2-{[2,8-Bis(trifluoro­meth­yl)quinolin-4-yl](hy­droxy)meth­yl}piperidin-1-ium 3-amino-5-nitro­benzoate sesquihydrate

Souza, M.V.N. de; Wardell, J.L.; Wardell, S.M.S.V.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S160053681104270X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages o3019-o3020

doi:10.1107/S160053681104270X

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2-{[2,8-Bis(trifluoromethyl)quinolin-4-yl](hydroxy)methyl}piperidin-1-ium 3-amino-5-nitrobenzoate sesquihydrate

Marcus V. N. de Souza,^a James L. Wardell,^b ‡ Solange M. S. V. Wardell,^c Seik Weng Ng ^d,^e and Edward R. T. Tiekink ^d ^*

^aFundação Oswaldo Cruz, Instituto de Tecnologia em Fármacos – Farmanguinhos, R. Sizenando Nabuco 100, Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, ^bCentro de Desenvolvimento Tecnológico em Saúde (CDTS), Fundação Oswaldo Cruz (FIOCRUZ), Casa Amarela, Campus de Manguinhos, Av. Brasil 4365, 21040-900 Rio de Janeiro, RJ, Brazil, ^cCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland, ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^eChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 11 October 2011; accepted 14 October 2011; online 22 October 2011)

The asymmetric unit of the title salt solvate, C₁₇H₁₇F₆N₂O⁺·C₇H₅N₂O₄⁻·1.5H₂O, comprises a piperidin-1-ium cation, a 3-amino-5-nitrobenzoate anion, and three fractionally occupied [i.e. 0.414 (3), 0.627 (6) and 0.459 (5)] disordered water molecules of solvation. The cation has an L shape with a C—C—C—C torsion angle of −102.9 (3)° for the atoms linking the quinolinyl group to the rest of the cation. In the anion, the carboxylate and nitro groups are essentially coplanar with the benzene ring [O—C—C—C torsion angle = 179.7 (2)° and O—N—C—C torsion angle = −3.9 (3)°]. In the crystal, extensive O—H⋯O, O—H⋯F and N—H⋯·O hydrogen bonding leads to the formation of a layer in the ab plane.

Related literature

For background information on mefloquine and derivatives, see: Kunin & Ellis (2007 ); Maguire et al. (2006 ); Dow et al. (2004 ). For selected crystal structures of mefloquine and its salts, see: Obaleye et al. (2009 ); Skórska et al. (2005 ); Karle & Karle (1991 , 2002 ); Wardell et al. (2010 , 2011 ).

Experimental

Crystal data

C₁₇H₁₇F₆N₂O⁺·C₇H₅N₂O₄⁻·1.5H₂O
M_r = 587.48
Triclinic, $[P \overline 1]$
a = 9.1705 (5) Å
b = 12.5446 (9) Å
c = 12.7788 (8) Å
α = 66.278 (4)°
β = 77.261 (4)°
γ = 71.537 (4)°
V = 1269.23 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 120 K
0.28 × 0.16 × 0.10 mm

Data collection

Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.640, T_max = 0.746
25681 measured reflections
5832 independent reflections
3477 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.174
S = 1.03
5832 reflections
416 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84 (1)	1.83 (1)	2.669 (3)	178 (3)
N4—H41⋯O2ⁱ	0.88 (1)	2.04 (1)	2.900 (3)	164 (3)
N2—H21⋯O3ⁱⁱ	0.89 (1)	1.87 (1)	2.717 (3)	159 (3)
N4—H42⋯O5ⁱⁱⁱ	0.88 (1)	2.27 (2)	3.101 (3)	159 (3)
N2—H22⋯O2W	0.89 (1)	2.05 (1)	2.916 (4)	165 (3)
N2—H22⋯O3W	0.89 (1)	1.98 (2)	2.727 (5)	141 (3)
OWw—H1W1⋯O1	0.84 (1)	2.08 (4)	2.867 (5)	156 (8)
O1W—H1W2⋯F6^iv	0.84 (1)	2.47 (7)	2.867 (5)	110 (6)
O2W—H2W1⋯O1W	0.85 (1)	2.07 (2)	2.859 (6)	154 (4)
O2W—H2W2⋯O4^v	0.85 (1)	2.30 (2)	3.119 (4)	165 (4)
O3W—H3W1⋯O3	0.84 (1)	2.21 (1)	3.049 (5)	174 (7)
O3W—H3W2⋯O4^v	0.84 (1)	2.37 (3)	3.158 (5)	156 (7)
O3W—H3W2⋯O5^v	0.84 (1)	2.32 (6)	3.016 (5)	140 (7)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1; (iii) -x+1, -y+3, -z+1; (iv) x, y+1, z; (v) -x, -y+3, -z+1.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681104270X/lh5355sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104270X/lh5355Isup2.hkl

