Supra­molecular association in proton-transfer adducts containing benz­amidinium cations. III. Three mole­cular salts of 3-meth­oxy-, 4-meth­oxy- and 3,4,5-tri­meth­oxy­benzoates with benzamidine

Three mol­ecular salts, benzamidinium 3-meth­oxy­benzoate, C₇H₉N₂⁺·C₈H₇O₃⁻, (I), benzamidinium 4-meth­oxy­benzoate, C₇H₉N₂⁺·C₈H₇O₃⁻, (II), and benzamidinium 3,4,5-tri­meth­oxy­benzoate monohydrate, C₇H₉N₂⁺·C₁₀H₁₁O₅⁻·H₂O, (III), were formed from the proton-transfer reactions of 3-meth­oxy, 4-meth­oxy- and 3,4,5-tri­meth­oxy­benzoic acids with benzami­d­ine (benzene­carboximidamide, benzam). Monoclinic salts (I) and (II) have a 1:1 ratio of cation to anion. In monoclinic salt (III), two cation–anion pairs and two water mol­ecules constitute the asymmetric unit. In all three mol­ecular salts, the amidinium fragments and the carboxyl­ate groups are completely delocalized, and the delocalization favours the aggregation of the mol­ecular components into nonplanar dimers with an R²₂(8) graph-set motif by N⁺—H...O⁻ (±) charge-assisted hydrogen bonding (CAHB). Of the three mol­ecular salts, (I) and (II) show similar conformations of the anionic components and exhibit bidimensional isostructurality, which consists of alternating R²₂(8) and R⁴₆(16) rings resulting in a corrugated sheet propagated parallel to the crystallographic ab plane. In mol­ecular salt (III), the R²₂(8) synthon is retained but the supra­molecular structure is different, due to the presence of three bulky meth­oxy substituents and a water mol­ecule. The structures reported here further demonstrate the robustness of R²₂(8) hydrogen-bonded synthons having the benzamidinium cation as a building block, whereas N⁺—H...O⁻ hydrogen bonds external to the salt bridge contribute to the overall structure organization.

S1. Introduction

The protonated analogue of benzamidine is of special inter­est in forming strong inter­molecular hydrogen bonds, as its amidinium group exhibits ideal properties for coupling with carboxyl­ate groups in a crystal structure. The ability of these organic salts to aggregate readily through dimer heterosynthons via N⁺—H···O^- (±)(CAHB) (charge-assisted hydrogen bonds with plus and minus charges on the donor and acceptor atoms, respectively; Gilli & Gilli, 2009), relies on ΔpK_a [ΔpK_a = pK_a (conjugate acid of the base) - pK_a (acid), where the pK_a values are for aqueous solutions at 298 K]. Generally, a sufficiently large ΔpK_a value (i.e. greater than 3) should result in a salt (Bhogala et al., 2005). With smaller ΔpK_a values, a cocrystal can be expected, but that parameter seems inappropriate for accurately predicting salt or cocrystal formation in the solid state when 0 < ΔpK_a < 3 (Portalone & Colapietro, 2009; Portalone, 2011a). This dimeric motif is commonly observed in biological systems between arginine and aspartic and glutamic acids (Saenger, 1984). To date, the only exception to the complementarity of the amidinium and carboxyl­ate groups has been reported for benzamidinium isoorotate (2,4-dioxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate) (Portalone, 2010).

As a continuation of the systematic study carried out in this laboratory to test the robustness of the R₂²(8) hydrogen-bond synthon (Bernstein et al., 1995; Motherwell et al., 1999) formed by benzamidine with benzoic acid derivatives in a 1:1 ratio (Irrera et al., 2012), the molecular and supra­molecular structures of three acid–base complexes formed by benzamidine with benzoic acids, namely benzamidinium 3-meth­oxy­benzoate, (I), benzamidinium 4-meth­oxy­benzoate, (II), and benzamidinium 3,4,5-tri­meth­oxy­benzoate monohydrate, (III), are reported. With pK_a values of 11.6 for benzamidine (Hafelinger, 1975), 4.1 and 4.5 for 3- and 4-meth­oxy­benzoic acids, respectively (https://research.chem.psu.edu/brpgroup/pKa_compilation.pdf [Is this available in a peer-reviewed form anywhere?]), and 4.2 for 3,4,5-tri­meth­oxy­benzoic acid (expected value based on two similar acids, namely 2,3,4- and 2,4,5-tri­meth­oxy­benzoic acid, both showing pK_a = 4.24; Kaza­kevich & Lobrutto, 2007), for these acid–base complexes the ΔpK_a falls in the range 7.1–7.5 and leads to the formation of molecular salts.

S2. Experimental

S2.1. Synthesis and crystallization

Salts (I)–(III) were obtained by the reaction of equimolar qu­anti­ties (1 mmol) of benzamidine (Fluka, 95%) and 3-meth­oxy­benzoic acid (Sigma–Aldrich, 99%), 4-meth­oxy­benzoic acid (Sigma–Aldrich, 99%) and 3,4,5-tri­meth­oxy­benzoic acid (Sigma–Aldrich, 99%) dissolved in ethanol (20 ml). The reaction mixtures were heated under reflux at 323 K for 8 h and then, after cooling to ambient temperature, the solvent was removed under vacuum. The solid residues were recrystallized by room-temperature evaporation of hot-filtered water solutions to give, after 10 d, good X-ray diffraction quality colourless crystals.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were originally found in a difference Fourier map but subsequently treated differently. All C-bound H atoms were placed in calculated positions, with C—H = 0.97 (phenyl) or 0.95–1.00 Å (methyl), and refined as riding on their carrier atoms, with U_iso(H) = 1.2U_eq(C) for aromatic H atoms or 1.5U_eq(C) for methyl H atoms. The H atoms of the methyl groups were allowed to rotate with a fixed angle around the C—C bond to best fit the experimental electron density [HFIX 138 in the SHELXL program suite (Sheldrick, 2008)]. The positional and displacement parameters of the H atoms of the amidinium groups and of one of the two water molecules of (III) were freely refined, giving N—H distances in the range 0.85 (2)–1.00 (2) Å and O—H distances in the range 0.84 (3)–0.89 (3) Å. The O—H distances for the H atoms attached to atom O7 of the second water molecule of (III) were restrained to 0.90 (2)–0.99 (2) Å, and the H atoms were refined with U_iso(H) = 1.2U_eq(O7). It is worthy of note that, of the two H atoms attached to atom O7 (H71 and H72), only H72 participates in the formation of O—H···O hydrogen bonds.

S3. Results and discussion

Benzamidinium 3-meth­oxy­benzoate (benzamH⁺.3mb^-), (I) (Fig. 1), and benzamidinium 4-meth­oxy­benzoate (benzamH⁺.4mb^-), (II) (Fig. 2), both crystallize in the monoclinic space group P2₁/n, with one crystallographically independent dimer of monoprotonated benzamidinium cations (benzamH⁺) and benzoate anions (3mb^- and 4mb^-, respectively) in the asymmetric unit. The asymmetric unit of benzamidinium 3,4,5-tri­meth­oxy­benzoate monohydrate (benzamH⁺.345mb^-.H₂O), (III) (Fig. 3), which crystallizes in the monoclinic space group P2₁/c, is noticeably more complex than those of (I) and (II), and consists of two benzamH⁺ cations counterbalanced by two 345mb^- anions, completed by two water molecules of crystallization (Fig. 3). The molecular structures of salts (I)–(III) are very similar with regard to inter­atomic distances and angles.

In the cationic substructures, where protonation takes place at the same site of the amidine group, the benzamH⁺ cations are not planar. The dihedral angles between the mean plane of the benzene ring and the amidinium group are in the range 30.7 (1)–42.3 (1)°, larger than the values observed in benzamidinium (2-acetamido­benzoyl)­formate [16 (3)°; Joshi et al., 1994], benzamidinium acetyl­salicylate [15.2 (2)°; Kolev et al., 2009] or the two polymorphic forms of benzamidinium 2,6-di­meth­oxy­benzoate [20.2 (1), 14.4 (1) and 23.6 (1)°; Irrera et al., 2012]. For all compounds, this disposition is a consequence of the steric hindrance between the NH₂ group and the benzene ring, as indicated by the N—C(ortho) contacts which are in the range 2.888 (2)–2.969 (2) Å, and it prevents conjugation between the amidinium group and the benzene ring. Indeed, the C—C(amidine) distances are in the range 1.472 (3)–1.484 (3) Å and compare well with the expected Csp²—Csp² single-bond length of 1.482 (1) Å (Allen et al., 1987). This nonplanar conformation is commonly observed in small-molecule crystal structures, whereas in benzamidinium-containing structures in the Protein Data Bank (PDB; Berman et al., 2000) the most frequently encountered conformation is the planar one (Li et al., 2009). The C—N bond lengths are in the range 1.307 (2)–1.315 (2) Å, evidencing the delocalization of the π-electrons and double-bond character when compared with the corresponding bond lengths found in benzamidine [1.294 (3) and 1.344 (3) Å; Barker et al., 1996] and benzdi­amidine [1.283 (2) and 1.349 (2) Å; Jokić et al., 2001].

