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In bis­(2-amino­anilinum) fumarate, 2C6H9N2+·C4H2O42-, (I), the asymmetric unit consists of two amino­anilinium cations and one fumarate dianion, whereas in 3-methyl­anilinium hydrogen fumarate, C7H10N+·C4H3O4-, (II), and 4-chloro­anilinium hydrogen fumarate, C6H7ClN+·C4H3O4-, (III), the asymmetric unit contains two symmetry-independent hydrogen fumate anions and anilinium cations with a slight difference in their geometric parameters; the two salts are isostructural. In (II) and (III), the carb­oxy­lic acid H atoms of the anions are disordered across both ends of the anion, with equal site occupancies of 0.50. Both the 4-chloro­anilinium cations of (III) are disordered over two orientations with major occupancies fixed at 0.60 in each case. The hydrogen fumarate anions of (II) and (III) form one-dimensional anionic chains linked through O-H...O hydrogen bonds. Salts (II) and (III) form two-dimensional supra­molecular sheets built from R44(16), R44(18), R55(25) and C22(14) motifs extending parallel to the (010) plane, whereas in (I), an (010) sheet is formed built from two R43(13) motifs, two R22(9) motifs and an R44(18) motif.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017629/uk3068sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017629/uk3068Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017629/uk3068IIsup3.hkl
Contains datablock II

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017629/uk3068IIIsup4.hkl
Contains datablock III

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017629/uk3068Isup5.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017629/uk3068IIsup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017629/uk3068IIIsup7.cml
Supplementary material

CCDC references: 964798; 964799; 964800

Introduction top

Hydrogen bonding is considered to be one of the best noncovalent inter­actions in supra­molecular networks because of its relative strength and highly directional nature (Desiraju, 2002; Aakeroy et al., 2005). Various hydrogen-bonded motifs and frameworks revealed in the field of crystal engineering have become tools to explain various physicochemical properties, such as nonlinear optical, magnetic, catalytic and storage properties (Gomes et al., 2006; Fábry et al., 2000; Ivasenko & Perepichka, 2011). Di­carb­oxy­lic acids possessing very good donors and acceptors are of special inter­est in forming strong inter­molecular hydrogen bonds between cations, anions or molecular constituents when they form salts or cocrystals with amines, amides and other metal complexes (Jagan & Sivakumar, 2011; Lyakhov et al., 2012; Jin et al., 2011; Farrell et al., 2002). Maleic and fumaric acids are the Z and E isomers, respectively, of butenedioic acid, and they form inter­esting one-, two- and three-dimensional supra­molecular architectures as adducts with various amines (Franklin & Balasubramanian, 2009; Bowes et al., 2003; Jin et al., 2003; Batchelor et al., 2000). Cis- and trans-di­carb­oxy­lic acids such as maleic and fumaric acids have the inter­esting property of forming isomers on changes in their physical environment such as heat or light etc., thereby enhancing their bonding capability (Kalita & Baruah, 2010). Consequently, numerous recent articles have been focused on the construction of fumarate salts with different bases, showing innovative supra­molecular assemblies (Haynes & Pietersen, 2008; Hemamalini & Fun, 2010). We report herein the crystal structures of the salts bis­(2-amino­anilinum) fumarate, (I), 3-methyl­anilinium hydrogen fumarate, (II), and 4-chloro­anilinium hydrogen fumarate, (III), in order to study their hydrogen-bonding patterns and the consequential network present in the solid state. Even though we have chosen maleic acid for (I) in the preparation of the salt, unexpectedly the isomerization of maleic to fumaric acid has taken place in the formation of the title salt. A similar kind of geometric isomerization has been observed in the previously reported structures of 4,4'-bi­pyridyl­amine and 4,4'-tri­methyl­enedi­pyridine fumaric acids (Chatterjee et al., 1998; Bowes et al., 2003).

Experimental top

Synthesis and crystallization top

A solution containing equimolar qu­anti­ties of maleic acid and 2-amino­aniline in methanol was warmed for 10 min and set aside to crystallize. Brown crystals suitable for diffraction analysis were obtained by slow evaporation after a few days. Unexpectedly, the isomerization of maleic to fumaric acid had taken place during the salt formation. The resulting salt, (I), contained a 1:2 molar ratio of the fumarate dianion and the 2-amino­anilinium cation, although the chosen crystal was in a 1:1 molar ratio. Similarly, salts (II) and (III) were prepared from equimolar ratios of fumaric acid with 3-methyl­aniline and 4-chloro­aniline, respectively, dissolved in ethanol. Both ethanol solutions were mixed together and stirred for 20 min and the resulting mixture was kept for crystallization. Good diffraction-quality colourless crystals were obtained by slow evaporation after a few days.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. In salts (II) and (III), the carb­oxy­lic acid H atoms of the anions were disordered over two positions showing equal site occupancies of 0.50. The appearance of strong difference electron-density peaks, and their distances from the nearest atoms O1A, O1B, O4A and O4B, revealed the presence of H atoms. The carboxyl C—O bond lengths and the improvement in the refinement confirmed the occupancy of the H atoms. Both the 4-chloro­anilinium cations of (III) experience positional disorder, and the occupancies were refined and fixed at 0.60 and 0.40 for cations A and B, respectively. A considerable number of restraints were used in the refinement for the accurate disordered positions of the cations. The disordered C—C bond lengths of the benzene rings were restrained to a distance of 1.39 (1) Å and the C—Cl bond lengths were restrained to 1.72 (1) Å. The atomic displacement parameters of the disordered components were made similar to those of neighbouring atoms using standard similarity restraints, with an s.u. of 0.02 Å2 for ring atoms or 0.04 Å2 for terminal atoms, followed by rigid-bond restraints, with an s.u. of 0.01 Å. Salt (I) shows a meaningless Flack parameter (Flack, 1983) value of 0.1 (18). This is due to the molecular structure of (I) having light atoms (< Si) with no significant anomalous scattering effects. In this case, the Flack parameter is indeterminate with Mo radiation and hence the absolute structure cannot be determined. The positions of all the H atoms were initially identified from the difference electron-density map. C-bound H atoms were allowed to ride on their parent atom, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3, and C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms. O-bound H atoms were positioned from the difference electron-density map and restrained to O—H = 0.85 (1) Å for salts (II) and (III), with Uiso(H) = 1.2Ueq(O). The H atoms associated with both the NH2 and NH3+ groups were restrained to N—H = 0.90 (1)Å for (I), (II) and (III), with Uiso(H) = 1.2Ueq(N).

Results and discussion top

The asymmetric unit of (I) (Fig. 1) contains two 2-amino­anilinium cations and one fumarate dianion, whereas salts (II) and (III) (Figs. 2 and 3) consist of two sets of symmetry-independent cations and anions having a slight difference in their geometric parameters. The C—O bond lengths of (I) [C1—O1 = 1.242 (3) Å, C1—O2 = 1.259 (3) Å, C4—O3 = 1.256 (3) Å and C4—O4 = 1.265 (3) Å] suggest the two carboxyl­ate groups are deprotonated in the crystal structure. In salts (II) and (III), the carb­oxy­lic acid H atoms of the hydrogen fumarate anions are disordered over two positions, with site occupancies of 0.50. Also in (III), both of the 4-chloro­anilinium cations are positionally disordered, with major and minor occupancies of 0.60 and 0.40 for cations A and B, respectively. In salt (I), the fumarate anion is almost planar compared with the hydrogen fumarate anions of (II) and (III), as shown by the dihedral angles between the carb­oxy­lic acid–carboxyl­ate groups of 1.57 (6)° for (I), 40.03 (7) and 25.93 (2)° for (II), and 25.80 (3) and 42.43 (1)° for (III). Inter­estingly, the adjacent hydrogen fumarate anions of (II) and (III) form very strong hydrogen bonds, with donor–acceptor distances of O1A···O4B = 2.4678 (11) Å and O1B···O4A = 2.4703 (11) Å for (II), and O2A···O4B = 2.4590 (15) Å and O2B···O4A = 2.4592 (15) Å for (III).

In (I), all the O atoms in the fumarate dianion form bifurcated hydrogen bonds with the anilinium cations. In the asymmetric unit, both carboxyl­ate O atoms of the anion inter­act with adjacent 2-amino­anilinium cations through four N—H···O hydrogen bonds (N1—H1B···O1, N2—H2C···O2, N3—H3B···O3 and N4—H4B···O4; Table 2) forming two R22(9) motifs (Bernstein et al., 1995). These asymmetric unit pairs are further linked through four N—H···O hydrogen bonds (N1—H1A···O1iv, N3—H3A···O3iii, N2iii—H2A···O2 and N4iv—H4C···O4; see Table 2 for symmetry codes), forming a molecular ladder in which the cations form the uprights and the anions form the rungs, built through R42(18) and two R22(9) motifs, as illustrated in Fig. 4. The molecular ladder runs along the line at (x, 1/4, 0). Protonated atoms N2 and N4 of the cations at (x, y, z) form hydrogen bonds with acceptors O2 at (-x + 1, y, z - 1/2), O3 at (x, y, z - 1), O1 at (x, y, z + 1) and O4 at (-x, y, z + 1/2), connecting adjacent molecular ladders and hence generating an infinite two-dimensional sheet parallel to the (010) plane. The (010) molecular sheet is constructed through two R34(13) motifs, two R22(9) motifs and an R24(18) motif.