checkCIF report

Comment top

A synthetic analogue of quinine, mefloquine, is manufactured as the racemic erythro hydrochloride salt, and is used in the prevention and treatment of malaria in combination with other drugs (Maguire et al., 2006). While it is known that both enantiomers of erythro mefloquinium hydrochloride are active, the (+) form is the more potent against the D6 and W2 strains of Plasmodium falciparum (Karle & Karle, 2002). After its introduction in 1971, mefloquine has proved to be an effective anti-malarial agent, in part due to its long half-life and the fact that it is a good prophylactic. A widespread resistance of Plasmodium sp. developed by the end of the 20th century. This, together with undesirable side-effects [e.g. anxiety, aggression, seizures, nightmares, neuropathy, insomnia, acute depression and urinary disorders] have resulted in a decline in its use (Dow et al., 2004). Derivatives of mefloquine are also been investigated against for efficacy against other diseases, e.g. as anti-viral and anti-tuberculosis agents (Kunin & Ellis, 2007). A few crystal structures of mefloquine (Skórska et al., 2005) and mefloquinium salts, including the hydrated chloride (Karle & Karle, 2002; Skórska et al., 2005), methylsulfonate (Karle & Karle, 1991), tetrachlorocobaltate (Skórska et al., 2005), and tetrachlorocuprate and tetrabromocadmate salts (Obaleye et al., 2009) have been reported. We now report the structure of the title salt, (I), in continuation of structural studies in this area (Wardell et al., 2010; Wardell et al., 2011).

The asymmetric unit of (I) comprises a piperidin-1-ium cation, a 3-amino-5-nitrobenzoate anion, and three fractionally occupied [i.e. 0.414 (3), 0.627 (6) and 0.459 (5)] disordered water molecules of solvation; the ions are illustrated in Fig. 1. The confirmation of protonation at the amine-N2 atom is found in the nature of the intermolecular interactions, see below, as well as in the equivalence of the C—O bond distances [O2—C18 = 1.251 (4) Å and O3—C18 = 1.246 (4) Å] in the anion. Overall, the cation has an L-shaped conformation as the quinolinyl residue is approximately orthogonal to the rest of the cation; the C2–C3–C12–C13 torsion angle is -102.9 (3) °. The six-membered piperidin-1-ium ring adopts a chair conformation. The anion is effectively planar with both of the carboxylate [O2—C18—C19—C20 torsion angle = 179.7 (2)°] and nitro [O4—N3—C21—C20 torsion angle = -3.9 (3)°] groups being co-planar with the benzene ring to which it is connected

The crystal packing is stabilized by hydrogen bonding, Table 1, that leads to layers in the ab plane. The carboxylate-O2 atom accepts two hydrogen bonds, one from the cation-OH and the other from the anion-amino-H. The carboxylate-O3 atom accepts a single interaction, i.e. from an ammonium-H. The second amino-H atom connects to nitro-O while the second ammonium-H hydrogen bonds water-O atoms. Water molecules form hydrogen bonds with each other and also donor hydrogen bonds to the cation-O atom, anion-O atoms and a weak contact to the F6 atom, Table 1. A view of the unit-cell contents is shown in Fig. 2 indicating layers stack along the c axis.

Related literature top

For background information on mefloquine and derivatives, see: Kunin & Ellis (2007); Maguire et al. (2006); Dow et al. (2004). For selected crystal structures of mefloquine and its salts, see: Obaleye et al. (2009); Skórska et al. (2005); Karle & Karle (1991, 2002); Wardell et al. (2010, 2011)..

Experimental top

A solution of mefloquine (0.383 g, 1 mmol) and 3-amino-5-nitrobenzoic acid (0.18 g. 1 mmol) in EtOH (15 ml) was refluxed for 20 min. On maintaining the reaction mixture at room temperature, crystals of the title salt slowly formed. M.pt.: 503–504 K (dec.). IR ν: 3600–2200(br), 1632, 1612, 1555, 1518, 1472, 1435, 1389, 1344, 1310, 1265, 1217, 1184, 1150, 1109, 1078, 1013, 970, 934, 918, 899, 887, 866, 839, 795, 783, 743, 725, 665, 542, 444 cm^-1.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structures of the components comprising the asymmetric unit in (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. The disordered water molecules of solvation have been omitted for reasons of clarity.
	Fig. 2. A view in projection along the a axis of the unit-cell contents in (I) showing the alternation of cations and anions along the c axis. The O—H···O, N—H···O and O—H···F interactions are shown as orange, blue and green dashed lines, respectively.

