Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017629/uk3068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017629/uk3068Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017629/uk3068IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017629/uk3068IIIsup4.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017629/uk3068Isup5.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017629/uk3068IIsup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017629/uk3068IIIsup7.cml |
CCDC references: 964798; 964799; 964800
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).
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.
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).
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.
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).
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).
2C6H9N2+·C4H2O42− | Dx = 1.365 Mg m−3 |
Mr = 332.36 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Iba2 | Cell parameters from 2905 reflections |
a = 10.0424 (2) Å | θ = 3.5–25.1° |
b = 42.9871 (11) Å | µ = 0.10 mm−1 |
c = 7.4930 (2) Å | T = 296 K |
V = 3234.68 (14) Å3 | Block, brown |
Z = 8 | 0.35 × 0.30 × 0.20 mm |
F(000) = 1408 |
Bruker Kappa APEXII CCD area-detector diffractometer | 3406 independent reflections |
Radiation source: fine-focus sealed tube | 2751 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω and ϕ scan | θmax = 27.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −12→12 |
Tmin = 0.916, Tmax = 0.980 | k = −51→54 |
9034 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H 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 parameters | Δρmax = 0.47 e Å−3 |
11 restraints | Δρmin = −0.23 e Å−3 |
2C6H9N2+·C4H2O42− | V = 3234.68 (14) Å3 |
Mr = 332.36 | Z = 8 |
Orthorhombic, Iba2 | Mo Kα radiation |
a = 10.0424 (2) Å | µ = 0.10 mm−1 |
b = 42.9871 (11) Å | T = 296 K |
c = 7.4930 (2) Å | 0.35 × 0.30 × 0.20 mm |
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 = 0.980 | Rint = 0.035 |
9034 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 11 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.47 e Å−3 |
3406 reflections | Δρmin = −0.23 e Å−3 |
247 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.18034 (16) | 0.14454 (4) | −0.1617 (3) | 0.0395 (5) | |
O2 | 0.37362 (16) | 0.16817 (4) | −0.1217 (3) | 0.0380 (4) | |
O3 | 0.32426 (16) | 0.10635 (4) | 0.4447 (3) | 0.0385 (5) | |
O4 | 0.13050 (16) | 0.08258 (4) | 0.3996 (3) | 0.0364 (4) | |
C1 | 0.2828 (2) | 0.14979 (6) | −0.0738 (4) | 0.0317 (6) | |
C2 | 0.3010 (2) | 0.13358 (6) | 0.1019 (4) | 0.0318 (6) | |
H2 | 0.3831 | 0.1351 | 0.1587 | 0.038* | |
C3 | 0.2061 (2) | 0.11726 (6) | 0.1795 (4) | 0.0318 (6) | |
H3 | 0.1240 | 0.1159 | 0.1226 | 0.038* | |
C4 | 0.2225 (2) | 0.10090 (6) | 0.3523 (4) | 0.0295 (6) | |
N1 | 0.0970 (2) | 0.16414 (6) | −0.5187 (5) | 0.0419 (7) | |
N2 | 0.3732 (2) | 0.16971 (6) | −0.4896 (4) | 0.0324 (6) | |
H2A | 0.4607 (12) | 0.1698 (5) | −0.515 (5) | 0.039* | |
H2B | 0.348 (2) | 0.1498 (3) | −0.517 (4) | 0.039* | |
H2C | 0.367 (3) | 0.1741 (7) | −0.3726 (16) | 0.039* | |
N3 | 0.4001 (2) | 0.08449 (6) | 0.8046 (4) | 0.0423 (7) | |
N4 | 0.1225 (2) | 0.08156 (6) | 0.7672 (3) | 0.0310 (6) | |
H4A | 0.154 (2) | 0.1008 (3) | 0.791 (4) | 0.037* | |
H4B | 0.138 (3) | 0.0804 (7) | 0.6490 (16) | 0.037* | |
H4C | 0.0354 (12) | 0.0802 (5) | 0.793 (4) | 0.037* | |
C5 | 0.1595 (2) | 0.18828 (6) | −0.6058 (4) | 0.0342 (6) | |
C6 | 0.2966 (2) | 0.19186 (6) | −0.5963 (4) | 0.0316 (6) | |
C7 | 0.3632 (3) | 0.21460 (6) | −0.6930 (5) | 0.0402 (7) | |
H7 | 0.4553 | 0.2164 | −0.6852 | 0.048* | |
C8 | 0.2920 (3) | 0.23443 (7) | −0.8004 (6) | 0.0519 (9) | |
H8 | 0.3352 | 0.2500 | −0.8644 | 0.062* | |
C9 | 0.1553 (3) | 0.23101 (7) | −0.8123 (6) | 0.0547 (9) | |
H9 | 0.1069 | 0.2442 | −0.8860 | 0.066* | |
C10 | 0.0903 (3) | 0.20854 (6) | −0.7176 (5) | 0.0437 (8) | |
H10 | −0.0016 | 0.2067 | −0.7278 | 0.052* | |
C11 | 0.3317 (2) | 0.06137 (6) | 0.8908 (4) | 0.0323 (6) | |
C12 | 0.1931 (2) | 0.05889 (6) | 0.8757 (4) | 0.0300 (6) | |
C13 | 0.1221 (3) | 0.03638 (6) | 0.9653 (5) | 0.0399 (7) | |
H13 | 0.0307 | 0.0346 | 0.9476 | 0.048* | |
C14 | 0.1864 (4) | 0.01653 (6) | 1.0811 (7) | 0.0540 (9) | |
H14 | 0.1387 | 0.0017 | 1.1449 | 0.065* | |
C15 | 0.3215 (4) | 0.01895 (6) | 1.1010 (6) | 0.0539 (9) | |
H15 | 0.3651 | 0.0057 | 1.1798 | 0.065* | |
C16 | 0.3939 (3) | 0.04054 (7) | 1.0073 (5) | 0.0481 (9) | |
H16 | 0.4859 | 0.0413 | 1.0215 | 0.058* | |
H3A | 0.4876 (13) | 0.0838 (6) | 0.829 (6) | 0.058* | |
H1A | 0.0092 (12) | 0.1607 (6) | −0.536 (5) | 0.058* | |
H3B | 0.373 (3) | 0.0918 (7) | 0.698 (2) | 0.058* | |
H1B | 0.126 (3) | 0.1614 (8) | −0.406 (2) | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0316 (8) | 0.0557 (12) | 0.0313 (11) | −0.0067 (8) | −0.0029 (9) | 0.0087 (10) |
O2 | 0.0347 (8) | 0.0477 (10) | 0.0316 (11) | −0.0097 (7) | 0.0001 (8) | 0.0089 (9) |
O3 | 0.0304 (8) | 0.0527 (11) | 0.0326 (11) | −0.0048 (7) | −0.0060 (9) | 0.0089 (9) |
O4 | 0.0333 (8) | 0.0473 (10) | 0.0285 (11) | −0.0104 (7) | −0.0021 (8) | 0.0080 (8) |
C1 | 0.0295 (11) | 0.0366 (14) | 0.0288 (17) | 0.0014 (10) | 0.0029 (14) | 0.0056 (12) |
C2 | 0.0292 (12) | 0.0412 (14) | 0.0249 (15) | 0.0006 (10) | −0.0015 (11) | 0.0025 (10) |
C3 | 0.0286 (11) | 0.0426 (15) | 0.0243 (15) | −0.0024 (10) | −0.0007 (11) | 0.0008 (10) |
C4 | 0.0326 (11) | 0.0352 (13) | 0.0208 (16) | 0.0003 (10) | −0.0019 (13) | 0.0004 (11) |
N1 | 0.0315 (11) | 0.0542 (14) | 0.0401 (17) | −0.0003 (10) | −0.0007 (12) | 0.0095 (13) |
