Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614001090/bg3168sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614001090/bg3168Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614001090/bg3168IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614001090/bg3168IIIsup4.hkl
Contains datablock III

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614001090/bg3168Isup5.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614001090/bg3168IIsup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614001090/bg3168IIIsup7.cml
Supplementary material

CCDC references: 981710; 981711; 981712

Introduction top

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 ΔpKa [ΔpKa = pKa (conjugate acid of the base) - pKa (acid), where the pKa values are for aqueous solutions at 298 K]. Generally, a sufficiently large ΔpKa value (i.e. greater than 3) should result in a salt (Bhogala et al., 2005). With smaller ΔpKa values, a cocrystal can be expected, but that parameter seems inappropriate for accurately predicting salt or cocrystal formation in the solid state when 0 < ΔpKa < 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 pKa 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 pKa = 4.24; Kaza­kevich & Lobrutto, 2007), for these acid–base complexes the ΔpKa falls in the range 7.1–7.5 and leads to the formation of molecular salts.

Experimental top

Synthesis and crystallization top

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.

Refinement top

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 Uiso(H) = 1.2Ueq(C) for aromatic H atoms or 1.5Ueq(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 Uiso(H) = 1.2Ueq(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.

Results and discussion top

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 CO 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 Owater—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···Owater and Owater—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 top

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 top

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 top
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 top
Crystal data top
C7H9N2+·C8H7O3F(000) = 576
Mr = 272.30Dx = 1.251 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 3122 reflections
a = 9.4532 (9) Åθ = 2.9–29.0°
b = 6.1789 (8) ŵ = 0.09 mm1
c = 24.906 (3) ÅT = 298 K
β = 96.513 (11)°Tablet, colourless
V = 1445.4 (3) Å30.40 × 0.35 × 0.18 mm
Z = 4
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
2598 independent reflections
Radiation source: Enhance (Mo) X-ray Source1762 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 16.0696 pixels mm-1θmax = 25.3°, θmin = 3.1°
ω and φ scansh = 1110
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 77
Tmin = 0.788, Tmax = 0.984l = 2929
8118 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.053P)2 + 0.348P]
where P = (Fo2 + 2Fc2)/3
2598 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C7H9N2+·C8H7O3V = 1445.4 (3) Å3
Mr = 272.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.4532 (9) ŵ = 0.09 mm1
b = 6.1789 (8) ÅT = 298 K
c = 24.906 (3) Å0.40 × 0.35 × 0.18 mm
β = 96.513 (11)°
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
2598 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
1762 reflections with I > 2σ(I)
Tmin = 0.788, Tmax = 0.984Rint = 0.029
8118 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.13 e Å3
2598 reflectionsΔρmin = 0.14 e Å3
199 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N10.60558 (19)0.0342 (4)0.77780 (8)0.0562 (6)
H1A0.611 (2)0.079 (4)0.7497 (10)0.071 (7)*
H1B0.680 (2)0.101 (3)0.7911 (9)0.052 (7)*
N20.37107 (19)0.0366 (4)0.77946 (8)0.0577 (6)
H2A0.378 (2)0.154 (4)0.7556 (9)0.059 (7)*
H2B0.287 (3)0.003 (4)0.7886 (9)0.066 (7)*
C10.47839 (19)0.2439 (4)0.83797 (8)0.0451 (5)
C20.5632 (2)0.4271 (4)0.83802 (10)0.0584 (6)
H20.62460.44670.80970.070*
C30.5610 (3)0.5811 (4)0.87769 (11)0.0733 (8)
H30.62020.70920.87720.088*
C40.4744 (3)0.5531 (5)0.91816 (11)0.0811 (9)
H40.47410.66030.94660.097*
C50.3888 (3)0.3740 (5)0.91826 (11)0.0769 (8)
H50.32710.35620.94650.092*
C60.3900 (2)0.2194 (4)0.87857 (9)0.0585 (6)
H60.32910.09320.87890.070*