2-{[2,8-Bis(trifluoromethyl)quinolin-4-yl](hydroxy)methyl}piperidin-1-ium 3-amino-5-nitrobenzoate sesquihydrate top

Crystal data top

C₁₇H₁₇F₆N₂O⁺·C₇H₅N₂O₄⁻·1.5H₂O	Z = 2
M_r = 587.48	F(000) = 606
Triclinic, P1	D_x = 1.537 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1705 (5) Å	Cell parameters from 30639 reflections
b = 12.5446 (9) Å	θ = 2.9–27.5°
c = 12.7788 (8) Å	µ = 0.14 mm⁻¹
α = 66.278 (4)°	T = 120 K
β = 77.261 (4)°	Block, orange
γ = 71.537 (4)°	0.28 × 0.16 × 0.10 mm
V = 1269.23 (14) Å³

Data collection top

Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer	5832 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3477 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	R_int = 0.078
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.0°
ϕ & ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −16→16
T_min = 0.640, T_max = 0.746	l = −16→16
25681 measured reflections

Refinement top

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)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.174	w = 1/[σ²(F_o²) + (0.0836P)² + 0.2367P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5832 reflections	Δρ_max = 0.39 e Å⁻³
416 parameters	Δρ_min = −0.38 e Å⁻³
15 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (4)

Crystal data top

C₁₇H₁₇F₆N₂O⁺·C₇H₅N₂O₄⁻·1.5H₂O	γ = 71.537 (4)°
M_r = 587.48	V = 1269.23 (14) Å³
Triclinic, P1	Z = 2
a = 9.1705 (5) Å	Mo Kα radiation
b = 12.5446 (9) Å	µ = 0.14 mm⁻¹
c = 12.7788 (8) Å	T = 120 K
α = 66.278 (4)°	0.28 × 0.16 × 0.10 mm
β = 77.261 (4)°

