research communications
2-{[2,8-Bis(trifluoromethyl)quinolin-4-yl](hydroxy)methyl}piperidin-1-ium trichloroacetate:
and Hirshfeld surface analysisaFundaçaö Oswaldo Cruz, Instituto de Tecnologia em Fármacos-Far Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and cResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The 17H17F6N2O+·C2Cl3O2−, comprises a single ion-pair. The hydroxy-O and ammonium-N atoms lie to the same side of the cation, a disposition maintained by a charge-assisted ammonium-N—H⋯O(hydroxy) hydrogen bond [the Oh—Cm—Cm–Na (h = hydroxy, m = methine, a = ammonium) torsion angle is 58.90 (19)°]. The piperidin-1-ium group is approximately perpendicular to the quinolinyl residue [Cq—Cm—Cm–Na (q = quinolinyl) is −178.90 (15)°] so that the cation, to a first approximation, has the shape of the letter L. The most prominent feature of the supramolecular association in the crystal is the formation of chains along the a-axis direction, being stabilized by charge-assisted hydrogen-bonds. Thus, ammonium-N+—H⋯O−(carboxylate) hydrogen bonds are formed whereby two ammonium cations bridge a pair of carboxylate-O atoms, leading to eight-membered {⋯O⋯HNH}2 synthons. The resulting four-ion aggregates are linked into the supramolecular chain via charge-assisted hydroxyl-O—H⋯O−(carboxylate) hydrogen bonds. The connections between the chains, leading to a three-dimensional architecture, are of the type C—X⋯π, for X = Cl and F. The analysis of the calculated Hirshfeld surface points to the importance of X⋯H contacts to the surface (X = F, 25.4% and X = Cl, 19.7%) along with a significant contribution from O⋯H hydrogen-bonds (10.2%). Conversely, H⋯H contacts, at 12.4%, make a relatively small contribution to the surface.
of the centrosymmetric title salt, CKeywords: crystal structure; mefloquine; salt; hydrogen-bonding; Hirshfeld surface analysis.
CCDC reference: 1879700
1. Chemical context
Kryptoracemic behaviour is an interesting but rare phenomenon whereby enantiomeric molecules crystallize in one of the 65 Sohncke space groups. Sohncke space groups lack an inversion centre, a rotatory inversion axis, a glide plane or a mirror plane, implying Z′ would usually be greater than 1 (unless the molecule lies on a rotation axis) and in which enantiomeric molecules, when present, are related by a e.g. a non-crystallographic centre of inversion. Reviews of this phenomenon have appeared for organic compounds (Fábián & Brock, 2010) and for coordination complexes (Bernal & Watkins, 2015). For organic molecules, kryptoracemic behaviour is uncommon and is found in only 0.1% of structures (Fábián & Brock, 2010). It is therefore of interest that pharmacologically relevant (Gonçalves et al., 2012) mefloquine/derivatives, for which there are about 30 structures included in the Cambridge Structural Database (Groom et al., 2016), present two examples of kryptoracemates (Jotani et al., 2016; Wardell, Wardell et al., 2016). In order to investigate reasons for this seemingly high propensity towards kryptoracemic behaviour in mefloquine derivatives, crystallographic studies of different mefloquinium salts have subsequently been performed (Wardell et al., 2018) and in a continuation of these, herein the crystal and molecular structures of the title salt, (I), isolated from the 1:1 crystallization of racemic mefloquine and trichloroacetic acid are described. This is complemented by an analysis of its calculated Hirshfeld surface.
2. Structural commentary
The two ions comprising the are shown in Fig. 1. The crystal of (I) is racemic. Each cation contains two chiral centres and the illustrated cation in the arbitrarily chosen is S at C12 and R at C13, i.e. conforming to the [(−)-erythro-mefloquinium] isomer. That protonation from the carboxylic acid to the base occurred during co-crystallization is readily seen in the equivalence of the C18 O2, O3 bond lengths, i.e. 1.238 (3) and 1.245 (3) Å, respectively. The formation of the piperidin-1-ium cation is supported by the pattern of hydrogen bonding involving the ammonium-N—H H atoms. Indeed, an intramolecular ammonium-N+—H⋯O(hydroxy) hydrogen bond is formed ensuring the hydroxyl-O1 and ammonium-N2 atoms are orientated to the same side of the cation with the O1—C12—C13—N2 torsion angle of 58.90 (19)° angle indicating a + syn-clinal relationship. The r.m.s. deviation for the 10 atoms comprising the quinolinyl residue is 0.0147 Å, with the hydroxy-O1 [−0.299 (3) Å] and ammonium-N2 [1.490 (4) Å] atoms lying to either side of the plane. The dihedral angle of 74.00 (5)° formed between the fused ring system and the best plane through the piperidin-1-ium ring indicates that, overall, the molecule has the shape of the letter L. This is confirmed by the +syn-clinal C3—C12—C13—C17 torsion angle of 60.1 (2)°.
of salt (I)In the anion, the r.m.s. deviation through the C2O2 atoms is 0.0131 Å with the Cl3 atom lying to one side of the plane [deviation = 1.7153 (3) Å] whereas the Cl1 [−0.9341 (3) Å] and Cl2 [−0.6170 (4) Å] atoms lie to the other side.