C70.48488 (19)0.0746 (4)0.79675 (8)0.0449 (5)
O10.62105 (14)0.2793 (2)0.69993 (6)0.0545 (4)
O20.40257 (14)0.3899 (3)0.70883 (7)0.0679 (5)
O30.7093 (2)0.6323 (4)0.52109 (8)0.0939 (7)
C80.5262 (2)0.5595 (4)0.64282 (8)0.0457 (5)
C90.6124 (2)0.5115 (4)0.60249 (9)0.0515 (6)
H90.66130.37350.60250.062*
C100.6277 (3)0.6620 (4)0.56249 (10)0.0634 (7)
C110.5623 (3)0.8616 (5)0.56397 (12)0.0784 (8)
H110.57690.96990.53690.094*
C120.4773 (3)0.9072 (4)0.60330 (13)0.0783 (8)
H120.43131.04740.60380.094*
C130.4559 (2)0.7553 (4)0.64254 (11)0.0631 (7)
H130.39230.78630.66950.076*
C140.5154 (2)0.3981 (4)0.68703 (9)0.0460 (5)
C150.7681 (4)0.4274 (6)0.51504 (13)0.1082 (13)
H15A0.819 (3)0.4261 (14)0.4827 (9)0.162*
H15B0.835 (2)0.393 (2)0.5472 (8)0.162*
H15C0.6916 (15)0.318 (2)0.5110 (10)0.162*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0291 (9)0.0776 (15)0.0634 (13)0.0030 (10)0.0113 (9)0.0223 (12)
N20.0313 (10)0.0728 (15)0.0706 (14)0.0019 (10)0.0133 (9)0.0190 (12)
C10.0308 (10)0.0580 (14)0.0469 (12)0.0064 (10)0.0058 (9)0.0001 (11)
C20.0498 (13)0.0651 (16)0.0620 (16)0.0022 (13)0.0135 (11)0.0010 (13)
C30.0683 (17)0.0638 (17)0.086 (2)0.0001 (14)0.0022 (15)0.0143 (16)
C40.0809 (19)0.087 (2)0.076 (2)0.0194 (18)0.0107 (16)0.0275 (17)
C50.0679 (16)0.107 (2)0.0601 (17)0.0165 (18)0.0244 (13)0.0112 (17)
C60.0477 (12)0.0736 (17)0.0568 (15)0.0057 (12)0.0168 (11)0.0027 (13)
C70.0298 (10)0.0584 (14)0.0472 (12)0.0017 (10)0.0068 (9)0.0000 (11)
O10.0318 (7)0.0664 (10)0.0671 (10)0.0046 (7)0.0135 (7)0.0193 (8)
O20.0329 (8)0.0944 (13)0.0799 (12)0.0113 (8)0.0208 (8)0.0218 (10)
O30.1144 (16)0.1075 (17)0.0653 (12)0.0149 (14)0.0343 (12)0.0192 (12)
C80.0320 (10)0.0515 (14)0.0520 (13)0.0037 (10)0.0029 (9)0.0025 (11)
C90.0456 (12)0.0562 (14)0.0527 (14)0.0049 (11)0.0050 (10)0.0056 (12)
C100.0615 (15)0.0710 (17)0.0573 (16)0.0160 (14)0.0054 (12)0.0112 (14)
C110.0807 (19)0.073 (2)0.078 (2)0.0110 (17)0.0091 (16)0.0292 (17)
C120.0686 (17)0.0534 (16)0.108 (2)0.0048 (14)0.0114 (16)0.0135 (17)
C130.0502 (13)0.0603 (16)0.0775 (18)0.0041 (13)0.0011 (12)0.0006 (15)
C140.0293 (10)0.0575 (14)0.0510 (13)0.0021 (10)0.0040 (9)0.0009 (11)
C150.137 (3)0.108 (3)0.091 (2)0.015 (2)0.063 (2)0.008 (2)
Geometric parameters (Å, º) top
N1—C71.307 (2)O1—C141.252 (2)
N1—H1A0.99 (3)O2—C141.252 (2)
N1—H1B0.85 (2)O3—C101.368 (3)
N2—C71.308 (3)O3—C151.398 (4)
N2—H2A0.94 (2)C8—C131.379 (3)
N2—H2B0.89 (2)C8—C91.395 (3)
C1—C21.387 (3)C8—C141.498 (3)
C1—C61.392 (3)C9—C101.382 (3)
C1—C71.472 (3)C9—H90.9700
C2—C31.374 (3)C10—C111.382 (4)
C2—H20.9700C11—C121.365 (4)
C3—C41.379 (4)C11—H110.9700
C3—H30.9700C12—C131.386 (4)
C4—C51.371 (4)C12—H120.9700
C4—H40.9700C13—H130.9700
C5—C61.375 (4)C15—H15A0.9855
C5—H50.9700C15—H15B0.9855
C6—H60.9700C15—H15C0.9855
C7—N1—H1A120.2 (14)C13—C8—C9120.2 (2)
C7—N1—H1B118.9 (15)C13—C8—C14121.0 (2)
H1A—N1—H1B121 (2)C9—C8—C14118.8 (2)
C7—N2—H2A119.9 (13)C10—C9—C8119.6 (2)
C7—N2—H2B120.0 (15)C10—C9—H9120.2
H2A—N2—H2B120 (2)C8—C9—H9120.2
C2—C1—C6118.9 (2)O3—C10—C11115.6 (3)
C2—C1—C7120.73 (18)O3—C10—C9124.5 (3)
C6—C1—C7120.4 (2)C11—C10—C9119.8 (3)
C3—C2—C1120.7 (2)C12—C11—C10120.3 (3)
C3—C2—H2119.7C12—C11—H11119.8
C1—C2—H2119.7C10—C11—H11119.8
C2—C3—C4119.8 (3)C11—C12—C13120.7 (3)
C2—C3—H3120.1C11—C12—H12119.6
C4—C3—H3120.1C13—C12—H12119.6
C5—C4—C3120.1 (3)C8—C13—C12119.3 (2)
C5—C4—H4119.9C8—C13—H13120.4
C3—C4—H4119.9C12—C13—H13120.4
C4—C5—C6120.4 (2)O2—C14—O1124.0 (2)
C4—C5—H5119.8O2—C14—C8118.57 (19)
C6—C5—H5119.8O1—C14—C8117.42 (17)
C5—C6—C1120.1 (2)O3—C15—H15A109.5
C5—C6—H6120.0O3—C15—H15B109.5
C1—C6—H6120.0H15A—C15—H15B109.5
N1—C7—N2120.0 (2)O3—C15—H15C109.5
N1—C7—C1119.67 (19)H15A—C15—H15C109.5
N2—C7—C1120.36 (18)H15B—C15—H15C109.5
C10—O3—C15117.9 (2)
C6—C1—C2—C30.5 (3)C15—O3—C10—C11174.8 (3)
C7—C1—C2—C3177.5 (2)C15—O3—C10—C97.7 (4)
C1—C2—C3—C40.4 (4)C8—C9—C10—O3180.0 (2)
C2—C3—C4—C51.2 (4)C8—C9—C10—C112.6 (3)
C3—C4—C5—C60.9 (4)O3—C10—C11—C12179.3 (3)
C4—C5—C6—C10.0 (4)C9—C10—C11—C123.1 (4)
C2—C1—C6—C50.8 (3)C10—C11—C12—C130.5 (4)
C7—C1—C6—C5177.3 (2)C9—C8—C13—C123.0 (3)
C2—C1—C7—N133.3 (3)C14—C8—C13—C12175.0 (2)
C6—C1—C7—N1144.7 (2)C11—C12—C13—C82.6 (4)
C2—C1—C7—N2147.4 (2)C13—C8—C14—O231.5 (3)
C6—C1—C7—N234.6 (3)C9—C8—C14—O2150.4 (2)
C13—C8—C9—C100.4 (3)C13—C8—C14—O1148.4 (2)