In the anionic substructures, the benzene rings of salts (I)–(III) show small deviations from planarity, with a maximum deviation from the least-squares plane of the benzene ring in (I) of 0.019 (2) Å for atom C10, and the carboxyl­ate groups are twisted with respect to the plane of the aromatic fragment by 22.3 (1)–31.3 (1)°. In these anions, the bond lengths and angles of the benzene ring are in accord with corresponding values obtained for both the orthorhombic and tetra­gonal forms of 2,6-di­meth­oxy­benzoic acid (Portalone, 2009, 2011b), for 4-meth­oxy­benzamidinium 2,6-di­meth­oxy­benzoate (Portalone, 2012) and for benzamidinium 2-meth­oxy­benzoate (Portalone, 2013). The C—O distances range from 1.252 (2) to 1.262 (2) Å, indicating that the carboxyl­ate groups are deprotonated in the crystal structure. The meth­oxy groups attached at atom C13 in the 3mb^- anion and at atom C14 in the 4mb^- anion are nearly coplanar with the benzene ring, with C15—O3—C10—C9 and C15—O3—C11—C10 torsion angles of -7.7 (4) and -3.8 (2)°, respectively. In the 345mb^- anion, the two meth­oxy substituents in meta positions with respect to the carboxyl­ate group are coplanar with the benzene ring and force the remaining meth­oxy group to be almost orthogonal to the plane of the aromatic fragment [the twist angles between the benzene ring and the meth­oxy group in the para position are 74.1 (2) and 107.4 (2)°].

The most attractive aspect of the three structures resides in their hydrogen-bonding scheme, which is dominated by N⁺—H···O^- (±)CAHB (Tables 2–4).

The ionic components of the three title molecular salts are strongly inter­linked into a dimeric hydrogen-bonded structure with graph-set motif R₂²₂(8) by N⁺—H···O^- (±)CAHB. Remarkably, at variance with the well known carb­oxy­lic dimer R₂²(8) motif, in these compounds the carboxyl­ate–amidinium pairs are not planar. A difference in the rotation from the plane of the benzene rings of the amidinium and carboxyl­ate groups results in a slight twist of the amidinium–carboxyl­ate dimer [the dihedral angles for the planes defined by the CN₂⁺ and CO₂^- atoms are in the range 8.8 (1)–14.2 (1)°]. Nonetheless, the inter­face is very stable, as indicated by the N⁺—H···O^- parameters: N⁺···O^- distances are in the range 2.751 (3)–2.892 (2) Å and N⁺—H···O^- angles are in the range 161 (2)–180 (2)°. Larger deviations from planarity of the carboxyl­ate–amidinium pairs have been reported previously for two concomitant polymorphs of the molecular salt of benzamidinium 2,6-di­meth­oxy­benzoate (Irrera et al., 2012) and for benzamidinium 2-meth­oxy­benzoate (Portalone, 2013), in which the CN₂⁺/CO₂^- dihedral angles are in the range 18.6 (1)–29.5 (1)°.

The supra­molecular structures of salts (I) and (II) are very similar and only the molecular arrangement of (I) is shown (Fig. 4). As mentioned previously, each subunit, built from the ion pairs of the asymmetric unit, forms a ring motif of the type R₂²(8) via the bidentate inter­action of the N—H and C═O groups. These subunits then inter­act with adjacent ion pairs to form R₆⁴(16) rings through the remaining N⁺—H···O^- hydrogen bonds, resulting in a corrugated-like plane approximately parallel to the ab plane.

The supra­molecular structure of (III), in which the water molecules play a key role, shows a completely different arrangement of molecules through a diversity of noncovalent inter­actions. Eleven hydrogen bonds, namely four N⁺—H···O^-, four N⁺—H···O and three O_water—H···O, involve all donor sites apart from atom O7, which remains partially unsaturated (Fig. 5). For descriptive purposes, it is convenient to select the asymmetric unit as the elemental building block of the crystal structure. In the asymmetric unit, the two R₂²(8) dimers, two water molecules and one para-meth­oxy group offer favourable dispositions to form hydrogen-bonded rings with a graph-set motif of R₅⁴(16). These hydrogen-bonded rings are further inter­connected with symmetry-related rings by N⁺—H···O^- hydrogen bonds, leading to the formation of tapes along the a axis. These tapes are then crosslinked by N⁺—H···O^-, N⁺—H···O_water and O_water—H···O^- hydrogen bonds into a two-dimensional network approximately parallel to the ac plane.

In conclusion, as only those synthons that occurr repeatedly in crystal structures are useful in crystal design (Nangia & Desiraju, 1998), the structures reported here further demonstrate the robustness of the benzamidinium cation as a (±)CAHB synthon with benzoic acids in two-component 1:1 salts. The strong primary electrostatic inter­action between the two inter­facial H atoms anti to the benzene ring, which mediate the two-point inter­action between the benzamidinium cation and the carboxyl­ate group, provides sufficient driving force for the directed assembly of binary molecular complexes, but inter­estingly leaves the remaining N⁺—H available for a variety of additional catenation of structural subunits. Indeed, due to the canting of the R₂²(8) heterosynthon, secondary N⁺—H···O^- hydrogen bonds, external to the amidinium–carboxyl­ate salt bridges, produce a different overall molecular disposition in the organic salts reported here and in benzamidinium 2-meth­oxy­benzoate (1/1) (tape structure; Portalone, 2013), in both the 2/2 monoclinic and 1/1 orthorhombic forms of benzamidinium 2,6-di­meth­oxy­benzoate (tape structures; Irrera et al., 2012), and in p-methyl­benzamidinium benzoate (1/1) (channel-like structure; Kuzmenko et al., 2001). The complementary inter­actions in the R₂²(8) amidinium/carboxyl­ate heterosynthon have been used to design layered magnetic materials, as in the case of the molecular salt 3-cyano­bemzamidinium 2,2,4,4-tetra­methyl­pyrroline-N-oxyl-3-carboxyl­ate (Papoutsakis et al., 1999).

An extension of this study, aimed at creating three-component salts by reducing the ratio of benzamidine to acid so as to deprotonate only half of the acid molecules, and then observing how the un-ionized acid molecules can be incorporated into the supra­molecular assembly, is currently under way in this laboratory.

Related literature

For related literature, see: Allen et al. (1987); Barker et al. (1996); Berman et al. (2000); Bernstein et al. (1995); Bhogala et al. (2005); Gilli & Gilli (2009); Hafelinger (1975); Irrera et al. (2012); Jokić et al. (2001); Joshi et al. (1994); Kazakevich & Lobrutto (2007); Kolev et al. (2009); Kuzmenko et al. (2001); Li et al. (2009); Motherwell et al. (1999); Nangia & Desiraju (1998); Papoutsakis et al. (1999); Portalone (2009, 2010, 2011a, 2011b, 2012, 2013); Portalone & Colapietro (2009); Saenger (1984); Sheldrick (2008).

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme and hydrogen bonding (dashed lines). The asymmetric unit was selected so that the two ions are linked by N⁺—H···O^- (±)CAHB. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. The asymmetric unit of (II), showing the atom-labelling scheme and hydrogen bonding (dashed lines). The asymmetric unit was selected so that the two ions are linked by N⁺—H···O^- (±)CAHB. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 3. The asymmetric unit of (III), showing the atom-labelling scheme and hydrogen bonding (dashed lines). The asymmetric unit was selected so that three of the four ions, linked into dimers by N⁺—H···O^- (±)CAHB, are joined by N⁺—H···O and O—H···O hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 4. The supramolecular structure of (I), viewed approximately down c. All atoms are shown as small spheres of arbitrary radii. For the sake of clarity, H atoms not involved in hydrogen bonding and benzene rings have been omitted. Hydrogen bonding is indicated by dashed lines.

Fig. 5. The supramolecular structure of (III), viewed approximately down b. All atoms are shown as small spheres of arbitrary radii. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted. Hydrogen bonding is indicated by dashed lines.