Data collection top

Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer	5832 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	3477 reflections with I > 2σ(I)
T_min = 0.640, T_max = 0.746	R_int = 0.078
25681 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	15 restraints
wR(F²) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.39 e Å⁻³
5832 reflections	Δρ_min = −0.38 e Å⁻³
416 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
F1	0.87381 (17)	0.49471 (18)	0.83650 (15)	0.0532 (5)
F2	0.74544 (19)	0.50218 (18)	0.99348 (14)	0.0515 (5)
F3	0.7703 (2)	0.66464 (17)	0.8535 (2)	0.0766 (7)
F4	0.55227 (19)	0.21925 (14)	0.99220 (14)	0.0443 (4)
F5	0.69944 (17)	0.22502 (14)	0.83406 (15)	0.0457 (5)
F6	0.51655 (18)	0.13558 (14)	0.88618 (15)	0.0443 (4)
O1	0.3030 (2)	0.89697 (16)	0.68621 (16)	0.0321 (4)
H1	0.287 (4)	0.940 (2)	0.6179 (12)	0.048*
O2	0.2506 (2)	1.03009 (17)	0.46810 (18)	0.0442 (5)
O3	0.0666 (2)	1.19038 (17)	0.39087 (19)	0.0437 (5)
O4	0.0825 (2)	1.58565 (17)	0.37663 (17)	0.0409 (5)
O5	0.2815 (3)	1.60038 (18)	0.42819 (19)	0.0509 (6)
O1W	0.3447 (6)	1.0482 (5)	0.7901 (4)	0.0431 (14)	0.414 (3)
H1W1	0.358 (8)	0.991 (5)	0.768 (7)	0.065*	0.414 (3)
H1W2	0.413 (7)	1.086 (6)	0.754 (6)	0.065*	0.414 (3)
O2W	0.0428 (4)	1.1348 (3)	0.7158 (3)	0.0449 (11)	0.627 (6)
H2W1	0.128 (3)	1.133 (4)	0.733 (5)	0.067*	0.627 (6)
H2W2	−0.006 (5)	1.2078 (17)	0.689 (5)	0.067*	0.627 (6)
O3W	−0.0625 (6)	1.1518 (4)	0.6409 (4)	0.0467 (16)	0.459 (5)
H3W1	−0.022 (9)	1.158 (6)	0.573 (3)	0.070*	0.459 (5)
H3W2	−0.096 (9)	1.221 (3)	0.644 (6)	0.070*	0.459 (5)
N1	0.5885 (2)	0.46024 (19)	0.84811 (18)	0.0284 (5)
N2	−0.0203 (2)	0.9090 (2)	0.7489 (2)	0.0297 (5)
H21	−0.039 (3)	0.895 (3)	0.6913 (17)	0.036*
H22	0.008 (3)	0.9766 (16)	0.727 (2)	0.036*
N3	0.2069 (3)	1.5407 (2)	0.41647 (19)	0.0338 (5)
N4	0.6061 (3)	1.1835 (2)	0.5903 (2)	0.0467 (7)
H41	0.657 (3)	1.1130 (16)	0.585 (3)	0.056*
H42	0.660 (3)	1.230 (3)	0.590 (3)	0.056*
C1	0.6030 (3)	0.5648 (2)	0.8371 (2)	0.0273 (6)
C2	0.4964 (3)	0.6767 (2)	0.7926 (2)	0.0269 (6)
H2A	0.5132	0.7488	0.7899	0.032*
C3	0.3666 (3)	0.6788 (2)	0.7529 (2)	0.0261 (6)
C4	0.3486 (3)	0.5686 (2)	0.7576 (2)	0.0262 (6)
C5	0.2229 (3)	0.5601 (2)	0.7155 (2)	0.0295 (6)
H5	0.1475	0.6313	0.6800	0.035*
C6	0.2094 (3)	0.4515 (2)	0.7256 (2)	0.0320 (6)
H6A	0.1254	0.4478	0.6962	0.038*
C7	0.3189 (3)	0.3440 (2)	0.7793 (2)	0.0325 (6)
H7	0.3071	0.2686	0.7868	0.039*
C8	0.4418 (3)	0.3481 (2)	0.8204 (2)	0.0295 (6)
C9	0.4616 (3)	0.4604 (2)	0.8081 (2)	0.0273 (6)
C10	0.7471 (3)	0.5578 (2)	0.8802 (2)	0.0322 (6)
C11	0.5530 (3)	0.2330 (2)	0.8820 (3)	0.0350 (6)
C12	0.2441 (3)	0.7967 (2)	0.7111 (2)	0.0278 (6)
H12A	0.2092	0.8029	0.6396	0.033*
C13	0.1041 (3)	0.7996 (2)	0.8030 (2)	0.0281 (6)
H13	0.0664	0.7264	0.8232	0.034*
C14	−0.1666 (3)	0.9248 (3)	0.8275 (3)	0.0371 (7)
H14A	−0.2144	0.8581	0.8453	0.045*
H14B	−0.2404	1.0013	0.7885	0.045*
C15	−0.1351 (3)	0.9265 (3)	0.9384 (2)	0.0374 (7)
H15A	−0.2316	0.9299	0.9914	0.045*
H15B	−0.1005	0.9994	0.9217	0.045*
C16	−0.0107 (3)	0.8142 (3)	0.9959 (2)	0.0385 (7)
H16A	0.0126	0.8192	1.0656	0.046*
H16B	−0.0491	0.7416	1.0196	0.046*
C17	0.1353 (3)	0.8042 (3)	0.9131 (2)	0.0328 (6)
H17A	0.2141	0.7304	0.9506	0.039*
H17B	0.1773	0.8742	0.8939	0.039*
C18	0.1878 (3)	1.1404 (2)	0.4389 (2)	0.0297 (6)
C19	0.2628 (3)	1.2185 (2)	0.4629 (2)	0.0273 (6)
C20	0.1963 (3)	1.3416 (2)	0.4311 (2)	0.0275 (6)
H20	0.1021	1.3781	0.3969	0.033*
C21	0.2735 (3)	1.4088 (2)	0.4515 (2)	0.0294 (6)
C22	0.4084 (3)	1.3611 (2)	0.5017 (2)	0.0322 (6)