C14—C8—C9—C10177.62 (19)C9—C8—C14—O129.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.99 (3)1.76 (3)2.756 (3)180 (2)
N1—H1B···O1i0.85 (2)2.01 (2)2.827 (2)161 (2)
N2—H2A···O20.94 (2)1.90 (3)2.840 (3)177 (2)
N2—H2B···O2ii0.89 (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 top
Crystal data top
C7H9N2+·C8H7O3F(000) = 576
Mr = 272.30Dx = 1.279 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 3892 reflections
a = 9.4676 (7) Åθ = 2.8–32.3°
b = 6.8888 (6) ŵ = 0.09 mm1
c = 21.7018 (12) ÅT = 298 K
β = 92.4498 (7)°Tablet, colourless
V = 1414.11 (18) Å30.20 × 0.15 × 0.12 mm
Z = 4
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
4450 independent reflections
Radiation source: Enhance (Mo) X-ray Source2282 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
Detector resolution: 16.0696 pixels mm-1θmax = 31.0°, θmin = 3.1°
ω and φ scansh = 1313
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 99
Tmin = 0.982, Tmax = 0.989l = 3130
16608 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 0.93 w = 1/[σ2(Fo2) + (0.0512P)2]
where P = (Fo2 + 2Fc2)/3
4450 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C7H9N2+·C8H7O3V = 1414.11 (18) Å3
Mr = 272.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.4676 (7) ŵ = 0.09 mm1
b = 6.8888 (6) ÅT = 298 K
c = 21.7018 (12) Å0.20 × 0.15 × 0.12 mm
β = 92.4498 (7)°
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
4450 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
2282 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.989Rint = 0.047
16608 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 0.93Δρmax = 0.14 e Å3
4450 reflectionsΔρmin = 0.19 e Å3
199 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N10.61398 (12)0.6703 (2)0.77793 (6)0.0419 (3)
H1A0.6152 (17)0.778 (2)0.7469 (8)0.071 (5)*
H1B0.6950 (17)0.609 (2)0.7918 (7)0.051 (4)*
N20.37592 (12)0.71579 (19)0.78353 (6)0.0410 (3)
H2A0.3803 (16)0.828 (2)0.7544 (8)0.066 (5)*
H2B0.2893 (17)0.664 (2)0.7939 (7)0.058 (5)*
C10.48329 (13)0.4516 (2)0.84168 (6)0.0348 (3)
C20.55623 (16)0.2820 (2)0.83054 (7)0.0463 (4)
H20.61770.27500.79600.056*
C30.54190 (18)0.1226 (2)0.86833 (9)0.0605 (5)
H30.59160.00310.85980.073*
C40.4571 (2)0.1338 (3)0.91803 (9)0.0694 (5)
H40.44670.02180.94460.083*
C50.3876 (2)0.3020 (3)0.93008 (9)0.0751 (6)
H50.33020.31010.96590.090*
C60.39809 (17)0.4602 (3)0.89194 (7)0.0558 (5)
H60.34580.57780.90020.067*
C70.49184 (13)0.6192 (2)0.79915 (6)0.0332 (3)
O10.62222 (9)0.98657 (14)0.69631 (5)0.0418 (3)
O20.39227 (9)1.04057 (14)0.70488 (5)0.0442 (3)
O30.55062 (12)1.78274 (15)0.54881 (5)0.0575 (3)
C80.52366 (13)1.26625 (19)0.64766 (6)0.0328 (3)
C90.62649 (14)1.2858 (2)0.60453 (6)0.0395 (3)
H90.69171.17960.59840.047*
C100.63826 (15)1.4548 (2)0.56979 (7)0.0427 (4)
H100.70921.46440.53900.051*
C110.54809 (15)1.6085 (2)0.57956 (6)0.0407 (4)
C120.44611 (15)1.5920 (2)0.62300 (7)0.0449 (4)
H120.38381.70040.63050.054*
C130.43284 (15)1.4228 (2)0.65555 (7)0.0402 (4)
H130.35851.41180.68470.048*
C140.51163 (13)1.0842 (2)0.68516 (6)0.0330 (3)
C150.65851 (18)1.8127 (3)0.50625 (8)0.0629 (5)
H15A0.7527 (9)1.8088 (17)0.5286 (2)0.094*
H15B0.6450 (8)1.9416 (15)0.4860 (5)0.094*
H15C0.6535 (8)1.7086 (14)0.4743 (4)0.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0230 (6)0.0480 (8)0.0549 (8)0.0027 (6)0.0042 (6)0.0093 (7)
N20.0229 (6)0.0396 (8)0.0609 (8)0.0020 (6)0.0059 (6)0.0086 (7)
C10.0238 (6)0.0363 (8)0.0440 (8)0.0026 (6)0.0013 (6)0.0003 (7)
C20.0416 (9)0.0452 (9)0.0516 (9)0.0075 (7)0.0037 (7)0.0043 (8)
C30.0610 (11)0.0401 (10)0.0786 (13)0.0061 (8)0.0192 (10)0.0028 (9)
C40.0667 (12)0.0636 (13)0.0767 (13)0.0094 (10)0.0100 (10)0.0305 (11)
C50.0701 (13)0.0858 (15)0.0713 (13)0.0083 (11)0.0241 (10)0.0288 (12)
C60.0521 (10)0.0567 (11)0.0600 (10)0.0095 (8)0.0183 (8)0.0098 (9)
C70.0252 (7)0.0344 (8)0.0400 (7)0.0002 (6)0.0027 (6)0.0043 (6)
O10.0233 (5)0.0420 (6)0.0599 (6)0.0016 (4)0.0010 (4)0.0093 (5)
O20.0252 (5)0.0427 (6)0.0650 (7)0.0004 (4)0.0062 (5)0.0110 (5)
O30.0701 (8)0.0439 (7)0.0587 (7)0.0019 (6)0.0040 (6)0.0149 (6)
C80.0260 (7)0.0360 (8)0.0359 (7)0.0040 (6)0.0041 (6)0.0019 (6)
C90.0331 (8)0.0410 (9)0.0444 (8)0.0012 (6)0.0021 (6)0.0003 (7)
C100.0386 (8)0.0495 (10)0.0402 (8)0.0044 (7)0.0049 (6)0.0033 (7)