(I) [Amino(phenyl)methylidene]azanium 3-methoxybenzoate

Crystal data

C7H9N2^+·C8H7O3^−	F(000) = 576
Mr = 272.30	Dx = 1.251 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3122 reflections
a = 9.4532 (9) Å	θ = 2.9–29.0°
b = 6.1789 (8) Å	µ = 0.09 mm^−1
c = 24.906 (3) Å	T = 298 K
β = 96.513 (11)°	Tablet, colourless
V = 1445.4 (3) Å^3	0.40 × 0.35 × 0.18 mm
Z = 4

Data collection

Agilent Xcalibur Sapphire3 diffractometer	2598 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1762 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.0696 pixels mm^-1	θmax = 25.3°, θmin = 3.1°
ω and φ scans	h = −11→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→7
Tmin = 0.788, Tmax = 0.984	l = −29→29
8118 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.348P] where P = (Fo^2 + 2Fc^2)/3
2598 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.60558 (19)	0.0342 (4)	0.77780 (8)	0.0562 (6)
H1A	0.611 (2)	−0.079 (4)	0.7497 (10)	0.071 (7)*
H1B	0.680 (2)	0.101 (3)	0.7911 (9)	0.052 (7)*
N2	0.37107 (19)	−0.0366 (4)	0.77946 (8)	0.0577 (6)
H2A	0.378 (2)	−0.154 (4)	0.7556 (9)	0.059 (7)*
H2B	0.287 (3)	0.003 (4)	0.7886 (9)	0.066 (7)*
C1	0.47839 (19)	0.2439 (4)	0.83797 (8)	0.0451 (5)
C2	0.5632 (2)	0.4271 (4)	0.83802 (10)	0.0584 (6)
H2	0.6246	0.4467	0.8097	0.070*
C3	0.5610 (3)	0.5811 (4)	0.87769 (11)	0.0733 (8)
H3	0.6202	0.7092	0.8772	0.088*
C4	0.4744 (3)	0.5531 (5)	0.91816 (11)	0.0811 (9)
H4	0.4741	0.6603	0.9466	0.097*
C5	0.3888 (3)	0.3740 (5)	0.91826 (11)	0.0769 (8)
H5	0.3271	0.3562	0.9465	0.092*
C6	0.3900 (2)	0.2194 (4)	0.87857 (9)	0.0585 (6)
H6	0.3291	0.0932	0.8789	0.070*
C7	0.48488 (19)	0.0746 (4)	0.79675 (8)	0.0449 (5)
O1	0.62105 (14)	−0.2793 (2)	0.69993 (6)	0.0545 (4)
O2	0.40257 (14)	−0.3899 (3)	0.70883 (7)	0.0679 (5)
O3	0.7093 (2)	−0.6323 (4)	0.52109 (8)	0.0939 (7)
C8	0.5262 (2)	−0.5595 (4)	0.64282 (8)	0.0457 (5)
C9	0.6124 (2)	−0.5115 (4)	0.60249 (9)	0.0515 (6)
H9	0.6613	−0.3735	0.6025	0.062*
C10	0.6277 (3)	−0.6620 (4)	0.56249 (10)	0.0634 (7)
C11	0.5623 (3)	−0.8616 (5)	0.56397 (12)	0.0784 (8)
H11	0.5769	−0.9699	0.5369	0.094*
C12	0.4773 (3)	−0.9072 (4)	0.60330 (13)	0.0783 (8)
H12	0.4313	−1.0474	0.6038	0.094*
C13	0.4559 (2)	−0.7553 (4)	0.64254 (11)	0.0631 (7)
H13	0.3923	−0.7863	0.6695	0.076*
C14	0.5154 (2)	−0.3981 (4)	0.68703 (9)	0.0460 (5)
C15	0.7681 (4)	−0.4274 (6)	0.51504 (13)	0.1082 (13)
H15A	0.819 (3)	−0.4261 (14)	0.4827 (9)	0.162*
H15B	0.835 (2)	−0.393 (2)	0.5472 (8)	0.162*
H15C	0.6916 (15)	−0.318 (2)	0.5110 (10)	0.162*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0291 (9)	0.0776 (15)	0.0634 (13)	−0.0030 (10)	0.0113 (9)	−0.0223 (12)
N2	0.0313 (10)	0.0728 (15)	0.0706 (14)	−0.0019 (10)	0.0133 (9)	−0.0190 (12)
C1	0.0308 (10)	0.0580 (14)	0.0469 (12)	0.0064 (10)	0.0058 (9)	0.0001 (11)
C2	0.0498 (13)	0.0651 (16)	0.0620 (16)	0.0022 (13)	0.0135 (11)	−0.0010 (13)
C3	0.0683 (17)	0.0638 (17)	0.086 (2)	−0.0001 (14)	0.0022 (15)	−0.0143 (16)
C4	0.0809 (19)	0.087 (2)	0.076 (2)	0.0194 (18)	0.0107 (16)	−0.0275 (17)
C5	0.0679 (16)	0.107 (2)	0.0601 (17)	0.0165 (18)	0.0244 (13)	−0.0112 (17)
C6	0.0477 (12)	0.0736 (17)	0.0568 (15)	0.0057 (12)	0.0168 (11)	−0.0027 (13)
C7	0.0298 (10)	0.0584 (14)	0.0472 (12)	0.0017 (10)	0.0068 (9)	0.0000 (11)
O1	0.0318 (7)	0.0664 (10)	0.0671 (10)	−0.0046 (7)	0.0135 (7)	−0.0193 (8)
O2	0.0329 (8)	0.0944 (13)	0.0799 (12)	−0.0113 (8)	0.0208 (8)	−0.0218 (10)
O3	0.1144 (16)	0.1075 (17)	0.0653 (12)	0.0149 (14)	0.0343 (12)	−0.0192 (12)
C8	0.0320 (10)	0.0515 (14)	0.0520 (13)	0.0037 (10)	−0.0029 (9)	−0.0025 (11)
C9	0.0456 (12)	0.0562 (14)	0.0527 (14)	0.0049 (11)	0.0050 (10)	−0.0056 (12)
C10	0.0615 (15)	0.0710 (17)	0.0573 (16)	0.0160 (14)	0.0054 (12)	−0.0112 (14)
C11	0.0807 (19)	0.073 (2)	0.078 (2)	0.0110 (17)	−0.0091 (16)	−0.0292 (17)
C12	0.0686 (17)	0.0534 (16)	0.108 (2)	−0.0048 (14)	−0.0114 (16)	−0.0135 (17)
C13	0.0502 (13)	0.0603 (16)	0.0775 (18)	−0.0041 (13)	0.0011 (12)	0.0006 (15)
C14	0.0293 (10)	0.0575 (14)	0.0510 (13)	0.0021 (10)	0.0040 (9)	0.0009 (11)
C15	0.137 (3)	0.108 (3)	0.091 (2)	0.015 (2)	0.063 (2)	0.008 (2)

Geometric parameters (Å, º)

N1—C7	1.307 (2)	O1—C14	1.252 (2)
N1—H1A	0.99 (3)	O2—C14	1.252 (2)
N1—H1B	0.85 (2)	O3—C10	1.368 (3)
N2—C7	1.308 (3)	O3—C15	1.398 (4)
N2—H2A	0.94 (2)	C8—C13	1.379 (3)
N2—H2B	0.89 (2)	C8—C9	1.395 (3)
C1—C2	1.387 (3)	C8—C14	1.498 (3)
C1—C6	1.392 (3)	C9—C10	1.382 (3)
C1—C7	1.472 (3)	C9—H9	0.9700
C2—C3	1.374 (3)	C10—C11	1.382 (4)
C2—H2	0.9700	C11—C12	1.365 (4)
C3—C4	1.379 (4)	C11—H11	0.9700
C3—H3	0.9700	C12—C13	1.386 (4)
C4—C5	1.371 (4)	C12—H12	0.9700
C4—H4	0.9700	C13—H13	0.9700
C5—C6	1.375 (4)	C15—H15A	0.9855
C5—H5	0.9700	C15—H15B	0.9855
C6—H6	0.9700	C15—H15C	0.9855
C7—N1—H1A	120.2 (14)	C13—C8—C9	120.2 (2)
C7—N1—H1B	118.9 (15)	C13—C8—C14	121.0 (2)
H1A—N1—H1B	121 (2)	C9—C8—C14	118.8 (2)
C7—N2—H2A	119.9 (13)	C10—C9—C8	119.6 (2)
C7—N2—H2B	120.0 (15)	C10—C9—H9	120.2
H2A—N2—H2B	120 (2)	C8—C9—H9	120.2
C2—C1—C6	118.9 (2)	O3—C10—C11	115.6 (3)
C2—C1—C7	120.73 (18)	O3—C10—C9	124.5 (3)
C6—C1—C7	120.4 (2)	C11—C10—C9	119.8 (3)
C3—C2—C1	120.7 (2)	C12—C11—C10	120.3 (3)
C3—C2—H2	119.7	C12—C11—H11	119.8
C1—C2—H2	119.7	C10—C11—H11	119.8
C2—C3—C4	119.8 (3)	C11—C12—C13	120.7 (3)
C2—C3—H3	120.1	C11—C12—H12	119.6
C4—C3—H3	120.1	C13—C12—H12	119.6
C5—C4—C3	120.1 (3)	C8—C13—C12	119.3 (2)
C5—C4—H4	119.9	C8—C13—H13	120.4
C3—C4—H4	119.9	C12—C13—H13	120.4
C4—C5—C6	120.4 (2)	O2—C14—O1	124.0 (2)
C4—C5—H5	119.8	O2—C14—C8	118.57 (19)
C6—C5—H5	119.8	O1—C14—C8	117.42 (17)
C5—C6—C1	120.1 (2)	O3—C15—H15A	109.5
C5—C6—H6	120.0	O3—C15—H15B	109.5
C1—C6—H6	120.0	H15A—C15—H15B	109.5
N1—C7—N2	120.0 (2)	O3—C15—H15C	109.5
N1—C7—C1	119.67 (19)	H15A—C15—H15C	109.5
N2—C7—C1	120.36 (18)	H15B—C15—H15C	109.5
C10—O3—C15	117.9 (2)
C6—C1—C2—C3	0.5 (3)	C15—O3—C10—C11	174.8 (3)
C7—C1—C2—C3	−177.5 (2)	C15—O3—C10—C9	−7.7 (4)
C1—C2—C3—C4	0.4 (4)	C8—C9—C10—O3	180.0 (2)
C2—C3—C4—C5	−1.2 (4)	C8—C9—C10—C11	−2.6 (3)
C3—C4—C5—C6	0.9 (4)	O3—C10—C11—C12	−179.3 (3)
C4—C5—C6—C1	0.0 (4)	C9—C10—C11—C12	3.1 (4)
C2—C1—C6—C5	−0.8 (3)	C10—C11—C12—C13	−0.5 (4)
C7—C1—C6—C5	177.3 (2)	C9—C8—C13—C12	3.0 (3)
C2—C1—C7—N1	33.3 (3)	C14—C8—C13—C12	−175.0 (2)
C6—C1—C7—N1	−144.7 (2)	C11—C12—C13—C8	−2.6 (4)
C2—C1—C7—N2	−147.4 (2)	C13—C8—C14—O2	−31.5 (3)
C6—C1—C7—N2	34.6 (3)	C9—C8—C14—O2	150.4 (2)
C13—C8—C9—C10	−0.4 (3)	C13—C8—C14—O1	148.4 (2)
C14—C8—C9—C10	177.62 (19)	C9—C8—C14—O1	−29.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.99 (3)	1.76 (3)	2.756 (3)	180 (2)
N1—H1B···O1^i	0.85 (2)	2.01 (2)	2.827 (2)	161 (2)
N2—H2A···O2	0.94 (2)	1.90 (3)	2.840 (3)	177 (2)
N2—H2B···O2^ii	0.89 (2)	1.91 (3)	2.787 (2)	167 (2)