In salts (II) and (III), O—H···O hydrogen bonds formed by the disordered minor components are not included in the discussion. Adjacent A and B hydrogen fumarate anions of (II) are inter­linked through two O—H···O hydrogen bonds (O4A—H4A···O1Biv and and O4B—H4B···O1A; see Table 3 for details), forming a C22(14) chain motif which extends further along the [101] direction, generating an infinite molecular chain (Fig. 5). A similar type of motif is also observed in (III), as these two salts are isostructural. The molecular planes of the hydrogen fumarate anions are approximately perpendicular to one another, with angles between the planes of 87.70° for (II) and 87.64° for (III). Parallel anionic chains are crosslinked [in (II) or (III)?] by anilinium cations through four N—H···O hydrogen bonds (N1A—H1AC···O4Biii, N1A—H1AA···O3A, N1B—H1BB···O2Ai and N1B—H1BC···O1Bii; see Table 3 for details), forming R44(16) and R66(32) motifs to construct a two-dimensional brick-wall structure propagating parallel to the (010) plane (Fig. 6). Inversion-related two-dimensional (010) brick-wall structures are fused together through two N—H···O hydrogen bonds (N1B—H1BA···O3B and N1A—H1AB···O2Bii; Table 3) to form a molecular sheet built from a combination of R44(16), R44(18), R55(25) and C22(14) motifs extending parallel to the ac plane. The A and B cations are pendant from both faces of the molecular network (Fig. 7a). Salt (III) (Table 4) also shows a similar two-dimensional supra­molecular sheet along the (010) plane, with cations pendant from both faces of the (010) sheet (Fig. 7b).

The cations of salts (I), (II) and (III) are closely similar, as all three are substituted anilines with a protonated NH3+ group. The substitution differs in each, being 2-amino in (I), 3-methyl in (II) and 4-chloro in (III). Inter­estingly, salts (II) and (III) show similar hydrogen-bonded supra­molecular architectures, as described above. It is observed that, for (I), the anion is doubly dissociated, although the difference in the supra­molecular networks can be explained by the presence of the amino group in the ortho position which forms additional hydrogen-bond donors with neighbouring acceptor O atoms. The methyl and chloro substitutents in (II) and (III) are nonfunctional groups and form hydrogen bonds with adjacent anions.

A search for fumarate salts in the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002) shows some specific features. The supra­molecular frameworks observed in bis­(2-phenyl­ethyl­ammonium) fumaratefumaric acid (CSD refcode COCPEQ; Haynes & Pietersen, 2008), bis­(anilinium) fumarate fumaric acid (COCPOA; Haynes & Pietersen, 2008) and benzyl­ammonium hydrogen fumarate (XINSAO; Ballabh et al., 2002), the cations of which are closely similar to the NH3+ substitution, form one-dimensional anionic supra­molecular chains similar to those observed in (II) and (III). The presence of the NH3+ group in (II) and (III) results in strong N—H···O hydrogen bonds inter­connecting the anionic chains through R44(16) and R55(25) motifs, constructing a two-dimensional sheet along with the C22(14) chain. In all these structures, cations pendant from both faces of the two-dimensional supra­molecular network are observed, as in (II) and (III). Also, bis­(2-cyano­ethyl­ammonium) fumarate (CSD refcode JIZJUX; Fawcett et al., 1991) and bis­(iso­propyl­ammonium) fumarate (NARDIT; Hosomi et al., 1998), though they exhibit NH3+ substitution, do not follow the supra­molecular pattern observed in the above structures. Obviously, JIZJUX and NARDIT have a fumarate dianion and the cations are different from the structures discussed above. A search for previously reported structures of dianionic fumarate salts shows that most of the fumarate dianions are constrained to a crystallographic centre of inversion. However, the anion of (I) is not constrained to a crystallographic inversion centre as the structure was resolved in a noncentrosymmetric space group. Only one structure, namely bis­[cis-(4S,5R)-4,5-di­ethyl-2-iminio-1,3-selenazolidine] fumarate (YAHQOO; Ueda et al., 2005), was found to crystallize in a noncentrosymmetric space group with a fumarate dianion. The CSD search does not show any close similarities in the supra­molecular structures to that of (I).

It is of inter­est to note that in, fumarate salts with a dianion, a heterocyclic amine with a substituted NH2 group in the ortho position is the most common category of cation. It is observed that the NH2 group and the ring NH+ form strong hydrogen bonds with both the –COO- groups of the anion, to construct a ring motif of the type R22(8), whereas in (I) the anions and cations form an R22(9) motif. From the above discussions it is to be concluded that, in salts, the formation of a hydrogen-bonded supra­molecular network relies strongly on the choice of cation in fumarate and hydrogen fumarate salts.

Related literature top

For related literature, see: Aakeroy et al. (2005); Allen (2002); Ballabh et al. (2002); Batchelor et al. (2000); Bernstein et al. (1995); Bowes et al. (2003); Chatterjee et al. (1998); Desiraju (2002); Fábry et al. (2000); Farrell et al. (2002); Fawcett et al. (1991); Flack (1983); Franklin & Balasubramanian (2009); Gomes et al. (2006); Haynes & Pietersen (2008); Hemamalini & Fun (2010); Hosomi et al. (1998); Ivasenko & Perepichka (2011); Jagan & Sivakumar (2011); Jin et al. (2003, 2011); Kalita & Baruah (2010); Lyakhov et al. (2012); Ueda et al. (2005).

