.5 (3)C30—C29—N4118.5 (3)
C14—C15—H15A110.0C29—C30—C25118.4 (4)
N2—C15—H15A110.0C29—C30—H30120.8
C14—C15—H15B110.0C25—C30—H30120.8
N2—C15—H15B110.0H11W—O1W—H12W105.3
H15A—C15—H15B108.4H21W—O2W—H22W108.8
N2—C16—C17104.5 (3)H31W—O3W—H32W105.5
N2—C16—H16A110.8
C22—O2—C2—C19.0 (6)C21—N2—C16—C1718.7 (4)
C22—O2—C2—C3170.0 (4)N2—C16—C17—C738.4 (4)
C6—C1—C2—O2179.3 (4)C5—C7—C17—C16167.4 (3)
C6—C1—C2—C31.7 (6)C21—C7—C17—C1643.1 (4)
C23—O3—C3—C41.3 (6)C8—C7—C17—C1678.8 (4)
C23—O3—C3—C2177.0 (3)N1—C8—C18—C1172.5 (4)
O2—C2—C3—O30.8 (5)C7—C8—C18—C11171.1 (3)
C1—C2—C3—O3179.9 (4)N1—C8—C18—C19155.9 (3)
O2—C2—C3—C4179.2 (3)C7—C8—C18—C1939.6 (5)
C1—C2—C3—C41.7 (6)O1—C11—C18—C871.0 (4)
O3—C3—C4—C5179.8 (3)C10—C11—C18—C845.5 (4)
C2—C3—C4—C51.5 (6)O1—C11—C18—C1957.9 (5)
C3—C4—C5—C61.5 (6)C10—C11—C18—C19174.5 (3)
C3—C4—C5—C7175.2 (4)C13—C14—C19—C20176.5 (4)
C4—C5—C6—C11.6 (6)C15—C14—C19—C203.8 (5)
C7—C5—C6—C1176.4 (4)C13—C14—C19—C1858.4 (5)
C4—C5—C6—N1179.2 (4)C15—C14—C19—C18121.9 (4)
C7—C5—C6—N16.1 (4)C8—C18—C19—C1459.7 (4)
C2—C1—C6—C51.7 (6)C11—C18—C19—C1466.2 (5)
C2—C1—C6—N1178.8 (4)C8—C18—C19—C2060.7 (4)
C9—N1—C6—C5160.6 (4)C11—C18—C19—C20173.3 (3)
C8—N1—C6—C55.3 (4)C14—C19—C20—C2154.6 (4)
C9—N1—C6—C116.8 (7)C18—C19—C20—C2169.3 (4)
C8—N1—C6—C1172.1 (4)C19—C20—C21—N260.6 (4)
C6—C5—C7—C17104.7 (4)C19—C20—C21—C757.3 (4)
C4—C5—C7—C1769.6 (5)C16—N2—C21—C20132.4 (3)
C6—C5—C7—C21138.6 (3)C15—N2—C21—C207.4 (4)
C4—C5—C7—C2147.1 (6)C16—N2—C21—C78.2 (4)
C6—C5—C7—C814.0 (4)C15—N2—C21—C7116.9 (3)
C4—C5—C7—C8171.8 (4)C5—C7—C21—C2085.1 (4)
C9—N1—C8—C1846.7 (4)C17—C7—C21—C20152.4 (3)
C6—N1—C8—C18110.8 (3)C8—C7—C21—C2033.1 (5)
C9—N1—C8—C7171.2 (3)C5—C7—C21—N2153.8 (3)
C6—N1—C8—C713.7 (4)C17—C7—C21—N231.3 (3)
C5—C7—C8—N116.2 (4)C8—C7—C21—N288.0 (4)
C17—C7—C8—N1104.1 (3)O6—C24—C25—C3022.0 (6)
C21—C7—C8—N1141.5 (3)O5—C24—C25—C30158.4 (4)
C5—C7—C8—C18101.2 (4)O6—C24—C25—C26155.9 (4)
C17—C7—C8—C18138.5 (3)O5—C24—C25—C2623.8 (6)
C21—C7—C8—C1824.1 (5)C30—C25—C26—C271.0 (6)
C6—N1—C9—O423.4 (6)C24—C25—C26—C27176.8 (4)
C8—N1—C9—O4176.4 (4)C25—C26—C27—C281.9 (6)
C6—N1—C9—C10158.1 (4)C25—C26—C27—N3176.3 (4)
C8—N1—C9—C105.1 (5)O7—N3—C27—C28178.0 (4)
O4—C9—C10—C11148.7 (4)O8—N3—C27—C281.6 (5)
N1—C9—C10—C1132.7 (5)O7—N3—C27—C263.7 (6)
C12—O1—C11—C1871.1 (4)O8—N3—C27—C26176.7 (4)
C12—O1—C11—C10169.1 (3)C26—C27—C28—C290.3 (6)
C9—C10—C11—O1126.8 (3)N3—C27—C28—C29177.9 (4)
C9—C10—C11—C184.8 (5)C27—C28—C29—C302.3 (6)
C11—O1—C12—C1389.4 (4)C27—C28—C29—N4179.3 (3)
O1—C12—C13—C1461.9 (5)O9—N4—C29—C28168.0 (4)
C12—C13—C14—C15175.9 (4)O10—N4—C29—C2810.0 (5)
C12—C13—C14—C194.4 (6)O9—N4—C29—C3013.5 (5)
C13—C14—C15—N2124.9 (4)O10—N4—C29—C30168.5 (3)
C19—C14—C15—N255.3 (4)C28—C29—C30—C253.2 (6)
C16—N2—C15—C1473.7 (4)N4—C29—C30—C25178.4 (4)
C21—N2—C15—C1448.8 (4)C26—C25—C30—C291.4 (6)
C15—N2—C16—C17144.8 (3)C24—C25—C30—C29179.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.931.722.632 (4)168
O1W—H11W···O4i0.881.942.817 (4)175.4