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

(II) [Amino(phenyl)methylidene]azanium 4-methoxybenzoate

Crystal data

C7H9N2^+·C8H7O3^−	F(000) = 576
Mr = 272.30	Dx = 1.279 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3892 reflections
a = 9.4676 (7) Å	θ = 2.8–32.3°
b = 6.8888 (6) Å	µ = 0.09 mm^−1
c = 21.7018 (12) Å	T = 298 K
β = 92.4498 (7)°	Tablet, colourless
V = 1414.11 (18) Å^3	0.20 × 0.15 × 0.12 mm
Z = 4

Data collection

Agilent Xcalibur Sapphire3 diffractometer	4450 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2282 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 16.0696 pixels mm^-1	θmax = 31.0°, θmin = 3.1°
ω and φ scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −9→9
Tmin = 0.982, Tmax = 0.989	l = −31→30
16608 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0512P)^2] where P = (Fo^2 + 2Fc^2)/3
4450 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
N1	0.61398 (12)	0.6703 (2)	0.77793 (6)	0.0419 (3)
H1A	0.6152 (17)	0.778 (2)	0.7469 (8)	0.071 (5)*
H1B	0.6950 (17)	0.609 (2)	0.7918 (7)	0.051 (4)*
N2	0.37592 (12)	0.71579 (19)	0.78353 (6)	0.0410 (3)
H2A	0.3803 (16)	0.828 (2)	0.7544 (8)	0.066 (5)*
H2B	0.2893 (17)	0.664 (2)	0.7939 (7)	0.058 (5)*
C1	0.48329 (13)	0.4516 (2)	0.84168 (6)	0.0348 (3)
C2	0.55623 (16)	0.2820 (2)	0.83054 (7)	0.0463 (4)
H2	0.6177	0.2750	0.7960	0.056*
C3	0.54190 (18)	0.1226 (2)	0.86833 (9)	0.0605 (5)
H3	0.5916	0.0031	0.8598	0.073*
C4	0.4571 (2)	0.1338 (3)	0.91803 (9)	0.0694 (5)
H4	0.4467	0.0218	0.9446	0.083*
C5	0.3876 (2)	0.3020 (3)	0.93008 (9)	0.0751 (6)
H5	0.3302	0.3101	0.9659	0.090*
C6	0.39809 (17)	0.4602 (3)	0.89194 (7)	0.0558 (5)
H6	0.3458	0.5778	0.9002	0.067*
C7	0.49184 (13)	0.6192 (2)	0.79915 (6)	0.0332 (3)
O1	0.62222 (9)	0.98657 (14)	0.69631 (5)	0.0418 (3)
O2	0.39227 (9)	1.04057 (14)	0.70488 (5)	0.0442 (3)
O3	0.55062 (12)	1.78274 (15)	0.54881 (5)	0.0575 (3)
C8	0.52366 (13)	1.26625 (19)	0.64766 (6)	0.0328 (3)
C9	0.62649 (14)	1.2858 (2)	0.60453 (6)	0.0395 (3)
H9	0.6917	1.1796	0.5984	0.047*
C10	0.63826 (15)	1.4548 (2)	0.56979 (7)	0.0427 (4)
H10	0.7092	1.4644	0.5390	0.051*
C11	0.54809 (15)	1.6085 (2)	0.57956 (6)	0.0407 (4)
C12	0.44611 (15)	1.5920 (2)	0.62300 (7)	0.0449 (4)
H12	0.3838	1.7004	0.6305	0.054*
C13	0.43284 (15)	1.4228 (2)	0.65555 (7)	0.0402 (4)
H13	0.3585	1.4118	0.6847	0.048*
C14	0.51163 (13)	1.0842 (2)	0.68516 (6)	0.0330 (3)
C15	0.65851 (18)	1.8127 (3)	0.50625 (8)	0.0629 (5)
H15A	0.7527 (9)	1.8088 (17)	0.5286 (2)	0.094*
H15B	0.6450 (8)	1.9416 (15)	0.4860 (5)	0.094*
H15C	0.6535 (8)	1.7086 (14)	0.4743 (4)	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0230 (6)	0.0480 (8)	0.0549 (8)	0.0027 (6)	0.0042 (6)	0.0093 (7)
N2	0.0229 (6)	0.0396 (8)	0.0609 (8)	0.0020 (6)	0.0059 (6)	0.0086 (7)
C1	0.0238 (6)	0.0363 (8)	0.0440 (8)	−0.0026 (6)	−0.0013 (6)	−0.0003 (7)
C2	0.0416 (9)	0.0452 (9)	0.0516 (9)	0.0075 (7)	−0.0037 (7)	−0.0043 (8)
C3	0.0610 (11)	0.0401 (10)	0.0786 (13)	0.0061 (8)	−0.0192 (10)	0.0028 (9)
C4	0.0667 (12)	0.0636 (13)	0.0767 (13)	−0.0094 (10)	−0.0100 (10)	0.0305 (11)
C5	0.0701 (13)	0.0858 (15)	0.0713 (13)	0.0083 (11)	0.0241 (10)	0.0288 (12)
C6	0.0521 (10)	0.0567 (11)	0.0600 (10)	0.0095 (8)	0.0183 (8)	0.0098 (9)
C7	0.0252 (7)	0.0344 (8)	0.0400 (7)	−0.0002 (6)	0.0027 (6)	−0.0043 (6)
O1	0.0233 (5)	0.0420 (6)	0.0599 (6)	0.0016 (4)	0.0010 (4)	0.0093 (5)
O2	0.0252 (5)	0.0427 (6)	0.0650 (7)	−0.0004 (4)	0.0062 (5)	0.0110 (5)
O3	0.0701 (8)	0.0439 (7)	0.0587 (7)	−0.0019 (6)	0.0040 (6)	0.0149 (6)
C8	0.0260 (7)	0.0360 (8)	0.0359 (7)	−0.0040 (6)	−0.0041 (6)	−0.0019 (6)
C9	0.0331 (8)	0.0410 (9)	0.0444 (8)	0.0012 (6)	0.0021 (6)	−0.0003 (7)
C10	0.0386 (8)	0.0495 (10)	0.0402 (8)	−0.0044 (7)	0.0049 (6)	0.0033 (7)
C11	0.0460 (9)	0.0351 (8)	0.0403 (8)	−0.0064 (7)	−0.0058 (7)	0.0025 (7)
C12	0.0437 (9)	0.0354 (9)	0.0556 (9)	0.0046 (7)	0.0026 (7)	−0.0010 (7)
C13	0.0358 (8)	0.0369 (8)	0.0483 (8)	−0.0008 (7)	0.0074 (6)	−0.0007 (7)
C14	0.0239 (7)	0.0348 (8)	0.0401 (7)	−0.0029 (6)	−0.0005 (6)	−0.0030 (6)
C15	0.0646 (12)	0.0617 (12)	0.0624 (11)	−0.0161 (9)	0.0003 (9)	0.0222 (9)

Geometric parameters (Å, º)