N2 | 0.0281 (9) | 0.0421 (12) | 0.0271 (14) | −0.0016 (9) | −0.0018 (10) | 0.0043 (11) |
N3 | 0.0285 (10) | 0.0559 (15) | 0.0426 (19) | −0.0001 (10) | 0.0012 (12) | 0.0098 (14) |
N4 | 0.0279 (10) | 0.0400 (12) | 0.0250 (14) | −0.0011 (9) | −0.0017 (10) | 0.0031 (10) |
C5 | 0.0363 (12) | 0.0373 (13) | 0.0290 (16) | 0.0044 (10) | −0.0011 (14) | −0.0028 (13) |
C6 | 0.0364 (12) | 0.0344 (13) | 0.0239 (15) | 0.0029 (10) | −0.0046 (13) | −0.0001 (12) |
C7 | 0.0411 (13) | 0.0408 (14) | 0.0388 (19) | −0.0068 (11) | −0.0012 (14) | 0.0026 (14) |
C8 | 0.0676 (19) | 0.0416 (17) | 0.047 (2) | −0.0016 (14) | −0.0005 (19) | 0.0146 (17) |
C9 | 0.0630 (19) | 0.0549 (18) | 0.046 (2) | 0.0154 (15) | −0.0066 (19) | 0.0115 (18) |
C10 | 0.0425 (14) | 0.0486 (16) | 0.0401 (19) | 0.0067 (12) | −0.0088 (14) | 0.0013 (14) |
C11 | 0.0358 (11) | 0.0354 (13) | 0.0258 (15) | 0.0076 (9) | −0.0020 (13) | −0.0034 (12) |
C12 | 0.0369 (12) | 0.0313 (12) | 0.0219 (16) | 0.0014 (9) | −0.0029 (12) | −0.0005 (12) |
C13 | 0.0436 (13) | 0.0373 (14) | 0.0387 (19) | −0.0021 (11) | −0.0014 (14) | 0.0053 (14) |
C14 | 0.0682 (19) | 0.0407 (16) | 0.053 (2) | 0.0002 (14) | 0.003 (2) | 0.0174 (17) |
C15 | 0.075 (2) | 0.0403 (15) | 0.047 (2) | 0.0123 (14) | −0.0159 (19) | 0.0150 (16) |
C16 | 0.0452 (14) | 0.0503 (16) | 0.049 (2) | 0.0119 (13) | −0.0138 (14) | 0.0023 (16) |
O1—C1 | 1.242 (3) | N4—H4C | 0.898 (10) |
O2—C1 | 1.259 (3) | C5—C6 | 1.387 (3) |
O3—C4 | 1.256 (3) | C5—C10 | 1.394 (4) |
O4—C4 | 1.265 (3) | C6—C7 | 1.388 (4) |
C1—C2 | 1.501 (4) | C7—C8 | 1.372 (5) |
C2—C3 | 1.318 (3) | C7—H7 | 0.9300 |
C2—H2 | 0.9300 | C8—C9 | 1.384 (5) |
C3—C4 | 1.483 (4) | C8—H8 | 0.9300 |
C3—H3 | 0.9300 | C9—C10 | 1.365 (5) |
N1—C5 | 1.377 (4) | C9—H9 | 0.9300 |
N1—H1A | 0.904 (10) | C10—H10 | 0.9300 |
N1—H1B | 0.899 (10) | C11—C16 | 1.398 (4) |
N2—C6 | 1.462 (4) | C11—C12 | 1.401 (4) |
N2—H2A | 0.899 (10) | C12—C13 | 1.377 (4) |
N2—H2B | 0.915 (10) | C13—C14 | 1.378 (5) |
N2—H2C | 0.900 (10) | C13—H13 | 0.9300 |
N3—C11 | 1.370 (4) | C14—C15 | 1.368 (5) |
N3—H3A | 0.899 (10) | C14—H14 | 0.9300 |
N3—H3B | 0.898 (10) | C15—C16 | 1.373 (5) |
N4—C12 | 1.454 (4) | C15—H15 | 0.9300 |
N4—H4A | 0.905 (10) | C16—H16 | 0.9300 |
N4—H4B | 0.901 (10) | ||
O1—C1—O2 | 124.3 (3) | C5—C6—C7 | 122.0 (2) |
O1—C1—C2 | 118.8 (2) | C5—C6—N2 | 118.5 (2) |
O2—C1—C2 | 116.9 (3) | C7—C6—N2 | 119.4 (2) |
C3—C2—C1 | 123.1 (2) | C8—C7—C6 | 119.5 (3) |
C3—C2—H2 | 118.4 | C8—C7—H7 | 120.2 |
C1—C2—H2 | 118.4 | C6—C7—H7 | 120.2 |
C2—C3—C4 | 123.9 (2) | C7—C8—C9 | 119.2 (3) |
C2—C3—H3 | 118.1 | C7—C8—H8 | 120.4 |
C4—C3—H3 | 118.1 | C9—C8—H8 | 120.4 |
O3—C4—O4 | 123.8 (3) | C10—C9—C8 | 121.1 (3) |
O3—C4—C3 | 118.9 (2) | C10—C9—H9 | 119.5 |
O4—C4—C3 | 117.3 (2) | C8—C9—H9 | 119.5 |
C5—N1—H1A | 120 (2) | C9—C10—C5 | 121.1 (3) |
C5—N1—H1B | 113 (2) | C9—C10—H10 | 119.5 |
H1A—N1—H1B | 116 (3) | C5—C10—H10 | 119.5 |
C6—N2—H2A | 113.4 (19) | N3—C11—C16 | 122.4 (2) |
C6—N2—H2B | 110.0 (19) | N3—C11—C12 | 121.0 (2) |
H2A—N2—H2B | 103 (2) | C16—C11—C12 | 116.5 (2) |
C6—N2—H2C | 111.0 (19) | C13—C12—C11 | 121.9 (2) |
H2A—N2—H2C | 106 (3) | C13—C12—N4 | 119.4 (2) |
H2B—N2—H2C | 114 (3) | C11—C12—N4 | 118.6 (2) |
C11—N3—H3A | 112 (2) | C12—C13—C14 | 120.0 (3) |
C11—N3—H3B | 122 (2) | C12—C13—H13 | 120.0 |
H3A—N3—H3B | 119 (3) | C14—C13—H13 | 120.0 |
C12—N4—H4A | 109.4 (19) | C15—C14—C13 | 119.1 (3) |
C12—N4—H4B | 115.2 (19) | C15—C14—H14 | 120.5 |
H4A—N4—H4B | 101 (3) | C13—C14—H14 | 120.5 |
C12—N4—H4C | 108.1 (19) | C14—C15—C16 | 121.4 (3) |
H4A—N4—H4C | 111 (2) | C14—C15—H15 | 119.3 |
H4B—N4—H4C | 112 (3) | C16—C15—H15 | 119.3 |
N1—C5—C6 | 120.8 (2) | C15—C16—C11 | 121.0 (3) |
N1—C5—C10 | 121.9 (2) | C15—C16—H16 | 119.5 |
C6—C5—C10 | 117.1 (3) | C11—C16—H16 | 119.5 |
O1—C1—C2—C3 | −9.5 (4) | N1—C5—C10—C9 | −175.5 (3) |
O2—C1—C2—C3 | 170.1 (2) | C6—C5—C10—C9 | −0.4 (5) |
C1—C2—C3—C4 | 179.5 (3) | N3—C11—C12—C13 | −178.1 (3) |
C2—C3—C4—O3 | 11.2 (4) | C16—C11—C12—C13 | −2.4 (4) |
C2—C3—C4—O4 | −170.3 (2) | N3—C11—C12—N4 | −0.4 (4) |
N1—C5—C6—C7 | 175.3 (3) | C16—C11—C12—N4 | 175.3 (3) |
C10—C5—C6—C7 | 0.2 (4) | C11—C12—C13—C14 | 3.5 (5) |
N1—C5—C6—N2 | −0.9 (4) | N4—C12—C13—C14 | −174.1 (3) |
C10—C5—C6—N2 | −176.0 (3) | C12—C13—C14—C15 | −2.0 (5) |
C5—C6—C7—C8 | 0.6 (5) | C13—C14—C15—C16 | −0.5 (5) |
N2—C6—C7—C8 | 176.7 (3) | C14—C15—C16—C11 | 1.5 (6) |
C6—C7—C8—C9 | −1.1 (5) | N3—C11—C16—C15 | 175.5 (4) |
C7—C8—C9—C10 | 0.8 (5) | C12—C11—C16—C15 | −0.1 (5) |
C8—C9—C10—C5 | 0.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4C···O4i | 0.90 (1) | 1.85 (1) | 2.728 (3) | 165 (3) |
N2—H2A···O2ii | 0.90 (1) | 1.85 (1) | 2.729 (3) | 166 (3) |
N3—H3A···O3iii | 0.90 (1) | 2.29 (2) | 3.106 (3) | 150 (2) |
N1—H1A···O1iv | 0.90 (1) | 2.23 (2) | 3.101 (3) | 161 (3) |
N2—H2B···O3v | 0.92 (1) | 1.91 (1) | 2.811 (3) | 170 (2) |
N4—H4A···O1vi | 0.91 (1) | 1.93 (1) | 2.820 (3) | 167 (2) |
N3—H3B···O3 | 0.90 (1) | 2.06 (1) | 2.956 (4) | 175 (3) |
N1—H1B···O1 | 0.90 (1) | 2.05 (1) | 2.926 (4) | 166 (3) |
N4—H4B···O4 | 0.90 (1) | 1.87 (1) | 2.756 (3) | 166 (3) |
N2—H2C···O2 | 0.90 (1) | 1.90 (2) | 2.758 (4) | 159 (3) |
Symmetry codes: (i) −x, y, z+1/2; (ii) −x+1, y, z−1/2; (iii) −x+1, y, z+1/2; (iv) −x, y, z−1/2; (v) x, y, z−1; (vi) x, y, z+1. |
C7H10N+·C4H3O4− | F(000) = 944 |
Mr = 223.22 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4576 (3) Å | Cell parameters from 5904 reflections |
b = 20.8915 (6) Å | θ = 2.4–30.5° |
c = 10.8787 (3) Å | µ = 0.11 mm−1 |
β = 92.611 (2)° | T = 296 K |