3. Supramolecular features
The presence of charge-assisted hydrogen bonds between the constituent ions lead to linear, supramolecular chains along the a-axis direction in the crystal of (I), Table 1 and Fig. 2(a). The most prominent feature of the packing is the formation of centrosymmetric, eight-membered {⋯O⋯HNH}2 synthons, which arise as a result of ammonium-N+—H⋯O−(carboxylate) hydrogen bonds whereby two ammonium cations bridge, via both hydrogen atoms, a pair of carboxylate-O2 atoms. The four-ion aggregates are linked into the chain via charge-assisted hydroxyl-O—H⋯O−(carboxylate) hydrogen bonds. These lead to larger centrosymmetric agglomerates, i.e. 18-membered {⋯OCO⋯HOC2NH}2 synthons. The connections between the chains are of the type C—X⋯π, for X = Cl and F. Such interactions are inherently weak, providing energies of stabilization less than 4 kcal mol−1, with those for interactions involving chloride atoms being greater than those with fluoride (Tsuzuki et al., 2016). In the crystal of (I), C—Cl⋯π(C6-quinolinyl) interactions are formed whereby the C—Cl bond is approximately parallel to the C6 ring. Each of the fluoride atoms bound to the C10 atom participates in a C—F⋯π contact as these CF3 groups lie in regions flanked by quinolinyl residues. Two of the contacts are as for the chloride atom, i.e. side on, whereas the other is best described as an end-on C—F⋯π contact as the angle subtended at the F1 atom is 170.95 (14)°. The aforementioned interactions combine to form a three-dimensional architecture. A view of the unit-cell contents is shown in Fig. 2(b).
4. Hirshfeld surface analysis
The Hirshfeld surface calculations for the title salt (I) were performed in accord with an earlier publication on a related organic salt (Jotani et al., 2018). This analysis provides a convenient means to describe the formation of the salt through the charge-assisted N—H⋯O hydrogen bonds and C—H⋯O contacts, and the influence of weak interactions involving halide substituents in the crystal. The pair of overlapping bright-red spots near the ammonium-H2N atom and carboxylate-O2 and O3 atoms of the anion on the Hirshfeld surfaces mapped over dnorm in Fig. 3 represent the charge-assisted N—H⋯O hydrogen-bonds; the methylene-C13—H⋯O3 contact, Table 2, on the Hirshfeld surface is evident as the diminutive-red spot between the respective atoms in Fig. 3(b). The presence of bright- and broad-red spots near the ammonium-H1N and H2N, hydroxyl-H1O, carboxylate-O2 and O3 atoms on the dnorm-mapped Hirshfeld surfaces indicate the influence of the charge-assisted N—H⋯O and O—H⋯O hydrogen bonds, as indicated in Fig. 4(a) and (b). The donors and acceptors of intermolecular interactions in the crystals of (I) are also highlighted with blue and red regions corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surfaces mapped over electrostatic potentials in Fig. 5. The presence of the faint-red spots near the CF3 atoms as well as the other atoms of the cation, Fig. 4(a) and (c), and the Cl1 atom, Fig. 3(b), indicate the involvement of these atoms in short interatomic contacts, Table 2. The effect of intermolecular C—X⋯π interactions (X = F, Cl), Table 1, is illustrated in Fig. 6 through the blue and orange regions near the respective donors and acceptors on the Hirshfeld surfaces mapped with shape-index properties.
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The overall two-dimensional fingerprint plot for (I), Fig. 7, and those delineated into H⋯H, O⋯H/H⋯O, F⋯H/H⋯F, F⋯F, C⋯F/F⋯C, C⋯Cl/Cl⋯C, Cl⋯H/H⋯Cl and Cl⋯Cl contacts (McKinnon et al., 2007) are illustrated in Fig. 7; the percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are summarized in Table 3. The relatively small contribution, i.e. 12.4%, from H⋯H contacts to the Hirshfeld surfaces of (I) is due to the presence of terminal halide substituents in both the cation and anion and their relatively high contribution to a major portion of the surface.