N1—C7	1.3109 (16)	O1—C14	1.2591 (15)
N1—H1A	1.001 (18)	O2—C14	1.2617 (14)
N1—H1B	0.916 (17)	O3—C11	1.3741 (17)
N2—C7	1.3153 (17)	O3—C15	1.4212 (18)
N2—H2A	0.998 (17)	C8—C9	1.3857 (17)
N2—H2B	0.932 (16)	C8—C13	1.3943 (18)
C1—C2	1.3840 (19)	C8—C14	1.5019 (19)
C1—C6	1.3853 (19)	C9—C10	1.394 (2)
C1—C7	1.4824 (19)	C9—H9	0.9700
C2—C3	1.380 (2)	C10—C11	1.382 (2)
C2—H2	0.9700	C10—H10	0.9700
C3—C4	1.374 (2)	C11—C12	1.3827 (19)
C3—H3	0.9700	C12—C13	1.371 (2)
C4—C5	1.363 (3)	C12—H12	0.9700
C4—H4	0.9700	C13—H13	0.9700
C5—C6	1.375 (2)	C15—H15A	0.9966
C5—H5	0.9700	C15—H15B	0.9966
C6—H6	0.9700	C15—H15C	0.9966
C7—N1—H1A	118.1 (9)	C9—C8—C13	117.55 (13)
C7—N1—H1B	120.0 (9)	C9—C8—C14	121.25 (12)
H1A—N1—H1B	121.9 (13)	C13—C8—C14	121.19 (12)
C7—N2—H2A	119.8 (9)	C8—C9—C10	121.42 (13)
C7—N2—H2B	118.4 (10)	C8—C9—H9	119.3
H2A—N2—H2B	120.8 (14)	C10—C9—H9	119.3
C2—C1—C6	119.02 (14)	C11—C10—C9	119.51 (13)
C2—C1—C7	120.53 (12)	C11—C10—H10	120.2
C6—C1—C7	120.41 (13)	C9—C10—H10	120.2
C3—C2—C1	120.35 (14)	O3—C11—C10	124.83 (13)
C3—C2—H2	119.8	O3—C11—C12	115.47 (13)
C1—C2—H2	119.8	C10—C11—C12	119.70 (14)
C4—C3—C2	119.85 (16)	C13—C12—C11	120.20 (14)
C4—C3—H3	120.1	C13—C12—H12	119.9
C2—C3—H3	120.1	C11—C12—H12	119.9
C5—C4—C3	120.07 (17)	C12—C13—C8	121.57 (13)
C5—C4—H4	120.0	C12—C13—H13	119.2
C3—C4—H4	120.0	C8—C13—H13	119.2
C4—C5—C6	120.69 (17)	O1—C14—O2	123.85 (13)
C4—C5—H5	119.7	O1—C14—C8	117.93 (11)
C6—C5—H5	119.7	O2—C14—C8	118.19 (12)
C5—C6—C1	119.98 (16)	O3—C15—H15A	109.5
C5—C6—H6	120.0	O3—C15—H15B	109.5
C1—C6—H6	120.0	H15A—C15—H15B	109.5
N1—C7—N2	120.83 (14)	O3—C15—H15C	109.5
N1—C7—C1	120.02 (13)	H15A—C15—H15C	109.5
N2—C7—C1	119.15 (12)	H15B—C15—H15C	109.5
C11—O3—C15	118.05 (12)
C6—C1—C2—C3	1.3 (2)	C8—C9—C10—C11	1.7 (2)
C7—C1—C2—C3	−176.44 (14)	C15—O3—C11—C10	−3.8 (2)
C1—C2—C3—C4	−1.4 (2)	C15—O3—C11—C12	176.31 (14)
C2—C3—C4—C5	−0.2 (3)	C9—C10—C11—O3	179.17 (14)
C3—C4—C5—C6	1.8 (3)	C9—C10—C11—C12	−0.9 (2)
C4—C5—C6—C1	−1.9 (3)	O3—C11—C12—C13	178.86 (13)
C2—C1—C6—C5	0.4 (2)	C10—C11—C12—C13	−1.1 (2)
C7—C1—C6—C5	178.08 (16)	C11—C12—C13—C8	2.3 (2)
C2—C1—C7—N1	−43.30 (19)	C9—C8—C13—C12	−1.4 (2)
C6—C1—C7—N1	139.04 (15)	C14—C8—C13—C12	177.77 (13)
C2—C1—C7—N2	137.18 (15)	C9—C8—C14—O1	28.51 (19)
C6—C1—C7—N2	−40.5 (2)	C13—C8—C14—O1	−150.69 (13)
C13—C8—C9—C10	−0.6 (2)	C9—C8—C14—O2	−153.20 (13)
C14—C8—C9—C10	−179.80 (13)	C13—C8—C14—O2	27.61 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	1.001 (18)	1.813 (18)	2.8110 (17)	175.0 (15)
N1—H1B···O1^i	0.916 (17)	1.932 (17)	2.8344 (16)	168.0 (13)
N2—H2A···O2	0.998 (17)	1.825 (18)	2.8224 (17)	176.7 (15)
N2—H2B···O2^ii	0.932 (16)	1.918 (17)	2.8323 (15)	166.5 (14)

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

(III) [Amino(phenyl)methylidene]azanium 3,4,5-trimethoxybenzoate monohydrate

Crystal data

C7H9N2^+·C10H11O5^−·H2O	F(000) = 1488
Mr = 350.37	Dx = 1.259 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 17484 reflections
a = 22.8771 (15) Å	θ = 2.6–28.9°
b = 7.8631 (3) Å	µ = 0.10 mm^−1
c = 23.1789 (13) Å	T = 298 K
β = 117.515 (8)°	Tablet, colourless
V = 3697.9 (3) Å^3	0.28 × 0.25 × 0.15 mm
Z = 8