H22A	0.4565	1.4115	0.5137	0.039*
C23	0.4745 (3)	1.2369 (2)	0.5350 (2)	0.0325 (6)
C24	0.3990 (3)	1.1676 (2)	0.5141 (2)	0.0297 (6)
H24	0.4425	1.0832	0.5356	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0231 (8)	0.0818 (14)	0.0522 (11)	−0.0005 (8)	−0.0032 (7)	−0.0318 (10)
F2	0.0431 (10)	0.0790 (14)	0.0330 (9)	−0.0209 (9)	−0.0030 (7)	−0.0173 (9)
F3	0.0609 (12)	0.0301 (11)	0.140 (2)	−0.0128 (9)	−0.0556 (13)	−0.0075 (12)
F4	0.0490 (10)	0.0316 (10)	0.0437 (10)	−0.0045 (7)	−0.0151 (8)	−0.0043 (8)
F5	0.0274 (8)	0.0313 (9)	0.0670 (12)	0.0030 (7)	−0.0015 (8)	−0.0161 (9)
F6	0.0432 (9)	0.0209 (9)	0.0658 (11)	−0.0029 (7)	−0.0133 (8)	−0.0129 (8)
O1	0.0339 (10)	0.0219 (10)	0.0374 (10)	−0.0080 (8)	−0.0063 (8)	−0.0055 (8)
O2	0.0627 (13)	0.0206 (11)	0.0550 (13)	−0.0047 (9)	−0.0330 (11)	−0.0102 (9)
O3	0.0380 (11)	0.0283 (11)	0.0703 (14)	−0.0028 (9)	−0.0203 (10)	−0.0201 (11)
O4	0.0492 (12)	0.0263 (11)	0.0478 (12)	−0.0050 (9)	−0.0130 (10)	−0.0133 (10)
O5	0.0781 (15)	0.0252 (11)	0.0601 (14)	−0.0162 (10)	−0.0286 (12)	−0.0129 (10)
O1W	0.050 (3)	0.044 (3)	0.040 (3)	−0.017 (2)	−0.003 (2)	−0.019 (3)
O2W	0.043 (2)	0.032 (2)	0.056 (2)	−0.0070 (15)	−0.0043 (17)	−0.0147 (18)
O3W	0.049 (3)	0.030 (3)	0.055 (3)	−0.005 (2)	−0.003 (2)	−0.014 (2)
N1	0.0231 (11)	0.0252 (12)	0.0322 (12)	−0.0050 (9)	0.0003 (9)	−0.0081 (10)
N2	0.0301 (11)	0.0209 (12)	0.0385 (13)	−0.0007 (9)	−0.0104 (10)	−0.0120 (10)
N3	0.0525 (15)	0.0229 (12)	0.0296 (12)	−0.0110 (11)	−0.0067 (11)	−0.0107 (10)
N4	0.0625 (17)	0.0285 (14)	0.0600 (17)	−0.0056 (12)	−0.0316 (14)	−0.0185 (13)
C1	0.0240 (12)	0.0243 (14)	0.0288 (13)	−0.0051 (10)	−0.0005 (10)	−0.0066 (11)
C2	0.0273 (13)	0.0208 (13)	0.0288 (13)	−0.0066 (10)	0.0010 (10)	−0.0069 (11)
C3	0.0259 (13)	0.0218 (13)	0.0250 (12)	−0.0032 (10)	−0.0005 (10)	−0.0060 (11)
C4	0.0239 (12)	0.0234 (14)	0.0273 (13)	−0.0038 (10)	−0.0009 (10)	−0.0077 (11)
C5	0.0267 (13)	0.0240 (14)	0.0338 (14)	0.0004 (10)	−0.0028 (11)	−0.0119 (12)
C6	0.0265 (13)	0.0310 (15)	0.0389 (15)	−0.0043 (11)	−0.0037 (11)	−0.0152 (13)
C7	0.0300 (14)	0.0257 (15)	0.0416 (15)	−0.0041 (11)	−0.0019 (12)	−0.0153 (13)
C8	0.0256 (13)	0.0246 (14)	0.0354 (14)	−0.0014 (10)	−0.0016 (11)	−0.0125 (12)
C9	0.0207 (12)	0.0269 (14)	0.0299 (13)	−0.0044 (10)	0.0010 (10)	−0.0089 (11)
C10	0.0311 (14)	0.0240 (14)	0.0366 (15)	−0.0069 (11)	−0.0026 (12)	−0.0065 (12)
C11	0.0308 (14)	0.0220 (14)	0.0465 (17)	−0.0028 (11)	−0.0034 (12)	−0.0099 (13)
C12	0.0268 (13)	0.0188 (13)	0.0336 (14)	−0.0023 (10)	−0.0065 (11)	−0.0061 (11)
C13	0.0261 (13)	0.0150 (13)	0.0379 (14)	−0.0004 (10)	−0.0057 (11)	−0.0067 (11)
C14	0.0246 (13)	0.0301 (16)	0.0555 (18)	−0.0004 (11)	−0.0057 (12)	−0.0186 (14)
C15	0.0319 (14)	0.0318 (16)	0.0440 (16)	−0.0014 (12)	0.0000 (12)	−0.0162 (14)
C16	0.0350 (15)	0.0324 (16)	0.0402 (16)	−0.0012 (12)	0.0003 (12)	−0.0131 (14)
C17	0.0294 (13)	0.0281 (15)	0.0371 (15)	−0.0019 (11)	−0.0072 (11)	−0.0102 (12)
C18	0.0413 (15)	0.0230 (14)	0.0255 (13)	−0.0078 (12)	−0.0068 (11)	−0.0081 (11)
C19	0.0386 (14)	0.0244 (14)	0.0201 (12)	−0.0106 (11)	−0.0022 (11)	−0.0077 (11)
C20	0.0354 (14)	0.0232 (14)	0.0258 (13)	−0.0089 (11)	−0.0023 (11)	−0.0102 (11)
C21	0.0457 (16)	0.0197 (13)	0.0235 (13)	−0.0080 (11)	−0.0043 (11)	−0.0083 (11)
C22	0.0469 (16)	0.0258 (15)	0.0300 (14)	−0.0127 (12)	−0.0069 (12)	−0.0121 (12)
C23	0.0470 (16)	0.0283 (15)	0.0272 (13)	−0.0104 (12)	−0.0108 (12)	−0.0106 (12)
C24	0.0422 (15)	0.0213 (14)	0.0254 (13)	−0.0069 (11)	−0.0070 (11)	−0.0073 (11)