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot of salt (I), drawn at the 40% probability level and showing the atom-labelling scheme. The dashed lines between the ions represent hydrogen bonds.
[Figure 2] Fig. 2. Displacement ellipsoid plot of salt (II), drawn at the 40% probability level and showing the atom-labelling scheme. The dashed lines between the ions represent hydrogen bonds.
[Figure 3] Fig. 3. Displacement ellipsoid plot of salt (III), drawn at the 40% probability level and showing the atom-labelling scheme. The dashed lines between the ions represent the hydrogen bonds. The minor components of the cations are represented as single dashed lines.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of the supramolecular ladder linked through N—H···O hydrogen bonds. [Symmetry codes: (iii) -x + 1, y, z + 1/2; (iv) -x, y, z - 1/2.]
[Figure 5] Fig. 5. Part of the crystal strucure of (II), showing the formation of the one-dimensional anionic chain linked through O4A—H4A···O1Biv and O4B—H4B···O1A hydrogen bonds. [Symmetry code: (iv) x - 1, y, z + 1.]
[Figure 6] Fig. 6. Part of the crystal structure of (II), showing the formation of the O—H···O and N—H···O hydrogen-bonded supramolecular R44(16) and R66(32) motifs constructing a two-dimensional brick-wall structure propagating parallel to the (010) plane. [Symmetry codes as in Fig. 4? Comparable plot for compound (III)?]
[Figure 7] Fig. 7. The inversion-related (010) brick-wall structures fused together to form a two-dimensional supramolecular sheet of anions and cations extending parallel to the (010) plane, with the cations pendant from both faces, observed in (a) salt (II) and (b) salt (III). The two different colours represent the two inversion-related sheets.
(I) Bis(2-aminoanilinium) fumarate top
Crystal data top
2C6H9N2+·C4H2O42Dx = 1.365 Mg m3
Mr = 332.36Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Iba2Cell parameters from 2905 reflections
a = 10.0424 (2) Åθ = 3.5–25.1°
b = 42.9871 (11) ŵ = 0.10 mm1
c = 7.4930 (2) ÅT = 296 K
V = 3234.68 (14) Å3Block, brown
Z = 80.35 × 0.30 × 0.20 mm
F(000) = 1408
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
3406 independent reflections
Radiation source: fine-focus sealed tube2751 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω and ϕ scanθmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1212
Tmin = 0.916, Tmax = 0.980k = 5154
9034 measured reflectionsl = 99
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0802P)2 + 0.6958P]
where P = (Fo2 + 2Fc2)/3
3406 reflections(Δ/σ)max < 0.001
247 parametersΔρmax = 0.47 e Å3
11 restraintsΔρmin = 0.23 e Å3
Crystal data top
2C6H9N2+·C4H2O42V = 3234.68 (14) Å3
Mr = 332.36Z = 8
Orthorhombic, Iba2Mo Kα radiation
a = 10.0424 (2) ŵ = 0.10 mm1
b = 42.9871 (11) ÅT = 296 K
c = 7.4930 (2) Å0.35 × 0.30 × 0.20 mm
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
3406 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
2751 reflections with I > 2σ(I)
Tmin = 0.916, Tmax = 0.980Rint = 0.035
9034 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04911 restraints
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.47 e Å3
3406 reflectionsΔρmin = 0.23 e Å3
247 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.18034 (16)0.14454 (4)0.1617 (3)0.0395 (5)
O20.37362 (16)0.16817 (4)0.1217 (3)0.0380 (4)
O30.32426 (16)0.10635 (4)0.4447 (3)0.0385 (5)
O40.13050 (16)0.08258 (4)0.3996 (3)0.0364 (4)
C10.2828 (2)0.14979 (6)0.0738 (4)0.0317 (6)
C20.3010 (2)0.13358 (6)0.1019 (4)0.0318 (6)
H20.38310.13510.15870.038*
C30.2061 (2)0.11726 (6)0.1795 (4)0.0318 (6)
H30.12400.11590.12260.038*
C40.2225 (2)0.10090 (6)0.3523 (4)0.0295 (6)
N10.0970 (2)0.16414 (6)0.5187 (5)0.0419 (7)
N20.3732 (2)0.16971 (6)0.4896 (4)0.0324 (6)
H2A0.4607 (12)0.1698 (5)0.515 (5)0.039*
H2B0.348 (2)0.1498 (3)0.517 (4)0.039*
H2C0.367 (3)0.1741 (7)0.3726 (16)0.039*
N30.4001 (2)0.08449 (6)0.8046 (4)0.0423 (7)
N40.1225 (2)0.08156 (6)0.7672 (3)0.0310 (6)
H4A0.154 (2)0.1008 (3)0.791 (4)0.037*
H4B0.138 (3)0.0804 (7)0.6490 (16)0.037*
H4C0.0354 (12)0.0802 (5)0.793 (4)0.037*
C50.1595 (2)0.18828 (6)0.6058 (4)0.0342 (6)
C60.2966 (2)0.19186 (6)0.5963 (4)0.0316 (6)
C70.3632 (3)0.21460 (6)0.6930 (5)0.0402 (7)
H70.45530.21640.68520.048*
C80.2920 (3)0.23443 (7)0.8004 (6)0.0519 (9)
H80.33520.25000.86440.062*
C90.1553 (3)0.23101 (7)0.8123 (6)0.0547 (9)
H90.10690.24420.88600.066*
C100.0903 (3)0.20854 (6)0.7176 (5)0.0437 (8)
H100.00160.20670.72780.052*
C110.3317 (2)0.06137 (6)0.8908 (4)0.0323 (6)
C120.1931 (2)0.05889 (6)0.8757 (4)0.0300 (6)
C130.1221 (3)0.03638 (6)0.9653 (5)0.0399 (7)
H130.03070.03460.94760.048*
C140.1864 (4)0.01653 (6)1.0811 (7)0.0540 (9)
H140.13870.00171.14490.065*
C150.3215 (4)0.01895 (6)1.1010 (6)0.0539 (9)
H150.36510.00571.17980.065*
C160.3939 (3)0.04054 (7)1.0073 (5)0.0481 (9)
H160.48590.04131.02150.058*
H3A0.4876 (13)0.0838 (6)0.829 (6)0.058*
H1A0.0092 (12)0.1607 (6)0.536 (5)0.058*
H3B0.373 (3)0.0918 (7)0.698 (2)0.058*
H1B0.126 (3)0.1614 (8)0.406 (2)0.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0316 (8)0.0557 (12)0.0313 (11)0.0067 (8)0.0029 (9)0.0087 (10)
O20.0347 (8)0.0477 (10)0.0316 (11)0.0097 (7)0.0001 (8)0.0089 (9)
O30.0304 (8)0.0527 (11)0.0326 (11)0.0048 (7)0.0060 (9)0.0089 (9)
O40.0333 (8)0.0473 (10)0.0285 (11)0.0104 (7)0.0021 (8)0.0080 (8)
C10.0295 (11)0.0366 (14)0.0288 (17)0.0014 (10)0.0029 (14)0.0056 (12)
C20.0292 (12)0.0412 (14)0.0249 (15)0.0006 (10)0.0015 (11)0.0025 (10)
C30.0286 (11)0.0426 (15)0.0243 (15)0.0024 (10)0.0007 (11)0.0008 (10)
C40.0326 (11)0.0352 (13)0.0208 (16)0.0003 (10)0.0019 (13)0.0004 (11)
N10.0315 (11)0.0542 (14)0.0401 (17)0.0003 (10)0.0007 (12)0.0095 (13)
N20.0281 (9)0.0421 (12)0.0271 (14)0.0016 (9)0.0018 (10)0.0043 (11)
N30.0285 (10)0.0559 (15)0.0426 (19)0.0001 (10)0.0012 (12)0.0098 (14)
N40.0279 (10)0.0400 (12)0.0250 (14)0.0011 (9)0.0017 (10)0.0031 (10)
C50.0363 (12)0.0373 (13)0.0290 (16)0.0044 (10)0.0011 (14)0.0028 (13)
C60.0364 (12)0.0344 (13)0.0239 (15)0.0029 (10)0.0046 (13)0.0001 (12)
C70.0411 (13)0.0408 (14)0.0388 (19)0.0068 (11)0.0012 (14)0.0026 (14)
C80.0676 (19)0.0416 (17)0.047 (2)0.0016 (14)0.0005 (19)0.0146 (17)
C90.0630 (19)0.0549 (18)0.046 (2)0.0154 (15)0.0066 (19)0.0115 (18)
C100.0425 (14)0.0486 (16)0.0401 (19)0.0067 (12)0.0088 (14)0.0013 (14)
C110.0358 (11)0.0354 (13)0.0258 (15)0.0076 (9)0.0020 (13)0.0034 (12)
C120.0369 (12)0.0313 (12)0.0219 (16)0.0014 (9)0.0029 (12)0.0005 (12)
C130.0436 (13)0.0373 (14)0.0387 (19)0.0021 (11)0.0014 (14)0.0053 (14)
C140.0682 (19)0.0407 (16)0.053 (2)0.0002 (14)0.003 (2)0.0174 (17)
C150.075 (2)0.0403 (15)0.047 (2)0.0123 (14)0.0159 (19)0.0150 (16)
C160.0452 (14)0.0503 (16)0.049 (2)0.0119 (13)0.0138 (14)0.0023 (16)
Geometric parameters (Å, º) top
O1—C11.242 (3)N4—H4C0.898 (10)