Data collection

Agilent Xcalibur Sapphire3 diffractometer	7977 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 16.0696 pixels mm^-1	θmax = 27.0°, θmin = 2.7°
ω and φ scans	h = −29→28
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→9
Tmin = 0.974, Tmax = 0.986	l = −29→29
39513 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0571P)^2 + 1.3989P] where P = (Fo^2 + 2Fc^2)/3
7977 reflections	(Δ/σ)max < 0.001
509 parameters	Δρmax = 0.37 e Å^−3
2 restraints	Δρmin = −0.37 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.02943 (9)	0.1527 (3)	−0.18277 (8)	0.0426 (4)
H11	0.0067 (11)	0.056 (3)	−0.1935 (10)	0.049 (6)*
H12	0.0343 (11)	0.216 (3)	−0.2135 (11)	0.052 (6)*
N2	0.06208 (10)	0.0938 (3)	−0.07614 (8)	0.0482 (5)
H21	0.0348 (12)	−0.001 (3)	−0.0876 (10)	0.052 (6)*
H22	0.0799 (11)	0.129 (3)	−0.0341 (12)	0.055 (7)*
C1	0.10844 (10)	0.3402 (3)	−0.10177 (9)	0.0379 (5)
C2	0.09016 (12)	0.4877 (3)	−0.13879 (10)	0.0495 (5)
H2	0.0480	0.4935	−0.1776	0.059*
C3	0.13206 (15)	0.6270 (3)	−0.12041 (13)	0.0712 (8)
H3	0.1192	0.7304	−0.1461	0.085*
C4	0.19203 (17)	0.6178 (4)	−0.06548 (14)	0.0865 (10)
H4	0.2218	0.7143	−0.0529	0.104*
C5	0.20973 (15)	0.4733 (4)	−0.02855 (13)	0.0844 (10)
H5	0.2517	0.4687	0.0105	0.101*
C6	0.16860 (12)	0.3342 (3)	−0.04619 (11)	0.0606 (7)
H6	0.1817	0.2321	−0.0197	0.073*
C7	0.06455 (10)	0.1898 (2)	−0.12121 (9)	0.0356 (4)
O1	−0.03470 (7)	−0.16975 (17)	−0.21315 (6)	0.0398 (3)
O2	−0.02164 (7)	−0.18551 (18)	−0.11224 (6)	0.0460 (4)
O3	−0.22588 (7)	−0.5999 (2)	−0.32500 (7)	0.0526 (4)
O4	−0.20976 (7)	−0.81817 (17)	−0.23164 (7)	0.0460 (4)
O5	−0.11516 (8)	−0.7746 (2)	−0.10893 (7)	0.0540 (4)
C8	−0.08640 (9)	−0.3972 (2)	−0.18667 (8)	0.0307 (4)
C9	−0.13495 (9)	−0.4223 (2)	−0.25008 (8)	0.0334 (4)
H9	−0.1406	−0.3413	−0.2838	0.040*
C10	−0.17561 (9)	−0.5647 (2)	−0.26493 (9)	0.0348 (4)
C11	−0.16711 (9)	−0.6822 (2)	−0.21664 (9)	0.0345 (4)
C12	−0.11810 (9)	−0.6556 (2)	−0.15292 (9)	0.0357 (4)
C13	−0.07796 (9)	−0.5129 (2)	−0.13820 (8)	0.0337 (4)
H13	−0.0440	−0.4940	−0.0940	0.040*
C14	−0.04420 (9)	−0.2394 (2)	−0.16937 (8)	0.0315 (4)
C15	−0.23578 (14)	−0.4835 (3)	−0.37567 (11)	0.0703 (8)
H15A	−0.1955 (7)	−0.4779 (18)	−0.3812 (6)	0.105*
H15B	−0.2455 (10)	−0.369 (2)	−0.3643 (5)	0.105*
H15C	−0.2732 (9)	−0.5221 (15)	−0.4167 (7)	0.105*
C16	−0.18281 (13)	−0.9795 (3)	−0.23523 (15)	0.0700 (8)
H16A	−0.1438 (8)	−1.0010 (12)	−0.1952 (7)	0.105*
H16B	−0.1719 (9)	−0.9787 (9)	−0.2705 (8)	0.105*
H16C	−0.2147 (6)	−1.0671 (15)	−0.2424 (9)	0.105*
C17	−0.07224 (13)	−0.7409 (4)	−0.04212 (11)	0.0662 (7)
H17A	−0.0842 (6)	−0.632 (2)	−0.0299 (3)	0.099*
H17B	−0.0266 (7)	−0.736 (2)	−0.0352 (2)	0.099*
H17C	−0.0763 (7)	−0.8320 (19)	−0.0153 (5)	0.099*
N1A	−0.34065 (10)	−0.7370 (3)	−0.25036 (11)	0.0575 (6)
H11A	−0.3394 (12)	−0.648 (3)	−0.2271 (12)	0.062 (7)*
H12A	−0.3044 (14)	−0.765 (3)	−0.2542 (12)	0.068 (8)*
N2A	−0.43765 (9)	−0.8170 (3)	−0.25429 (9)	0.0451 (4)
H21A	−0.4366 (12)	−0.718 (3)	−0.2319 (12)	0.063 (7)*
H22A	−0.4722 (12)	−0.886 (3)	−0.2682 (11)	0.052 (7)*
C1A	−0.38967 (10)	−1.0001 (3)	−0.30509 (10)	0.0422 (5)
C2A	−0.36041 (12)	−0.9960 (3)	−0.34601 (11)	0.0553 (6)
H2A	−0.3390	−0.8933	−0.3499	0.066*
C3A	−0.36219 (15)	−1.1412 (4)	−0.38129 (13)	0.0744 (8)
H3A	−0.3427	−1.1390	−0.4106	0.089*
C4A	−0.39150 (17)	−1.2876 (4)	−0.37464 (15)	0.0809 (9)
H4A	−0.3921	−1.3884	−0.3990	0.097*
C5A	−0.41992 (15)	−1.2925 (3)	−0.33385 (15)	0.0738 (8)
H5A	−0.4404	−1.3963	−0.3294	0.089*
C6A	−0.41927 (12)	−1.1490 (3)	−0.29923 (12)	0.0549 (6)
H6A	−0.4396	−1.1521	−0.2706	0.066*
C7A	−0.38933 (10)	−0.8453 (3)	−0.26833 (9)	0.0399 (5)
O1A	−0.33571 (7)	−0.4675 (2)	−0.17252 (9)	0.0632 (5)
O2A	−0.44023 (7)	−0.50113 (17)	−0.19559 (7)	0.0426 (3)
O3A	−0.28328 (8)	0.1161 (2)	−0.05716 (8)	0.0628 (5)
O4A	−0.36974 (7)	0.14227 (17)	−0.00979 (6)	0.0426 (3)
O5A	−0.46283 (7)	−0.08962 (18)	−0.03569 (7)	0.0472 (4)
C8A	−0.38068 (9)	−0.2731 (2)	−0.12550 (9)	0.0340 (4)
C9A	−0.33213 (10)	−0.1517 (3)	−0.11168 (9)	0.0406 (5)
H9A	−0.3005	−0.1646	−0.1283	0.049*
C10A	−0.32888 (10)	−0.0109 (3)	−0.07384 (9)	0.0393 (5)
C11A	−0.37375 (9)	0.0070 (2)	−0.04923 (8)	0.0334 (4)
C12A	−0.42161 (9)	−0.1175 (2)	−0.06245 (8)	0.0328 (4)
C13A	−0.42517 (9)	−0.2573 (2)	−0.10056 (9)	0.0336 (4)
H13A	−0.4586	−0.3436	−0.1097	0.040*
C14A	−0.38590 (10)	−0.4248 (2)	−0.16757 (9)	0.0370 (4)
C15A	−0.23845 (13)	0.1145 (3)	−0.08348 (14)	0.0665 (7)
H15D	−0.2629 (4)	0.112 (2)	−0.1309 (7)	0.100*
H15E	−0.2103 (8)	0.014 (2)	−0.0679 (8)	0.100*
H15F	−0.2112 (8)	0.217 (2)	−0.0698 (8)	0.100*