O1W—H12W···O60.881.932.805 (4)174.4
O2W—H21W···O9ii0.882.353.163 (4)153.5
O2W—H22W···O3W0.881.992.850 (4)166.2
O3W—H31W···O5iii0.881.932.801 (4)167.4
O3W—H32W···O1W0.871.962.826 (4)170.1
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1/2, y+5/2, z+1; (iii) x1/2, y+3/2, z+1.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC23H27N2O4+·C7H3N2O6·CH4OC23H27N2O4+·C7H3N2O6·2CH4OC23H27N2O4+·C7H3N2O6·3H2O
Mr638.62670.66660.63
Crystal system, space groupOrthorhombic, P212121Orthorhombic, P212121Orthorhombic, P212121
Temperature (K)100100100
a, b, c (Å)11.8539 (18), 12.2726 (18), 19.498 (3)7.1733 (18), 19.100 (2), 21.955 (2)8.2499 (8), 12.5379 (12), 29.109 (3)
V3)2836.5 (7)3008.0 (9)3010.9 (5)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.120.110.12
Crystal size (mm)0.30 × 0.30 × 0.250.30 × 0.30 × 0.300.30 × 0.25 × 0.25
Data collection
DiffractometerKuma KM-4 CCD
diffractometer
Kuma KM-4 CCD
diffractometer
Kuma KM-4 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
18431, 3470, 2929 20084, 3707, 3407 20148, 3700, 3036
Rint0.0770.0850.070
(sin θ/λ)max1)0.6390.6390.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.094, 1.08 0.047, 0.124, 1.10 0.057, 0.127, 1.12
No. of reflections347037073700
No. of parameters415433424
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.260.31, 0.440.26, 0.25
Absolute structureFrom known structure (Toda et al., 1985)From known structure (Toda et al., 1985)From known structure (Toda et al., 1985)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2001), CrysAlis RED (Oxford Diffraction, 2001), CrysAlis RED, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Bruker, 1999), SHELXL97.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.931.732.643 (3)166.1
O31—H31···O50.831.972.766 (3)161.1
ππ interactions (Å,°) in (I). Cg represents the centroids of the rings, as follows: Cg1 ring C1/C2/C3/C4/C5/C6 and Cg2 ring C25/C26/C27/C28/C29/C30. top
CgICgJCg···CgInterplanar angleCgI_perp'CgJ_PerpSlippage
Cg(1)Cg(2)i3.690 (4)3.25 (4)3.3103.2711.71
Cg···Cg is the distance between ring centroids. The interplanar angle is that between the planes of the rings CgI and CgJ. CgI_perp is the perpendicular distance of CgI from ring J. CgJ_perp is the perpendicular distance of CgJ from ring I. Symmetry code: (i) −x + 1.5, −y, z + 0.5.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.931.792.708 (3)169.1
O31—H31···O50.832.032.852 (4)172.0
O32—H32···O60.821.962.778 (3)174.6
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.931.722.632 (4)168.0
O1W—H11W···O4i0.881.942.817 (4)175.4
O1W—H12W···O60.881.932.805 (4)174.4
O2W—H21W···O9ii0.882.353.163 (4)153.5
O2W—H22W···O3W0.881.992.850 (4)166.2
O3W—H31W···O5iii0.881.932.801 (4)167.4
O3W—H32W···O1W0.871.962.826 (4)170.1
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1/2, y+5/2, z+1; (iii) x1/2, y+3/2, z+1.
 

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