O2—C11.259 (3)C5—C61.387 (3)
O3—C41.256 (3)C5—C101.394 (4)
O4—C41.265 (3)C6—C71.388 (4)
C1—C21.501 (4)C7—C81.372 (5)
C2—C31.318 (3)C7—H70.9300
C2—H20.9300C8—C91.384 (5)
C3—C41.483 (4)C8—H80.9300
C3—H30.9300C9—C101.365 (5)
N1—C51.377 (4)C9—H90.9300
N1—H1A0.904 (10)C10—H100.9300
N1—H1B0.899 (10)C11—C161.398 (4)
N2—C61.462 (4)C11—C121.401 (4)
N2—H2A0.899 (10)C12—C131.377 (4)
N2—H2B0.915 (10)C13—C141.378 (5)
N2—H2C0.900 (10)C13—H130.9300
N3—C111.370 (4)C14—C151.368 (5)
N3—H3A0.899 (10)C14—H140.9300
N3—H3B0.898 (10)C15—C161.373 (5)
N4—C121.454 (4)C15—H150.9300
N4—H4A0.905 (10)C16—H160.9300
N4—H4B0.901 (10)
O1—C1—O2124.3 (3)C5—C6—C7122.0 (2)
O1—C1—C2118.8 (2)C5—C6—N2118.5 (2)
O2—C1—C2116.9 (3)C7—C6—N2119.4 (2)
C3—C2—C1123.1 (2)C8—C7—C6119.5 (3)
C3—C2—H2118.4C8—C7—H7120.2
C1—C2—H2118.4C6—C7—H7120.2
C2—C3—C4123.9 (2)C7—C8—C9119.2 (3)
C2—C3—H3118.1C7—C8—H8120.4
C4—C3—H3118.1C9—C8—H8120.4
O3—C4—O4123.8 (3)C10—C9—C8121.1 (3)
O3—C4—C3118.9 (2)C10—C9—H9119.5
O4—C4—C3117.3 (2)C8—C9—H9119.5
C5—N1—H1A120 (2)C9—C10—C5121.1 (3)
C5—N1—H1B113 (2)C9—C10—H10119.5
H1A—N1—H1B116 (3)C5—C10—H10119.5
C6—N2—H2A113.4 (19)N3—C11—C16122.4 (2)
C6—N2—H2B110.0 (19)N3—C11—C12121.0 (2)
H2A—N2—H2B103 (2)C16—C11—C12116.5 (2)
C6—N2—H2C111.0 (19)C13—C12—C11121.9 (2)
H2A—N2—H2C106 (3)C13—C12—N4119.4 (2)
H2B—N2—H2C114 (3)C11—C12—N4118.6 (2)
C11—N3—H3A112 (2)C12—C13—C14120.0 (3)
C11—N3—H3B122 (2)C12—C13—H13120.0
H3A—N3—H3B119 (3)C14—C13—H13120.0
C12—N4—H4A109.4 (19)C15—C14—C13119.1 (3)
C12—N4—H4B115.2 (19)C15—C14—H14120.5
H4A—N4—H4B101 (3)C13—C14—H14120.5
C12—N4—H4C108.1 (19)C14—C15—C16121.4 (3)
H4A—N4—H4C111 (2)C14—C15—H15119.3
H4B—N4—H4C112 (3)C16—C15—H15119.3
N1—C5—C6120.8 (2)C15—C16—C11121.0 (3)
N1—C5—C10121.9 (2)C15—C16—H16119.5
C6—C5—C10117.1 (3)C11—C16—H16119.5
O1—C1—C2—C39.5 (4)N1—C5—C10—C9175.5 (3)
O2—C1—C2—C3170.1 (2)C6—C5—C10—C90.4 (5)
C1—C2—C3—C4179.5 (3)N3—C11—C12—C13178.1 (3)
C2—C3—C4—O311.2 (4)C16—C11—C12—C132.4 (4)
C2—C3—C4—O4170.3 (2)N3—C11—C12—N40.4 (4)
N1—C5—C6—C7175.3 (3)C16—C11—C12—N4175.3 (3)
C10—C5—C6—C70.2 (4)C11—C12—C13—C143.5 (5)
N1—C5—C6—N20.9 (4)N4—C12—C13—C14174.1 (3)
C10—C5—C6—N2176.0 (3)C12—C13—C14—C152.0 (5)
C5—C6—C7—C80.6 (5)C13—C14—C15—C160.5 (5)
N2—C6—C7—C8176.7 (3)C14—C15—C16—C111.5 (6)
C6—C7—C8—C91.1 (5)N3—C11—C16—C15175.5 (4)
C7—C8—C9—C100.8 (5)C12—C11—C16—C150.1 (5)
C8—C9—C10—C50.0 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4C···O4i0.90 (1)1.85 (1)2.728 (3)165 (3)
N2—H2A···O2ii0.90 (1)1.85 (1)2.729 (3)166 (3)
N3—H3A···O3iii0.90 (1)2.29 (2)3.106 (3)150 (2)
N1—H1A···O1iv0.90 (1)2.23 (2)3.101 (3)161 (3)
N2—H2B···O3v0.92 (1)1.91 (1)2.811 (3)170 (2)
N4—H4A···O1vi0.91 (1)1.93 (1)2.820 (3)167 (2)
N3—H3B···O30.90 (1)2.06 (1)2.956 (4)175 (3)
N1—H1B···O10.90 (1)2.05 (1)2.926 (4)166 (3)
N4—H4B···O40.90 (1)1.87 (1)2.756 (3)166 (3)
N2—H2C···O20.90 (1)1.90 (2)2.758 (4)159 (3)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1, y, z1/2; (iii) x+1, y, z+1/2; (iv) x, y, z1/2; (v) x, y, z1; (vi) x, y, z+1.
(II) 3-Methylanilinium hydrogen fumarate top
Crystal data top
C7H10N+·C4H3O4F(000) = 944
Mr = 223.22Dx = 1.381 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.4576 (3) ÅCell parameters from 5904 reflections
b = 20.8915 (6) Åθ = 2.4–30.5°
c = 10.8787 (3) ŵ = 0.11 mm1
β = 92.611 (2)°T = 296 K
V = 2147.22 (11) Å3Block, colourless
Z = 80.35 × 0.30 × 0.25 mm
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
6714 independent reflections
Radiation source: fine-focus sealed tube5066 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ω and ϕ scanθmax = 30.8°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1313
Tmin = 0.904, Tmax = 0.974k = 3030
37301 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130 w = 1/[σ2(Fo2) + (0.0656P)2 + 0.4207P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
6714 reflectionsΔρmax = 0.38 e Å3
322 parametersΔρmin = 0.21 e Å3
10 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0060 (10)
Crystal data top
C7H10N+·C4H3O4V = 2147.22 (11) Å3
Mr = 223.22Z = 8
Monoclinic, P21/nMo Kα radiation
a = 9.4576 (3) ŵ = 0.11 mm1
b = 20.8915 (6) ÅT = 296 K
c = 10.8787 (3) Å0.35 × 0.30 × 0.25 mm
β = 92.611 (2)°
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
6714 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
5066 reflections with I > 2σ(I)
Tmin = 0.904, Tmax = 0.974Rint = 0.036
37301 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04410 restraints
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.38 e Å3
6714 reflectionsΔρmin = 0.21 e Å3
322 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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*/UeqOcc. (<1)
C1A0.43546 (11)0.56348 (5)0.44152 (10)0.0259 (2)
C2A0.31851 (12)0.55954 (5)0.52835 (10)0.0280 (2)
H2A0.34200.55580.61200.034*
C3A0.18389 (12)0.56107 (5)0.49284 (10)0.0281 (2)
H3A0.16030.56390.40910.034*
C4A0.06734 (11)0.55850 (5)0.58021 (10)0.0264 (2)
O1A0.40168 (9)0.54851 (5)0.32929 (8)0.0354 (2)
O2A0.55489 (9)0.57959 (4)0.47927 (8)0.0354 (2)
O3A0.05203 (9)0.57690 (5)0.54875 (8)0.0371 (2)
O4A0.10196 (9)0.53535 (5)0.68711 (8)0.0352 (2)
C1B0.88224 (12)0.46968 (6)0.13235 (10)0.0295 (2)
C2B0.77182 (12)0.46345 (6)0.03965 (11)0.0313 (2)
H2B0.73050.42350.02980.038*
C3B0.72912 (11)0.51058 (6)0.02893 (10)0.0294 (2)
H3B0.76780.55110.01880.035*
C4B0.62057 (11)0.50152 (6)0.12285 (10)0.0281 (2)
O1B0.90421 (9)0.52618 (4)0.17321 (8)0.0360 (2)
O2B0.94424 (11)0.42135 (5)0.16464 (10)0.0482 (3)
O4B0.59879 (9)0.55150 (5)0.18837 (8)0.0389 (2)
O3B0.55996 (10)0.45025 (5)0.13320 (9)0.0408 (2)
C5A0.19758 (12)0.67781 (6)0.29071 (11)0.0305 (2)
C6A0.29400 (13)0.70841 (6)0.36168 (11)0.0316 (2)
H6A0.34020.68570.42150.038*
C7A0.32236 (13)0.77315 (6)0.34397 (11)0.0337 (3)
C8A0.25155 (16)0.80515 (7)0.25361 (14)0.0441 (3)
H8A0.26780.84860.24120.053*
C9A0.15808 (19)0.77375 (8)0.18226 (15)0.0547 (4)
H9A0.11320.79600.12110.066*
C10A0.12960 (16)0.70941 (7)0.19992 (14)0.0470 (3)
H10A0.06610.68810.15150.056*
C11A0.42577 (16)0.80720 (8)0.42128 (15)0.0510 (4)
H11A0.38410.81380.50240.077*
H11B0.50990.78180.42630.077*
H11C0.44960.84780.38460.077*
C5B0.30755 (12)0.34139 (6)0.23939 (11)0.0308 (2)
C6B0.22138 (13)0.30665 (6)0.31376 (11)0.0322 (2)
H6B0.18220.32620.38110.039*
C7B0.19288 (14)0.24264 (6)0.28849 (13)0.0378 (3)
C8B0.25360 (17)0.21530 (7)0.18802 (16)0.0518 (4)
H8B0.23780.17220.17070.062*
C9B0.3370 (2)0.25066 (9)0.11311 (17)0.0606 (5)
H9B0.37490.23140.04490.073*
C10B0.36536 (16)0.31450 (8)0.13761 (14)0.0478 (3)
H10B0.42170.33850.08700.057*
C11B0.09656 (18)0.20500 (7)0.36745 (16)0.0531 (4)
H11D0.09200.16150.33930.080*
H11E0.00350.22340.36210.080*
H11F0.13260.20600.45140.080*
N1A0.16802 (12)0.60972 (5)0.31027 (11)0.0371 (2)
N1B0.33623 (11)0.40851 (5)0.26898 (10)0.0337 (2)
H1AA0.1419 (16)0.6026 (7)0.3892 (9)0.040*