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The intermolecular N—H⋯O and O—H⋯O hydrogen-bonds in the packing of (I) indicate a significant contribution from O⋯H/H⋯O contacts to the surface and these are evident as the two pairs of superimposed long spikes with the tips at de + di ∼1.7 Å in the delineated fingerprint plot. The largest percentage contribution to the Hirshfeld surface are from F⋯H/H⋯F contacts, i.e. 25.4%. This is due to the presence of a number of short interatomic H⋯F contacts, Table 2, which are characterized as the pair of short spikes at de + di ∼ 2.5 Å in the corresponding delineated fingerprint plot. An arrow-like tip at de + di ∼ 2.8 Å in the fingerprint delineated into F⋯F contacts is due to the effect of the short interatomic F⋯F contact summarized in Table 2. The presence of short interatomic C⋯F/F⋯C contacts, Table 2, and C—F⋯π contacts (Table 1) involving fluoride atoms substituted at the methyl-C10 atom is evident from the forceps-like distribution of points in the fingerprint plot delineated into these contacts. The C—Cl⋯π contact, Table 1, involving the carboxylate-Cl3 atom, Fig. 6(a), is viewed as the spear-shaped distribution of points with the pair of adjoining tips at de + di ∼ 3.5 Å in the fingerprint plot delineated into C⋯Cl/Cl⋯C contacts. Although the interatomic Cl⋯H/H⋯Cl and Cl⋯Cl contacts make significant contributions to the Hirshfeld surface of (I), Table 3, and are reflected in the forceps-like and pencil-tip like distributions of points, respectively, in their delineated fingerprint plots, they occur at van der Waals separations. The small contribution from the other interatomic contacts to the Hirshfeld surface of (I), listed in Table 3, show negligible influence upon the packing.
5. Database survey
As noted in the Chemical context, there are two mefloquine derivatives that exhibit kryptoracemic behaviour with both examples being isolated after attempts at chiral resolution of racemic mefloquine with different carboxylic acids. In one example, two mefloquinium cations are related across a pseudo centre of inversion, and the charge balance is provided by two crystallographically independent 3,3,3-trifluoro-2-methoxy-2-phenylpropanoate anions, i.e. (+)-PhC(CF3)(OMe)CO2− (Wardell, Wardell et al., 2016). That it is not necessary to have chiral carboxylate anions is seen in the second example of kryptoracemic behaviour whereby, as a result of incomplete substitution of chloride by 4-fluorobenzenesulfonate during an experiment, the comprises a pair of pseudo-enantiomeric mefloquinium cations with equal numbers of chloride and 4-fluorobenzenesulfonate counter-ions (Jotani et al., 2016).
There are a number of other structurally characterized mefloquinium salts, namely three isomeric n-nitrobenzoates (Wardell et al., 2011), 3-amino-5-nitrobenzoate sesquihydrate (de Souza et al., 2011), hydroxy(phenyl)acetate hemihydrate (Wardell, Jotani et al., 2016) and trifluoroacetate trifluoroacetic acid hemihydrate (Low & Wardell, 2017), and all of these crystallize in centrosymmetric space groups with equal numbers of the mefloquinium enantiomers. Further studies into the interesting phenomenon of kryptoracemic behaviour in mefloquinium salts are underway.
6. Synthesis and crystallization
A solution of mefloquinium chloride (1 mmol) and sodium difluorochoroacetate (1 mmol) in EtOH (10 ml) was refluxed for 20 min. The reaction mixture was left at room temperature and after two days, colourless slabs of (I) were collected; m.p. 473–475 K. 1H NMR (DMSO-d6) δ: 1.20–1.35(2H, m), 1.55–1.75(4H, m), 3.04 (1H, br,t), 3.53 (1H, br.d), 5.90 (1H, s), 6.94 (1H, br.d), 8.01 (1H, t, J = 8.0Hz), 8.13 (1H, s), 8.42 (1H, d, J = 8.02Hz), 8.72 (1H, d, J = 8.0Hz), 9.48 (1H, br,s); resonances due to OH and NH were not observed. 13C NMR (DMSO-d6) δ: 21.43 (2×), 21.59, 44.51, 58.90, 67.85, 135.50. 121.17 (JC,F = 273.8 Hz), 121.21 (JC,F = 311.0 Hz), 123.64 (JC,F = 271.7 Hz), 126.37, 127.93 (JC,F = 29.2 Hz), 128.32, 128.68. 129.9 (JC,F = 5.2Hz), 142.78, 146.73 (JC,F = 34.5 Hz), 150.97, 159.82 (JC,F = 25.2 Hz). 19F NMR (DMSO-d6) δ: −58.65, −58.84, −66.68.
7. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The O- and N-bound H atoms were refined with distance restraints 0.84±0.01 and 0.88±0.01 Å, respectively, and refined with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N), respectively. Owing to poor agreement, most likely due to interference from the beam-stop, two reflections, i.e. (100) and (101), were omitted from the final cycles of refinement.
details are summarized in Table 4
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Supporting information
CCDC reference: 1879700
https://doi.org/10.1107/S2056989018016389/hb7786sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018016389/hb7786Isup2.hkl
Data collection: COLLECT (Hooft, 1998); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C17H17F6N2O·C2Cl3O2 | Z = 2 |
Mr = 541.69 | F(000) = 548 |
Triclinic, P1 | Dx = 1.601 Mg m−3 |
a = 6.8087 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.8568 (5) Å | Cell parameters from 25711 reflections |
c = 15.2562 (6) Å | θ = 2.9–27.5° |
α = 67.473 (2)° | µ = 0.48 mm−1 |
β = 81.663 (2)° | T = 120 K |
γ = 89.824 (3)° | Slab, colourless |
V = 1123.77 (7) Å3 | 0.30 × 0.26 × 0.21 mm |
Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer | 5114 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 3880 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.4°, θmin = 2.9° |
φ & ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | k = −15→15 |
Tmin = 0.636, Tmax = 0.746 | l = −19→19 |
23628 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.133 | w = 1/[σ2(Fo2) + (0.0695P)2 + 0.5906P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
5114 reflections | Δρmax = 0.81 e Å−3 |
307 parameters | Δρmin = −0.59 e Å−3 |
3 restraints |
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. Owing to poor agreement, perhaps owing to interference from the beam-stop, two reflections, i.e. (1 0 0) and (1 0 1), were omitted from the final cycles of the refinement. |
x | y | z | Uiso*/Ueq | ||
F1 | −0.22880 (19) | −0.00170 (13) | 1.00487 (9) | 0.0378 (3) | |
F2 | −0.38289 (18) | 0.05158 (14) | 0.88298 (9) | 0.0392 (3) | |
F3 | −0.36487 (19) | 0.17017 (13) | 0.95862 (9) | 0.0384 (3) | |
F4 | 0.1664 (2) | 0.31406 (13) | 1.01713 (9) | 0.0430 (3) | |
F5 | 0.0401 (2) | 0.46009 (13) | 0.91079 (10) | 0.0454 (4) | |
F6 | 0.3286 (3) | 0.48695 (15) | 0.94377 (13) | 0.0590 (5) | |
O1 | 0.1401 (2) | 0.03503 (14) | 0.64074 (11) | 0.0300 (3) | |
H1O | 0.058 (3) | 0.084 (2) | 0.6145 (19) | 0.045* | |
N1 | 0.0200 (3) | 0.23331 (16) | 0.88257 (12) | 0.0255 (4) | |
N2 | 0.5142 (3) | −0.04940 (16) | 0.63900 (12) | 0.0246 (4) | |
H1N | 0.420 (3) | −0.084 (2) | 0.6219 (17) | 0.029* | |
H2N | 0.565 (3) | 0.0117 (16) | 0.5858 (11) | 0.029* | |
C1 | −0.0699 (3) | 0.15108 (19) | 0.86236 (14) | 0.0248 (4) | |
C2 | 0.0070 (3) | 0.10584 (19) | 0.79255 (14) | 0.0253 (4) | |
H2 | −0.0687 | 0.0471 | 0.7811 | 0.030* | |