Geometric parameters (Å, º) top

F1—C10	1.333 (3)	C4—C5	1.423 (4)
F2—C10	1.329 (3)	C4—C9	1.425 (4)
F3—C10	1.318 (3)	C5—C6	1.359 (4)
F4—C11	1.346 (3)	C5—H5	0.9500
F5—C11	1.338 (3)	C6—C7	1.414 (4)
F6—C11	1.345 (3)	C6—H6A	0.9500
O1—C12	1.417 (3)	C7—C8	1.367 (4)
O1—H1	0.839 (10)	C7—H7	0.9500
O2—C18	1.249 (3)	C8—C9	1.419 (4)
O3—C18	1.248 (3)	C8—C11	1.501 (4)
O4—N3	1.223 (3)	C12—C13	1.540 (3)
O5—N3	1.230 (3)	C12—H12A	1.0000
O1W—H1W1	0.843 (10)	C13—C17	1.523 (4)
O1W—H1W2	0.843 (10)	C13—H13	1.0000
O2W—H2W1	0.849 (10)	C14—C15	1.516 (4)
O2W—H2W2	0.845 (10)	C14—H14A	0.9900
O3W—H2W2	1.36 (5)	C14—H14B	0.9900
O3W—H3W1	0.843 (10)	C15—C16	1.532 (4)
O3W—H3W2	0.843 (10)	C15—H15A	0.9900
N1—C1	1.307 (3)	C15—H15B	0.9900
N1—C9	1.370 (3)	C16—C17	1.518 (4)
N2—C14	1.499 (3)	C16—H16A	0.9900
N2—C13	1.502 (3)	C16—H16B	0.9900
N2—H21	0.885 (10)	C17—H17A	0.9900
N2—H22	0.886 (10)	C17—H17B	0.9900
N3—C21	1.481 (3)	C18—C19	1.513 (4)
N4—C23	1.374 (4)	C19—C24	1.384 (4)
N4—H41	0.881 (10)	C19—C20	1.389 (4)
N4—H42	0.877 (10)	C20—C21	1.384 (3)
C1—C2	1.409 (4)	C20—H20	0.9500
C1—C10	1.506 (4)	C21—C22	1.368 (4)
C2—C3	1.382 (4)	C22—C23	1.399 (4)
C2—H2A	0.9500	C22—H22A	0.9500
C3—C4	1.420 (4)	C23—C24	1.399 (4)
C3—C12	1.520 (3)	C24—H24	0.9500

C12—O1—H1	105 (2)	O1—C12—C3	111.4 (2)
H1W1—O1W—H1W2	108.9 (18)	O1—C12—C13	108.89 (19)
H2W1—O2W—H2W2	107.6 (17)	C3—C12—C13	110.1 (2)
H2W2—O3W—H3W1	114 (6)	O1—C12—H12A	108.8
H2W2—O3W—H3W2	49 (6)	C3—C12—H12A	108.8
H3W1—O3W—H3W2	108.9 (18)	C13—C12—H12A	108.8
C1—N1—C9	116.9 (2)	N2—C13—C17	109.3 (2)
C14—N2—C13	113.7 (2)	N2—C13—C12	106.8 (2)
C14—N2—H21	108.8 (18)	C17—C13—C12	115.0 (2)
C13—N2—H21	103.5 (19)	N2—C13—H13	108.5
C14—N2—H22	105.2 (18)	C17—C13—H13	108.5
C13—N2—H22	112.4 (19)	C12—C13—H13	108.5
H21—N2—H22	113 (3)	N2—C14—C15	111.1 (2)
O4—N3—O5	122.9 (2)	N2—C14—H14A	109.4
O4—N3—C21	119.5 (2)	C15—C14—H14A	109.4
O5—N3—C21	117.6 (2)	N2—C14—H14B	109.4
C23—N4—H41	114 (2)	C15—C14—H14B	109.4
C23—N4—H42	118 (2)	H14A—C14—H14B	108.0
H41—N4—H42	117 (3)	C14—C15—C16	110.9 (2)
N1—C1—C2	125.9 (2)	C14—C15—H15A	109.5
N1—C1—C10	114.0 (2)	C16—C15—H15A	109.5
C2—C1—C10	120.1 (2)	C14—C15—H15B	109.5
C3—C2—C1	118.1 (2)	C16—C15—H15B	109.5
C3—C2—H2A	121.0	H15A—C15—H15B	108.1
C1—C2—H2A	121.0	C17—C16—C15	110.0 (2)
C2—C3—C4	118.5 (2)	C17—C16—H16A	109.7
C2—C3—C12	119.6 (2)	C15—C16—H16A	109.7
C4—C3—C12	121.8 (2)	C17—C16—H16B	109.7
C3—C4—C5	123.5 (2)	C15—C16—H16B	109.7
C3—C4—C9	118.3 (2)	H16A—C16—H16B	108.2
C5—C4—C9	118.2 (2)	C16—C17—C13	111.5 (2)
C6—C5—C4	120.8 (2)	C16—C17—H17A	109.3
C6—C5—H5	119.6	C13—C17—H17A	109.3
C4—C5—H5	119.6	C16—C17—H17B	109.3
C5—C6—C7	120.8 (2)	C13—C17—H17B	109.3
C5—C6—H6A	119.6	H17A—C17—H17B	108.0
C7—C6—H6A	119.6	O3—C18—O2	123.9 (2)
C8—C7—C6	120.3 (2)	O3—C18—C19	117.8 (2)
C8—C7—H7	119.9	O2—C18—C19	118.3 (2)
C6—C7—H7	119.9	C24—C19—C20	120.2 (2)
C7—C8—C9	120.2 (2)	C24—C19—C18	119.9 (2)
C7—C8—C11	119.6 (2)	C20—C19—C18	119.8 (2)
C9—C8—C11	120.1 (2)	C21—C20—C19	117.0 (2)
N1—C9—C8	118.1 (2)	C21—C20—H20	121.5
N1—C9—C4	122.2 (2)	C19—C20—H20	121.5
C8—C9—C4	119.6 (2)	C22—C21—C20	124.0 (2)
F3—C10—F2	108.0 (2)	C22—C21—N3	117.7 (2)
F3—C10—F1	106.2 (2)	C20—C21—N3	118.2 (2)
F2—C10—F1	105.0 (2)	C21—C22—C23	119.0 (2)
F3—C10—C1	112.7 (2)	C21—C22—H22A	120.5
F2—C10—C1	112.3 (2)	C23—C22—H22A	120.5
F1—C10—C1	112.1 (2)	N4—C23—C24	120.7 (2)
F5—C11—F6	106.4 (2)	N4—C23—C22	121.4 (2)
F5—C11—F4	106.9 (2)	C24—C23—C22	117.8 (2)
F6—C11—F4	105.7 (2)	C19—C24—C23	121.9 (2)
F5—C11—C8	113.6 (2)	C19—C24—H24	119.1
F6—C11—C8	112.1 (2)	C23—C24—H24	119.1
F4—C11—C8	111.6 (2)