V = 2147.22 (11) Å3 | Block, colourless |
Z = 8 | 0.35 × 0.30 × 0.25 mm |
Bruker Kappa APEXII CCD area-detector diffractometer | 6714 independent reflections |
Radiation source: fine-focus sealed tube | 5066 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω and ϕ scan | θmax = 30.8°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −13→13 |
Tmin = 0.904, Tmax = 0.974 | k = −30→30 |
37301 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H 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 reflections | Δρmax = 0.38 e Å−3 |
322 parameters | Δρmin = −0.21 e Å−3 |
10 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0060 (10) |
C7H10N+·C4H3O4− | V = 2147.22 (11) Å3 |
Mr = 223.22 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4576 (3) Å | µ = 0.11 mm−1 |
b = 20.8915 (6) Å | T = 296 K |
c = 10.8787 (3) Å | 0.35 × 0.30 × 0.25 mm |
β = 92.611 (2)° |
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 = 0.974 | Rint = 0.036 |
37301 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 10 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.38 e Å−3 |
6714 reflections | Δρmin = −0.21 e Å−3 |
322 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1A | 0.43546 (11) | 0.56348 (5) | 0.44152 (10) | 0.0259 (2) | |
C2A | 0.31851 (12) | 0.55954 (5) | 0.52835 (10) | 0.0280 (2) | |
H2A | 0.3420 | 0.5558 | 0.6120 | 0.034* | |
C3A | 0.18389 (12) | 0.56107 (5) | 0.49284 (10) | 0.0281 (2) | |
H3A | 0.1603 | 0.5639 | 0.4091 | 0.034* | |
C4A | 0.06734 (11) | 0.55850 (5) | 0.58021 (10) | 0.0264 (2) | |
O1A | 0.40168 (9) | 0.54851 (5) | 0.32929 (8) | 0.0354 (2) | |
O2A | 0.55489 (9) | 0.57959 (4) | 0.47927 (8) | 0.0354 (2) | |
O3A | −0.05203 (9) | 0.57690 (5) | 0.54875 (8) | 0.0371 (2) | |
O4A | 0.10196 (9) | 0.53535 (5) | 0.68711 (8) | 0.0352 (2) | |
C1B | 0.88224 (12) | 0.46968 (6) | −0.13235 (10) | 0.0295 (2) | |
C2B | 0.77182 (12) | 0.46345 (6) | −0.03965 (11) | 0.0313 (2) | |
H2B | 0.7305 | 0.4235 | −0.0298 | 0.038* | |
C3B | 0.72912 (11) | 0.51058 (6) | 0.02893 (10) | 0.0294 (2) | |
H3B | 0.7678 | 0.5511 | 0.0188 | 0.035* | |
C4B | 0.62057 (11) | 0.50152 (6) | 0.12285 (10) | 0.0281 (2) | |
O1B | 0.90421 (9) | 0.52618 (4) | −0.17321 (8) | 0.0360 (2) | |
O2B | 0.94424 (11) | 0.42135 (5) | −0.16464 (10) | 0.0482 (3) | |
O4B | 0.59879 (9) | 0.55150 (5) | 0.18837 (8) | 0.0389 (2) | |
O3B | 0.55996 (10) | 0.45025 (5) | 0.13320 (9) | 0.0408 (2) | |
C5A | −0.19758 (12) | 0.67781 (6) | 0.29071 (11) | 0.0305 (2) | |
C6A | −0.29400 (13) | 0.70841 (6) | 0.36168 (11) | 0.0316 (2) | |
H6A | −0.3402 | 0.6857 | 0.4215 | 0.038* | |
C7A | −0.32236 (13) | 0.77315 (6) | 0.34397 (11) | 0.0337 (3) | |
C8A | −0.25155 (16) | 0.80515 (7) | 0.25361 (14) | 0.0441 (3) | |
H8A | −0.2678 | 0.8486 | 0.2412 | 0.053* | |
C9A | −0.15808 (19) | 0.77375 (8) | 0.18226 (15) | 0.0547 (4) | |
H9A | −0.1132 | 0.7960 | 0.1211 | 0.066* | |
C10A | −0.12960 (16) | 0.70941 (7) | 0.19992 (14) | 0.0470 (3) | |
H10A | −0.0661 | 0.6881 | 0.1515 | 0.056* | |
C11A | −0.42577 (16) | 0.80720 (8) | 0.42128 (15) | 0.0510 (4) | |
H11A | −0.3841 | 0.8138 | 0.5024 | 0.077* | |
H11B | −0.5099 | 0.7818 | 0.4263 | 0.077* | |
H11C | −0.4496 | 0.8478 | 0.3846 | 0.077* | |
C5B | 0.30755 (12) | 0.34139 (6) | 0.23939 (11) | 0.0308 (2) | |
C6B | 0.22138 (13) | 0.30665 (6) | 0.31376 (11) | 0.0322 (2) | |
H6B | 0.1822 | 0.3262 | 0.3811 | 0.039* | |
C7B | 0.19288 (14) | 0.24264 (6) | 0.28849 (13) | 0.0378 (3) | |
C8B | 0.25360 (17) | 0.21530 (7) | 0.18802 (16) | 0.0518 (4) | |
H8B | 0.2378 | 0.1722 | 0.1707 | 0.062* | |
C9B | 0.3370 (2) | 0.25066 (9) | 0.11311 (17) | 0.0606 (5) | |
H9B | 0.3749 | 0.2314 | 0.0449 | 0.073* | |
C10B | 0.36536 (16) | 0.31450 (8) | 0.13761 (14) | 0.0478 (3) | |
H10B | 0.4217 | 0.3385 | 0.0870 | 0.057* | |
C11B | 0.09656 (18) | 0.20500 (7) | 0.36745 (16) | 0.0531 (4) | |
H11D | 0.0920 | 0.1615 | 0.3393 | 0.080* | |
H11E | 0.0035 | 0.2234 | 0.3621 | 0.080* | |
H11F | 0.1326 | 0.2060 | 0.4514 | 0.080* | |
N1A | −0.16802 (12) | 0.60972 (5) | 0.31027 (11) | 0.0371 (2) | |
N1B | 0.33623 (11) | 0.40851 (5) | 0.26898 (10) | 0.0337 (2) | |
H1AA | −0.1419 (16) | 0.6026 (7) | 0.3892 (9) | 0.040* | |
H1BB | 0.3568 (16) | 0.4140 (7) | 0.3498 (9) | 0.040* | |
H1AB | −0.0963 (13) | 0.5934 (7) | 0.2631 (12) | 0.040* | |
H1BC | 0.2561 (12) | 0.4312 (7) | 0.2519 (15) | 0.040* | |
H1BA | 0.4085 (13) | 0.4254 (7) | 0.2269 (13) | 0.040* | |
H1AC | −0.2438 (12) | 0.5854 (6) | 0.2849 (13) | 0.040* | |
H4A | 0.032 (2) | 0.5302 (16) | 0.733 (2) | 0.040* | 0.50 |
H4B | 0.527 (2) | 0.5499 (16) | 0.233 (2) | 0.040* | 0.50 |
H1A | 0.472 (2) | 0.5492 (16) | 0.284 (2) | 0.040* | 0.50 |
H1B | 0.975 (2) | 0.5291 (16) | −0.219 (2) | 0.040* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0268 (5) | 0.0239 (5) | 0.0277 (5) | 0.0019 (4) | 0.0087 (4) | 0.0026 (4) |
C2A | 0.0310 (5) | 0.0297 (5) | 0.0240 (5) | 0.0009 (4) | 0.0095 (4) | 0.0008 (4) |
C3A | 0.0312 (5) | 0.0302 (5) | 0.0237 (5) | −0.0009 (4) | 0.0096 (4) | 0.0003 (4) |
C4A | 0.0276 (5) | 0.0248 (5) | 0.0272 (5) | −0.0017 (4) | 0.0077 (4) | −0.0029 (4) |
O1A | 0.0301 (4) | 0.0499 (5) | 0.0271 (4) | −0.0023 (4) | 0.0108 (3) | −0.0046 (4) |
O2A | 0.0306 (4) | 0.0413 (5) | 0.0348 (4) | −0.0063 (4) | 0.0062 (3) | 0.0011 (4) |
O3A | 0.0303 (4) | 0.0456 (5) | 0.0359 (5) | 0.0073 (4) | 0.0067 (3) | 0.0009 (4) |
O4A | 0.0286 (4) | 0.0490 (5) | 0.0290 (4) | 0.0027 (4) | 0.0110 (3) | 0.0078 (4) |
C1B | 0.0301 (5) | 0.0327 (6) | 0.0265 (5) | 0.0037 (4) | 0.0101 (4) | −0.0006 (4) |