C3 | 0.1930 (3) | 0.14755 (18) | 0.74109 (14) | 0.0232 (4) | |
C4 | 0.2993 (3) | 0.23707 (18) | 0.76020 (14) | 0.0234 (4) | |
C5 | 0.4941 (3) | 0.28638 (19) | 0.71304 (15) | 0.0280 (4) | |
H5 | 0.5585 | 0.2614 | 0.6645 | 0.034* | |
C6 | 0.5892 (3) | 0.3690 (2) | 0.73676 (17) | 0.0330 (5) | |
H6 | 0.7195 | 0.4006 | 0.7048 | 0.040* | |
C7 | 0.4967 (4) | 0.4085 (2) | 0.80829 (17) | 0.0341 (5) | |
H7 | 0.5657 | 0.4656 | 0.8244 | 0.041* | |
C8 | 0.3084 (3) | 0.36492 (19) | 0.85441 (15) | 0.0294 (5) | |
C9 | 0.2044 (3) | 0.27756 (18) | 0.83188 (14) | 0.0244 (4) | |
C10 | −0.2631 (3) | 0.0942 (2) | 0.92713 (15) | 0.0283 (4) | |
C11 | 0.2098 (4) | 0.4061 (2) | 0.93101 (17) | 0.0365 (5) | |
C12 | 0.2837 (3) | 0.09461 (19) | 0.66926 (14) | 0.0236 (4) | |
H12 | 0.3575 | 0.1615 | 0.6113 | 0.028* | |
C13 | 0.4279 (3) | −0.00337 (18) | 0.71443 (14) | 0.0233 (4) | |
H13 | 0.5380 | 0.0361 | 0.7315 | 0.028* | |
C14 | 0.6690 (3) | −0.1405 (2) | 0.67050 (17) | 0.0317 (5) | |
H14A | 0.7833 | −0.1014 | 0.6836 | 0.038* | |
H14B | 0.7175 | −0.1693 | 0.6187 | 0.038* | |
C15 | 0.5805 (3) | −0.2485 (2) | 0.76066 (17) | 0.0330 (5) | |
H15A | 0.6859 | −0.3051 | 0.7841 | 0.040* | |
H15B | 0.4774 | −0.2935 | 0.7452 | 0.040* | |
C16 | 0.4882 (4) | −0.2063 (2) | 0.83963 (16) | 0.0332 (5) | |
H16A | 0.4233 | −0.2776 | 0.8957 | 0.040* | |
H16B | 0.5940 | −0.1701 | 0.8607 | 0.040* | |
C17 | 0.3350 (3) | −0.11181 (19) | 0.80364 (15) | 0.0291 (5) | |
H17A | 0.2230 | −0.1503 | 0.7883 | 0.035* | |
H17B | 0.2819 | −0.0829 | 0.8548 | 0.035* | |
Cl1 | 0.91440 (9) | 0.34265 (7) | 0.30595 (4) | 0.04821 (19) | |
Cl2 | 1.10599 (11) | 0.35855 (7) | 0.45615 (5) | 0.0571 (2) | |
Cl3 | 0.70646 (12) | 0.44205 (6) | 0.43618 (6) | 0.0577 (2) | |
O2 | 0.6471 (2) | 0.16019 (15) | 0.46652 (12) | 0.0369 (4) | |
O3 | 0.8236 (2) | 0.16197 (15) | 0.57789 (11) | 0.0352 (4) | |
C18 | 0.7750 (3) | 0.20401 (19) | 0.49632 (15) | 0.0259 (4) | |
C19 | 0.8759 (3) | 0.3309 (2) | 0.42622 (16) | 0.0319 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0324 (7) | 0.0401 (8) | 0.0286 (7) | 0.0043 (6) | −0.0029 (5) | −0.0006 (6) |
F2 | 0.0299 (7) | 0.0574 (9) | 0.0320 (7) | −0.0063 (6) | −0.0034 (5) | −0.0194 (7) |
F3 | 0.0352 (7) | 0.0435 (8) | 0.0343 (7) | 0.0093 (6) | 0.0029 (6) | −0.0156 (6) |
F4 | 0.0635 (9) | 0.0430 (8) | 0.0268 (7) | 0.0074 (7) | −0.0131 (6) | −0.0160 (6) |
F5 | 0.0657 (10) | 0.0403 (8) | 0.0359 (8) | 0.0224 (7) | −0.0090 (7) | −0.0208 (7) |
F6 | 0.0770 (11) | 0.0524 (10) | 0.0639 (11) | −0.0129 (8) | −0.0020 (9) | −0.0435 (9) |
O1 | 0.0328 (8) | 0.0348 (9) | 0.0298 (8) | 0.0081 (6) | −0.0138 (6) | −0.0174 (7) |
N1 | 0.0295 (9) | 0.0247 (9) | 0.0230 (8) | 0.0073 (7) | −0.0070 (7) | −0.0088 (7) |
N2 | 0.0304 (9) | 0.0238 (9) | 0.0227 (9) | 0.0022 (7) | −0.0058 (7) | −0.0118 (7) |
C1 | 0.0274 (10) | 0.0259 (10) | 0.0204 (10) | 0.0069 (8) | −0.0062 (8) | −0.0072 (8) |