C110.0460 (9)0.0351 (8)0.0403 (8)0.0064 (7)0.0058 (7)0.0025 (7)
C120.0437 (9)0.0354 (9)0.0556 (9)0.0046 (7)0.0026 (7)0.0010 (7)
C130.0358 (8)0.0369 (8)0.0483 (8)0.0008 (7)0.0074 (6)0.0007 (7)
C140.0239 (7)0.0348 (8)0.0401 (7)0.0029 (6)0.0005 (6)0.0030 (6)
C150.0646 (12)0.0617 (12)0.0624 (11)0.0161 (9)0.0003 (9)0.0222 (9)
Geometric parameters (Å, º) top
N1—C71.3109 (16)O1—C141.2591 (15)
N1—H1A1.001 (18)O2—C141.2617 (14)
N1—H1B0.916 (17)O3—C111.3741 (17)
N2—C71.3153 (17)O3—C151.4212 (18)
N2—H2A0.998 (17)C8—C91.3857 (17)
N2—H2B0.932 (16)C8—C131.3943 (18)
C1—C21.3840 (19)C8—C141.5019 (19)
C1—C61.3853 (19)C9—C101.394 (2)
C1—C71.4824 (19)C9—H90.9700
C2—C31.380 (2)C10—C111.382 (2)
C2—H20.9700C10—H100.9700
C3—C41.374 (2)C11—C121.3827 (19)
C3—H30.9700C12—C131.371 (2)
C4—C51.363 (3)C12—H120.9700
C4—H40.9700C13—H130.9700
C5—C61.375 (2)C15—H15A0.9966
C5—H50.9700C15—H15B0.9966
C6—H60.9700C15—H15C0.9966
C7—N1—H1A118.1 (9)C9—C8—C13117.55 (13)
C7—N1—H1B120.0 (9)C9—C8—C14121.25 (12)
H1A—N1—H1B121.9 (13)C13—C8—C14121.19 (12)
C7—N2—H2A119.8 (9)C8—C9—C10121.42 (13)
C7—N2—H2B118.4 (10)C8—C9—H9119.3
H2A—N2—H2B120.8 (14)C10—C9—H9119.3
C2—C1—C6119.02 (14)C11—C10—C9119.51 (13)
C2—C1—C7120.53 (12)C11—C10—H10120.2
C6—C1—C7120.41 (13)C9—C10—H10120.2
C3—C2—C1120.35 (14)O3—C11—C10124.83 (13)
C3—C2—H2119.8O3—C11—C12115.47 (13)
C1—C2—H2119.8C10—C11—C12119.70 (14)
C4—C3—C2119.85 (16)C13—C12—C11120.20 (14)
C4—C3—H3120.1C13—C12—H12119.9
C2—C3—H3120.1C11—C12—H12119.9
C5—C4—C3120.07 (17)C12—C13—C8121.57 (13)
C5—C4—H4120.0C12—C13—H13119.2
C3—C4—H4120.0C8—C13—H13119.2
C4—C5—C6120.69 (17)O1—C14—O2123.85 (13)
C4—C5—H5119.7O1—C14—C8117.93 (11)
C6—C5—H5119.7O2—C14—C8118.19 (12)
C5—C6—C1119.98 (16)O3—C15—H15A109.5
C5—C6—H6120.0O3—C15—H15B109.5
C1—C6—H6120.0H15A—C15—H15B109.5
N1—C7—N2120.83 (14)O3—C15—H15C109.5
N1—C7—C1120.02 (13)H15A—C15—H15C109.5
N2—C7—C1119.15 (12)H15B—C15—H15C109.5
C11—O3—C15118.05 (12)
C6—C1—C2—C31.3 (2)C8—C9—C10—C111.7 (2)
C7—C1—C2—C3176.44 (14)C15—O3—C11—C103.8 (2)
C1—C2—C3—C41.4 (2)C15—O3—C11—C12176.31 (14)
C2—C3—C4—C50.2 (3)C9—C10—C11—O3179.17 (14)
C3—C4—C5—C61.8 (3)C9—C10—C11—C120.9 (2)
C4—C5—C6—C11.9 (3)O3—C11—C12—C13178.86 (13)
C2—C1—C6—C50.4 (2)C10—C11—C12—C131.1 (2)
C7—C1—C6—C5178.08 (16)C11—C12—C13—C82.3 (2)
C2—C1—C7—N143.30 (19)C9—C8—C13—C121.4 (2)
C6—C1—C7—N1139.04 (15)C14—C8—C13—C12177.77 (13)
C2—C1—C7—N2137.18 (15)C9—C8—C14—O128.51 (19)
C6—C1—C7—N240.5 (2)C13—C8—C14—O1150.69 (13)
C13—C8—C9—C100.6 (2)C9—C8—C14—O2153.20 (13)
C14—C8—C9—C10179.80 (13)C13—C8—C14—O227.61 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O11.001 (18)1.813 (18)2.8110 (17)175.0 (15)
N1—H1B···O1i0.916 (17)1.932 (17)2.8344 (16)168.0 (13)
N2—H2A···O20.998 (17)1.825 (18)2.8224 (17)176.7 (15)
N2—H2B···O2ii0.932 (16)1.918 (17)2.8323 (15)166.5 (14)
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+3/2.
(III) [Amino(phenyl)methylidene]azanium 3,4,5-trimethoxybenzoate monohydrate top
Crystal data top
C7H9N2+·C10H11O5·H2OF(000) = 1488
Mr = 350.37Dx = 1.259 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 17484 reflections
a = 22.8771 (15) Åθ = 2.6–28.9°
b = 7.8631 (3) ŵ = 0.10 mm1
c = 23.1789 (13) ÅT = 298 K
β = 117.515 (8)°Tablet, colourless
V = 3697.9 (3) Å30.28 × 0.25 × 0.15 mm
Z = 8
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
7977 independent reflections
Radiation source: Enhance (Mo) X-ray Source5752 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 16.0696 pixels mm-1θmax = 27.0°, θmin = 2.7°
ω and φ scansh = 2928
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 109
Tmin = 0.974, Tmax = 0.986l = 2929
39513 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0571P)2 + 1.3989P]
where P = (Fo2 + 2Fc2)/3
7977 reflections(Δ/σ)max < 0.001
509 parametersΔρmax = 0.37 e Å3
2 restraintsΔρmin = 0.37 e Å3
Crystal data top
C7H9N2+·C10H11O5·H2OV = 3697.9 (3) Å3
Mr = 350.37Z = 8
Monoclinic, P21/cMo Kα radiation
a = 22.8771 (15) ŵ = 0.10 mm1
b = 7.8631 (3) ÅT = 298 K
c = 23.1789 (13) Å0.28 × 0.25 × 0.15 mm
β = 117.515 (8)°
Data collection top
Agilent Xcalibur Sapphire3
diffractometer
7977 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
5752 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.986Rint = 0.030