C2B | 0.0326 (6) | 0.0301 (6) | 0.0325 (6) | −0.0008 (4) | 0.0146 (4) | 0.0019 (4) |
C3B | 0.0285 (5) | 0.0332 (6) | 0.0276 (5) | −0.0039 (4) | 0.0119 (4) | −0.0006 (4) |
C4B | 0.0241 (5) | 0.0366 (6) | 0.0244 (5) | 0.0000 (4) | 0.0074 (4) | 0.0003 (4) |
O1B | 0.0353 (4) | 0.0343 (4) | 0.0401 (5) | 0.0037 (4) | 0.0215 (4) | 0.0059 (4) |
O2B | 0.0569 (6) | 0.0379 (5) | 0.0521 (6) | 0.0144 (4) | 0.0293 (5) | 0.0013 (4) |
O4B | 0.0348 (4) | 0.0445 (5) | 0.0392 (5) | −0.0047 (4) | 0.0192 (4) | −0.0126 (4) |
O3B | 0.0406 (5) | 0.0392 (5) | 0.0442 (5) | −0.0083 (4) | 0.0207 (4) | −0.0002 (4) |
C5A | 0.0319 (6) | 0.0286 (5) | 0.0309 (5) | 0.0016 (4) | −0.0005 (4) | −0.0010 (4) |
C6A | 0.0342 (6) | 0.0317 (6) | 0.0291 (5) | −0.0021 (5) | 0.0036 (4) | −0.0004 (4) |
C7A | 0.0344 (6) | 0.0320 (6) | 0.0347 (6) | 0.0020 (5) | −0.0005 (5) | −0.0060 (5) |
C8A | 0.0528 (8) | 0.0297 (6) | 0.0500 (8) | 0.0025 (6) | 0.0029 (6) | 0.0065 (5) |
C9A | 0.0650 (10) | 0.0482 (8) | 0.0528 (9) | 0.0016 (7) | 0.0230 (8) | 0.0170 (7) |
C10A | 0.0511 (8) | 0.0465 (8) | 0.0451 (7) | 0.0080 (6) | 0.0197 (6) | 0.0031 (6) |
C11A | 0.0478 (8) | 0.0480 (8) | 0.0577 (9) | 0.0093 (7) | 0.0064 (7) | −0.0159 (7) |
C5B | 0.0313 (5) | 0.0286 (5) | 0.0325 (6) | 0.0011 (4) | 0.0010 (4) | −0.0018 (4) |
C6B | 0.0349 (6) | 0.0301 (6) | 0.0316 (6) | 0.0004 (5) | 0.0024 (4) | −0.0012 (4) |
C7B | 0.0394 (6) | 0.0292 (6) | 0.0441 (7) | −0.0015 (5) | −0.0052 (5) | 0.0020 (5) |
C8B | 0.0573 (9) | 0.0348 (7) | 0.0633 (10) | −0.0007 (6) | 0.0025 (7) | −0.0173 (7) |
C9B | 0.0670 (11) | 0.0565 (10) | 0.0597 (10) | 0.0014 (8) | 0.0191 (8) | −0.0269 (8) |
C10B | 0.0495 (8) | 0.0501 (8) | 0.0453 (8) | −0.0048 (7) | 0.0171 (6) | −0.0088 (6) |
C11B | 0.0580 (9) | 0.0404 (8) | 0.0603 (9) | −0.0138 (7) | −0.0036 (7) | 0.0107 (7) |
N1A | 0.0376 (6) | 0.0305 (5) | 0.0431 (6) | 0.0048 (4) | 0.0010 (5) | −0.0017 (4) |
N1B | 0.0337 (5) | 0.0293 (5) | 0.0386 (5) | −0.0032 (4) | 0.0065 (4) | 0.0004 (4) |
C1A—O2A | 1.2310 (14) | C8A—C9A | 1.370 (2) |
C1A—O1A | 1.2864 (14) | C8A—H8A | 0.9300 |
C1A—C2A | 1.4892 (14) | C9A—C10A | 1.383 (2) |
C2A—C3A | 1.3139 (16) | C9A—H9A | 0.9300 |
C2A—H2A | 0.9300 | C10A—H10A | 0.9300 |
C3A—C4A | 1.4889 (15) | C11A—H11A | 0.9600 |
C3A—H3A | 0.9300 | C11A—H11B | 0.9600 |
C4A—O3A | 1.2265 (14) | C11A—H11C | 0.9600 |
C4A—O4A | 1.2879 (14) | C5B—C10B | 1.3767 (18) |
O1A—H1A | 0.852 (10) | C5B—C6B | 1.3804 (17) |
O4A—H4A | 0.853 (10) | C5B—N1B | 1.4614 (15) |
C1B—O2B | 1.2270 (14) | C6B—C7B | 1.3892 (17) |
C1B—O1B | 1.2816 (14) | C6B—H6B | 0.9300 |
C1B—C2B | 1.4901 (15) | C7B—C8B | 1.381 (2) |
C2B—C3B | 1.3102 (16) | C7B—C11B | 1.502 (2) |
C2B—H2B | 0.9300 | C8B—C9B | 1.375 (2) |
C3B—C4B | 1.4930 (14) | C8B—H8B | 0.9300 |
C3B—H3B | 0.9300 | C9B—C10B | 1.384 (2) |
C4B—O3B | 1.2225 (14) | C9B—H9B | 0.9300 |
C4B—O4B | 1.2860 (14) | C10B—H10B | 0.9300 |
O1B—H1B | 0.856 (10) | C11B—H11D | 0.9600 |
O4B—H4B | 0.851 (10) | C11B—H11E | 0.9600 |
C5A—C10A | 1.3721 (18) | C11B—H11F | 0.9600 |
C5A—C6A | 1.3786 (17) | N1A—H1AA | 0.895 (9) |
C5A—N1A | 1.4633 (15) | N1A—H1AB | 0.933 (9) |
C6A—C7A | 1.3906 (17) | N1A—H1AC | 0.911 (9) |
C6A—H6A | 0.9300 | N1B—H1BB | 0.899 (9) |
C7A—C8A | 1.3862 (19) | N1B—H1BC | 0.907 (9) |
C7A—C11A | 1.4983 (18) | N1B—H1BA | 0.911 (9) |
O2A—C1A—O1A | 124.58 (10) | C5A—C10A—H10A | 120.9 |
O2A—C1A—C2A | 120.01 (10) | C9A—C10A—H10A | 120.9 |
O1A—C1A—C2A | 115.40 (10) | C7A—C11A—H11A | 109.5 |
C3A—C2A—C1A | 123.36 (10) | C7A—C11A—H11B | 109.5 |
C3A—C2A—H2A | 118.3 | H11A—C11A—H11B | 109.5 |
C1A—C2A—H2A | 118.3 | C7A—C11A—H11C | 109.5 |
C2A—C3A—C4A | 123.17 (10) | H11A—C11A—H11C | 109.5 |
C2A—C3A—H3A | 118.4 | H11B—C11A—H11C | 109.5 |
C4A—C3A—H3A | 118.4 | C10B—C5B—C6B | 121.58 (12) |
O3A—C4A—O4A | 124.24 (10) | C10B—C5B—N1B | 119.48 (12) |
O3A—C4A—C3A | 120.62 (10) | C6B—C5B—N1B | 118.94 (11) |
O4A—C4A—C3A | 115.14 (10) | C5B—C6B—C7B | 120.29 (12) |
C1A—O1A—H1A | 112 (2) | C5B—C6B—H6B | 119.9 |
C4A—O4A—H4A | 114 (2) | C7B—C6B—H6B | 119.9 |
O2B—C1B—O1B | 124.85 (10) | C8B—C7B—C6B | 118.08 (13) |
O2B—C1B—C2B | 118.73 (11) | C8B—C7B—C11B | 121.38 (13) |
O1B—C1B—C2B | 116.42 (10) | C6B—C7B—C11B | 120.53 (13) |
C3B—C2B—C1B | 124.29 (11) | C9B—C8B—C7B | 121.15 (14) |
C3B—C2B—H2B | 117.9 | C9B—C8B—H8B | 119.4 |
C1B—C2B—H2B | 117.9 | C7B—C8B—H8B | 119.4 |
C2B—C3B—C4B | 122.27 (11) | C8B—C9B—C10B | 120.99 (14) |
C2B—C3B—H3B | 118.9 | C8B—C9B—H9B | 119.5 |
C4B—C3B—H3B | 118.9 | C10B—C9B—H9B | 119.5 |
O3B—C4B—O4B | 124.94 (10) | C5B—C10B—C9B | 117.87 (14) |
O3B—C4B—C3B | 120.93 (10) | C5B—C10B—H10B | 121.1 |
O4B—C4B—C3B | 114.14 (10) | C9B—C10B—H10B | 121.1 |
C1B—O1B—H1B | 114 (2) | C7B—C11B—H11D | 109.5 |
C4B—O4B—H4B | 116 (2) | C7B—C11B—H11E | 109.5 |
C10A—C5A—C6A | 121.58 (12) | H11D—C11B—H11E | 109.5 |
C10A—C5A—N1A | 118.66 (12) | C7B—C11B—H11F | 109.5 |
C6A—C5A—N1A | 119.75 (11) | H11D—C11B—H11F | 109.5 |
C5A—C6A—C7A | 120.12 (11) | H11E—C11B—H11F | 109.5 |
C5A—C6A—H6A | 119.9 | C5A—N1A—H1AA | 110.1 (10) |
C7A—C6A—H6A | 119.9 | C5A—N1A—H1AB | 114.5 (10) |
C8A—C7A—C6A | 118.09 (12) | H1AA—N1A—H1AB | 106.9 (13) |
C8A—C7A—C11A | 121.20 (13) | C5A—N1A—H1AC | 110.8 (10) |
C6A—C7A—C11A | 120.71 (12) | H1AA—N1A—H1AC | 112.1 (14) |
C9A—C8A—C7A | 121.06 (13) | H1AB—N1A—H1AC | 102.2 (13) |
C9A—C8A—H8A | 119.5 | C5B—N1B—H1BB | 111.6 (10) |
C7A—C8A—H8A | 119.5 | C5B—N1B—H1BC | 108.2 (10) |
C8A—C9A—C10A | 120.90 (14) | H1BB—N1B—H1BC | 105.9 (14) |
C8A—C9A—H9A | 119.6 | C5B—N1B—H1BA | 113.4 (10) |
C10A—C9A—H9A | 119.6 | H1BB—N1B—H1BA | 107.9 (14) |