C2 | 0.0281 (10) | 0.0247 (10) | 0.0243 (10) | 0.0032 (8) | −0.0076 (8) | −0.0097 (8) |
C3 | 0.0292 (10) | 0.0202 (10) | 0.0200 (9) | 0.0044 (8) | −0.0059 (8) | −0.0068 (8) |
C4 | 0.0290 (10) | 0.0187 (9) | 0.0216 (10) | 0.0052 (8) | −0.0066 (8) | −0.0060 (8) |
C5 | 0.0324 (11) | 0.0231 (10) | 0.0258 (10) | 0.0023 (8) | −0.0023 (8) | −0.0073 (8) |
C6 | 0.0346 (11) | 0.0231 (11) | 0.0356 (12) | −0.0030 (9) | −0.0024 (9) | −0.0062 (9) |
C7 | 0.0433 (13) | 0.0210 (10) | 0.0381 (13) | −0.0012 (9) | −0.0123 (10) | −0.0092 (9) |
C8 | 0.0416 (12) | 0.0208 (10) | 0.0269 (11) | 0.0042 (9) | −0.0084 (9) | −0.0094 (9) |
C9 | 0.0310 (10) | 0.0203 (10) | 0.0220 (10) | 0.0052 (8) | −0.0073 (8) | −0.0072 (8) |
C10 | 0.0301 (11) | 0.0312 (11) | 0.0239 (10) | 0.0066 (9) | −0.0068 (8) | −0.0103 (9) |
C11 | 0.0532 (14) | 0.0278 (11) | 0.0333 (12) | 0.0029 (10) | −0.0092 (11) | −0.0162 (10) |
C12 | 0.0274 (10) | 0.0253 (10) | 0.0195 (9) | 0.0032 (8) | −0.0056 (8) | −0.0094 (8) |
C13 | 0.0284 (10) | 0.0240 (10) | 0.0206 (9) | 0.0032 (8) | −0.0050 (8) | −0.0117 (8) |
C14 | 0.0305 (11) | 0.0312 (12) | 0.0374 (12) | 0.0072 (9) | −0.0062 (9) | −0.0174 (10) |
C15 | 0.0360 (12) | 0.0257 (11) | 0.0382 (13) | 0.0059 (9) | −0.0094 (10) | −0.0121 (10) |
C16 | 0.0425 (12) | 0.0259 (11) | 0.0289 (11) | 0.0054 (9) | −0.0102 (9) | −0.0063 (9) |
C17 | 0.0361 (11) | 0.0272 (11) | 0.0225 (10) | 0.0056 (9) | −0.0053 (9) | −0.0077 (9) |
Cl1 | 0.0439 (3) | 0.0694 (5) | 0.0241 (3) | 0.0045 (3) | −0.0020 (2) | −0.0114 (3) |
Cl2 | 0.0573 (4) | 0.0519 (4) | 0.0510 (4) | −0.0245 (3) | −0.0205 (3) | −0.0033 (3) |
Cl3 | 0.0819 (5) | 0.0298 (3) | 0.0581 (4) | 0.0197 (3) | −0.0082 (4) | −0.0145 (3) |
O2 | 0.0414 (9) | 0.0423 (9) | 0.0345 (9) | −0.0046 (7) | −0.0039 (7) | −0.0238 (8) |
O3 | 0.0335 (8) | 0.0359 (9) | 0.0297 (8) | 0.0021 (7) | −0.0083 (7) | −0.0045 (7) |
C18 | 0.0260 (10) | 0.0250 (10) | 0.0294 (11) | 0.0046 (8) | −0.0019 (8) | −0.0145 (9) |
C19 | 0.0379 (12) | 0.0302 (12) | 0.0265 (11) | 0.0027 (9) | −0.0079 (9) | −0.0088 (9) |
F1—C10 | 1.341 (2) | C7—C8 | 1.367 (3) |
F2—C10 | 1.341 (2) | C7—H7 | 0.9500 |
F3—C10 | 1.324 (2) | C8—C9 | 1.429 (3) |
F4—C11 | 1.340 (3) | C8—C11 | 1.504 (3) |
F5—C11 | 1.337 (3) | C12—C13 | 1.538 (3) |
F6—C11 | 1.344 (3) | C12—H12 | 1.0000 |
O1—C12 | 1.417 (2) | C13—C17 | 1.523 (3) |
O1—H1O | 0.835 (10) | C13—H13 | 1.0000 |
N1—C1 | 1.307 (3) | C14—C15 | 1.519 (3) |
N1—C9 | 1.364 (3) | C14—H14A | 0.9900 |
N2—C13 | 1.500 (2) | C14—H14B | 0.9900 |
N2—C14 | 1.501 (3) | C15—C16 | 1.529 (3) |
N2—H1N | 0.882 (10) | C15—H15A | 0.9900 |
N2—H2N | 0.879 (10) | C15—H15B | 0.9900 |
C1—C2 | 1.404 (3) | C16—C17 | 1.527 (3) |
C1—C10 | 1.510 (3) | C16—H16A | 0.9900 |
C2—C3 | 1.372 (3) | C16—H16B | 0.9900 |
C2—H2 | 0.9500 | C17—H17A | 0.9900 |
C3—C4 | 1.428 (3) | C17—H17B | 0.9900 |
C3—C12 | 1.518 (3) | Cl1—C19 | 1.766 (2) |
C4—C9 | 1.428 (3) | Cl2—C19 | 1.759 (2) |