39513 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0572 restraints
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.37 e Å3
7977 reflectionsΔρmin = 0.37 e Å3
509 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N10.02943 (9)0.1527 (3)0.18277 (8)0.0426 (4)
H110.0067 (11)0.056 (3)0.1935 (10)0.049 (6)*
H120.0343 (11)0.216 (3)0.2135 (11)0.052 (6)*
N20.06208 (10)0.0938 (3)0.07614 (8)0.0482 (5)
H210.0348 (12)0.001 (3)0.0876 (10)0.052 (6)*
H220.0799 (11)0.129 (3)0.0341 (12)0.055 (7)*
C10.10844 (10)0.3402 (3)0.10177 (9)0.0379 (5)
C20.09016 (12)0.4877 (3)0.13879 (10)0.0495 (5)
H20.04800.49350.17760.059*
C30.13206 (15)0.6270 (3)0.12041 (13)0.0712 (8)
H30.11920.73040.14610.085*
C40.19203 (17)0.6178 (4)0.06548 (14)0.0865 (10)
H40.22180.71430.05290.104*
C50.20973 (15)0.4733 (4)0.02855 (13)0.0844 (10)
H50.25170.46870.01050.101*
C60.16860 (12)0.3342 (3)0.04619 (11)0.0606 (7)
H60.18170.23210.01970.073*
C70.06455 (10)0.1898 (2)0.12121 (9)0.0356 (4)
O10.03470 (7)0.16975 (17)0.21315 (6)0.0398 (3)
O20.02164 (7)0.18551 (18)0.11224 (6)0.0460 (4)
O30.22588 (7)0.5999 (2)0.32500 (7)0.0526 (4)
O40.20976 (7)0.81817 (17)0.23164 (7)0.0460 (4)
O50.11516 (8)0.7746 (2)0.10893 (7)0.0540 (4)
C80.08640 (9)0.3972 (2)0.18667 (8)0.0307 (4)
C90.13495 (9)0.4223 (2)0.25008 (8)0.0334 (4)
H90.14060.34130.28380.040*
C100.17561 (9)0.5647 (2)0.26493 (9)0.0348 (4)
C110.16711 (9)0.6822 (2)0.21664 (9)0.0345 (4)
C120.11810 (9)0.6556 (2)0.15292 (9)0.0357 (4)
C130.07796 (9)0.5129 (2)0.13820 (8)0.0337 (4)
H130.04400.49400.09400.040*
C140.04420 (9)0.2394 (2)0.16937 (8)0.0315 (4)
C150.23578 (14)0.4835 (3)0.37567 (11)0.0703 (8)
H15A0.1955 (7)0.4779 (18)0.3812 (6)0.105*
H15B0.2455 (10)0.369 (2)0.3643 (5)0.105*
H15C0.2732 (9)0.5221 (15)0.4167 (7)0.105*
C160.18281 (13)0.9795 (3)0.23523 (15)0.0700 (8)
H16A0.1438 (8)1.0010 (12)0.1952 (7)0.105*
H16B0.1719 (9)0.9787 (9)0.2705 (8)0.105*
H16C0.2147 (6)1.0671 (15)0.2424 (9)0.105*
C170.07224 (13)0.7409 (4)0.04212 (11)0.0662 (7)
H17A0.0842 (6)0.632 (2)0.0299 (3)0.099*
H17B0.0266 (7)0.736 (2)0.0352 (2)0.099*
H17C0.0763 (7)0.8320 (19)0.0153 (5)0.099*
N1A0.34065 (10)0.7370 (3)0.25036 (11)0.0575 (6)
H11A0.3394 (12)0.648 (3)0.2271 (12)0.062 (7)*
H12A0.3044 (14)0.765 (3)0.2542 (12)0.068 (8)*
N2A0.43765 (9)0.8170 (3)0.25429 (9)0.0451 (4)
H21A0.4366 (12)0.718 (3)0.2319 (12)0.063 (7)*
H22A0.4722 (12)0.886 (3)0.2682 (11)0.052 (7)*
C1A0.38967 (10)1.0001 (3)0.30509 (10)0.0422 (5)
C2A0.36041 (12)0.9960 (3)0.34601 (11)0.0553 (6)
H2A0.33900.89330.34990.066*
C3A0.36219 (15)1.1412 (4)0.38129 (13)0.0744 (8)
H3A0.34271.13900.41060.089*
C4A0.39150 (17)1.2876 (4)0.37464 (15)0.0809 (9)
H4A0.39211.38840.39900.097*
C5A0.41992 (15)1.2925 (3)0.33385 (15)0.0738 (8)
H5A0.44041.39630.32940.089*
C6A0.41927 (12)1.1490 (3)0.29923 (12)0.0549 (6)
H6A0.43961.15210.27060.066*
C7A0.38933 (10)0.8453 (3)0.26833 (9)0.0399 (5)
O1A0.33571 (7)0.4675 (2)0.17252 (9)0.0632 (5)
O2A0.44023 (7)0.50113 (17)0.19559 (7)0.0426 (3)
O3A0.28328 (8)0.1161 (2)0.05716 (8)0.0628 (5)
O4A0.36974 (7)0.14227 (17)0.00979 (6)0.0426 (3)
O5A0.46283 (7)0.08962 (18)0.03569 (7)0.0472 (4)
C8A0.38068 (9)0.2731 (2)0.12550 (9)0.0340 (4)
C9A0.33213 (10)0.1517 (3)0.11168 (9)0.0406 (5)
H9A0.30050.16460.12830.049*
C10A0.32888 (10)0.0109 (3)0.07384 (9)0.0393 (5)
C11A0.37375 (9)0.0070 (2)0.04923 (8)0.0334 (4)
C12A0.42161 (9)0.1175 (2)0.06245 (8)0.0328 (4)
C13A0.42517 (9)0.2573 (2)0.10056 (9)0.0336 (4)
H13A0.45860.34360.10970.040*
C14A0.38590 (10)0.4248 (2)0.16757 (9)0.0370 (4)
C15A0.23845 (13)0.1145 (3)0.08348 (14)0.0665 (7)
H15D0.2629 (4)0.112 (2)0.1309 (7)0.100*
H15E0.2103 (8)0.014 (2)0.0679 (8)0.100*
H15F0.2112 (8)0.217 (2)0.0698 (8)0.100*
C16A0.39094 (14)0.3015 (3)0.04267 (12)0.0585 (6)
H16D0.4367 (7)0.2958 (8)0.0724 (8)0.088*
H16E0.3667 (7)0.3257 (11)0.0658 (8)0.088*
H16F0.3835 (8)0.3891 (14)0.0117 (5)0.088*
C17A0.51430 (13)0.2093 (3)0.05021 (14)0.0630 (7)
H17D0.4951 (3)0.3224 (18)0.0332 (8)0.095*
H17E0.5420 (7)0.2162 (17)0.0979 (7)0.095*
H17F0.5417 (7)0.1726 (13)0.0297 (8)0.095*
O60.10494 (11)0.1977 (3)0.05230 (8)0.0660 (5)
H610.0785 (14)0.192 (3)0.0710 (13)0.071 (8)*
H620.1406 (15)0.245 (4)0.0776 (14)0.075 (9)*
O70.21854 (13)0.3380 (4)0.15097 (18)0.1440 (14)