H1BB0.3568 (16)0.4140 (7)0.3498 (9)0.040*
H1AB0.0963 (13)0.5934 (7)0.2631 (12)0.040*
H1BC0.2561 (12)0.4312 (7)0.2519 (15)0.040*
H1BA0.4085 (13)0.4254 (7)0.2269 (13)0.040*
H1AC0.2438 (12)0.5854 (6)0.2849 (13)0.040*
H4A0.032 (2)0.5302 (16)0.733 (2)0.040*0.50
H4B0.527 (2)0.5499 (16)0.233 (2)0.040*0.50
H1A0.472 (2)0.5492 (16)0.284 (2)0.040*0.50
H1B0.975 (2)0.5291 (16)0.219 (2)0.040*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0268 (5)0.0239 (5)0.0277 (5)0.0019 (4)0.0087 (4)0.0026 (4)
C2A0.0310 (5)0.0297 (5)0.0240 (5)0.0009 (4)0.0095 (4)0.0008 (4)
C3A0.0312 (5)0.0302 (5)0.0237 (5)0.0009 (4)0.0096 (4)0.0003 (4)
C4A0.0276 (5)0.0248 (5)0.0272 (5)0.0017 (4)0.0077 (4)0.0029 (4)
O1A0.0301 (4)0.0499 (5)0.0271 (4)0.0023 (4)0.0108 (3)0.0046 (4)
O2A0.0306 (4)0.0413 (5)0.0348 (4)0.0063 (4)0.0062 (3)0.0011 (4)
O3A0.0303 (4)0.0456 (5)0.0359 (5)0.0073 (4)0.0067 (3)0.0009 (4)
O4A0.0286 (4)0.0490 (5)0.0290 (4)0.0027 (4)0.0110 (3)0.0078 (4)
C1B0.0301 (5)0.0327 (6)0.0265 (5)0.0037 (4)0.0101 (4)0.0006 (4)
C2B0.0326 (6)0.0301 (6)0.0325 (6)0.0008 (4)0.0146 (4)0.0019 (4)
C3B0.0285 (5)0.0332 (6)0.0276 (5)0.0039 (4)0.0119 (4)0.0006 (4)
C4B0.0241 (5)0.0366 (6)0.0244 (5)0.0000 (4)0.0074 (4)0.0003 (4)
O1B0.0353 (4)0.0343 (4)0.0401 (5)0.0037 (4)0.0215 (4)0.0059 (4)
O2B0.0569 (6)0.0379 (5)0.0521 (6)0.0144 (4)0.0293 (5)0.0013 (4)
O4B0.0348 (4)0.0445 (5)0.0392 (5)0.0047 (4)0.0192 (4)0.0126 (4)
O3B0.0406 (5)0.0392 (5)0.0442 (5)0.0083 (4)0.0207 (4)0.0002 (4)
C5A0.0319 (6)0.0286 (5)0.0309 (5)0.0016 (4)0.0005 (4)0.0010 (4)
C6A0.0342 (6)0.0317 (6)0.0291 (5)0.0021 (5)0.0036 (4)0.0004 (4)
C7A0.0344 (6)0.0320 (6)0.0347 (6)0.0020 (5)0.0005 (5)0.0060 (5)
C8A0.0528 (8)0.0297 (6)0.0500 (8)0.0025 (6)0.0029 (6)0.0065 (5)
C9A0.0650 (10)0.0482 (8)0.0528 (9)0.0016 (7)0.0230 (8)0.0170 (7)
C10A0.0511 (8)0.0465 (8)0.0451 (7)0.0080 (6)0.0197 (6)0.0031 (6)
C11A0.0478 (8)0.0480 (8)0.0577 (9)0.0093 (7)0.0064 (7)0.0159 (7)
C5B0.0313 (5)0.0286 (5)0.0325 (6)0.0011 (4)0.0010 (4)0.0018 (4)
C6B0.0349 (6)0.0301 (6)0.0316 (6)0.0004 (5)0.0024 (4)0.0012 (4)
C7B0.0394 (6)0.0292 (6)0.0441 (7)0.0015 (5)0.0052 (5)0.0020 (5)
C8B0.0573 (9)0.0348 (7)0.0633 (10)0.0007 (6)0.0025 (7)0.0173 (7)
C9B0.0670 (11)0.0565 (10)0.0597 (10)0.0014 (8)0.0191 (8)0.0269 (8)
C10B0.0495 (8)0.0501 (8)0.0453 (8)0.0048 (7)0.0171 (6)0.0088 (6)
C11B0.0580 (9)0.0404 (8)0.0603 (9)0.0138 (7)0.0036 (7)0.0107 (7)
N1A0.0376 (6)0.0305 (5)0.0431 (6)0.0048 (4)0.0010 (5)0.0017 (4)
N1B0.0337 (5)0.0293 (5)0.0386 (5)0.0032 (4)0.0065 (4)0.0004 (4)
Geometric parameters (Å, º) top
C1A—O2A1.2310 (14)C8A—C9A1.370 (2)
C1A—O1A1.2864 (14)C8A—H8A0.9300
C1A—C2A1.4892 (14)C9A—C10A1.383 (2)
C2A—C3A1.3139 (16)C9A—H9A0.9300
C2A—H2A0.9300C10A—H10A0.9300
C3A—C4A1.4889 (15)C11A—H11A0.9600
C3A—H3A0.9300C11A—H11B0.9600
C4A—O3A1.2265 (14)C11A—H11C0.9600
C4A—O4A1.2879 (14)C5B—C10B1.3767 (18)
O1A—H1A0.852 (10)C5B—C6B1.3804 (17)
O4A—H4A0.853 (10)C5B—N1B1.4614 (15)
C1B—O2B1.2270 (14)C6B—C7B1.3892 (17)
C1B—O1B1.2816 (14)C6B—H6B0.9300
C1B—C2B1.4901 (15)C7B—C8B1.381 (2)
C2B—C3B1.3102 (16)C7B—C11B1.502 (2)
C2B—H2B0.9300C8B—C9B1.375 (2)
C3B—C4B1.4930 (14)C8B—H8B0.9300
C3B—H3B0.9300C9B—C10B1.384 (2)
C4B—O3B1.2225 (14)C9B—H9B0.9300
C4B—O4B1.2860 (14)C10B—H10B0.9300
O1B—H1B0.856 (10)C11B—H11D0.9600
O4B—H4B0.851 (10)C11B—H11E0.9600
C5A—C10A1.3721 (18)C11B—H11F0.9600
C5A—C6A1.3786 (17)N1A—H1AA0.895 (9)
C5A—N1A1.4633 (15)N1A—H1AB0.933 (9)
C6A—C7A1.3906 (17)N1A—H1AC0.911 (9)
C6A—H6A0.9300N1B—H1BB0.899 (9)
C7A—C8A1.3862 (19)N1B—H1BC0.907 (9)
C7A—C11A1.4983 (18)N1B—H1BA0.911 (9)
O2A—C1A—O1A124.58 (10)C5A—C10A—H10A120.9
O2A—C1A—C2A120.01 (10)C9A—C10A—H10A120.9
O1A—C1A—C2A115.40 (10)C7A—C11A—H11A109.5
C3A—C2A—C1A123.36 (10)C7A—C11A—H11B109.5
C3A—C2A—H2A118.3H11A—C11A—H11B109.5
C1A—C2A—H2A118.3C7A—C11A—H11C109.5
C2A—C3A—C4A123.17 (10)H11A—C11A—H11C109.5
C2A—C3A—H3A118.4H11B—C11A—H11C109.5
C4A—C3A—H3A118.4C10B—C5B—C6B121.58 (12)
O3A—C4A—O4A124.24 (10)C10B—C5B—N1B119.48 (12)
O3A—C4A—C3A120.62 (10)C6B—C5B—N1B118.94 (11)
O4A—C4A—C3A115.14 (10)C5B—C6B—C7B120.29 (12)
C1A—O1A—H1A112 (2)C5B—C6B—H6B119.9
C4A—O4A—H4A114 (2)C7B—C6B—H6B119.9
O2B—C1B—O1B124.85 (10)C8B—C7B—C6B118.08 (13)
O2B—C1B—C2B118.73 (11)C8B—C7B—C11B121.38 (13)
O1B—C1B—C2B116.42 (10)C6B—C7B—C11B120.53 (13)
C3B—C2B—C1B124.29 (11)C9B—C8B—C7B121.15 (14)
C3B—C2B—H2B117.9C9B—C8B—H8B119.4
C1B—C2B—H2B117.9C7B—C8B—H8B119.4
C2B—C3B—C4B122.27 (11)C8B—C9B—C10B120.99 (14)
C2B—C3B—H3B118.9C8B—C9B—H9B119.5
C4B—C3B—H3B118.9C10B—C9B—H9B119.5
O3B—C4B—O4B124.94 (10)C5B—C10B—C9B117.87 (14)
O3B—C4B—C3B120.93 (10)C5B—C10B—H10B121.1
O4B—C4B—C3B114.14 (10)C9B—C10B—H10B121.1
C1B—O1B—H1B114 (2)C7B—C11B—H11D109.5
C4B—O4B—H4B116 (2)C7B—C11B—H11E109.5
C10A—C5A—C6A121.58 (12)H11D—C11B—H11E109.5
C10A—C5A—N1A118.66 (12)C7B—C11B—H11F109.5
C6A—C5A—N1A119.75 (11)H11D—C11B—H11F109.5
C5A—C6A—C7A120.12 (11)H11E—C11B—H11F109.5
C5A—C6A—H6A119.9C5A—N1A—H1AA110.1 (10)
C7A—C6A—H6A119.9C5A—N1A—H1AB114.5 (10)
C8A—C7A—C6A118.09 (12)H1AA—N1A—H1AB106.9 (13)
C8A—C7A—C11A121.20 (13)C5A—N1A—H1AC110.8 (10)
C6A—C7A—C11A120.71 (12)H1AA—N1A—H1AC112.1 (14)
C9A—C8A—C7A121.06 (13)H1AB—N1A—H1AC102.2 (13)
C9A—C8A—H8A119.5C5B—N1B—H1BB111.6 (10)
C7A—C8A—H8A119.5C5B—N1B—H1BC108.2 (10)
C8A—C9A—C10A120.90 (14)H1BB—N1B—H1BC105.9 (14)
C8A—C9A—H9A119.6C5B—N1B—H1BA113.4 (10)
C10A—C9A—H9A119.6H1BB—N1B—H1BA107.9 (14)
C5A—C10A—C9A118.23 (13)H1BC—N1B—H1BA109.5 (14)
O2A—C1A—C2A—C3A159.72 (11)C11A—C7A—C8A—C9A179.36 (14)
O1A—C1A—C2A—C3A20.98 (16)C7A—C8A—C9A—C10A1.2 (3)
C1A—C2A—C3A—C4A178.66 (10)C6A—C5A—C10A—C9A1.2 (2)
C2A—C3A—C4A—O3A160.34 (12)N1A—C5A—C10A—C9A179.91 (14)
C2A—C3A—C4A—O4A20.44 (16)C8A—C9A—C10A—C5A0.1 (3)
O2B—C1B—C2B—C3B158.56 (13)C10B—C5B—C6B—C7B1.22 (19)
O1B—C1B—C2B—C3B21.96 (18)N1B—C5B—C6B—C7B179.58 (11)
C1B—C2B—C3B—C4B178.44 (10)C5B—C6B—C7B—C8B0.31 (19)
C2B—C3B—C4B—O3B5.18 (18)C5B—C6B—C7B—C11B178.63 (12)
C2B—C3B—C4B—O4B174.99 (12)C6B—C7B—C8B—C9B1.6 (2)
C10A—C5A—C6A—C7A1.35 (19)C11B—C7B—C8B—C9B177.31 (15)
N1A—C5A—C6A—C7A179.78 (11)C7B—C8B—C9B—C10B1.4 (3)
C5A—C6A—C7A—C8A0.18 (18)C6B—C5B—C10B—C9B1.4 (2)
C5A—C6A—C7A—C11A179.37 (12)N1B—C5B—C10B—C9B179.40 (14)
C6A—C7A—C8A—C9A1.1 (2)C8B—C9B—C10B—C5B0.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1B—H1BB···O2Ai0.90 (1)2.01 (1)2.8924 (14)168 (1)
N1A—H1AB···O2Bii0.93 (1)1.86 (1)2.7777 (15)168 (1)
N1B—H1BC···O1Bii0.91 (1)1.93 (1)2.8111 (14)165 (2)
N1A—H1AC···O4Biii0.91 (1)1.92 (1)2.7993 (15)162 (1)
O4A—H4A···O1Biv0.85 (1)1.62 (1)2.4703 (11)175 (3)
O1B—H1B···O4Av0.86 (1)1.62 (1)2.4703 (11)176 (3)
N1A—H1AA···O3A0.90 (1)1.97 (1)2.8539 (15)168 (1)
N1B—H1BA···O3B0.91 (1)1.87 (1)2.7757 (13)173 (1)
O4B—H4B···O1A0.85 (1)1.62 (1)2.4678 (11)175 (3)
O1A—H1A···O4B0.85 (1)1.62 (1)2.4678 (11)176 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) x1, y, z; (iv) x1, y, z+1; (v) x+1, y, z1.