C4—C5 | 1.423 (3) | Cl3—C19 | 1.784 (2) |
C5—C6 | 1.361 (3) | O2—C18 | 1.238 (3) |
C5—H5 | 0.9500 | O3—C18 | 1.245 (3) |
C6—C7 | 1.413 (3) | C18—C19 | 1.562 (3) |
C6—H6 | 0.9500 | ||
C12—O1—H1O | 110 (2) | F6—C11—C8 | 111.3 (2) |
C1—N1—C9 | 116.91 (17) | O1—C12—C3 | 112.85 (16) |
C13—N2—C14 | 113.36 (16) | O1—C12—C13 | 105.73 (16) |
C13—N2—H1N | 110.4 (15) | C3—C12—C13 | 110.13 (16) |
C14—N2—H1N | 108.4 (16) | O1—C12—H12 | 109.3 |
C13—N2—H2N | 110.7 (16) | C3—C12—H12 | 109.3 |
C14—N2—H2N | 109.4 (16) | C13—C12—H12 | 109.3 |
H1N—N2—H2N | 104 (2) | N2—C13—C17 | 108.72 (16) |
N1—C1—C2 | 125.37 (19) | N2—C13—C12 | 107.06 (16) |
N1—C1—C10 | 115.36 (18) | C17—C13—C12 | 115.11 (17) |
C2—C1—C10 | 119.01 (18) | N2—C13—H13 | 108.6 |
C3—C2—C1 | 119.12 (19) | C17—C13—H13 | 108.6 |
C3—C2—H2 | 120.4 | C12—C13—H13 | 108.6 |
C1—C2—H2 | 120.4 | N2—C14—C15 | 109.75 (17) |
C2—C3—C4 | 118.17 (18) | N2—C14—H14A | 109.7 |
C2—C3—C12 | 119.94 (18) | C15—C14—H14A | 109.7 |
C4—C3—C12 | 121.84 (17) | N2—C14—H14B | 109.7 |
C9—C4—C5 | 118.59 (18) | C15—C14—H14B | 109.7 |
C9—C4—C3 | 117.62 (18) | H14A—C14—H14B | 108.2 |
C5—C4—C3 | 123.78 (18) | C14—C15—C16 | 111.18 (18) |
C6—C5—C4 | 120.7 (2) | C14—C15—H15A | 109.4 |
C6—C5—H5 | 119.6 | C16—C15—H15A | 109.4 |
C4—C5—H5 | 119.6 | C14—C15—H15B | 109.4 |
C5—C6—C7 | 121.0 (2) | C16—C15—H15B | 109.4 |
C5—C6—H6 | 119.5 | H15A—C15—H15B | 108.0 |
C7—C6—H6 | 119.5 | C17—C16—C15 | 110.84 (18) |
C8—C7—C6 | 120.3 (2) | C17—C16—H16A | 109.5 |
C8—C7—H7 | 119.9 | C15—C16—H16A | 109.5 |
C6—C7—H7 | 119.9 | C17—C16—H16B | 109.5 |
C7—C8—C9 | 120.4 (2) | C15—C16—H16B | 109.5 |
C7—C8—C11 | 120.5 (2) | H16A—C16—H16B | 108.1 |
C9—C8—C11 | 119.1 (2) | C13—C17—C16 | 110.83 (18) |
N1—C9—C4 | 122.80 (18) | C13—C17—H17A | 109.5 |
N1—C9—C8 | 118.09 (18) | C16—C17—H17A | 109.5 |
C4—C9—C8 | 119.07 (19) | C13—C17—H17B | 109.5 |
F3—C10—F1 | 106.88 (17) | C16—C17—H17B | 109.5 |
F3—C10—F2 | 107.34 (17) | H17A—C17—H17B | 108.1 |
F1—C10—F2 | 106.53 (17) | O2—C18—O3 | 127.3 (2) |
F3—C10—C1 | 113.66 (18) | O2—C18—C19 | 116.35 (19) |
F1—C10—C1 | 110.42 (16) | O3—C18—C19 | 116.19 (18) |
F2—C10—C1 | 111.64 (17) | C18—C19—Cl2 | 111.80 (15) |
F5—C11—F4 | 106.7 (2) | C18—C19—Cl1 | 111.57 (15) |
F5—C11—F6 | 106.71 (19) | Cl2—C19—Cl1 | 108.50 (12) |
F4—C11—F6 | 105.65 (19) | C18—C19—Cl3 | 105.96 (14) |
F5—C11—C8 | 113.08 (19) | Cl2—C19—Cl3 | 110.39 (13) |
F4—C11—C8 | 112.85 (19) | Cl1—C19—Cl3 | 108.56 (12) |
C9—N1—C1—C2 | −0.6 (3) | N1—C1—C10—F2 | 154.97 (17) |
C9—N1—C1—C10 | 173.54 (17) | C2—C1—C10—F2 | −30.5 (3) |
N1—C1—C2—C3 | 1.3 (3) | C7—C8—C11—F5 | 120.8 (2) |
C10—C1—C2—C3 | −172.61 (18) | C9—C8—C11—F5 | −60.6 (3) |
C1—C2—C3—C4 | −0.9 (3) | C7—C8—C11—F4 | −118.0 (2) |
C1—C2—C3—C12 | 176.57 (18) | C9—C8—C11—F4 | 60.7 (3) |
C2—C3—C4—C9 | −0.1 (3) | C7—C8—C11—F6 | 0.7 (3) |
C12—C3—C4—C9 | −177.48 (17) | C9—C8—C11—F6 | 179.31 (19) |
C2—C3—C4—C5 | 179.01 (19) | C2—C3—C12—O1 | 19.3 (3) |