C5A—C10A—C9A | 118.23 (13) | H1BC—N1B—H1BA | 109.5 (14) |
O2A—C1A—C2A—C3A | 159.72 (11) | C11A—C7A—C8A—C9A | −179.36 (14) |
O1A—C1A—C2A—C3A | −20.98 (16) | C7A—C8A—C9A—C10A | −1.2 (3) |
C1A—C2A—C3A—C4A | −178.66 (10) | C6A—C5A—C10A—C9A | 1.2 (2) |
C2A—C3A—C4A—O3A | 160.34 (12) | N1A—C5A—C10A—C9A | −179.91 (14) |
C2A—C3A—C4A—O4A | −20.44 (16) | C8A—C9A—C10A—C5A | 0.1 (3) |
O2B—C1B—C2B—C3B | 158.56 (13) | C10B—C5B—C6B—C7B | 1.22 (19) |
O1B—C1B—C2B—C3B | −21.96 (18) | N1B—C5B—C6B—C7B | −179.58 (11) |
C1B—C2B—C3B—C4B | −178.44 (10) | C5B—C6B—C7B—C8B | 0.31 (19) |
C2B—C3B—C4B—O3B | −5.18 (18) | C5B—C6B—C7B—C11B | −178.63 (12) |
C2B—C3B—C4B—O4B | 174.99 (12) | C6B—C7B—C8B—C9B | −1.6 (2) |
C10A—C5A—C6A—C7A | −1.35 (19) | C11B—C7B—C8B—C9B | 177.31 (15) |
N1A—C5A—C6A—C7A | 179.78 (11) | C7B—C8B—C9B—C10B | 1.4 (3) |
C5A—C6A—C7A—C8A | 0.18 (18) | C6B—C5B—C10B—C9B | −1.4 (2) |
C5A—C6A—C7A—C11A | −179.37 (12) | N1B—C5B—C10B—C9B | 179.40 (14) |
C6A—C7A—C8A—C9A | 1.1 (2) | C8B—C9B—C10B—C5B | 0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1BB···O2Ai | 0.90 (1) | 2.01 (1) | 2.8924 (14) | 168 (1) |
N1A—H1AB···O2Bii | 0.93 (1) | 1.86 (1) | 2.7777 (15) | 168 (1) |
N1B—H1BC···O1Bii | 0.91 (1) | 1.93 (1) | 2.8111 (14) | 165 (2) |
N1A—H1AC···O4Biii | 0.91 (1) | 1.92 (1) | 2.7993 (15) | 162 (1) |
O4A—H4A···O1Biv | 0.85 (1) | 1.62 (1) | 2.4703 (11) | 175 (3) |
O1B—H1B···O4Av | 0.86 (1) | 1.62 (1) | 2.4703 (11) | 176 (3) |
N1A—H1AA···O3A | 0.90 (1) | 1.97 (1) | 2.8539 (15) | 168 (1) |
N1B—H1BA···O3B | 0.91 (1) | 1.87 (1) | 2.7757 (13) | 173 (1) |
O4B—H4B···O1A | 0.85 (1) | 1.62 (1) | 2.4678 (11) | 175 (3) |
O1A—H1A···O4B | 0.85 (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) x−1, y, z; (iv) x−1, y, z+1; (v) x+1, y, z−1. |
C6H7ClN+·C4H3O4− | F(000) = 1008 |
Mr = 243.64 | Dx = 1.413 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2335 (4) Å | Cell parameters from 7356 reflections |
b = 23.8248 (11) Å | θ = 2.1–27.5° |
c = 10.4424 (5) Å | µ = 0.33 mm−1 |
β = 94.338 (2)° | T = 293 K |
V = 2290.60 (18) Å3 | Block, colourless |
Z = 8 | 0.35 × 0.30 × 0.25 mm |
Bruker Kappa APEXII CCD area-detector diffractometer | 5334 independent reflections |
Radiation source: fine-focus sealed tube | 3844 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω and ϕ scan | θmax = 27.7°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −12→8 |
Tmin = 0.903, Tmax = 0.912 | k = −31→26 |
25081 measured reflections | l = −13→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H 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 reflections | Δρmax = 0.40 e Å−3 |
428 parameters | Δρmin = −0.35 e Å−3 |
186 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0023 (5) |
C6H7ClN+·C4H3O4− | V = 2290.60 (18) Å3 |
Mr = 243.64 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2335 (4) Å | µ = 0.33 mm−1 |
b = 23.8248 (11) Å | T = 293 K |
c = 10.4424 (5) Å | 0.35 × 0.30 × 0.25 mm |
β = 94.338 (2)° |
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 = 0.912 | Rint = 0.032 |
25081 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 186 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.40 e Å−3 |
5334 reflections | Δρmin = −0.35 e Å−3 |
428 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1A | 0.45233 (13) | 0.45321 (5) | 0.86500 (11) | 0.0392 (3) | |
O2A | 0.40559 (12) | 0.54353 (5) | 0.82388 (11) | 0.0377 (3) | |
O3A | 0.03580 (15) | 0.41827 (6) | 1.14927 (13) | 0.0501 (4) | |
O4A | 0.08360 (12) | 0.50962 (5) | 1.16641 (11) | 0.0363 (3) | |
C1A | 0.38491 (16) | 0.49659 (7) | 0.88114 (14) | 0.0293 (3) | |
C2A | 0.26941 (16) | 0.49907 (7) | 0.97269 (14) | 0.0296 (3) | |
H2A | 0.2271 | 0.5337 | 0.9869 | 0.036* | |
C3A | 0.22344 (18) | 0.45567 (7) | 1.03456 (15) | 0.0333 (4) | |
H3A | 0.2659 | 0.4208 | 1.0227 | 0.040* | |
C4A | 0.10521 (17) | 0.46028 (7) | 1.12346 (14) | 0.0316 (3) | |
N1A | 0.67802 (16) | 0.42400 (6) | 0.72415 (15) | 0.0353 (3) | |
O1B | 1.05186 (12) | 0.56708 (5) | 0.43583 (11) | 0.0381 (3) | |
O2B | 0.88377 (12) | 0.52594 (5) | 0.30481 (11) | 0.0360 (3) | |
O3B | 0.43745 (12) | 0.57146 (5) | 0.53098 (11) | 0.0371 (3) | |
O4B | 0.60682 (12) | 0.54637 (6) | 0.68265 (10) | 0.0373 (3) | |
C1B | 0.92659 (16) | 0.55032 (6) | 0.41052 (14) | 0.0278 (3) | |
C2B | 0.81511 (17) | 0.55607 (7) | 0.50457 (14) | 0.0295 (3) | |
H2B | 0.8459 | 0.5613 | 0.5906 | 0.035* | |
C3B | 0.67561 (17) | 0.55410 (6) | 0.47239 (14) | 0.0291 (3) | |
H3B | 0.6450 | 0.5499 | 0.3860 | 0.035* | |
C4B | 0.56337 (16) | 0.55830 (6) | 0.56690 (14) | 0.0270 (3) | |
C5B | 1.19842 (19) | 0.65786 (7) | 0.68682 (17) | 0.0379 (4) | |
N1B | 1.17013 (16) | 0.59776 (6) | 0.67927 (16) | 0.0393 (3) | |
C5A | 0.71203 (19) | 0.36559 (7) | 0.75475 (17) | 0.0392 (4) | |
Cl1A | 0.8205 (6) | 0.19030 (12) | 0.8738 (3) | 0.1745 (16) | 0.60 |
C6A | 0.8285 (10) | 0.3569 (4) | 0.8412 (9) | 0.063 (2) | 0.60 |
H6A | 0.8845 | 0.3869 | 0.8733 | 0.075* | 0.60 |
C7A | 0.8618 (11) | 0.3023 (3) | 0.8805 (8) | 0.079 (2) | 0.60 |
H7A | 0.9378 | 0.2956 | 0.9422 | 0.095* | 0.60 |
C8A | 0.7828 (13) | 0.2588 (3) | 0.8281 (9) | 0.082 (3) | 0.60 |
C9A | 0.6726 (12) | 0.2674 (4) | 0.7360 (15) | 0.088 (3) | 0.60 |
H9A | 0.6223 | 0.2370 | 0.6988 | 0.105* | 0.60 |
C10A | 0.6357 (11) | 0.3215 (4) | 0.6978 (15) | 0.065 (3) | 0.60 |
H10A | 0.5608 | 0.3279 | 0.6349 | 0.078* | 0.60 |
Cl1C | 0.8042 (6) | 0.18209 (15) | 0.8052 (4) | 0.1186 (12) | 0.40 |
C6C | 0.8332 (12) | 0.3474 (6) | 0.8268 (15) | 0.060 (4) | 0.40 |
H6C | 0.8968 | 0.3732 | 0.8675 | 0.072* | 0.40 |