C16A	−0.39094 (14)	0.3015 (3)	−0.04267 (12)	0.0585 (6)
H16D	−0.4367 (7)	0.2958 (8)	−0.0724 (8)	0.088*
H16E	−0.3667 (7)	0.3257 (11)	−0.0658 (8)	0.088*
H16F	−0.3835 (8)	0.3891 (14)	−0.0117 (5)	0.088*
C17A	−0.51430 (13)	−0.2093 (3)	−0.05021 (14)	0.0630 (7)
H17D	−0.4951 (3)	−0.3224 (18)	−0.0332 (8)	0.095*
H17E	−0.5420 (7)	−0.2162 (17)	−0.0979 (7)	0.095*
H17F	−0.5417 (7)	−0.1726 (13)	−0.0297 (8)	0.095*
O6	−0.10494 (11)	−0.1977 (3)	−0.05230 (8)	0.0660 (5)
H61	−0.0785 (14)	−0.192 (3)	−0.0710 (13)	0.071 (8)*
H62	−0.1406 (15)	−0.245 (4)	−0.0776 (14)	0.075 (9)*
O7	−0.21854 (13)	−0.3380 (4)	−0.15097 (18)	0.1440 (14)
H71	−0.215 (3)	−0.431 (5)	−0.121 (2)	0.173*
H72	−0.2611 (11)	−0.366 (6)	−0.175 (2)	0.173*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0531 (11)	0.0444 (11)	0.0323 (9)	−0.0210 (9)	0.0215 (8)	−0.0057 (8)
N2	0.0612 (12)	0.0521 (12)	0.0314 (9)	−0.0277 (10)	0.0215 (9)	−0.0053 (8)
C1	0.0444 (12)	0.0421 (11)	0.0306 (9)	−0.0133 (9)	0.0204 (9)	−0.0061 (8)
C2	0.0593 (14)	0.0452 (13)	0.0413 (11)	−0.0124 (11)	0.0211 (10)	−0.0038 (10)
C3	0.099 (2)	0.0471 (15)	0.0616 (15)	−0.0274 (14)	0.0316 (16)	−0.0029 (12)
C4	0.101 (2)	0.079 (2)	0.0643 (17)	−0.0592 (18)	0.0249 (16)	−0.0118 (15)
C5	0.0720 (19)	0.097 (2)	0.0548 (15)	−0.0470 (17)	0.0046 (13)	0.0032 (15)
C6	0.0573 (15)	0.0653 (16)	0.0453 (12)	−0.0238 (13)	0.0118 (11)	0.0057 (11)
C7	0.0385 (11)	0.0402 (11)	0.0316 (9)	−0.0085 (9)	0.0192 (8)	−0.0039 (8)
O1	0.0521 (9)	0.0394 (8)	0.0327 (7)	−0.0119 (6)	0.0237 (6)	−0.0042 (6)
O2	0.0549 (9)	0.0545 (9)	0.0311 (7)	−0.0263 (7)	0.0221 (6)	−0.0116 (6)
O3	0.0424 (9)	0.0550 (9)	0.0400 (8)	−0.0074 (7)	0.0018 (7)	−0.0106 (7)
O4	0.0302 (7)	0.0350 (8)	0.0703 (10)	−0.0062 (6)	0.0210 (7)	−0.0092 (7)
O5	0.0525 (10)	0.0544 (9)	0.0492 (9)	−0.0149 (8)	0.0184 (7)	0.0131 (7)
C8	0.0283 (10)	0.0350 (10)	0.0306 (9)	−0.0028 (8)	0.0153 (8)	−0.0044 (8)
C9	0.0340 (10)	0.0355 (10)	0.0296 (9)	−0.0004 (8)	0.0139 (8)	−0.0016 (8)
C10	0.0265 (10)	0.0391 (11)	0.0337 (9)	0.0013 (8)	0.0095 (8)	−0.0091 (8)
C11	0.0254 (10)	0.0315 (10)	0.0484 (11)	−0.0034 (8)	0.0186 (8)	−0.0070 (8)
C12	0.0318 (10)	0.0375 (11)	0.0412 (10)	0.0001 (8)	0.0196 (8)	0.0044 (8)
C13	0.0286 (10)	0.0418 (11)	0.0292 (9)	−0.0051 (8)	0.0121 (7)	−0.0012 (8)
C14	0.0307 (10)	0.0365 (10)	0.0291 (9)	−0.0033 (8)	0.0153 (8)	−0.0029 (8)
C15	0.0680 (18)	0.0676 (17)	0.0381 (12)	0.0028 (14)	−0.0071 (11)	−0.0037 (12)
C16	0.0549 (16)	0.0390 (13)	0.109 (2)	−0.0013 (11)	0.0317 (15)	−0.0143 (14)
C17	0.0603 (16)	0.0817 (18)	0.0459 (13)	−0.0152 (14)	0.0154 (12)	0.0217 (13)
N1A	0.0357 (11)	0.0553 (13)	0.0862 (15)	−0.0098 (9)	0.0321 (11)	−0.0359 (11)
N2A	0.0330 (10)	0.0452 (11)	0.0561 (11)	−0.0044 (9)	0.0197 (9)	−0.0171 (9)
C1A	0.0300 (11)	0.0434 (12)	0.0444 (11)	0.0054 (9)	0.0097 (9)	−0.0094 (9)
C2A	0.0530 (14)	0.0556 (14)	0.0585 (13)	0.0083 (11)	0.0267 (12)	−0.0069 (11)
C3A	0.089 (2)	0.076 (2)	0.0650 (16)	0.0188 (17)	0.0413 (16)	−0.0136 (14)
C4A	0.096 (2)	0.0576 (18)	0.0795 (19)	0.0058 (16)	0.0326 (18)	−0.0296 (15)
C5A	0.080 (2)	0.0471 (15)	0.088 (2)	−0.0049 (14)	0.0333 (17)	−0.0204 (14)
C6A	0.0497 (14)	0.0468 (14)	0.0615 (14)	−0.0007 (11)	0.0199 (11)	−0.0105 (11)
C7A	0.0276 (10)	0.0413 (11)	0.0448 (11)	0.0032 (9)	0.0114 (8)	−0.0087 (9)
O1A	0.0383 (9)	0.0651 (10)	0.0955 (12)	−0.0120 (8)	0.0390 (9)	−0.0418 (9)
O2A	0.0321 (7)	0.0399 (8)	0.0568 (8)	−0.0045 (6)	0.0213 (6)	−0.0165 (7)
O3A	0.0533 (10)	0.0643 (11)	0.0851 (12)	−0.0303 (8)	0.0442 (9)	−0.0357 (9)
O4A	0.0516 (9)	0.0368 (8)	0.0379 (7)	−0.0028 (6)	0.0193 (7)	−0.0095 (6)
O5A	0.0547 (9)	0.0457 (8)	0.0582 (9)	−0.0114 (7)	0.0404 (8)	−0.0159 (7)
C8A	0.0303 (10)	0.0338 (10)	0.0355 (9)	0.0014 (8)	0.0132 (8)	−0.0042 (8)
C9A	0.0323 (11)	0.0467 (12)	0.0466 (11)	−0.0045 (9)	0.0214 (9)	−0.0115 (9)
C10A	0.0328 (11)	0.0400 (11)	0.0425 (10)	−0.0092 (9)	0.0152 (9)	−0.0087 (9)
C11A	0.0356 (10)	0.0328 (10)	0.0272 (8)	0.0007 (8)	0.0105 (8)	−0.0041 (8)
C12A	0.0331 (10)	0.0353 (10)	0.0308 (9)	0.0026 (8)	0.0154 (8)	0.0008 (8)
C13A	0.0313 (10)	0.0319 (10)	0.0384 (10)	−0.0016 (8)	0.0167 (8)	−0.0026 (8)
C14A	0.0317 (11)	0.0365 (11)	0.0437 (11)	0.0005 (9)	0.0181 (9)	−0.0067 (9)
C15A	0.0559 (16)	0.0694 (17)	0.0890 (19)	−0.0224 (13)	0.0461 (15)	−0.0157 (14)
C16A	0.0708 (17)	0.0381 (13)	0.0709 (16)	0.0010 (12)	0.0364 (14)	−0.0024 (11)
C17A	0.0683 (17)	0.0596 (15)	0.0904 (18)	−0.0191 (13)	0.0615 (15)	−0.0233 (13)
O6	0.0624 (12)	0.0984 (15)	0.0465 (9)	−0.0279 (11)	0.0332 (9)	−0.0265 (9)
O7	0.0675 (16)	0.181 (3)	0.205 (3)	−0.0598 (19)	0.082 (2)	−0.131 (3)