C9—N1—C1—C2	3.1 (4)	C9—C8—C11—F4	61.3 (3)
C9—N1—C1—C10	−178.5 (2)	C2—C3—C12—O1	18.0 (3)
N1—C1—C2—C3	−2.3 (4)	C4—C3—C12—O1	−164.9 (2)
C10—C1—C2—C3	179.3 (2)	C2—C3—C12—C13	−102.9 (3)
C1—C2—C3—C4	−0.9 (3)	C4—C3—C12—C13	74.2 (3)
C1—C2—C3—C12	176.3 (2)	C14—N2—C13—C17	−55.4 (3)
C2—C3—C4—C5	−177.6 (2)	C14—N2—C13—C12	179.6 (2)
C12—C3—C4—C5	5.3 (4)	O1—C12—C13—N2	66.0 (2)
C2—C3—C4—C9	3.0 (3)	C3—C12—C13—N2	−171.6 (2)
C12—C3—C4—C9	−174.1 (2)	O1—C12—C13—C17	−55.4 (3)
C3—C4—C5—C6	−177.9 (2)	C3—C12—C13—C17	67.0 (3)
C9—C4—C5—C6	1.4 (4)	C13—N2—C14—C15	55.0 (3)
C4—C5—C6—C7	0.7 (4)	N2—C14—C15—C16	−54.2 (3)
C5—C6—C7—C8	−1.0 (4)	C14—C15—C16—C17	56.0 (3)
C6—C7—C8—C9	−0.9 (4)	C15—C16—C17—C13	−57.8 (3)
C6—C7—C8—C11	177.1 (2)	N2—C13—C17—C16	56.6 (3)
C1—N1—C9—C8	−179.1 (2)	C12—C13—C17—C16	176.7 (2)
C1—N1—C9—C4	−0.6 (3)	O3—C18—C19—C24	−178.8 (2)
C7—C8—C9—N1	−178.4 (2)	O2—C18—C19—C24	1.1 (3)
C11—C8—C9—N1	3.6 (3)	O3—C18—C19—C20	−0.2 (3)
C7—C8—C9—C4	3.0 (4)	O2—C18—C19—C20	179.7 (2)
C11—C8—C9—C4	−175.0 (2)	C24—C19—C20—C21	0.9 (3)
C3—C4—C9—N1	−2.3 (3)	C18—C19—C20—C21	−177.7 (2)
C5—C4—C9—N1	178.3 (2)	C19—C20—C21—C22	−0.8 (4)
C3—C4—C9—C8	176.1 (2)	C19—C20—C21—N3	178.9 (2)
C5—C4—C9—C8	−3.2 (3)	O4—N3—C21—C22	−176.4 (2)
N1—C1—C10—F3	170.9 (2)	O5—N3—C21—C22	4.3 (3)
C2—C1—C10—F3	−10.5 (3)	O4—N3—C21—C20	3.9 (3)
N1—C1—C10—F2	−66.8 (3)	O5—N3—C21—C20	−175.4 (2)
C2—C1—C10—F2	111.7 (3)	C20—C21—C22—C23	0.0 (4)
N1—C1—C10—F1	51.2 (3)	N3—C21—C22—C23	−179.6 (2)
C2—C1—C10—F1	−130.3 (2)	C21—C22—C23—N4	−177.1 (3)
C7—C8—C11—F5	122.3 (3)	C21—C22—C23—C24	0.6 (4)
C9—C8—C11—F5	−59.7 (3)	C20—C19—C24—C23	−0.3 (4)
C7—C8—C11—F6	1.7 (3)	C18—C19—C24—C23	178.3 (2)
C9—C8—C11—F6	179.7 (2)	N4—C23—C24—C19	177.3 (3)
C7—C8—C11—F4	−116.7 (3)	C22—C23—C24—C19	−0.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84 (1)	1.83 (1)	2.669 (3)	178 (3)
N4—H41···O2ⁱ	0.88 (1)	2.04 (1)	2.900 (3)	164 (3)
N2—H21···O3ⁱⁱ	0.89 (1)	1.87 (1)	2.717 (3)	159 (3)
N4—H42···O5ⁱⁱⁱ	0.88 (1)	2.27 (2)	3.101 (3)	159 (3)
N2—H22···O2W	0.89 (1)	2.05 (1)	2.916 (4)	165 (3)
N2—H22···O3W	0.89 (1)	1.98 (2)	2.727 (5)	141 (3)
OWw—H1W1···O1	0.84 (1)	2.08 (4)	2.867 (5)	156 (8)
O1W—H1W2···F6^iv	0.84 (1)	2.47 (7)	2.867 (5)	110 (6)
O2W—H2W1···O1W	0.85 (1)	2.07 (2)	2.859 (6)	154 (4)
O2W—H2W2···O4^v	0.85 (1)	2.30 (2)	3.119 (4)	165 (4)
O3W—H3W1···O3	0.84 (1)	2.21 (1)	3.049 (5)	174 (7)
O3W—H3W2···O4^v	0.84 (1)	2.37 (3)	3.158 (5)	156 (7)
O3W—H3W2···O5^v	0.84 (1)	2.32 (6)	3.016 (5)	140 (7)