C12—C3—C4—C5 | 1.6 (3) | C4—C3—C12—O1 | −163.38 (17) |
C9—C4—C5—C6 | 1.0 (3) | C2—C3—C12—C13 | −98.6 (2) |
C3—C4—C5—C6 | −178.1 (2) | C4—C3—C12—C13 | 78.7 (2) |
C4—C5—C6—C7 | −0.4 (3) | C14—N2—C13—C17 | −58.8 (2) |
C5—C6—C7—C8 | −0.6 (3) | C14—N2—C13—C12 | 176.26 (16) |
C6—C7—C8—C9 | 1.0 (3) | O1—C12—C13—N2 | 58.90 (19) |
C6—C7—C8—C11 | 179.6 (2) | C3—C12—C13—N2 | −178.90 (15) |
C1—N1—C9—C4 | −0.5 (3) | O1—C12—C13—C17 | −62.1 (2) |
C1—N1—C9—C8 | −178.23 (18) | C3—C12—C13—C17 | 60.1 (2) |
C5—C4—C9—N1 | −178.32 (18) | C13—N2—C14—C15 | 57.8 (2) |
C3—C4—C9—N1 | 0.8 (3) | N2—C14—C15—C16 | −54.6 (2) |
C5—C4—C9—C8 | −0.6 (3) | C14—C15—C16—C17 | 55.1 (2) |
C3—C4—C9—C8 | 178.53 (18) | N2—C13—C17—C16 | 57.1 (2) |
C7—C8—C9—N1 | 177.45 (19) | C12—C13—C17—C16 | 177.17 (17) |
C11—C8—C9—N1 | −1.2 (3) | C15—C16—C17—C13 | −56.5 (2) |
C7—C8—C9—C4 | −0.4 (3) | O2—C18—C19—Cl2 | −159.24 (16) |
C11—C8—C9—C4 | −179.02 (19) | O3—C18—C19—Cl2 | 25.0 (2) |
N1—C1—C10—F3 | 33.4 (2) | O2—C18—C19—Cl1 | −37.5 (2) |
C2—C1—C10—F3 | −152.12 (18) | O3—C18—C19—Cl1 | 146.68 (16) |
N1—C1—C10—F1 | −86.7 (2) | O2—C18—C19—Cl3 | 80.4 (2) |
C2—C1—C10—F1 | 87.8 (2) | O3—C18—C19—Cl3 | −95.35 (19) |
Cg1 and Cg2 are the centroids of the C4–C9 and N1/C1–C4/C9 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O1 | 0.88 (2) | 2.42 (2) | 2.734 (3) | 102 (2) |
N2—H1N···O2i | 0.88 (2) | 1.99 (2) | 2.769 (3) | 146 (2) |
O1—H1O···O3ii | 0.83 (2) | 1.89 (2) | 2.702 (2) | 165 (2) |
N2—H2N···O2 | 0.88 (2) | 2.00 (2) | 2.869 (2) | 173 (2) |
N2—H2N···O3 | 0.88 (2) | 2.47 (2) | 3.043 (3) | 124 (1) |
C19—Cl3···Cg1iii | 1.78 (1) | 3.61 (1) | 4.709 (3) | 118 (1) |
C10—F1···Cg2iv | 1.34 (1) | 3.07 (1) | 4.395 (2) | 171 (1) |
C10—F2···Cg1ii | 1.34 (1) | 3.44 (1) | 3.788 (2) | 95 (1) |
C10—F3···Cg1ii | 1.32 (1) | 3.24 (1) | 3.788 (2) | 104 (1) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x, −y, −z+2. |
Contact | Distance | Symmetry operation |
C1···F1 | 3.130 (2) | -x, -y, 2 - z |
C7···F3 | 3.127 (3) | 1 + x, y, z |
O3···H13 | 2.49 | x, y, z |
F1···F2 | 2.8618 (18) | -1 - x, -y, 2 - z |
F1···H17B | 2.58 | -x, -y, 2 - z |
F5···Cl1 | 3.2065 (16) | 1 - x, 1 - y, 1 - z |
F2···H13 | 2.46 | -1 + x, y, z |
Note: (a) Values are as calculated in CrystalExplorer (Spackman & Jayatilaka, 2009). |
Percentage contribution | |
Contact | (I) |
H···H | 12.4 |
O···H/H···O | 10.2 |
F···H/H···F | 25.4 |
F···F | 7.7 |
Cl···H/H···Cl | 19.7 |
C···F/F···C | 5.4 |
C···Cl/Cl···C | 5.3 |
Cl···Cl | 4.6 |
C···H/H···C | 3.4 |
Cl···F/F···Cl | 2.7 |
N···H/H···N | 1.3 |
N···F/F···N | 1.0 |
O···O | 0.5 |
C···C | 0.3 |
C···O/O···C | 0.2 |
Cl···O/O···Cl | 0.1 |
Footnotes
‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.
Acknowledgements
The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged.
Funding information
JLW acknowledges support from CNPq (Brazil).
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