Geometric parameters (Å, º)

N1—C7	1.307 (2)	N1A—H12A	0.90 (3)
N1—H11	0.89 (2)	N2A—C7A	1.308 (3)
N1—H12	0.92 (2)	N2A—H21A	0.93 (3)
N2—C7	1.311 (2)	N2A—H22A	0.89 (2)
N2—H21	0.93 (2)	C1A—C6A	1.390 (3)
N2—H22	0.91 (2)	C1A—C2A	1.391 (3)
C1—C6	1.385 (3)	C1A—C7A	1.484 (3)
C1—C2	1.388 (3)	C2A—C3A	1.394 (3)
C1—C7	1.480 (3)	C2A—H2A	0.9700
C2—C3	1.387 (3)	C3A—C4A	1.377 (4)
C2—H2	0.9700	C3A—H3A	0.9700
C3—C4	1.376 (4)	C4A—C5A	1.373 (4)
C3—H3	0.9700	C4A—H4A	0.9700
C4—C5	1.367 (4)	C5A—C6A	1.381 (3)
C4—H4	0.9700	C5A—H5A	0.9700
C5—C6	1.376 (3)	C6A—H6A	0.9700
C5—H5	0.9700	O1A—C14A	1.252 (2)
C6—H6	0.9700	O2A—C14A	1.258 (2)
O1—C14	1.257 (2)	O3A—C10A	1.364 (2)
O2—C14	1.252 (2)	O3A—C15A	1.415 (3)
O3—C10	1.363 (2)	O4A—C11A	1.378 (2)
O3—C15	1.422 (3)	O4A—C16A	1.429 (3)
O4—C11	1.379 (2)	O5A—C12A	1.365 (2)
O4—C16	1.430 (3)	O5A—C17A	1.421 (3)
O5—C12	1.363 (2)	C8A—C9A	1.386 (3)
O5—C17	1.424 (3)	C8A—C13A	1.389 (3)
C8—C9	1.387 (2)	C8A—C14A	1.510 (3)
C8—C13	1.388 (2)	C9A—C10A	1.393 (3)
C8—C14	1.509 (3)	C9A—H9A	0.9700
C9—C10	1.394 (3)	C10A—C11A	1.393 (3)
C9—H9	0.9700	C11A—C12A	1.393 (3)
C10—C11	1.394 (3)	C12A—C13A	1.389 (3)
C11—C12	1.397 (3)	C13A—H13A	0.9700
C12—C13	1.389 (3)	C15A—H15D	0.9757
C13—H13	0.9700	C15A—H15E	0.9757
C15—H15A	0.9892	C15A—H15F	0.9757
C15—H15B	0.9892	C16A—H16D	0.9514
C15—H15C	0.9892	C16A—H16E	0.9514
C16—H16A	0.9595	C16A—H16F	0.9514
C16—H16B	0.9595	C17A—H17D	0.9900
C16—H16C	0.9595	C17A—H17E	0.9900
C17—H17A	0.9806	C17A—H17F	0.9900
C17—H17B	0.9806	O6—H61	0.89 (3)
C17—H17C	0.9806	O6—H62	0.84 (3)
N1A—C7A	1.308 (3)	O7—H71	0.993 (19)
N1A—H11A	0.88 (3)	O7—H72	0.897 (19)
C7—N1—H11	118.8 (14)	C7A—N1A—H12A	119.8 (17)
C7—N1—H12	119.6 (14)	H11A—N1A—H12A	119 (2)
H11—N1—H12	121 (2)	C7A—N2A—H21A	118.4 (15)
C7—N2—H21	120.3 (13)	C7A—N2A—H22A	121.2 (15)
C7—N2—H22	121.0 (14)	H21A—N2A—H22A	120 (2)
H21—N2—H22	117 (2)	C6A—C1A—C2A	119.7 (2)
C6—C1—C2	119.32 (19)	C6A—C1A—C7A	120.55 (19)
C6—C1—C7	119.92 (19)	C2A—C1A—C7A	119.7 (2)
C2—C1—C7	120.75 (18)	C1A—C2A—C3A	119.2 (2)
C3—C2—C1	120.2 (2)	C1A—C2A—H2A	120.4
C3—C2—H2	119.9	C3A—C2A—H2A	120.4
C1—C2—H2	119.9	C4A—C3A—C2A	120.2 (3)
C4—C3—C2	119.7 (2)	C4A—C3A—H3A	119.9
C4—C3—H3	120.2	C2A—C3A—H3A	119.9
C2—C3—H3	120.2	C5A—C4A—C3A	120.7 (2)
C5—C4—C3	120.2 (2)	C5A—C4A—H4A	119.6
C5—C4—H4	119.9	C3A—C4A—H4A	119.6
C3—C4—H4	119.9	C4A—C5A—C6A	119.7 (3)
C4—C5—C6	120.7 (2)	C4A—C5A—H5A	120.1
C4—C5—H5	119.6	C6A—C5A—H5A	120.1
C6—C5—H5	119.6	C5A—C6A—C1A	120.4 (2)
C5—C6—C1	119.9 (2)	C5A—C6A—H6A	119.8
C5—C6—H6	120.0	C1A—C6A—H6A	119.8
C1—C6—H6	120.0	N2A—C7A—N1A	120.2 (2)
N1—C7—N2	120.67 (18)	N2A—C7A—C1A	120.14 (19)
N1—C7—C1	119.95 (17)	N1A—C7A—C1A	119.68 (19)
N2—C7—C1	119.37 (17)	C10A—O3A—C15A	118.88 (17)
C10—O3—C15	116.76 (17)	C11A—O4A—C16A	114.88 (15)
C11—O4—C16	115.37 (16)	C12A—O5A—C17A	117.20 (15)
C12—O5—C17	117.18 (17)	C9A—C8A—C13A	120.36 (17)
C9—C8—C13	120.58 (17)	C9A—C8A—C14A	120.63 (17)
C9—C8—C14	119.94 (16)	C13A—C8A—C14A	119.01 (17)
C13—C8—C14	119.43 (15)	C8A—C9A—C10A	119.82 (18)
C8—C9—C10	119.48 (17)	C8A—C9A—H9A	120.1
C8—C9—H9	120.3	C10A—C9A—H9A	120.1
C10—C9—H9	120.3	O3A—C10A—C11A	114.95 (17)
O3—C10—C11	115.14 (17)	O3A—C10A—C9A	124.85 (18)
O3—C10—C9	124.55 (17)	C11A—C10A—C9A	120.20 (17)
C11—C10—C9	120.30 (16)	O4A—C11A—C10A	120.91 (17)
O4—C11—C10	119.42 (17)	O4A—C11A—C12A	119.54 (16)
O4—C11—C12	120.75 (17)	C10A—C11A—C12A	119.49 (16)
C10—C11—C12	119.72 (17)	O5A—C12A—C13A	124.50 (17)
O5—C12—C13	124.94 (17)	O5A—C12A—C11A	115.16 (16)
O5—C12—C11	115.23 (17)	C13A—C12A—C11A	120.34 (16)
C13—C12—C11	119.81 (17)	C8A—C13A—C12A	119.78 (17)
C8—C13—C12	120.11 (16)	C8A—C13A—H13A	120.1
C8—C13—H13	119.9	C12A—C13A—H13A	120.1
C12—C13—H13	119.9	O1A—C14A—O2A	123.66 (18)
O2—C14—O1	124.46 (17)	O1A—C14A—C8A	117.98 (17)
O2—C14—C8	117.38 (15)	O2A—C14A—C8A	118.36 (16)
O1—C14—C8	118.16 (15)	O3A—C15A—H15D	109.5
O3—C15—H15A	109.5	O3A—C15A—H15E	109.5
O3—C15—H15B	109.5	H15D—C15A—H15E	109.5
H15A—C15—H15B	109.5	O3A—C15A—H15F	109.5
O3—C15—H15C	109.5	H15D—C15A—H15F	109.5
H15A—C15—H15C	109.5	H15E—C15A—H15F	109.5
H15B—C15—H15C	109.5	O4A—C16A—H16D	109.5
O4—C16—H16A	109.5	O4A—C16A—H16E	109.5
O4—C16—H16B	109.5	H16D—C16A—H16E	109.5
H16A—C16—H16B	109.5	O4A—C16A—H16F	109.5
O4—C16—H16C	109.5	H16D—C16A—H16F	109.5
H16A—C16—H16C	109.5	H16E—C16A—H16F	109.5
H16B—C16—H16C	109.5	O5A—C17A—H17D	109.5
O5—C17—H17A	109.5	O5A—C17A—H17E	109.5
O5—C17—H17B	109.5	H17D—C17A—H17E	109.5
H17A—C17—H17B	109.5	O5A—C17A—H17F	109.5
O5—C17—H17C	109.5	H17D—C17A—H17F	109.5
H17A—C17—H17C	109.5	H17E—C17A—H17F	109.5
H17B—C17—H17C	109.5	H61—O6—H62	110 (2)
C7A—N1A—H11A	119.8 (16)	H71—O7—H72	88 (4)
C6—C1—C2—C3	0.5 (3)	C6A—C1A—C2A—C3A	0.9 (3)
C7—C1—C2—C3	−179.3 (2)	C7A—C1A—C2A—C3A	−178.7 (2)
C1—C2—C3—C4	0.4 (4)	C1A—C2A—C3A—C4A	−1.2 (4)
C2—C3—C4—C5	−1.2 (5)	C2A—C3A—C4A—C5A	0.7 (5)
C3—C4—C5—C6	1.1 (5)	C3A—C4A—C5A—C6A	0.2 (5)
C4—C5—C6—C1	−0.3 (5)	C4A—C5A—C6A—C1A	−0.4 (4)
C2—C1—C6—C5	−0.5 (4)	C2A—C1A—C6A—C5A	−0.1 (3)
C7—C1—C6—C5	179.2 (2)	C7A—C1A—C6A—C5A	179.5 (2)
C6—C1—C7—N1	−143.6 (2)	C6A—C1A—C7A—N2A	−30.5 (3)
C2—C1—C7—N1	36.1 (3)	C2A—C1A—C7A—N2A	149.2 (2)
C6—C1—C7—N2	35.5 (3)	C6A—C1A—C7A—N1A	149.9 (2)
C2—C1—C7—N2	−144.8 (2)	C2A—C1A—C7A—N1A	−30.4 (3)
C13—C8—C9—C10	0.2 (3)	C13A—C8A—C9A—C10A	−1.5 (3)
C14—C8—C9—C10	−177.14 (16)	C14A—C8A—C9A—C10A	178.74 (18)
C15—O3—C10—C11	−179.54 (19)	C15A—O3A—C10A—C11A	−175.9 (2)
C15—O3—C10—C9	1.5 (3)	C15A—O3A—C10A—C9A	5.0 (3)
C8—C9—C10—O3	178.21 (17)	C8A—C9A—C10A—O3A	179.9 (2)
C8—C9—C10—C11	−0.7 (3)	C8A—C9A—C10A—C11A	0.8 (3)
C16—O4—C11—C10	107.4 (2)	C16A—O4A—C11A—C10A	74.1 (2)
C16—O4—C11—C12	−76.5 (2)	C16A—O4A—C11A—C12A	−108.6 (2)
O3—C10—C11—O4	−2.0 (2)	O3A—C10A—C11A—O4A	−1.6 (3)
C9—C10—C11—O4	177.03 (16)	C9A—C10A—C11A—O4A	177.65 (17)
O3—C10—C11—C12	−178.22 (17)	O3A—C10A—C11A—C12A	−178.84 (17)
C9—C10—C11—C12	0.8 (3)	C9A—C10A—C11A—C12A	0.4 (3)
C17—O5—C12—C13	6.6 (3)	C17A—O5A—C12A—C13A	−2.5 (3)
C17—O5—C12—C11	−171.7 (2)	C17A—O5A—C12A—C11A	177.28 (19)
O4—C11—C12—O5	1.8 (3)	O4A—C11A—C12A—O5A	2.0 (2)
C10—C11—C12—O5	177.95 (17)	C10A—C11A—C12A—O5A	179.35 (17)
O4—C11—C12—C13	−176.54 (16)	O4A—C11A—C12A—C13A	−178.14 (16)
C10—C11—C12—C13	−0.4 (3)	C10A—C11A—C12A—C13A	−0.8 (3)
C9—C8—C13—C12	0.2 (3)	C9A—C8A—C13A—C12A	1.1 (3)
C14—C8—C13—C12	177.59 (16)	C14A—C8A—C13A—C12A	−179.18 (17)
O5—C12—C13—C8	−178.29 (18)	O5A—C12A—C13A—C8A	179.93 (17)
C11—C12—C13—C8	−0.1 (3)	C11A—C12A—C13A—C8A	0.1 (3)
C9—C8—C14—O2	151.48 (18)	C9A—C8A—C14A—O1A	22.1 (3)
C13—C8—C14—O2	−25.9 (3)	C13A—C8A—C14A—O1A	−157.68 (19)
C9—C8—C14—O1	−27.7 (3)	C9A—C8A—C14A—O2A	−157.97 (19)
C13—C8—C14—O1	154.95 (18)	C13A—C8A—C14A—O2A	22.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O1	0.89 (2)	1.96 (2)	2.850 (2)	174 (2)
N1—H12···O1^i	0.92 (2)	1.93 (2)	2.838 (2)	172 (2)
N2—H21···O2	0.93 (2)	1.85 (2)	2.777 (2)	178 (2)
N2—H22···O6^ii	0.91 (2)	1.89 (2)	2.792 (2)	172 (2)
N1A—H11A···O1A	0.88 (3)	1.88 (3)	2.751 (3)	176 (2)
N1A—H12A···O4	0.90 (3)	2.02 (3)	2.892 (2)	162 (2)
N2A—H21A···O2A	0.93 (3)	1.92 (3)	2.845 (2)	173 (2)
N2A—H22A···O2A^iii	0.89 (2)	1.99 (3)	2.873 (2)	169 (2)
O6—H61···O2	0.89 (3)	1.94 (3)	2.831 (2)	179 (3)
O6—H62···O7	0.84 (3)	1.95 (3)	2.776 (3)	167 (3)
O7—H72···O1A	0.90 (2)	1.91 (3)	2.690 (3)	145 (4)

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