(III) 4-Chloroanilinium hydrogen fumarate top
Crystal data top
C6H7ClN+·C4H3O4F(000) = 1008
Mr = 243.64Dx = 1.413 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.2335 (4) ÅCell parameters from 7356 reflections
b = 23.8248 (11) Åθ = 2.1–27.5°
c = 10.4424 (5) ŵ = 0.33 mm1
β = 94.338 (2)°T = 293 K
V = 2290.60 (18) Å3Block, colourless
Z = 80.35 × 0.30 × 0.25 mm
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
5334 independent reflections
Radiation source: fine-focus sealed tube3844 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω and ϕ scanθmax = 27.7°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 128
Tmin = 0.903, Tmax = 0.912k = 3126
25081 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122 w = 1/[σ2(Fo2) + (0.0556P)2 + 0.7547P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
5334 reflectionsΔρmax = 0.40 e Å3
428 parametersΔρmin = 0.35 e Å3
186 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0023 (5)
Crystal data top
C6H7ClN+·C4H3O4V = 2290.60 (18) Å3
Mr = 243.64Z = 8
Monoclinic, P21/nMo Kα radiation
a = 9.2335 (4) ŵ = 0.33 mm1
b = 23.8248 (11) ÅT = 293 K
c = 10.4424 (5) Å0.35 × 0.30 × 0.25 mm
β = 94.338 (2)°
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
5334 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
3844 reflections with I > 2σ(I)
Tmin = 0.903, Tmax = 0.912Rint = 0.032
25081 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043186 restraints
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.40 e Å3
5334 reflectionsΔρmin = 0.35 e Å3
428 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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*/UeqOcc. (<1)
O1A0.45233 (13)0.45321 (5)0.86500 (11)0.0392 (3)
O2A0.40559 (12)0.54353 (5)0.82388 (11)0.0377 (3)
O3A0.03580 (15)0.41827 (6)1.14927 (13)0.0501 (4)
O4A0.08360 (12)0.50962 (5)1.16641 (11)0.0363 (3)
C1A0.38491 (16)0.49659 (7)0.88114 (14)0.0293 (3)
C2A0.26941 (16)0.49907 (7)0.97269 (14)0.0296 (3)
H2A0.22710.53370.98690.036*
C3A0.22344 (18)0.45567 (7)1.03456 (15)0.0333 (4)
H3A0.26590.42081.02270.040*
C4A0.10521 (17)0.46028 (7)1.12346 (14)0.0316 (3)
N1A0.67802 (16)0.42400 (6)0.72415 (15)0.0353 (3)
O1B1.05186 (12)0.56708 (5)0.43583 (11)0.0381 (3)
O2B0.88377 (12)0.52594 (5)0.30481 (11)0.0360 (3)
O3B0.43745 (12)0.57146 (5)0.53098 (11)0.0371 (3)
O4B0.60682 (12)0.54637 (6)0.68265 (10)0.0373 (3)
C1B0.92659 (16)0.55032 (6)0.41052 (14)0.0278 (3)
C2B0.81511 (17)0.55607 (7)0.50457 (14)0.0295 (3)
H2B0.84590.56130.59060.035*
C3B0.67561 (17)0.55410 (6)0.47239 (14)0.0291 (3)
H3B0.64500.54990.38600.035*
C4B0.56337 (16)0.55830 (6)0.56690 (14)0.0270 (3)
C5B1.19842 (19)0.65786 (7)0.68682 (17)0.0379 (4)
N1B1.17013 (16)0.59776 (6)0.67927 (16)0.0393 (3)
C5A0.71203 (19)0.36559 (7)0.75475 (17)0.0392 (4)
Cl1A0.8205 (6)0.19030 (12)0.8738 (3)0.1745 (16)0.60
C6A0.8285 (10)0.3569 (4)0.8412 (9)0.063 (2)0.60
H6A0.88450.38690.87330.075*0.60
C7A0.8618 (11)0.3023 (3)0.8805 (8)0.079 (2)0.60
H7A0.93780.29560.94220.095*0.60
C8A0.7828 (13)0.2588 (3)0.8281 (9)0.082 (3)0.60
C9A0.6726 (12)0.2674 (4)0.7360 (15)0.088 (3)0.60
H9A0.62230.23700.69880.105*0.60
C10A0.6357 (11)0.3215 (4)0.6978 (15)0.065 (3)0.60
H10A0.56080.32790.63490.078*0.60
Cl1C0.8042 (6)0.18209 (15)0.8052 (4)0.1186 (12)0.40
C6C0.8332 (12)0.3474 (6)0.8268 (15)0.060 (4)0.40
H6C0.89680.37320.86750.072*0.40
C7C0.8602 (14)0.2904 (5)0.8386 (11)0.067 (3)0.40
H7C0.94530.27770.88240.080*0.40
C8C0.7604 (16)0.2526 (4)0.7850 (13)0.066 (3)0.40
C9C0.6310 (17)0.2708 (7)0.725 (2)0.071 (3)0.40
H9C0.56000.24510.69670.085*0.40
C10C0.6072 (18)0.3279 (5)0.708 (2)0.052 (3)0.40
H10C0.52150.34070.66500.062*0.40
Cl1B1.2799 (5)0.84239 (14)0.7279 (5)0.0938 (10)0.60
C6B1.1728 (10)0.6919 (4)0.5837 (8)0.054 (2)0.60
H6B1.13830.67650.50550.065*0.60
C7B1.1968 (10)0.7494 (5)0.5921 (10)0.068 (2)0.60
H7B1.17900.77220.52030.081*0.60
C8B1.2467 (18)0.7717 (3)0.7064 (10)0.061 (3)0.60
C9B1.2727 (12)0.7391 (4)0.8119 (10)0.071 (2)0.60
H9B1.30510.75470.89050.085*0.60
C10B1.2496 (12)0.6818 (4)0.7994 (7)0.061 (2)0.60
H10B1.26990.65890.87070.074*0.60
Cl1D1.2622 (10)0.8422 (2)0.7046 (8)0.116 (2)0.40
C6D1.1325 (17)0.6918 (7)0.5947 (13)0.062 (4)0.40
H6D1.07380.67720.52650.074*0.40
C7D1.1568 (16)0.7491 (7)0.6069 (15)0.072 (4)0.40
H7D1.11180.77360.54710.087*0.40
C8D1.246 (3)0.7698 (4)0.706 (2)0.070 (5)0.40
C9D1.3140 (18)0.7334 (6)0.7932 (16)0.077 (4)0.40
H9D1.37890.74770.85750.092*0.40
C10D1.2889 (18)0.6758 (6)0.7885 (13)0.072 (5)0.40
H10D1.33050.65130.85000.086*0.40
H1A10.607 (2)0.4371 (11)0.772 (2)0.086*
H1A20.645 (3)0.4270 (12)0.6399 (12)0.086*
H1A30.7564 (19)0.4463 (9)0.741 (3)0.086*
H1B11.137 (3)0.5896 (12)0.5976 (13)0.086*
H1B21.103 (2)0.5882 (11)0.734 (2)0.086*
H1B31.2527 (18)0.5780 (10)0.698 (2)0.086*
H2C0.474 (5)0.546 (3)0.774 (5)0.086*0.50
H2D0.948 (5)0.518 (3)0.254 (5)0.086*0.50
H4C0.013 (4)0.515 (3)1.214 (5)0.086*0.50
H4D0.540 (5)0.544 (3)0.735 (5)0.086*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0347 (7)0.0449 (7)0.0402 (6)0.0038 (5)0.0170 (5)0.0026 (5)
O2A0.0299 (7)0.0501 (7)0.0347 (6)0.0028 (5)0.0132 (5)0.0094 (5)
O3A0.0517 (8)0.0472 (8)0.0550 (8)0.0106 (6)0.0276 (6)0.0013 (6)
O4A0.0296 (6)0.0452 (7)0.0360 (6)0.0027 (5)0.0157 (5)0.0081 (5)
C1A0.0232 (8)0.0432 (9)0.0217 (7)0.0009 (7)0.0038 (6)0.0027 (6)
C2A0.0234 (8)0.0419 (9)0.0244 (7)0.0031 (6)0.0081 (6)0.0007 (6)
C3A0.0316 (9)0.0390 (9)0.0308 (8)0.0015 (7)0.0116 (6)0.0041 (7)
C4A0.0293 (8)0.0399 (9)0.0264 (7)0.0015 (7)0.0082 (6)0.0016 (6)
N1A0.0293 (8)0.0357 (7)0.0418 (8)0.0051 (6)0.0090 (6)0.0045 (6)
O1B0.0261 (6)0.0521 (7)0.0371 (6)0.0068 (5)0.0080 (5)0.0061 (5)
O2B0.0271 (6)0.0531 (7)0.0290 (6)0.0043 (5)0.0093 (4)0.0098 (5)
O3B0.0259 (6)0.0518 (7)0.0342 (6)0.0055 (5)0.0063 (5)0.0015 (5)
O4B0.0271 (6)0.0578 (8)0.0281 (6)0.0025 (5)0.0091 (4)0.0065 (5)
C1B0.0252 (8)0.0315 (8)0.0274 (7)0.0013 (6)0.0062 (6)0.0027 (6)
C2B0.0286 (8)0.0374 (8)0.0231 (7)0.0004 (7)0.0065 (6)0.0010 (6)
C3B0.0288 (8)0.0346 (8)0.0247 (7)0.0010 (6)0.0072 (6)0.0010 (6)
C4B0.0247 (8)0.0282 (7)0.0288 (8)0.0030 (6)0.0076 (6)0.0020 (6)
C5B0.0347 (9)0.0332 (8)0.0472 (10)0.0034 (7)0.0116 (8)0.0022 (7)
N1B0.0331 (8)0.0321 (7)0.0528 (9)0.0027 (6)0.0049 (7)0.0012 (7)
C5A0.0373 (10)0.0351 (9)0.0470 (10)0.0054 (7)0.0158 (8)0.0081 (8)
Cl1A0.292 (4)0.0439 (11)0.184 (3)0.0410 (15)0.007 (3)0.0360 (16)
C6A0.070 (5)0.040 (3)0.076 (4)0.015 (3)0.005 (3)0.017 (3)
C7A0.097 (4)0.048 (4)0.090 (5)0.021 (3)0.009 (4)0.016 (3)
C8A0.115 (6)0.036 (3)0.096 (6)0.011 (3)0.007 (4)0.018 (3)
C9A0.090 (8)0.036 (3)0.136 (6)0.006 (4)0.002 (5)0.000 (3)
C10A0.060 (5)0.049 (4)0.086 (5)0.004 (3)0.002 (4)0.006 (3)
Cl1C0.153 (2)0.0376 (11)0.163 (4)0.0109 (12)0.001 (3)0.0204 (18)
C6C0.034 (5)0.042 (5)0.101 (8)0.005 (3)0.007 (4)0.001 (4)