C7C | 0.8602 (14) | 0.2904 (5) | 0.8386 (11) | 0.067 (3) | 0.40 |
H7C | 0.9453 | 0.2777 | 0.8824 | 0.080* | 0.40 |
C8C | 0.7604 (16) | 0.2526 (4) | 0.7850 (13) | 0.066 (3) | 0.40 |
C9C | 0.6310 (17) | 0.2708 (7) | 0.725 (2) | 0.071 (3) | 0.40 |
H9C | 0.5600 | 0.2451 | 0.6967 | 0.085* | 0.40 |
C10C | 0.6072 (18) | 0.3279 (5) | 0.708 (2) | 0.052 (3) | 0.40 |
H10C | 0.5215 | 0.3407 | 0.6650 | 0.062* | 0.40 |
Cl1B | 1.2799 (5) | 0.84239 (14) | 0.7279 (5) | 0.0938 (10) | 0.60 |
C6B | 1.1728 (10) | 0.6919 (4) | 0.5837 (8) | 0.054 (2) | 0.60 |
H6B | 1.1383 | 0.6765 | 0.5055 | 0.065* | 0.60 |
C7B | 1.1968 (10) | 0.7494 (5) | 0.5921 (10) | 0.068 (2) | 0.60 |
H7B | 1.1790 | 0.7722 | 0.5203 | 0.081* | 0.60 |
C8B | 1.2467 (18) | 0.7717 (3) | 0.7064 (10) | 0.061 (3) | 0.60 |
C9B | 1.2727 (12) | 0.7391 (4) | 0.8119 (10) | 0.071 (2) | 0.60 |
H9B | 1.3051 | 0.7547 | 0.8905 | 0.085* | 0.60 |
C10B | 1.2496 (12) | 0.6818 (4) | 0.7994 (7) | 0.061 (2) | 0.60 |
H10B | 1.2699 | 0.6589 | 0.8707 | 0.074* | 0.60 |
Cl1D | 1.2622 (10) | 0.8422 (2) | 0.7046 (8) | 0.116 (2) | 0.40 |
C6D | 1.1325 (17) | 0.6918 (7) | 0.5947 (13) | 0.062 (4) | 0.40 |
H6D | 1.0738 | 0.6772 | 0.5265 | 0.074* | 0.40 |
C7D | 1.1568 (16) | 0.7491 (7) | 0.6069 (15) | 0.072 (4) | 0.40 |
H7D | 1.1118 | 0.7736 | 0.5471 | 0.087* | 0.40 |
C8D | 1.246 (3) | 0.7698 (4) | 0.706 (2) | 0.070 (5) | 0.40 |
C9D | 1.3140 (18) | 0.7334 (6) | 0.7932 (16) | 0.077 (4) | 0.40 |
H9D | 1.3789 | 0.7477 | 0.8575 | 0.092* | 0.40 |
C10D | 1.2889 (18) | 0.6758 (6) | 0.7885 (13) | 0.072 (5) | 0.40 |
H10D | 1.3305 | 0.6513 | 0.8500 | 0.086* | 0.40 |
H1A1 | 0.607 (2) | 0.4371 (11) | 0.772 (2) | 0.086* | |
H1A2 | 0.645 (3) | 0.4270 (12) | 0.6399 (12) | 0.086* | |
H1A3 | 0.7564 (19) | 0.4463 (9) | 0.741 (3) | 0.086* | |
H1B1 | 1.137 (3) | 0.5896 (12) | 0.5976 (13) | 0.086* | |
H1B2 | 1.103 (2) | 0.5882 (11) | 0.734 (2) | 0.086* | |
H1B3 | 1.2527 (18) | 0.5780 (10) | 0.698 (2) | 0.086* | |
H2C | 0.474 (5) | 0.546 (3) | 0.774 (5) | 0.086* | 0.50 |
H2D | 0.948 (5) | 0.518 (3) | 0.254 (5) | 0.086* | 0.50 |
H4C | 0.013 (4) | 0.515 (3) | 1.214 (5) | 0.086* | 0.50 |
H4D | 0.540 (5) | 0.544 (3) | 0.735 (5) | 0.086* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0347 (7) | 0.0449 (7) | 0.0402 (6) | 0.0038 (5) | 0.0170 (5) | −0.0026 (5) |
O2A | 0.0299 (7) | 0.0501 (7) | 0.0347 (6) | 0.0028 (5) | 0.0132 (5) | 0.0094 (5) |
O3A | 0.0517 (8) | 0.0472 (8) | 0.0550 (8) | −0.0106 (6) | 0.0276 (6) | 0.0013 (6) |
O4A | 0.0296 (6) | 0.0452 (7) | 0.0360 (6) | −0.0027 (5) | 0.0157 (5) | −0.0081 (5) |
C1A | 0.0232 (8) | 0.0432 (9) | 0.0217 (7) | −0.0009 (7) | 0.0038 (6) | −0.0027 (6) |
C2A | 0.0234 (8) | 0.0419 (9) | 0.0244 (7) | 0.0031 (6) | 0.0081 (6) | −0.0007 (6) |
C3A | 0.0316 (9) | 0.0390 (9) | 0.0308 (8) | 0.0015 (7) | 0.0116 (6) | −0.0041 (7) |
C4A | 0.0293 (8) | 0.0399 (9) | 0.0264 (7) | −0.0015 (7) | 0.0082 (6) | 0.0016 (6) |
N1A | 0.0293 (8) | 0.0357 (7) | 0.0418 (8) | 0.0051 (6) | 0.0090 (6) | 0.0045 (6) |
O1B | 0.0261 (6) | 0.0521 (7) | 0.0371 (6) | −0.0068 (5) | 0.0080 (5) | −0.0061 (5) |
O2B | 0.0271 (6) | 0.0531 (7) | 0.0290 (6) | −0.0043 (5) | 0.0093 (4) | −0.0098 (5) |
O3B | 0.0259 (6) | 0.0518 (7) | 0.0342 (6) | 0.0055 (5) | 0.0063 (5) | 0.0015 (5) |
O4B | 0.0271 (6) | 0.0578 (8) | 0.0281 (6) | 0.0025 (5) | 0.0091 (4) | 0.0065 (5) |
C1B | 0.0252 (8) | 0.0315 (8) | 0.0274 (7) | 0.0013 (6) | 0.0062 (6) | 0.0027 (6) |
C2B | 0.0286 (8) | 0.0374 (8) | 0.0231 (7) | 0.0004 (7) | 0.0065 (6) | −0.0010 (6) |
C3B | 0.0288 (8) | 0.0346 (8) | 0.0247 (7) | −0.0010 (6) | 0.0072 (6) | −0.0010 (6) |
C4B | 0.0247 (8) | 0.0282 (7) | 0.0288 (8) | −0.0030 (6) | 0.0076 (6) | −0.0020 (6) |
C5B | 0.0347 (9) | 0.0332 (8) | 0.0472 (10) | −0.0034 (7) | 0.0116 (8) | −0.0022 (7) |
N1B | 0.0331 (8) | 0.0321 (7) | 0.0528 (9) | −0.0027 (6) | 0.0049 (7) | −0.0012 (7) |
C5A | 0.0373 (10) | 0.0351 (9) | 0.0470 (10) | 0.0054 (7) | 0.0158 (8) | 0.0081 (8) |
Cl1A | 0.292 (4) | 0.0439 (11) | 0.184 (3) | 0.0410 (15) | −0.007 (3) | 0.0360 (16) |
C6A | 0.070 (5) | 0.040 (3) | 0.076 (4) | 0.015 (3) | −0.005 (3) | 0.017 (3) |
C7A | 0.097 (4) | 0.048 (4) | 0.090 (5) | 0.021 (3) | −0.009 (4) | 0.016 (3) |
C8A | 0.115 (6) | 0.036 (3) | 0.096 (6) | 0.011 (3) | 0.007 (4) | 0.018 (3) |
C9A | 0.090 (8) | 0.036 (3) | 0.136 (6) | −0.006 (4) | 0.002 (5) | 0.000 (3) |
C10A | 0.060 (5) | 0.049 (4) | 0.086 (5) | 0.004 (3) | 0.002 (4) | −0.006 (3) |
Cl1C | 0.153 (2) | 0.0376 (11) | 0.163 (4) | 0.0109 (12) | −0.001 (3) | 0.0204 (18) |
C6C | 0.034 (5) | 0.042 (5) | 0.101 (8) | 0.005 (3) | −0.007 (4) | 0.001 (4) |
C7C | 0.060 (4) | 0.046 (5) | 0.092 (7) | 0.018 (4) | −0.011 (5) | 0.001 (5) |
C8C | 0.070 (6) | 0.037 (3) | 0.088 (8) | 0.000 (3) | −0.003 (5) | 0.008 (4) |
C9C | 0.055 (6) | 0.047 (5) | 0.109 (7) | −0.007 (4) | 0.001 (5) | 0.010 (4) |
C10C | 0.043 (5) | 0.032 (4) | 0.082 (6) | 0.000 (4) | 0.010 (5) | 0.005 (4) |
Cl1B | 0.1114 (16) | 0.0391 (12) | 0.135 (2) | −0.0202 (10) | 0.0345 (15) | −0.0319 (13) |
C6B | 0.074 (6) | 0.046 (3) | 0.043 (2) | −0.006 (3) | 0.010 (3) | −0.0031 (19) |
C7B | 0.101 (6) | 0.042 (2) | 0.064 (3) | −0.002 (4) | 0.024 (4) | 0.009 (2) |
C8B | 0.082 (7) | 0.035 (4) | 0.071 (5) | −0.008 (5) | 0.029 (4) | −0.008 (4) |
C9B | 0.097 (6) | 0.049 (3) | 0.066 (3) | −0.011 (3) | 0.009 (4) | −0.022 (2) |
C10B | 0.093 (6) | 0.044 (3) | 0.046 (3) | −0.004 (3) | −0.005 (3) | 0.005 (2) |
Cl1D | 0.196 (6) | 0.0331 (19) | 0.120 (3) | −0.010 (2) | 0.029 (3) | 0.016 (2) |
C6D | 0.059 (7) | 0.041 (4) | 0.081 (7) | 0.000 (4) | −0.013 (5) | 0.007 (4) |