H710.215 (3)0.431 (5)0.121 (2)0.173*
H720.2611 (11)0.366 (6)0.175 (2)0.173*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0531 (11)0.0444 (11)0.0323 (9)0.0210 (9)0.0215 (8)0.0057 (8)
N20.0612 (12)0.0521 (12)0.0314 (9)0.0277 (10)0.0215 (9)0.0053 (8)
C10.0444 (12)0.0421 (11)0.0306 (9)0.0133 (9)0.0204 (9)0.0061 (8)
C20.0593 (14)0.0452 (13)0.0413 (11)0.0124 (11)0.0211 (10)0.0038 (10)
C30.099 (2)0.0471 (15)0.0616 (15)0.0274 (14)0.0316 (16)0.0029 (12)
C40.101 (2)0.079 (2)0.0643 (17)0.0592 (18)0.0249 (16)0.0118 (15)
C50.0720 (19)0.097 (2)0.0548 (15)0.0470 (17)0.0046 (13)0.0032 (15)
C60.0573 (15)0.0653 (16)0.0453 (12)0.0238 (13)0.0118 (11)0.0057 (11)
C70.0385 (11)0.0402 (11)0.0316 (9)0.0085 (9)0.0192 (8)0.0039 (8)
O10.0521 (9)0.0394 (8)0.0327 (7)0.0119 (6)0.0237 (6)0.0042 (6)
O20.0549 (9)0.0545 (9)0.0311 (7)0.0263 (7)0.0221 (6)0.0116 (6)
O30.0424 (9)0.0550 (9)0.0400 (8)0.0074 (7)0.0018 (7)0.0106 (7)
O40.0302 (7)0.0350 (8)0.0703 (10)0.0062 (6)0.0210 (7)0.0092 (7)
O50.0525 (10)0.0544 (9)0.0492 (9)0.0149 (8)0.0184 (7)0.0131 (7)
C80.0283 (10)0.0350 (10)0.0306 (9)0.0028 (8)0.0153 (8)0.0044 (8)
C90.0340 (10)0.0355 (10)0.0296 (9)0.0004 (8)0.0139 (8)0.0016 (8)
C100.0265 (10)0.0391 (11)0.0337 (9)0.0013 (8)0.0095 (8)0.0091 (8)
C110.0254 (10)0.0315 (10)0.0484 (11)0.0034 (8)0.0186 (8)0.0070 (8)
C120.0318 (10)0.0375 (11)0.0412 (10)0.0001 (8)0.0196 (8)0.0044 (8)
C130.0286 (10)0.0418 (11)0.0292 (9)0.0051 (8)0.0121 (7)0.0012 (8)
C140.0307 (10)0.0365 (10)0.0291 (9)0.0033 (8)0.0153 (8)0.0029 (8)
C150.0680 (18)0.0676 (17)0.0381 (12)0.0028 (14)0.0071 (11)0.0037 (12)
C160.0549 (16)0.0390 (13)0.109 (2)0.0013 (11)0.0317 (15)0.0143 (14)
C170.0603 (16)0.0817 (18)0.0459 (13)0.0152 (14)0.0154 (12)0.0217 (13)
N1A0.0357 (11)0.0553 (13)0.0862 (15)0.0098 (9)0.0321 (11)0.0359 (11)
N2A0.0330 (10)0.0452 (11)0.0561 (11)0.0044 (9)0.0197 (9)0.0171 (9)
C1A0.0300 (11)0.0434 (12)0.0444 (11)0.0054 (9)0.0097 (9)0.0094 (9)
C2A0.0530 (14)0.0556 (14)0.0585 (13)0.0083 (11)0.0267 (12)0.0069 (11)
C3A0.089 (2)0.076 (2)0.0650 (16)0.0188 (17)0.0413 (16)0.0136 (14)
C4A0.096 (2)0.0576 (18)0.0795 (19)0.0058 (16)0.0326 (18)0.0296 (15)
C5A0.080 (2)0.0471 (15)0.088 (2)0.0049 (14)0.0333 (17)0.0204 (14)
C6A0.0497 (14)0.0468 (14)0.0615 (14)0.0007 (11)0.0199 (11)0.0105 (11)
C7A0.0276 (10)0.0413 (11)0.0448 (11)0.0032 (9)0.0114 (8)0.0087 (9)
O1A0.0383 (9)0.0651 (10)0.0955 (12)0.0120 (8)0.0390 (9)0.0418 (9)
O2A0.0321 (7)0.0399 (8)0.0568 (8)0.0045 (6)0.0213 (6)0.0165 (7)
O3A0.0533 (10)0.0643 (11)0.0851 (12)0.0303 (8)0.0442 (9)0.0357 (9)
O4A0.0516 (9)0.0368 (8)0.0379 (7)0.0028 (6)0.0193 (7)0.0095 (6)
O5A0.0547 (9)0.0457 (8)0.0582 (9)0.0114 (7)0.0404 (8)0.0159 (7)
C8A0.0303 (10)0.0338 (10)0.0355 (9)0.0014 (8)0.0132 (8)0.0042 (8)
C9A0.0323 (11)0.0467 (12)0.0466 (11)0.0045 (9)0.0214 (9)0.0115 (9)
C10A0.0328 (11)0.0400 (11)0.0425 (10)0.0092 (9)0.0152 (9)0.0087 (9)
C11A0.0356 (10)0.0328 (10)0.0272 (8)0.0007 (8)0.0105 (8)0.0041 (8)
C12A0.0331 (10)0.0353 (10)0.0308 (9)0.0026 (8)0.0154 (8)0.0008 (8)
C13A0.0313 (10)0.0319 (10)0.0384 (10)0.0016 (8)0.0167 (8)0.0026 (8)
C14A0.0317 (11)0.0365 (11)0.0437 (11)0.0005 (9)0.0181 (9)0.0067 (9)
C15A0.0559 (16)0.0694 (17)0.0890 (19)0.0224 (13)0.0461 (15)0.0157 (14)
C16A0.0708 (17)0.0381 (13)0.0709 (16)0.0010 (12)0.0364 (14)0.0024 (11)
C17A0.0683 (17)0.0596 (15)0.0904 (18)0.0191 (13)0.0615 (15)0.0233 (13)
O60.0624 (12)0.0984 (15)0.0465 (9)0.0279 (11)0.0332 (9)0.0265 (9)
O70.0675 (16)0.181 (3)0.205 (3)0.0598 (19)0.082 (2)0.131 (3)
Geometric parameters (Å, º) top
N1—C71.307 (2)N1A—H12A0.90 (3)
N1—H110.89 (2)N2A—C7A1.308 (3)
N1—H120.92 (2)N2A—H21A0.93 (3)
N2—C71.311 (2)N2A—H22A0.89 (2)
N2—H210.93 (2)C1A—C6A1.390 (3)
N2—H220.91 (2)C1A—C2A1.391 (3)
C1—C61.385 (3)C1A—C7A1.484 (3)
C1—C21.388 (3)C2A—C3A1.394 (3)
C1—C71.480 (3)C2A—H2A0.9700
C2—C31.387 (3)C3A—C4A1.377 (4)
C2—H20.9700C3A—H3A0.9700
C3—C41.376 (4)C4A—C5A1.373 (4)
C3—H30.9700C4A—H4A0.9700
C4—C51.367 (4)C5A—C6A1.381 (3)
C4—H40.9700C5A—H5A0.9700
C5—C61.376 (3)C6A—H6A0.9700
C5—H50.9700O1A—C14A1.252 (2)
C6—H60.9700O2A—C14A1.258 (2)
O1—C141.257 (2)O3A—C10A1.364 (2)
O2—C141.252 (2)O3A—C15A1.415 (3)
O3—C101.363 (2)O4A—C11A1.378 (2)
O3—C151.422 (3)O4A—C16A1.429 (3)
O4—C111.379 (2)O5A—C12A1.365 (2)
O4—C161.430 (3)O5A—C17A1.421 (3)