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₇F₆N₂O⁺·C₇H₅N₂O₄⁻·1.5H₂O
M_r	587.48
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	9.1705 (5), 12.5446 (9), 12.7788 (8)
α, β, γ (°)	66.278 (4), 77.261 (4), 71.537 (4)
V (Å³)	1269.23 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.28 × 0.16 × 0.10

Data collection
Diffractometer	Bruker–Nonius APEXII CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.640, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	25681, 5832, 3477
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.174, 1.03
No. of reflections	5832
No. of parameters	416
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.38

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.839 (10)	1.831 (11)	2.669 (3)	178 (3)
N4—H41···O2ⁱ	0.881 (10)	2.043 (14)	2.900 (3)	164 (3)
N2—H21···O3ⁱⁱ	0.885 (10)	1.871 (14)	2.717 (3)	159 (3)
N4—H42···O5ⁱⁱⁱ	0.877 (10)	2.266 (16)	3.101 (3)	159 (3)
N2—H22···O2W	0.886 (10)	2.051 (13)	2.916 (4)	165 (3)
N2—H22···O3W	0.886 (10)	1.98 (2)	2.727 (5)	141 (3)
OWw—H1W1···O1	0.843 (10)	2.08 (4)	2.867 (5)	156 (8)
O1W—H1W2···F6^iv	0.843 (10)	2.47 (7)	2.867 (5)	110 (6)
O2W—H2W1···O1W	0.849 (10)	2.07 (2)	2.859 (6)	154 (4)
O2W—H2W2···O4^v	0.845 (10)	2.295 (18)	3.119 (4)	165 (4)
O3W—H3W1···O3	0.843 (10)	2.209 (14)	3.049 (5)	174 (7)
O3W—H3W2···O4^v	0.843 (10)	2.37 (3)	3.158 (5)	156 (7)
O3W—H3W2···O5^v	0.843 (10)	2.32 (6)	3.016 (5)	140 (7)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+3, −z+1; (iv) x, y+1, z; (v) −x, −y+3, −z+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. JLW acknowledges support from CAPES and FAPEMIG (Brazil).

References

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages o3019-o3020

doi:10.1107/S160053681104270X

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-{[2,8-Bis(tri­fluoro­meth­yl)quinolin-4-yl](hy­dr­oxy)meth­yl}piperidin-1-ium 3-amino-5-nitro­benzoate sesquihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

2-{[2,8-Bis(trifluoromethyl)quinolin-4-yl](hydroxy)methyl}piperidin-1-ium 3-amino-5-nitrobenzoate sesquihydrate