C7D | 0.076 (7) | 0.045 (4) | 0.095 (8) | 0.006 (4) | 0.007 (5) | 0.021 (5) |
C8D | 0.078 (11) | 0.028 (5) | 0.106 (11) | −0.010 (7) | 0.015 (8) | −0.002 (6) |
C9D | 0.083 (8) | 0.050 (4) | 0.095 (8) | −0.007 (5) | −0.013 (6) | −0.020 (5) |
C10D | 0.076 (8) | 0.040 (4) | 0.094 (8) | −0.004 (5) | −0.029 (6) | −0.013 (4) |
O1A—C1A | 1.2248 (19) | C5A—C10C | 1.383 (9) |
O2A—C1A | 1.289 (2) | Cl1A—C8A | 1.729 (6) |
O2A—H2C | 0.852 (10) | C6A—C7A | 1.391 (7) |
O3A—C4A | 1.229 (2) | C6A—H6A | 0.9300 |
O4A—C4A | 1.279 (2) | C7A—C8A | 1.358 (7) |
O4A—H4C | 0.855 (10) | C7A—H7A | 0.9300 |
C1A—C2A | 1.486 (2) | C8A—C9A | 1.362 (8) |
C2A—C3A | 1.307 (2) | C9A—C10A | 1.385 (8) |
C2A—H2A | 0.9300 | C9A—H9A | 0.9300 |
C3A—C4A | 1.490 (2) | C10A—H10A | 0.9300 |
C3A—H3A | 0.9300 | Cl1C—C8C | 1.737 (8) |
N1A—C5A | 1.457 (2) | C6C—C7C | 1.385 (9) |
N1A—H1A1 | 0.908 (10) | C6C—H6C | 0.9300 |
N1A—H1A2 | 0.912 (10) | C7C—C8C | 1.377 (8) |
N1A—H1A3 | 0.904 (10) | C7C—H7C | 0.9300 |
O1B—C1B | 1.2333 (19) | C8C—C9C | 1.376 (8) |
O2B—C1B | 1.2830 (19) | C9C—C10C | 1.387 (9) |
O2B—H2D | 0.850 (10) | C9C—H9C | 0.9300 |
O3B—C4B | 1.2348 (19) | C10C—H10C | 0.9300 |
O4B—C4B | 1.2765 (18) | Cl1B—C8B | 1.723 (6) |
O4B—H4D | 0.851 (10) | C6B—C7B | 1.388 (7) |
C1B—C2B | 1.482 (2) | C6B—H6B | 0.9300 |
C2B—C3B | 1.307 (2) | C7B—C8B | 1.356 (7) |
C2B—H2B | 0.9300 | C7B—H7B | 0.9300 |
C3B—C4B | 1.488 (2) | C8B—C9B | 1.355 (7) |
C3B—H3B | 0.9300 | C9B—C10B | 1.386 (7) |
C5B—C6B | 1.355 (6) | C9B—H9B | 0.9300 |
C5B—C10B | 1.359 (6) | C10B—H10B | 0.9300 |
C5B—C6D | 1.364 (9) | Cl1D—C8D | 1.730 (9) |
C5B—C10D | 1.369 (9) | C6D—C7D | 1.386 (9) |
C5B—N1B | 1.457 (2) | C6D—H6D | 0.9300 |
N1B—H1B1 | 0.905 (10) | C7D—C8D | 1.369 (9) |
N1B—H1B2 | 0.905 (10) | C7D—H7D | 0.9300 |
N1B—H1B3 | 0.905 (10) | C8D—C9D | 1.371 (9) |
C5A—C6A | 1.367 (7) | C9D—C10D | 1.392 (9) |
C5A—C6C | 1.370 (8) | C9D—H9D | 0.9300 |
C5A—C10A | 1.375 (7) | C10D—H10D | 0.9300 |
C1A—O2A—H2C | 120 (4) | C5A—C6A—C7A | 118.8 (9) |
C4A—O4A—H4C | 118 (4) | C5A—C6A—H6A | 120.6 |
O1A—C1A—O2A | 125.00 (14) | C7A—C6A—H6A | 120.6 |
O1A—C1A—C2A | 121.26 (14) | C8A—C7A—C6A | 119.6 (8) |
O2A—C1A—C2A | 113.74 (14) | C8A—C7A—H7A | 120.2 |
C3A—C2A—C1A | 124.21 (15) | C6A—C7A—H7A | 120.2 |
C3A—C2A—H2A | 117.9 | C7A—C8A—C9A | 121.4 (7) |
C1A—C2A—H2A | 117.9 | C7A—C8A—Cl1A | 121.2 (6) |
C2A—C3A—C4A | 122.03 (15) | C9A—C8A—Cl1A | 117.4 (7) |
C2A—C3A—H3A | 119.0 | C8A—C9A—C10A | 119.8 (9) |
C4A—C3A—H3A | 119.0 | C8A—C9A—H9A | 120.1 |
O3A—C4A—O4A | 125.00 (15) | C10A—C9A—H9A | 120.1 |
O3A—C4A—C3A | 119.69 (15) | C5A—C10A—C9A | 118.7 (10) |
O4A—C4A—C3A | 115.30 (14) | C5A—C10A—H10A | 120.7 |
C5A—N1A—H1A1 | 111.2 (17) | C9A—C10A—H10A | 120.7 |
C5A—N1A—H1A2 | 109.6 (18) | C5A—C6C—C7C | 119.5 (11) |
H1A1—N1A—H1A2 | 107 (2) | C5A—C6C—H6C | 120.3 |
C5A—N1A—H1A3 | 111.4 (17) | C7C—C6C—H6C | 120.3 |
H1A1—N1A—H1A3 | 107 (2) | C8C—C7C—C6C | 119.7 (11) |
H1A2—N1A—H1A3 | 110 (2) | C8C—C7C—H7C | 120.1 |
C1B—O2B—H2D | 117 (4) | C6C—C7C—H7C | 120.1 |
C4B—O4B—H4D | 115 (4) | C9C—C8C—C7C | 120.6 (10) |
O1B—C1B—O2B | 123.64 (14) | C9C—C8C—Cl1C | 123.2 (9) |
O1B—C1B—C2B | 121.02 (14) | C7C—C8C—Cl1C | 116.2 (9) |
O2B—C1B—C2B | 115.32 (13) | C8C—C9C—C10C | 119.6 (14) |
C3B—C2B—C1B | 123.14 (14) | C8C—C9C—H9C | 120.2 |
C3B—C2B—H2B | 118.4 | C10C—C9C—H9C | 120.2 |
C1B—C2B—H2B | 118.4 | C5A—C10C—C9C | 119.3 (14) |
C2B—C3B—C4B | 123.33 (14) | C5A—C10C—H10C | 120.3 |
C2B—C3B—H3B | 118.3 | C9C—C10C—H10C | 120.3 |
C4B—C3B—H3B | 118.3 | C5B—C6B—C7B | 121.5 (9) |
O3B—C4B—O4B | 124.43 (13) | C5B—C6B—H6B | 119.2 |
O3B—C4B—C3B | 120.19 (13) | C7B—C6B—H6B | 119.2 |
O4B—C4B—C3B | 115.36 (13) | C8B—C7B—C6B | 119.0 (10) |
C6B—C5B—C10B | 117.7 (6) | C8B—C7B—H7B | 120.5 |
C6B—C5B—C6D | 16.8 (10) | C6B—C7B—H7B | 120.5 |
C10B—C5B—C6D | 117.9 (9) | C9B—C8B—C7B | 121.2 (9) |
C6B—C5B—C10D | 119.3 (9) | C9B—C8B—Cl1B | 115.9 (7) |
C10B—C5B—C10D | 17.4 (12) | C7B—C8B—Cl1B | 123.0 (8) |
C6D—C5B—C10D | 125.1 (10) | C8B—C9B—C10B | 118.2 (9) |
C6B—C5B—N1B | 121.7 (5) | C8B—C9B—H9B | 120.9 |
C10B—C5B—N1B | 120.6 (4) | C10B—C9B—H9B | 120.9 |
C6D—C5B—N1B | 118.4 (8) | C5B—C10B—C9B | 122.4 (8) |
C10D—C5B—N1B | 116.5 (7) | C5B—C10B—H10B | 118.8 |
C5B—N1B—H1B1 | 108.0 (18) | C9B—C10B—H10B | 118.8 |
C5B—N1B—H1B2 | 110.0 (18) | C5B—C6D—C7D | 117.3 (15) |
H1B1—N1B—H1B2 | 110 (2) | C5B—C6D—H6D | 121.4 |
C5B—N1B—H1B3 | 110.7 (18) | C7D—C6D—H6D | 121.4 |
H1B1—N1B—H1B3 | 108 (2) | C8D—C7D—C6D | 120.6 (15) |
H1B2—N1B—H1B3 | 110 (2) | C8D—C7D—H7D | 119.7 |
C6A—C5A—C6C | 11.6 (10) | C6D—C7D—H7D | 119.7 |
C6A—C5A—C10A | 121.4 (7) | C7D—C8D—C9D | 119.5 (13) |
C6C—C5A—C10A | 111.5 (8) | C7D—C8D—Cl1D | 113.5 (13) |
C6A—C5A—C10C | 129.1 (8) | C9D—C8D—Cl1D | 127.0 (13) |
C6C—C5A—C10C | 120.7 (9) | C8D—C9D—C10D | 122.2 (14) |
C10A—C5A—C10C | 13.7 (14) | C8D—C9D—H9D | 118.9 |
C6A—C5A—N1A | 115.9 (5) | C10D—C9D—H9D | 118.9 |
C6C—C5A—N1A | 125.1 (6) | C5B—C10D—C9D | 115.2 (13) |
C10A—C5A—N1A | 122.7 (5) | C5B—C10D—H10D | 122.4 |
C10C—C5A—N1A | 114.1 (7) | C9D—C10D—H10D | 122.4 |
O1A—C1A—C2A—C3A | −5.3 (2) | C6A—C5A—C10C—C9C | −15 (3) |
O2A—C1A—C2A—C3A | 175.13 (16) | C6C—C5A—C10C—C9C | −5 (3) |
C1A—C2A—C3A—C4A | −178.80 (14) | C10A—C5A—C10C—C9C | 45 (5) |
C2A—C3A—C4A—O3A | 158.24 (17) | N1A—C5A—C10C—C9C | 176.7 (15) |
C2A—C3A—C4A—O4A | −21.0 (2) | C8C—C9C—C10C—C5A | −2 (3) |
O1B—C1B—C2B—C3B | 160.14 (16) | C10B—C5B—C6B—C7B | −0.4 (10) |
O2B—C1B—C2B—C3B | −21.4 (2) | C6D—C5B—C6B—C7B | 95 (4) |
C1B—C2B—C3B—C4B | 178.29 (14) | C10D—C5B—C6B—C7B | −20.2 (11) |