O5—C121.363 (2)C8A—C9A1.386 (3)
O5—C171.424 (3)C8A—C13A1.389 (3)
C8—C91.387 (2)C8A—C14A1.510 (3)
C8—C131.388 (2)C9A—C10A1.393 (3)
C8—C141.509 (3)C9A—H9A0.9700
C9—C101.394 (3)C10A—C11A1.393 (3)
C9—H90.9700C11A—C12A1.393 (3)
C10—C111.394 (3)C12A—C13A1.389 (3)
C11—C121.397 (3)C13A—H13A0.9700
C12—C131.389 (3)C15A—H15D0.9757
C13—H130.9700C15A—H15E0.9757
C15—H15A0.9892C15A—H15F0.9757
C15—H15B0.9892C16A—H16D0.9514
C15—H15C0.9892C16A—H16E0.9514
C16—H16A0.9595C16A—H16F0.9514
C16—H16B0.9595C17A—H17D0.9900
C16—H16C0.9595C17A—H17E0.9900
C17—H17A0.9806C17A—H17F0.9900
C17—H17B0.9806O6—H610.89 (3)
C17—H17C0.9806O6—H620.84 (3)
N1A—C7A1.308 (3)O7—H710.993 (19)
N1A—H11A0.88 (3)O7—H720.897 (19)
C7—N1—H11118.8 (14)C7A—N1A—H12A119.8 (17)
C7—N1—H12119.6 (14)H11A—N1A—H12A119 (2)
H11—N1—H12121 (2)C7A—N2A—H21A118.4 (15)
C7—N2—H21120.3 (13)C7A—N2A—H22A121.2 (15)
C7—N2—H22121.0 (14)H21A—N2A—H22A120 (2)
H21—N2—H22117 (2)C6A—C1A—C2A119.7 (2)
C6—C1—C2119.32 (19)C6A—C1A—C7A120.55 (19)
C6—C1—C7119.92 (19)C2A—C1A—C7A119.7 (2)
C2—C1—C7120.75 (18)C1A—C2A—C3A119.2 (2)
C3—C2—C1120.2 (2)C1A—C2A—H2A120.4
C3—C2—H2119.9C3A—C2A—H2A120.4
C1—C2—H2119.9C4A—C3A—C2A120.2 (3)
C4—C3—C2119.7 (2)C4A—C3A—H3A119.9
C4—C3—H3120.2C2A—C3A—H3A119.9
C2—C3—H3120.2C5A—C4A—C3A120.7 (2)
C5—C4—C3120.2 (2)C5A—C4A—H4A119.6
C5—C4—H4119.9C3A—C4A—H4A119.6
C3—C4—H4119.9C4A—C5A—C6A119.7 (3)
C4—C5—C6120.7 (2)C4A—C5A—H5A120.1
C4—C5—H5119.6C6A—C5A—H5A120.1
C6—C5—H5119.6C5A—C6A—C1A120.4 (2)
C5—C6—C1119.9 (2)C5A—C6A—H6A119.8
C5—C6—H6120.0C1A—C6A—H6A119.8
C1—C6—H6120.0N2A—C7A—N1A120.2 (2)
N1—C7—N2120.67 (18)N2A—C7A—C1A120.14 (19)
N1—C7—C1119.95 (17)N1A—C7A—C1A119.68 (19)
N2—C7—C1119.37 (17)C10A—O3A—C15A118.88 (17)
C10—O3—C15116.76 (17)C11A—O4A—C16A114.88 (15)
C11—O4—C16115.37 (16)C12A—O5A—C17A117.20 (15)
C12—O5—C17117.18 (17)C9A—C8A—C13A120.36 (17)
C9—C8—C13120.58 (17)C9A—C8A—C14A120.63 (17)
C9—C8—C14119.94 (16)C13A—C8A—C14A119.01 (17)
C13—C8—C14119.43 (15)C8A—C9A—C10A119.82 (18)
C8—C9—C10119.48 (17)C8A—C9A—H9A120.1
C8—C9—H9120.3C10A—C9A—H9A120.1
C10—C9—H9120.3O3A—C10A—C11A114.95 (17)
O3—C10—C11115.14 (17)O3A—C10A—C9A124.85 (18)
O3—C10—C9124.55 (17)C11A—C10A—C9A120.20 (17)
C11—C10—C9120.30 (16)O4A—C11A—C10A120.91 (17)
O4—C11—C10119.42 (17)O4A—C11A—C12A119.54 (16)
O4—C11—C12120.75 (17)C10A—C11A—C12A119.49 (16)
C10—C11—C12119.72 (17)O5A—C12A—C13A124.50 (17)
O5—C12—C13124.94 (17)O5A—C12A—C11A115.16 (16)
O5—C12—C11115.23 (17)C13A—C12A—C11A120.34 (16)
C13—C12—C11119.81 (17)C8A—C13A—C12A119.78 (17)
C8—C13—C12120.11 (16)C8A—C13A—H13A120.1
C8—C13—H13119.9C12A—C13A—H13A120.1
C12—C13—H13119.9O1A—C14A—O2A123.66 (18)
O2—C14—O1124.46 (17)O1A—C14A—C8A117.98 (17)
O2—C14—C8117.38 (15)O2A—C14A—C8A118.36 (16)
O1—C14—C8118.16 (15)O3A—C15A—H15D109.5
O3—C15—H15A109.5O3A—C15A—H15E109.5
O3—C15—H15B109.5H15D—C15A—H15E109.5
H15A—C15—H15B109.5O3A—C15A—H15F109.5
O3—C15—H15C109.5H15D—C15A—H15F109.5
H15A—C15—H15C109.5H15E—C15A—H15F109.5
H15B—C15—H15C109.5O4A—C16A—H16D109.5
O4—C16—H16A109.5O4A—C16A—H16E109.5
O4—C16—H16B109.5H16D—C16A—H16E109.5
H16A—C16—H16B109.5O4A—C16A—H16F109.5
O4—C16—H16C109.5H16D—C16A—H16F109.5
H16A—C16—H16C109.5H16E—C16A—H16F109.5
H16B—C16—H16C109.5O5A—C17A—H17D109.5
O5—C17—H17A109.5O5A—C17A—H17E109.5
O5—C17—H17B109.5H17D—C17A—H17E109.5
H17A—C17—H17B109.5O5A—C17A—H17F109.5
O5—C17—H17C109.5H17D—C17A—H17F109.5
H17A—C17—H17C109.5H17E—C17A—H17F109.5
H17B—C17—H17C109.5H61—O6—H62110 (2)
C7A—N1A—H11A119.8 (16)H71—O7—H7288 (4)
C6—C1—C2—C30.5 (3)C6A—C1A—C2A—C3A0.9 (3)
C7—C1—C2—C3179.3 (2)C7A—C1A—C2A—C3A178.7 (2)
C1—C2—C3—C40.4 (4)C1A—C2A—C3A—C4A1.2 (4)
C2—C3—C4—C51.2 (5)C2A—C3A—C4A—C5A0.7 (5)
C3—C4—C5—C61.1 (5)C3A—C4A—C5A—C6A0.2 (5)
C4—C5—C6—C10.3 (5)C4A—C5A—C6A—C1A0.4 (4)
C2—C1—C6—C50.5 (4)C2A—C1A—C6A—C5A0.1 (3)
C7—C1—C6—C5179.2 (2)C7A—C1A—C6A—C5A179.5 (2)
C6—C1—C7—N1143.6 (2)C6A—C1A—C7A—N2A30.5 (3)
C2—C1—C7—N136.1 (3)C2A—C1A—C7A—N2A149.2 (2)
C6—C1—C7—N235.5 (3)C6A—C1A—C7A—N1A149.9 (2)
C2—C1—C7—N2144.8 (2)C2A—C1A—C7A—N1A30.4 (3)
C13—C8—C9—C100.2 (3)C13A—C8A—C9A—C10A1.5 (3)
C14—C8—C9—C10177.14 (16)C14A—C8A—C9A—C10A178.74 (18)
C15—O3—C10—C11179.54 (19)C15A—O3A—C10A—C11A175.9 (2)
C15—O3—C10—C91.5 (3)C15A—O3A—C10A—C9A5.0 (3)
C8—C9—C10—O3178.21 (17)C8A—C9A—C10A—O3A179.9 (2)