C7C0.060 (4)0.046 (5)0.092 (7)0.018 (4)0.011 (5)0.001 (5)
C8C0.070 (6)0.037 (3)0.088 (8)0.000 (3)0.003 (5)0.008 (4)
C9C0.055 (6)0.047 (5)0.109 (7)0.007 (4)0.001 (5)0.010 (4)
C10C0.043 (5)0.032 (4)0.082 (6)0.000 (4)0.010 (5)0.005 (4)
Cl1B0.1114 (16)0.0391 (12)0.135 (2)0.0202 (10)0.0345 (15)0.0319 (13)
C6B0.074 (6)0.046 (3)0.043 (2)0.006 (3)0.010 (3)0.0031 (19)
C7B0.101 (6)0.042 (2)0.064 (3)0.002 (4)0.024 (4)0.009 (2)
C8B0.082 (7)0.035 (4)0.071 (5)0.008 (5)0.029 (4)0.008 (4)
C9B0.097 (6)0.049 (3)0.066 (3)0.011 (3)0.009 (4)0.022 (2)
C10B0.093 (6)0.044 (3)0.046 (3)0.004 (3)0.005 (3)0.005 (2)
Cl1D0.196 (6)0.0331 (19)0.120 (3)0.010 (2)0.029 (3)0.016 (2)
C6D0.059 (7)0.041 (4)0.081 (7)0.000 (4)0.013 (5)0.007 (4)
C7D0.076 (7)0.045 (4)0.095 (8)0.006 (4)0.007 (5)0.021 (5)
C8D0.078 (11)0.028 (5)0.106 (11)0.010 (7)0.015 (8)0.002 (6)
C9D0.083 (8)0.050 (4)0.095 (8)0.007 (5)0.013 (6)0.020 (5)
C10D0.076 (8)0.040 (4)0.094 (8)0.004 (5)0.029 (6)0.013 (4)
Geometric parameters (Å, º) top
O1A—C1A1.2248 (19)C5A—C10C1.383 (9)
O2A—C1A1.289 (2)Cl1A—C8A1.729 (6)
O2A—H2C0.852 (10)C6A—C7A1.391 (7)
O3A—C4A1.229 (2)C6A—H6A0.9300
O4A—C4A1.279 (2)C7A—C8A1.358 (7)
O4A—H4C0.855 (10)C7A—H7A0.9300
C1A—C2A1.486 (2)C8A—C9A1.362 (8)
C2A—C3A1.307 (2)C9A—C10A1.385 (8)
C2A—H2A0.9300C9A—H9A0.9300
C3A—C4A1.490 (2)C10A—H10A0.9300
C3A—H3A0.9300Cl1C—C8C1.737 (8)
N1A—C5A1.457 (2)C6C—C7C1.385 (9)
N1A—H1A10.908 (10)C6C—H6C0.9300
N1A—H1A20.912 (10)C7C—C8C1.377 (8)
N1A—H1A30.904 (10)C7C—H7C0.9300
O1B—C1B1.2333 (19)C8C—C9C1.376 (8)
O2B—C1B1.2830 (19)C9C—C10C1.387 (9)
O2B—H2D0.850 (10)C9C—H9C0.9300
O3B—C4B1.2348 (19)C10C—H10C0.9300
O4B—C4B1.2765 (18)Cl1B—C8B1.723 (6)
O4B—H4D0.851 (10)C6B—C7B1.388 (7)
C1B—C2B1.482 (2)C6B—H6B0.9300
C2B—C3B1.307 (2)C7B—C8B1.356 (7)
C2B—H2B0.9300C7B—H7B0.9300
C3B—C4B1.488 (2)C8B—C9B1.355 (7)
C3B—H3B0.9300C9B—C10B1.386 (7)
C5B—C6B1.355 (6)C9B—H9B0.9300
C5B—C10B1.359 (6)C10B—H10B0.9300
C5B—C6D1.364 (9)Cl1D—C8D1.730 (9)
C5B—C10D1.369 (9)C6D—C7D1.386 (9)
C5B—N1B1.457 (2)C6D—H6D0.9300
N1B—H1B10.905 (10)C7D—C8D1.369 (9)
N1B—H1B20.905 (10)C7D—H7D0.9300
N1B—H1B30.905 (10)C8D—C9D1.371 (9)
C5A—C6A1.367 (7)C9D—C10D1.392 (9)
C5A—C6C1.370 (8)C9D—H9D0.9300
C5A—C10A1.375 (7)C10D—H10D0.9300
C1A—O2A—H2C120 (4)C5A—C6A—C7A118.8 (9)
C4A—O4A—H4C118 (4)C5A—C6A—H6A120.6
O1A—C1A—O2A125.00 (14)C7A—C6A—H6A120.6
O1A—C1A—C2A121.26 (14)C8A—C7A—C6A119.6 (8)
O2A—C1A—C2A113.74 (14)C8A—C7A—H7A120.2
C3A—C2A—C1A124.21 (15)C6A—C7A—H7A120.2
C3A—C2A—H2A117.9C7A—C8A—C9A121.4 (7)
C1A—C2A—H2A117.9C7A—C8A—Cl1A121.2 (6)
C2A—C3A—C4A122.03 (15)C9A—C8A—Cl1A117.4 (7)
C2A—C3A—H3A119.0C8A—C9A—C10A119.8 (9)
C4A—C3A—H3A119.0C8A—C9A—H9A120.1
O3A—C4A—O4A125.00 (15)C10A—C9A—H9A120.1
O3A—C4A—C3A119.69 (15)C5A—C10A—C9A118.7 (10)
O4A—C4A—C3A115.30 (14)C5A—C10A—H10A120.7
C5A—N1A—H1A1111.2 (17)C9A—C10A—H10A120.7
C5A—N1A—H1A2109.6 (18)C5A—C6C—C7C119.5 (11)
H1A1—N1A—H1A2107 (2)C5A—C6C—H6C120.3
C5A—N1A—H1A3111.4 (17)C7C—C6C—H6C120.3
H1A1—N1A—H1A3107 (2)C8C—C7C—C6C119.7 (11)
H1A2—N1A—H1A3110 (2)C8C—C7C—H7C120.1
C1B—O2B—H2D117 (4)C6C—C7C—H7C120.1
C4B—O4B—H4D115 (4)C9C—C8C—C7C120.6 (10)
O1B—C1B—O2B123.64 (14)C9C—C8C—Cl1C123.2 (9)
O1B—C1B—C2B121.02 (14)C7C—C8C—Cl1C116.2 (9)
O2B—C1B—C2B115.32 (13)C8C—C9C—C10C119.6 (14)
C3B—C2B—C1B123.14 (14)C8C—C9C—H9C120.2
C3B—C2B—H2B118.4C10C—C9C—H9C120.2
C1B—C2B—H2B118.4C5A—C10C—C9C119.3 (14)
C2B—C3B—C4B123.33 (14)C5A—C10C—H10C120.3
C2B—C3B—H3B118.3C9C—C10C—H10C120.3
C4B—C3B—H3B118.3C5B—C6B—C7B121.5 (9)
O3B—C4B—O4B124.43 (13)C5B—C6B—H6B119.2
O3B—C4B—C3B120.19 (13)C7B—C6B—H6B119.2
O4B—C4B—C3B115.36 (13)C8B—C7B—C6B119.0 (10)
C6B—C5B—C10B117.7 (6)C8B—C7B—H7B120.5
C6B—C5B—C6D16.8 (10)C6B—C7B—H7B120.5
C10B—C5B—C6D117.9 (9)C9B—C8B—C7B121.2 (9)
C6B—C5B—C10D119.3 (9)C9B—C8B—Cl1B115.9 (7)
C10B—C5B—C10D17.4 (12)C7B—C8B—Cl1B123.0 (8)
C6D—C5B—C10D125.1 (10)C8B—C9B—C10B118.2 (9)
C6B—C5B—N1B121.7 (5)C8B—C9B—H9B120.9
C10B—C5B—N1B120.6 (4)C10B—C9B—H9B120.9
C6D—C5B—N1B118.4 (8)C5B—C10B—C9B122.4 (8)
C10D—C5B—N1B116.5 (7)C5B—C10B—H10B118.8
C5B—N1B—H1B1108.0 (18)C9B—C10B—H10B118.8
C5B—N1B—H1B2110.0 (18)C5B—C6D—C7D117.3 (15)
H1B1—N1B—H1B2110 (2)C5B—C6D—H6D121.4
C5B—N1B—H1B3110.7 (18)C7D—C6D—H6D121.4
H1B1—N1B—H1B3108 (2)C8D—C7D—C6D120.6 (15)
H1B2—N1B—H1B3110 (2)C8D—C7D—H7D119.7
C6A—C5A—C6C11.6 (10)C6D—C7D—H7D119.7
C6A—C5A—C10A121.4 (7)C7D—C8D—C9D119.5 (13)
C6C—C5A—C10A111.5 (8)C7D—C8D—Cl1D113.5 (13)
C6A—C5A—C10C129.1 (8)C9D—C8D—Cl1D127.0 (13)
C6C—C5A—C10C120.7 (9)C8D—C9D—C10D122.2 (14)
C10A—C5A—C10C13.7 (14)C8D—C9D—H9D118.9
C6A—C5A—N1A115.9 (5)C10D—C9D—H9D118.9
C6C—C5A—N1A125.1 (6)C5B—C10D—C9D115.2 (13)
C10A—C5A—N1A122.7 (5)C5B—C10D—H10D122.4
C10C—C5A—N1A114.1 (7)C9D—C10D—H10D122.4
O1A—C1A—C2A—C3A5.3 (2)C6A—C5A—C10C—C9C15 (3)
O2A—C1A—C2A—C3A175.13 (16)C6C—C5A—C10C—C9C5 (3)
C1A—C2A—C3A—C4A178.80 (14)C10A—C5A—C10C—C9C45 (5)
C2A—C3A—C4A—O3A158.24 (17)N1A—C5A—C10C—C9C176.7 (15)
C2A—C3A—C4A—O4A21.0 (2)C8C—C9C—C10C—C5A2 (3)
O1B—C1B—C2B—C3B160.14 (16)C10B—C5B—C6B—C7B0.4 (10)
O2B—C1B—C2B—C3B21.4 (2)C6D—C5B—C6B—C7B95 (4)
C1B—C2B—C3B—C4B178.29 (14)C10D—C5B—C6B—C7B20.2 (11)
C2B—C3B—C4B—O3B160.21 (16)N1B—C5B—C6B—C7B178.5 (4)
C2B—C3B—C4B—O4B21.2 (2)C5B—C6B—C7B—C8B0.2 (11)
C6C—C5A—C6A—C7A38 (5)C6B—C7B—C8B—C9B0.2 (17)
C10A—C5A—C6A—C7A5.8 (13)C6B—C7B—C8B—Cl1B179.8 (8)
C10C—C5A—C6A—C7A8.1 (15)C7B—C8B—C9B—C10B1.2 (18)
N1A—C5A—C6A—C7A176.3 (4)Cl1B—C8B—C9B—C10B179.1 (9)
C5A—C6A—C7A—C8A3.0 (10)C6B—C5B—C10B—C9B1.4 (13)
C6A—C7A—C8A—C9A1.2 (15)C6D—C5B—C10B—C9B17.6 (14)
C6A—C7A—C8A—Cl1A179.9 (6)C10D—C5B—C10B—C9B101 (4)
C7A—C8A—C9A—C10A3 (2)N1B—C5B—C10B—C9B177.5 (7)
Cl1A—C8A—C9A—C10A178.6 (11)C8B—C9B—C10B—C5B1.9 (16)
C6A—C5A—C10A—C9A4.3 (18)C6B—C5B—C6D—C7D76 (4)
C6C—C5A—C10A—C9A11.0 (16)C10B—C5B—C6D—C7D17.2 (11)
C10C—C5A—C10A—C9A124 (7)C10D—C5B—C6D—C7D1.5 (15)
N1A—C5A—C10A—C9A177.9 (10)N1B—C5B—C6D—C7D177.5 (5)
C8A—C9A—C10A—C5A0 (2)C5B—C6D—C7D—C8D1.6 (17)
C6A—C5A—C6C—C7C148 (6)C6D—C7D—C8D—C9D1 (3)
C10A—C5A—C6C—C7C2.8 (12)C6D—C7D—C8D—Cl1D179.9 (9)
C10C—C5A—C6C—C7C8.5 (18)C7D—C8D—C9D—C10D4 (3)
N1A—C5A—C6C—C7C173.7 (5)Cl1D—C8D—C9D—C10D177.3 (17)
C5A—C6C—C7C—C8C4.3 (13)C6B—C5B—C10D—C9D17.7 (18)
C6C—C7C—C8C—C9C3.1 (19)C10B—C5B—C10D—C9D72 (3)
C6C—C7C—C8C—Cl1C179.9 (7)C6D—C5B—C10D—C9D1 (2)
C7C—C8C—C9C—C10C6 (3)N1B—C5B—C10D—C9D180.0 (10)
Cl1C—C8C—C9C—C10C177.1 (16)C8D—C9D—C10D—C5B4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A2···O3Bi0.91 (1)1.89 (1)2.7958 (19)175 (3)
N1A—H1A3···O4Aii0.90 (1)2.00 (1)2.8759 (19)162 (2)
N1B—H1B2···O3Aii0.91 (1)1.84 (1)2.7354 (19)170 (3)
N1B—H1B3···O2Aiii0.91 (1)2.03 (2)2.860 (2)153 (2)
O2B—H2D···O4Aiv0.85 (1)1.62 (1)2.4592 (15)172 (6)
N1A—H1A1···O1A0.91 (1)1.83 (1)2.7302 (18)172 (3)
N1B—H1B1···O1B0.91 (1)1.89 (1)2.787 (2)173 (3)
O2A—H2C···O4B0.85 (1)1.61 (1)2.4590 (15)175 (6)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z+2; (iii) x+1, y, z; (iv) x+1, y, z1.

Experimental details

(I)(II)(III)
Crystal data
Chemical formula2C6H9N2+·C4H2O42C7H10N+·C4H3O4C6H7ClN+·C4H3O4
Mr332.36223.22243.64
Crystal system, space groupOrthorhombic, Iba2Monoclinic, P21/nMonoclinic, P21/n
Temperature (K)296296293
a, b, c (Å)10.0424 (2), 42.9871 (11), 7.4930 (2)9.4576 (3), 20.8915 (6), 10.8787 (3)9.2335 (4), 23.8248 (11), 10.4424 (5)
α, β, γ (°)90, 90, 9090, 92.611 (2), 9090, 94.338 (2), 90
V3)3234.68 (14)2147.22 (11)2290.60 (18)
Z888
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.100.110.33
Crystal size (mm)0.35 × 0.30 × 0.200.35 × 0.30 × 0.250.35 × 0.30 × 0.25
Data collection
DiffractometerBruker Kappa APEXII CCD area-detector
diffractometer
Bruker Kappa APEXII CCD area-detector
diffractometer
Bruker Kappa APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Multi-scan
(SADABS; Bruker, 2004)
Multi-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.916, 0.9800.904, 0.9740.903, 0.912
No. of measured, independent and
observed [I > 2σ(I)] reflections
9034, 3406, 2751 37301, 6714, 5066 25081, 5334, 3844
Rint0.0350.0360.032
(sin θ/λ)max1)0.6390.7200.655
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.140, 1.05 0.044, 0.130, 1.04 0.043, 0.122, 1.03
No. of reflections340667145334
No. of parameters247322428
No. of restraints1110186
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)0.47, 0.230.38, 0.210.40, 0.35

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N4—H4C···O4i0.898 (10)1.850 (13)2.728 (3)165 (3)
N2—H2A···O2ii0.899 (10)1.849 (13)2.729 (3)166 (3)
N3—H3A···O3iii0.899 (10)2.294 (17)3.106 (3)150 (2)
N1—H1A···O1iv0.904 (10)2.233 (16)3.101 (3)161 (3)
N2—H2B···O3v0.915 (10)1.905 (11)2.811 (3)170 (2)
N4—H4A···O1vi0.905 (10)1.930 (12)2.820 (3)167 (2)
N3—H3B···O30.898 (10)2.060 (11)2.956 (4)175 (3)
N1—H1B···O10.899 (10)2.045 (13)2.926 (4)166 (3)
N4—H4B···O40.901 (10)1.873 (13)2.756 (3)166 (3)
N2—H2C···O20.900 (10)1.899 (15)2.758 (4)159 (3)
Symmetry codes: (i) x, y, z+1/2; (ii) x+1, y, z1/2; (iii) x+1, y, z+1/2; (iv) x, y, z1/2; (v) x, y, z1; (vi) x, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1B—H1BB···O2Ai0.899 (9)2.008 (9)2.8924 (14)167.5 (14)
N1A—H1AB···O2Bii0.933 (9)1.858 (9)2.7777 (15)168.1 (14)
N1B—H1BC···O1Bii0.907 (9)1.925 (10)2.8111 (14)165.3 (15)
N1A—H1AC···O4Biii0.911 (9)1.918 (10)2.7993 (15)162.2 (14)
O4A—H4A···O1Biv0.853 (10)1.620 (10)2.4703 (11)175 (3)
O1B—H1B···O4Av0.856 (10)1.616 (10)2.4703 (11)176 (3)
N1A—H1AA···O3A0.895 (9)1.972 (9)2.8539 (15)168.1 (14)
N1B—H1BA···O3B0.911 (9)1.869 (9)2.7757 (13)173.1 (14)
O4B—H4B···O1A0.851 (10)1.619 (10)2.4678 (11)175 (3)
O1A—H1A···O4B0.852 (10)1.617 (10)2.4678 (11)176 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) x1, y, z; (iv) x1, y, z+1; (v) x+1, y, z1.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A2···O3Bi0.912 (10)1.887 (10)2.7958 (19)175 (3)
N1A—H1A3···O4Aii0.904 (10)2.003 (13)2.8759 (19)162 (2)
N1B—H1B2···O3Aii0.905 (10)1.839 (11)2.7354 (19)170 (3)
N1B—H1B3···O2Aiii0.905 (10)2.026 (15)2.860 (2)153 (2)
O2B—H2D···O4Aiv0.850 (10)1.615 (13)2.4592 (15)172 (6)
N1A—H1A1···O1A0.908 (10)1.829 (11)2.7302 (18)172 (3)
N1B—H1B1···O1B0.905 (10)1.887 (11)2.787 (2)173 (3)
O2A—H2C···O4B0.852 (10)1.609 (11)2.4590 (15)175 (6)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z+2; (iii) x+1, y, z; (iv) x+1, y, z1.
 

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