C2B—C3B—C4B—O3B | 160.21 (16) | N1B—C5B—C6B—C7B | 178.5 (4) |
C2B—C3B—C4B—O4B | −21.2 (2) | C5B—C6B—C7B—C8B | −0.2 (11) |
C6C—C5A—C6A—C7A | −38 (5) | C6B—C7B—C8B—C9B | −0.2 (17) |
C10A—C5A—C6A—C7A | −5.8 (13) | C6B—C7B—C8B—Cl1B | −179.8 (8) |
C10C—C5A—C6A—C7A | 8.1 (15) | C7B—C8B—C9B—C10B | 1.2 (18) |
N1A—C5A—C6A—C7A | 176.3 (4) | Cl1B—C8B—C9B—C10B | −179.1 (9) |
C5A—C6A—C7A—C8A | 3.0 (10) | C6B—C5B—C10B—C9B | 1.4 (13) |
C6A—C7A—C8A—C9A | 1.2 (15) | C6D—C5B—C10B—C9B | −17.6 (14) |
C6A—C7A—C8A—Cl1A | 179.9 (6) | C10D—C5B—C10B—C9B | 101 (4) |
C7A—C8A—C9A—C10A | −3 (2) | N1B—C5B—C10B—C9B | −177.5 (7) |
Cl1A—C8A—C9A—C10A | 178.6 (11) | C8B—C9B—C10B—C5B | −1.9 (16) |
C6A—C5A—C10A—C9A | 4.3 (18) | C6B—C5B—C6D—C7D | −76 (4) |
C6C—C5A—C10A—C9A | 11.0 (16) | C10B—C5B—C6D—C7D | 17.2 (11) |
C10C—C5A—C10A—C9A | −124 (7) | C10D—C5B—C6D—C7D | −1.5 (15) |
N1A—C5A—C10A—C9A | −177.9 (10) | N1B—C5B—C6D—C7D | 177.5 (5) |
C8A—C9A—C10A—C5A | 0 (2) | C5B—C6D—C7D—C8D | 1.6 (17) |
C6A—C5A—C6C—C7C | 148 (6) | C6D—C7D—C8D—C9D | 1 (3) |
C10A—C5A—C6C—C7C | −2.8 (12) | C6D—C7D—C8D—Cl1D | −179.9 (9) |
C10C—C5A—C6C—C7C | 8.5 (18) | C7D—C8D—C9D—C10D | −4 (3) |
N1A—C5A—C6C—C7C | −173.7 (5) | Cl1D—C8D—C9D—C10D | 177.3 (17) |
C5A—C6C—C7C—C8C | −4.3 (13) | C6B—C5B—C10D—C9D | 17.7 (18) |
C6C—C7C—C8C—C9C | −3.1 (19) | C10B—C5B—C10D—C9D | −72 (3) |
C6C—C7C—C8C—Cl1C | −179.9 (7) | C6D—C5B—C10D—C9D | −1 (2) |
C7C—C8C—C9C—C10C | 6 (3) | N1B—C5B—C10D—C9D | 180.0 (10) |
Cl1C—C8C—C9C—C10C | −177.1 (16) | C8D—C9D—C10D—C5B | 4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A2···O3Bi | 0.91 (1) | 1.89 (1) | 2.7958 (19) | 175 (3) |
N1A—H1A3···O4Aii | 0.90 (1) | 2.00 (1) | 2.8759 (19) | 162 (2) |
N1B—H1B2···O3Aii | 0.91 (1) | 1.84 (1) | 2.7354 (19) | 170 (3) |
N1B—H1B3···O2Aiii | 0.91 (1) | 2.03 (2) | 2.860 (2) | 153 (2) |
O2B—H2D···O4Aiv | 0.85 (1) | 1.62 (1) | 2.4592 (15) | 172 (6) |
N1A—H1A1···O1A | 0.91 (1) | 1.83 (1) | 2.7302 (18) | 172 (3) |
N1B—H1B1···O1B | 0.91 (1) | 1.89 (1) | 2.787 (2) | 173 (3) |
O2A—H2C···O4B | 0.85 (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, z−1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | 2C6H9N2+·C4H2O42− | C7H10N+·C4H3O4− | C6H7ClN+·C4H3O4− |
Mr | 332.36 | 223.22 | 243.64 |
Crystal system, space group | Orthorhombic, Iba2 | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 296 | 296 | 293 |
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, 90 | 90, 92.611 (2), 90 | 90, 94.338 (2), 90 |
V (Å3) | 3234.68 (14) | 2147.22 (11) | 2290.60 (18) |
Z | 8 | 8 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.11 | 0.33 |
Crystal size (mm) | 0.35 × 0.30 × 0.20 | 0.35 × 0.30 × 0.25 | 0.35 × 0.30 × 0.25 |
Data collection | |||
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.916, 0.980 | 0.904, 0.974 | 0.903, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9034, 3406, 2751 | 37301, 6714, 5066 | 25081, 5334, 3844 |
Rint | 0.035 | 0.036 | 0.032 |
(sin θ/λ)max (Å−1) | 0.639 | 0.720 | 0.655 |
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 reflections | 3406 | 6714 | 5334 |
No. of parameters | 247 | 322 | 428 |
No. of restraints | 11 | 10 | 186 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.23 | 0.38, −0.21 | 0.40, −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).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4C···O4i | 0.898 (10) | 1.850 (13) | 2.728 (3) | 165 (3) |
N2—H2A···O2ii | 0.899 (10) | 1.849 (13) | 2.729 (3) | 166 (3) |
N3—H3A···O3iii | 0.899 (10) | 2.294 (17) | 3.106 (3) | 150 (2) |
N1—H1A···O1iv | 0.904 (10) | 2.233 (16) | 3.101 (3) | 161 (3) |
N2—H2B···O3v | 0.915 (10) | 1.905 (11) | 2.811 (3) | 170 (2) |
N4—H4A···O1vi | 0.905 (10) | 1.930 (12) | 2.820 (3) | 167 (2) |
N3—H3B···O3 | 0.898 (10) | 2.060 (11) | 2.956 (4) | 175 (3) |
N1—H1B···O1 | 0.899 (10) | 2.045 (13) | 2.926 (4) | 166 (3) |
N4—H4B···O4 | 0.901 (10) | 1.873 (13) | 2.756 (3) | 166 (3) |
N2—H2C···O2 | 0.900 (10) | 1.899 (15) | 2.758 (4) | 159 (3) |
Symmetry codes: (i) −x, y, z+1/2; (ii) −x+1, y, z−1/2; (iii) −x+1, y, z+1/2; (iv) −x, y, z−1/2; (v) x, y, z−1; (vi) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1BB···O2Ai | 0.899 (9) | 2.008 (9) | 2.8924 (14) | 167.5 (14) |
N1A—H1AB···O2Bii | 0.933 (9) | 1.858 (9) | 2.7777 (15) | 168.1 (14) |
N1B—H1BC···O1Bii | 0.907 (9) | 1.925 (10) | 2.8111 (14) | 165.3 (15) |
N1A—H1AC···O4Biii | 0.911 (9) | 1.918 (10) | 2.7993 (15) | 162.2 (14) |
O4A—H4A···O1Biv | 0.853 (10) | 1.620 (10) | 2.4703 (11) | 175 (3) |
O1B—H1B···O4Av | 0.856 (10) | 1.616 (10) | 2.4703 (11) | 176 (3) |
N1A—H1AA···O3A | 0.895 (9) | 1.972 (9) | 2.8539 (15) | 168.1 (14) |
N1B—H1BA···O3B | 0.911 (9) | 1.869 (9) | 2.7757 (13) | 173.1 (14) |
O4B—H4B···O1A | 0.851 (10) | 1.619 (10) | 2.4678 (11) | 175 (3) |
O1A—H1A···O4B | 0.852 (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) x−1, y, z; (iv) x−1, y, z+1; (v) x+1, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A2···O3Bi | 0.912 (10) | 1.887 (10) | 2.7958 (19) | 175 (3) |
N1A—H1A3···O4Aii | 0.904 (10) | 2.003 (13) | 2.8759 (19) | 162 (2) |
N1B—H1B2···O3Aii | 0.905 (10) | 1.839 (11) | 2.7354 (19) | 170 (3) |
N1B—H1B3···O2Aiii | 0.905 (10) | 2.026 (15) | 2.860 (2) | 153 (2) |
O2B—H2D···O4Aiv | 0.850 (10) | 1.615 (13) | 2.4592 (15) | 172 (6) |
N1A—H1A1···O1A | 0.908 (10) | 1.829 (11) | 2.7302 (18) | 172 (3) |
N1B—H1B1···O1B | 0.905 (10) | 1.887 (11) | 2.787 (2) | 173 (3) |
O2A—H2C···O4B | 0.852 (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, z−1. |
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