C8—C9—C10—C110.7 (3)C8A—C9A—C10A—C11A0.8 (3)
C16—O4—C11—C10107.4 (2)C16A—O4A—C11A—C10A74.1 (2)
C16—O4—C11—C1276.5 (2)C16A—O4A—C11A—C12A108.6 (2)
O3—C10—C11—O42.0 (2)O3A—C10A—C11A—O4A1.6 (3)
C9—C10—C11—O4177.03 (16)C9A—C10A—C11A—O4A177.65 (17)
O3—C10—C11—C12178.22 (17)O3A—C10A—C11A—C12A178.84 (17)
C9—C10—C11—C120.8 (3)C9A—C10A—C11A—C12A0.4 (3)
C17—O5—C12—C136.6 (3)C17A—O5A—C12A—C13A2.5 (3)
C17—O5—C12—C11171.7 (2)C17A—O5A—C12A—C11A177.28 (19)
O4—C11—C12—O51.8 (3)O4A—C11A—C12A—O5A2.0 (2)
C10—C11—C12—O5177.95 (17)C10A—C11A—C12A—O5A179.35 (17)
O4—C11—C12—C13176.54 (16)O4A—C11A—C12A—C13A178.14 (16)
C10—C11—C12—C130.4 (3)C10A—C11A—C12A—C13A0.8 (3)
C9—C8—C13—C120.2 (3)C9A—C8A—C13A—C12A1.1 (3)
C14—C8—C13—C12177.59 (16)C14A—C8A—C13A—C12A179.18 (17)
O5—C12—C13—C8178.29 (18)O5A—C12A—C13A—C8A179.93 (17)
C11—C12—C13—C80.1 (3)C11A—C12A—C13A—C8A0.1 (3)
C9—C8—C14—O2151.48 (18)C9A—C8A—C14A—O1A22.1 (3)
C13—C8—C14—O225.9 (3)C13A—C8A—C14A—O1A157.68 (19)
C9—C8—C14—O127.7 (3)C9A—C8A—C14A—O2A157.97 (19)
C13—C8—C14—O1154.95 (18)C13A—C8A—C14A—O2A22.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11···O10.89 (2)1.96 (2)2.850 (2)174 (2)
N1—H12···O1i0.92 (2)1.93 (2)2.838 (2)172 (2)
N2—H21···O20.93 (2)1.85 (2)2.777 (2)178 (2)
N2—H22···O6ii0.91 (2)1.89 (2)2.792 (2)172 (2)
N1A—H11A···O1A0.88 (3)1.88 (3)2.751 (3)176 (2)
N1A—H12A···O40.90 (3)2.02 (3)2.892 (2)162 (2)
N2A—H21A···O2A0.93 (3)1.92 (3)2.845 (2)173 (2)
N2A—H22A···O2Aiii0.89 (2)1.99 (3)2.873 (2)169 (2)
O6—H61···O20.89 (3)1.94 (3)2.831 (2)179 (3)
O6—H62···O70.84 (3)1.95 (3)2.776 (3)167 (3)
O7—H72···O1A0.90 (2)1.91 (3)2.690 (3)145 (4)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z; (iii) x1, y1/2, z1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC7H9N2+·C8H7O3C7H9N2+·C8H7O3C7H9N2+·C10H11O5·H2O
Mr272.30272.30350.37
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/nMonoclinic, P21/c
Temperature (K)298298298
a, b, c (Å)9.4532 (9), 6.1789 (8), 24.906 (3)9.4676 (7), 6.8888 (6), 21.7018 (12)22.8771 (15), 7.8631 (3), 23.1789 (13)
β (°) 96.513 (11) 92.4498 (7) 117.515 (8)
V3)1445.4 (3)1414.11 (18)3697.9 (3)
Z448
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.090.090.10
Crystal size (mm)0.40 × 0.35 × 0.180.20 × 0.15 × 0.120.28 × 0.25 × 0.15
Data collection
DiffractometerAgilent Xcalibur Sapphire3
diffractometer
Agilent Xcalibur Sapphire3
diffractometer
Agilent Xcalibur Sapphire3
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2011)
Multi-scan
(CrysAlis PRO; Agilent, 2011)
Multi-scan
(CrysAlis PRO; Agilent, 2011)
Tmin, Tmax0.788, 0.9840.982, 0.9890.974, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
8118, 2598, 1762 16608, 4450, 2282 39513, 7977, 5752
Rint0.0290.0470.030
(sin θ/λ)max1)0.6000.7250.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.127, 1.05 0.054, 0.117, 0.93 0.057, 0.134, 1.04
No. of reflections259844507977
No. of parameters199199509
No. of restraints002
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.13, 0.140.14, 0.190.37, 0.37

Computer programs: CrysAlis PRO (Agilent, 2011), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.99 (3)1.76 (3)2.756 (3)180 (2)
N1—H1B···O1i0.85 (2)2.01 (2)2.827 (2)161 (2)
N2—H2A···O20.94 (2)1.90 (3)2.840 (3)177 (2)
N2—H2B···O2ii0.89 (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.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O11.001 (18)1.813 (18)2.8110 (17)175.0 (15)
N1—H1B···O1i0.916 (17)1.932 (17)2.8344 (16)168.0 (13)
N2—H2A···O20.998 (17)1.825 (18)2.8224 (17)176.7 (15)
N2—H2B···O2ii0.932 (16)1.918 (17)2.8323 (15)166.5 (14)
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H11···O10.89 (2)1.96 (2)2.850 (2)174 (2)
N1—H12···O1i0.92 (2)1.93 (2)2.838 (2)172 (2)
N2—H21···O20.93 (2)1.85 (2)2.777 (2)178 (2)
N2—H22···O6ii0.91 (2)1.89 (2)2.792 (2)172 (2)
N1A—H11A···O1A0.88 (3)1.88 (3)2.751 (3)176 (2)
N1A—H12A···O40.90 (3)2.02 (3)2.892 (2)162 (2)
N2A—H21A···O2A0.93 (3)1.92 (3)2.845 (2)173 (2)
N2A—H22A···O2Aiii0.89 (2)1.99 (3)2.873 (2)169 (2)
O6—H61···O20.89 (3)1.94 (3)2.831 (2)179 (3)
O6—H62···O70.84 (3)1.95 (3)2.776 (3)167 (3)
O7—H72···O1A0.897 (19)1.91 (3)2.690 (3)145 (4)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z; (iii) x1, y1/2, z1/2.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds