Enrofloxacinium picrate

Jasinski, J.P.; Butcher, R.J.; Siddegowda, M.S.; Yathirajan, H.S.; Siddaraju, B.P.

doi:10.1107/S160053681100170X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages o432-o433

doi:10.1107/S160053681100170X

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Enrofloxacinium picrate

Jerry P. Jasinski,^a ^* Ray J. Butcher,^b M. S. Siddegowda,^c H. S. Yathirajan ^c and B. P. Siddaraju ^c

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 27 December 2010; accepted 11 January 2011; online 22 January 2011)

There is one cation–anion pair in the asymmetric unit of the title compound [systematic name: 4-(3-carboxy-6-fluoro-4-oxo-1,4-dihydroquinolin-7-yl)-1-ethylpiperazin-1-ium 2,4,6-trinitrophenolate], C₁₉H₂₃FN₃O₃⁺·C₆H₂N₃O₇⁻. The six-membered piperazine group in the cation adopts a slightly distorted chair conformation and contains a protonated N atom. The dihedral angles between the mean planes of the cyclopropyl and piperazine rings in the cation with the 10-atom ring system of the quinolone group are 48.1 (1) and 69.9 (5)°, respectively. The picrate anion interacts with the protonated N atom of an adjacent cation through a bifurcated N—H⋯O three-center hydrogen bond, forming an R₁²(6) ring motif. Furthermore, there is an intramolecular O—H⋯O hydrogen bond. The dihedral angle between the mean planes of the anion benzene and cation piperizine, quinoline and cyclopropyl rings are 61.3 (6), 31.1 (4) and 70.4 (9)°, respectively. The mean planes of the two o-NO₂ and single p-NO₂ groups in the picrate anion are twisted by 6.7 (6), 38.3 (9) and 12.8 (7)° with respect to the mean plane of the benzene ring. Strong N—H⋯O and weak intermolecular C—H⋯O hydrogen bonds in concert with weak π–π stacking interactions [centroid–centroid distances = 3.5785 (13), 3.7451 (12) and 3.6587 (13) Å] dominate the crystal packing.

Related literature

For background to fluoroquinolones, see: Bhanot et al. (2001 ); Scholar (2003 ). For related structures, see: Hu & Yu, (2005 ); Jasinski et al. (2009 , 2010a , 2010b ); Recillas-Mota et al. (2007 ); Sun et al. (2004 ); Wang et al. (2005 ); Zou et al. (2005 ). For puckering parameters, see: Cremer & Pople (1975 ). For standard bond lengths, see: Allen et al. (1987).

Experimental

Crystal data

C₁₉H₂₃FN₃O₃⁺·C₆H₂N₃O₇⁻
M_r = 588.51
Triclinic, $[P \overline 1]$
a = 7.2111 (7) Å
b = 12.5766 (7) Å
c = 16.2362 (4) Å
α = 105.556 (2)°
β = 96.367 (6)°
γ = 96.223 (7)°
V = 1395.04 (16) Å³
Z = 2
Cu Kα radiation
μ = 0.98 mm⁻¹
T = 295 K
0.44 × 0.31 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England.]$ ) T_min = 0.896, T_max = 1.000
9440 measured reflections
5437 independent reflections
3425 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.177
S = 1.00
5437 reflections
382 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.82	1.78	2.536 (3)	151
N3—H3A⋯O1A	0.91	1.87	2.724 (3)	155
N3—H3A⋯O7A	0.91	2.38	3.024 (3)	128
C11—H11A⋯O3ⁱ	0.98	2.55	3.385 (3)	144
C15—H15B⋯O1ⁱⁱ	0.97	2.35	3.312 (3)	169
C17—H17B⋯O3Aⁱⁱⁱ	0.97	2.56	3.458 (4)	154
C3A—H3AA⋯O3^iv	0.93	2.55	3.331 (3)	142
C9—H9A⋯O4A^v	0.93	2.58	3.495 (3)	170
C14—H14B⋯O5A^vi	0.97	2.60	3.517 (4)	157
C18—H18A⋯O5A^vii	0.97	2.50	3.451 (5)	167
Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y+1, -z; (iii) -x, -y+1, -z+1; (iv) x, y, z+1; (v) x, y, z-1; (vi) -x, -y, -z+1; (vii) -x+1, -y, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100170X/bt5451sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100170X/bt5451Isup2.hkl

checkCIF report

Comment top

Enrofloxacin is a fluoroquinolone antibiotic and is a synthetic chemotherapeutic agent from the class of the fluoroquinolone carboxylic acid derivatives. It is sold by the Bayer Corporation under the trade name Baytril and has antibacterial activity against a broad spectrum of Gram-negative and Gram-positive bacteria. Its mechanism of action is not thoroughly understood, but it is believed to act by inhibiting bacterial DNA gyrase (a type-II topoisomerase), thereby preventing DNA supercoiling and DNA synthesis. The chemical and biological aspects of fluoroquinolones is described (Bhanot et al., 2001; Scholar, 2003). The crystal structure of norfloxacin hydrochloride (Zou et al., 2005) and norfloxacin methanol solvate (Wang et al., 2005) have already been reported. The crystal structure of a copper complex of enrofloxacin (Recillas-Mota et al., 2007), norfloxacin picrate (Hu & Yu, 2005) and 2-hydroxyethanaminium enrofloxacinate (Sun et al., 2004) are reported. Recently, the crystal structures of propiverine picrate (Jasinski et al., 2009), imatinibium dipicrate (Jasinski et al., 2010a) and chlorimipraminium picrate (Jasinski et al., 2010b) have been reported. In continuation of our work on picrates of biologically active compounds, this paper reports the crystal structure of C₁₉H₂₂FN₃O₃⁺ . C₆H₂N₃O₇^- obtained by the interaction of picric acid and enrofloxacin.

In the crystal structure of the title compound, (I), there is one cation-anion pair in the asymmetric unit (Fig. 1). One N atom in the 6-membered piperazine ring (N2/C14/C15/N3/C16/C17) in the enrofloxacinium cation is protonated which adopts a slightly distorted chair conformation with puckering parameters Q, θ and ϕ of 0.563 (3)A%, 4.0 (3)° and 358.0 (5)° (Cremer & Pople, 1975). The dihedral angles between the mean planes of the cyclopropyl and piperazine rings with the 10-atom ring system of the quinolone group are 48.1 (1)° and 69.9 (5)°, respectively. The picrate anion interacts with the protonated N atom of an adjacent cation through a bifurcated N—H···O three-center hydrogen bond forming a R₁²(6) ring motif. The dihedral angle between the mean planes of the anion benzene and cation piperizine, quinoline and cyclopropyl rings are 61.3 (6)°, 31.1 (4)° and 70.4 (9)°, respectively. The mean planes of the two o-NO₂ and single p-NO₂ groups in the picrate anion are twisted by 6.7 (6)°, 38.3 (9)° and 12.8 (7)° with respect to the mean planes of the 6-membered benzene ring. Bond distances and angles are in normal ranges (Allen et al., 1987). Strong N—H···O and weak intermolecular C—H···O hydrogen bonds in concert with weak π–π stacking interactions (Table 2) dominate the crystal packing creating a 2-D network structure along 011 (Fig. 2).

Related literature top

For background to fluoroquinolones, see: Bhanot et al. (2001); Scholar (2003). For related structures, see: Hu & Yu, (2005); Jasinski et al. (2009, 2010a, 2010b); Recillas-Mota et al. (2007); Sun et al. (2004); Wang et al. (2005); Zou et al. (2005). For puckering parameters, see: Cremer & Pople (1975). For standard bond lengths, see: Allen et al. (1987).

Experimental top

Enrofloxacin (3.59 g, 0.1 mol) and picric acid (2.99 g, 0.1 mol) were dissolved in a mixture of acetonitrile and dimethyl sulfoxide (80:20 v/v). The solution was stirred for 15 min over a heating magnetic stirrer at 333 K. The resulting solution was kept aside at room temperature. After few days, X-ray quality crystals of the title compound were grown by slow evaporation (m.p.: 490 – 493 K).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids. Dashed lines indicate a bifurcated N—H···O intermolecular, three-centered hydrogen bond formed between the protonated N atom from the enrofloxacin cation and the picrate anion providing a R₁²(6) ring motif.
	Fig. 2. Packing diagram of the title compound viewed down the a axis. Dashed lines indicate N—H···O hydrogen bonds and weak C—H···O intermolecular interactions creating a 2-D network structure along 011.

4-(3-carboxy-6-fluoro-4-oxo-1,4-dihydroquinolin-7-yl)-1-ethylpiperazin-1-ium 2,4,6-trinitrophenolate top

Crystal data top

C₁₉H₂₃FN₃O₃⁺·C₆H₂N₃O₇⁻	Z = 2
M_r = 588.51	F(000) = 612
Triclinic, P1	D_x = 1.401 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.2111 (7) Å	Cell parameters from 2958 reflections
b = 12.5766 (7) Å	θ = 5.3–73.4°
c = 16.2362 (4) Å	µ = 0.98 mm⁻¹
α = 105.556 (2)°	T = 295 K
β = 96.367 (6)°	Plate, pale yellow
γ = 96.223 (7)°	0.44 × 0.31 × 0.12 mm
V = 1395.04 (16) Å³

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5437 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3425 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 10.5081 pixels mm^-1	θ_max = 73.6°, θ_min = 5.3°
ω scans	h = −5→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −15→14
T_min = 0.896, T_max = 1.000	l = −20→20
9440 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)] = 0.055	H-atom parameters constrained
wR(F²) = 0.177	w = 1/[σ²(F_o²) + (0.0924P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
5437 reflections	Δρ_max = 0.20 e Å⁻³
382 parameters	Δρ_min = −0.20 e Å⁻³
0 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: 0.0007 (4)

Crystal data top

C₁₉H₂₃FN₃O₃⁺·C₆H₂N₃O₇⁻	γ = 96.223 (7)°
M_r = 588.51	V = 1395.04 (16) Å³
Triclinic, P1	Z = 2
a = 7.2111 (7) Å	Cu Kα radiation
b = 12.5766 (7) Å	µ = 0.98 mm⁻¹
c = 16.2362 (4) Å	T = 295 K
α = 105.556 (2)°	0.44 × 0.31 × 0.12 mm
β = 96.367 (6)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5437 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	3425 reflections with I > 2σ(I)
T_min = 0.896, T_max = 1.000	R_int = 0.032
9440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.00	Δρ_max = 0.20 e Å⁻³
5437 reflections	Δρ_min = −0.20 e Å⁻³
382 parameters

Special details top

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

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

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

	x	y	z	U_iso*/U_eq
F1	0.0392 (3)	0.14397 (14)	0.02905 (11)	0.0785 (5)
O1	0.4038 (4)	0.7253 (2)	−0.10088 (16)	0.0920 (8)
O2	0.3085 (3)	0.5648 (2)	−0.19916 (12)	0.0747 (6)
H2	0.2552	0.5031	−0.2008	0.112*
O3	0.2077 (3)	0.39341 (17)	−0.15203 (11)	0.0611 (5)
N1	0.2699 (3)	0.59410 (17)	0.09706 (12)	0.0456 (5)
N2	0.0978 (3)	0.27232 (19)	0.20117 (14)	0.0580 (6)
N3	0.3999 (3)	0.2675 (2)	0.33307 (14)	0.0591 (6)
H3A	0.3366	0.2332	0.3665	0.071*
C1	0.1315 (3)	0.3205 (2)	0.13528 (16)	0.0490 (6)
C2	0.1818 (3)	0.4344 (2)	0.14892 (15)	0.0460 (5)
H2A	0.1934	0.4819	0.2046	0.055*
C3	0.2153 (3)	0.47948 (19)	0.08107 (13)	0.0405 (5)
C4	0.3062 (3)	0.6357 (2)	0.03193 (15)	0.0465 (5)
H4A	0.3420	0.7123	0.0444	0.056*
C5	0.2938 (3)	0.5723 (2)	−0.05229 (15)	0.0469 (5)
C6	0.3401 (4)	0.6293 (3)	−0.11816 (18)	0.0617 (7)
C7	0.2321 (3)	0.4553 (2)	−0.07435 (14)	0.0465 (5)
C8	0.1951 (3)	0.4099 (2)	−0.00384 (14)	0.0448 (5)
C9	0.1368 (3)	0.2958 (2)	−0.01881 (16)	0.0510 (6)
H9A	0.1199	0.2484	−0.0748	0.061*
C10	0.1051 (4)	0.2543 (2)	0.04762 (17)	0.0553 (6)
C11	0.2678 (4)	0.6702 (2)	0.18217 (16)	0.0519 (6)
H11A	0.1420	0.6815	0.1971	0.062*
C12	0.4138 (4)	0.6777 (3)	0.25637 (18)	0.0645 (7)
H12A	0.3750	0.6903	0.3131	0.077*
H12B	0.5118	0.6306	0.2463	0.077*
C13	0.4137 (5)	0.7695 (3)	0.2158 (2)	0.0735 (8)
H13A	0.5119	0.7788	0.1810	0.088*
H13B	0.3752	0.8384	0.2478	0.088*
C14	0.1708 (5)	0.1684 (3)	0.2041 (2)	0.0691 (8)
H14A	0.1588	0.1193	0.1458	0.083*
H14B	0.0958	0.1309	0.2368	0.083*
C15	0.3727 (4)	0.1898 (3)	0.24448 (18)	0.0639 (7)
H15A	0.4143	0.1198	0.2470	0.077*
H15B	0.4494	0.2213	0.2090	0.077*
C16	0.3177 (5)	0.3719 (2)	0.33310 (18)	0.0650 (7)
H16A	0.3916	0.4147	0.3034	0.078*
H16B	0.3222	0.4172	0.3921	0.078*
C17	0.1147 (4)	0.3434 (3)	0.28845 (17)	0.0612 (7)
H17A	0.0393	0.3063	0.3213	0.073*
H17B	0.0651	0.4118	0.2874	0.073*
C18	0.6053 (5)	0.2905 (4)	0.3705 (3)	0.0917 (11)
H18A	0.6582	0.2213	0.3560	0.110*
H18B	0.6707	0.3413	0.3441	0.110*
C19	0.6391 (7)	0.3390 (4)	0.4650 (3)	0.1301 (18)
H19A	0.7709	0.3660	0.4836	0.195*
H19B	0.6006	0.2830	0.4923	0.195*
H19C	0.5677	0.3997	0.4807	0.195*
O1A	0.1749 (3)	0.2238 (2)	0.44767 (13)	0.0791 (7)
O2A	0.1956 (6)	0.4178 (2)	0.5795 (2)	0.1384 (15)
O3A	−0.0251 (4)	0.3840 (2)	0.64871 (17)	0.0934 (8)
O4A	0.0864 (4)	0.0906 (2)	0.78322 (15)	0.0947 (8)
O5A	0.2090 (4)	−0.0501 (2)	0.71552 (16)	0.0919 (8)
O6A	0.3078 (3)	−0.09139 (19)	0.42732 (14)	0.0761 (6)
O7A	0.3468 (4)	0.0487 (2)	0.37754 (15)	0.0939 (8)
N1A	0.0996 (4)	0.3558 (2)	0.60751 (17)	0.0724 (7)
N2A	0.1542 (4)	0.0399 (2)	0.72150 (14)	0.0640 (6)
N3A	0.2989 (3)	0.0068 (2)	0.43254 (14)	0.0594 (6)
C1A	0.1855 (3)	0.1834 (2)	0.50984 (16)	0.0528 (6)
C2A	0.1375 (4)	0.2406 (2)	0.59322 (17)	0.0531 (6)
C3A	0.1247 (4)	0.1958 (2)	0.65942 (16)	0.0526 (6)
H3AA	0.0879	0.2362	0.7103	0.063*
C4A	0.1673 (3)	0.0878 (2)	0.65059 (15)	0.0494 (6)
C5A	0.2252 (3)	0.0292 (2)	0.57639 (16)	0.0489 (5)
H5AA	0.2573	−0.0416	0.5717	0.059*
C6A	0.2361 (3)	0.0748 (2)	0.50884 (15)	0.0486 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.1083 (14)	0.0580 (10)	0.0638 (11)	−0.0030 (9)	0.0032 (9)	0.0181 (8)
O1	0.129 (2)	0.0800 (16)	0.0781 (15)	−0.0007 (15)	0.0328 (14)	0.0403 (13)
O2	0.0854 (14)	0.1032 (17)	0.0458 (11)	0.0184 (12)	0.0220 (9)	0.0319 (10)
O3	0.0700 (11)	0.0758 (12)	0.0350 (9)	0.0115 (9)	0.0124 (8)	0.0093 (8)
N1	0.0441 (10)	0.0565 (12)	0.0375 (10)	0.0120 (9)	0.0084 (8)	0.0128 (8)
N2	0.0635 (13)	0.0660 (14)	0.0527 (12)	0.0125 (11)	0.0111 (10)	0.0286 (11)
N3	0.0636 (13)	0.0714 (15)	0.0543 (13)	0.0129 (11)	0.0117 (10)	0.0358 (11)
C1	0.0479 (12)	0.0589 (15)	0.0458 (13)	0.0112 (11)	0.0087 (10)	0.0224 (11)
C2	0.0479 (12)	0.0560 (14)	0.0356 (11)	0.0150 (10)	0.0049 (9)	0.0130 (10)
C3	0.0372 (10)	0.0521 (13)	0.0344 (10)	0.0139 (9)	0.0058 (8)	0.0131 (9)
C4	0.0425 (11)	0.0555 (14)	0.0456 (13)	0.0111 (10)	0.0099 (9)	0.0182 (10)
C5	0.0433 (12)	0.0630 (15)	0.0403 (12)	0.0147 (11)	0.0100 (9)	0.0200 (11)
C6	0.0618 (16)	0.084 (2)	0.0526 (15)	0.0217 (15)	0.0219 (12)	0.0319 (14)
C7	0.0368 (11)	0.0665 (15)	0.0392 (12)	0.0155 (10)	0.0083 (9)	0.0157 (11)
C8	0.0400 (11)	0.0586 (14)	0.0383 (11)	0.0161 (10)	0.0055 (9)	0.0147 (10)
C9	0.0544 (13)	0.0554 (14)	0.0408 (12)	0.0149 (11)	0.0044 (10)	0.0077 (10)
C10	0.0579 (14)	0.0553 (15)	0.0515 (14)	0.0071 (12)	0.0039 (11)	0.0156 (11)
C11	0.0520 (13)	0.0588 (15)	0.0439 (13)	0.0149 (11)	0.0109 (10)	0.0087 (11)
C12	0.0591 (15)	0.0800 (19)	0.0465 (14)	0.0117 (14)	0.0044 (11)	0.0053 (13)
C13	0.087 (2)	0.0675 (19)	0.0558 (17)	−0.0051 (16)	0.0171 (15)	0.0045 (13)
C14	0.094 (2)	0.0607 (17)	0.0593 (17)	0.0093 (15)	0.0109 (15)	0.0299 (14)
C15	0.085 (2)	0.0666 (17)	0.0584 (16)	0.0319 (15)	0.0293 (14)	0.0329 (13)
C16	0.092 (2)	0.0609 (17)	0.0481 (15)	0.0189 (15)	0.0131 (13)	0.0205 (12)
C17	0.0722 (17)	0.0759 (18)	0.0541 (15)	0.0292 (14)	0.0270 (13)	0.0352 (13)
C18	0.073 (2)	0.114 (3)	0.100 (3)	0.014 (2)	−0.0005 (19)	0.054 (2)
C19	0.124 (4)	0.145 (4)	0.107 (4)	−0.007 (3)	−0.042 (3)	0.045 (3)
O1A	0.0990 (15)	0.1074 (17)	0.0575 (12)	0.0444 (13)	0.0295 (11)	0.0493 (12)
O2A	0.217 (4)	0.0739 (18)	0.162 (3)	0.035 (2)	0.101 (3)	0.061 (2)
O3A	0.1141 (19)	0.0871 (17)	0.0886 (17)	0.0479 (15)	0.0326 (15)	0.0208 (13)
O4A	0.158 (2)	0.0823 (16)	0.0574 (13)	0.0197 (15)	0.0483 (15)	0.0295 (11)
O5A	0.137 (2)	0.0827 (16)	0.0819 (16)	0.0374 (15)	0.0402 (15)	0.0491 (13)
O6A	0.0938 (15)	0.0690 (14)	0.0653 (13)	0.0195 (11)	0.0230 (11)	0.0112 (10)
O7A	0.143 (2)	0.0989 (17)	0.0629 (14)	0.0416 (16)	0.0566 (15)	0.0364 (12)
N1A	0.0965 (19)	0.0661 (16)	0.0625 (15)	0.0235 (14)	0.0164 (14)	0.0250 (12)
N2A	0.0870 (16)	0.0625 (15)	0.0475 (12)	0.0052 (12)	0.0192 (11)	0.0224 (11)
N3A	0.0624 (13)	0.0688 (16)	0.0470 (12)	0.0137 (11)	0.0110 (10)	0.0136 (11)
C1A	0.0504 (13)	0.0682 (16)	0.0464 (13)	0.0124 (12)	0.0100 (10)	0.0250 (12)
C2A	0.0553 (14)	0.0580 (15)	0.0505 (14)	0.0104 (11)	0.0113 (11)	0.0206 (11)
C3A	0.0556 (14)	0.0602 (15)	0.0410 (12)	0.0048 (11)	0.0099 (10)	0.0130 (11)
C4A	0.0541 (13)	0.0545 (14)	0.0415 (12)	0.0022 (11)	0.0105 (10)	0.0180 (10)
C5A	0.0489 (12)	0.0482 (13)	0.0495 (13)	0.0036 (10)	0.0071 (10)	0.0151 (10)
C6A	0.0468 (12)	0.0622 (15)	0.0360 (11)	0.0056 (11)	0.0072 (9)	0.0128 (10)

Geometric parameters (Å, º) top

F1—C10	1.358 (3)	C13—H13B	0.9700
O1—C6	1.191 (4)	C14—C15	1.493 (4)
O2—C6	1.327 (4)	C14—H14A	0.9700
O2—H2	0.8200	C14—H14B	0.9700
O3—C7	1.274 (3)	C15—H15A	0.9700
N1—C4	1.337 (3)	C15—H15B	0.9700
N1—C3	1.398 (3)	C16—C17	1.519 (4)
N1—C11	1.457 (3)	C16—H16A	0.9700
N2—C1	1.394 (3)	C16—H16B	0.9700
N2—C17	1.443 (4)	C17—H17A	0.9700
N2—C14	1.472 (4)	C17—H17B	0.9700
N3—C15	1.485 (4)	C18—C19	1.473 (6)
N3—C16	1.497 (4)	C18—H18A	0.9700
N3—C18	1.503 (4)	C18—H18B	0.9700
N3—H3A	0.9100	C19—H19A	0.9600
C1—C2	1.390 (3)	C19—H19B	0.9600
C1—C10	1.423 (4)	C19—H19C	0.9600
C2—C3	1.399 (3)	O1A—C1A	1.245 (3)
C2—H2A	0.9300	O2A—N1A	1.199 (4)
C3—C8	1.403 (3)	O3A—N1A	1.207 (3)
C4—C5	1.373 (3)	O4A—N2A	1.218 (3)
C4—H4A	0.9300	O5A—N2A	1.222 (3)
C5—C7	1.425 (4)	O6A—N3A	1.224 (3)
C5—C6	1.486 (3)	O7A—N3A	1.215 (3)
C7—C8	1.447 (3)	N1A—C2A	1.465 (4)
C8—C9	1.398 (4)	N2A—C4A	1.443 (3)
C9—C10	1.349 (4)	N3A—C6A	1.453 (3)
C9—H9A	0.9300	C1A—C6A	1.447 (4)
C11—C13	1.479 (4)	C1A—C2A	1.451 (4)
C11—C12	1.485 (4)	C2A—C3A	1.348 (3)
C11—H11A	0.9800	C3A—C4A	1.399 (4)
C12—C13	1.475 (5)	C3A—H3AA	0.9300
C12—H12A	0.9700	C4A—C5A	1.368 (3)
C12—H12B	0.9700	C5A—C6A	1.373 (3)
C13—H13A	0.9700	C5A—H5AA	0.9300

C6—O2—H2	109.5	N2—C14—H14A	109.3
C4—N1—C3	119.8 (2)	C15—C14—H14A	109.3
C4—N1—C11	119.3 (2)	N2—C14—H14B	109.3
C3—N1—C11	120.48 (19)	C15—C14—H14B	109.3
C1—N2—C17	118.9 (2)	H14A—C14—H14B	107.9
C1—N2—C14	120.3 (2)	N3—C15—C14	111.4 (2)
C17—N2—C14	108.4 (2)	N3—C15—H15A	109.3
C15—N3—C16	110.8 (2)	C14—C15—H15A	109.3
C15—N3—C18	110.0 (3)	N3—C15—H15B	109.3
C16—N3—C18	112.6 (3)	C14—C15—H15B	109.3
C15—N3—H3A	107.7	H15A—C15—H15B	108.0
C16—N3—H3A	107.7	N3—C16—C17	110.3 (2)
C18—N3—H3A	107.7	N3—C16—H16A	109.6
C2—C1—N2	123.5 (2)	C17—C16—H16A	109.6
C2—C1—C10	115.7 (2)	N3—C16—H16B	109.6
N2—C1—C10	120.7 (2)	C17—C16—H16B	109.6
C1—C2—C3	121.8 (2)	H16A—C16—H16B	108.1
C1—C2—H2A	119.1	N2—C17—C16	112.2 (2)
C3—C2—H2A	119.1	N2—C17—H17A	109.2
N1—C3—C2	120.5 (2)	C16—C17—H17A	109.2
N1—C3—C8	119.3 (2)	N2—C17—H17B	109.2
C2—C3—C8	120.3 (2)	C16—C17—H17B	109.2
N1—C4—C5	124.0 (2)	H17A—C17—H17B	107.9
N1—C4—H4A	118.0	C19—C18—N3	113.3 (3)
C5—C4—H4A	118.0	C19—C18—H18A	108.9
C4—C5—C7	119.5 (2)	N3—C18—H18A	108.9
C4—C5—C6	118.4 (2)	C19—C18—H18B	108.9
C7—C5—C6	122.1 (2)	N3—C18—H18B	108.9
O1—C6—O2	121.3 (3)	H18A—C18—H18B	107.7
O1—C6—C5	123.5 (3)	C18—C19—H19A	109.5
O2—C6—C5	115.2 (3)	C18—C19—H19B	109.5
O3—C7—C5	122.2 (2)	H19A—C19—H19B	109.5
O3—C7—C8	121.2 (2)	C18—C19—H19C	109.5
C5—C7—C8	116.6 (2)	H19A—C19—H19C	109.5
C9—C8—C3	118.4 (2)	H19B—C19—H19C	109.5
C9—C8—C7	120.8 (2)	O2A—N1A—O3A	123.2 (3)
C3—C8—C7	120.8 (2)	O2A—N1A—C2A	118.8 (3)
C10—C9—C8	120.2 (2)	O3A—N1A—C2A	118.0 (3)
C10—C9—H9A	119.9	O4A—N2A—O5A	123.8 (2)
C8—C9—H9A	119.9	O4A—N2A—C4A	118.1 (2)
C9—C10—F1	117.8 (2)	O5A—N2A—C4A	118.1 (2)
C9—C10—C1	123.5 (3)	O7A—N3A—O6A	121.8 (2)
F1—C10—C1	118.6 (2)	O7A—N3A—C6A	119.9 (2)
N1—C11—C13	119.6 (2)	O6A—N3A—C6A	118.2 (2)
N1—C11—C12	121.4 (2)	O1A—C1A—C6A	126.2 (2)
C13—C11—C12	59.7 (2)	O1A—C1A—C2A	122.3 (3)
N1—C11—H11A	115.0	C6A—C1A—C2A	111.4 (2)
C13—C11—H11A	115.0	C3A—C2A—C1A	124.9 (2)
C12—C11—H11A	115.0	C3A—C2A—N1A	116.8 (2)
C13—C12—C11	60.0 (2)	C1A—C2A—N1A	118.3 (2)
C13—C12—H12A	117.8	C2A—C3A—C4A	119.2 (2)
C11—C12—H12A	117.8	C2A—C3A—H3AA	120.4
C13—C12—H12B	117.8	C4A—C3A—H3AA	120.4
C11—C12—H12B	117.8	C5A—C4A—C3A	120.4 (2)
H12A—C12—H12B	114.9	C5A—C4A—N2A	120.3 (2)
C12—C13—C11	60.36 (19)	C3A—C4A—N2A	119.3 (2)
C12—C13—H13A	117.7	C4A—C5A—C6A	120.1 (2)
C11—C13—H13A	117.7	C4A—C5A—H5AA	120.0
C12—C13—H13B	117.7	C6A—C5A—H5AA	120.0
C11—C13—H13B	117.7	C5A—C6A—C1A	123.7 (2)
H13A—C13—H13B	114.9	C5A—C6A—N3A	116.4 (2)
N2—C14—C15	111.8 (2)	C1A—C6A—N3A	119.9 (2)

C17—N2—C1—C2	0.3 (4)	C3—N1—C11—C12	74.5 (3)
C14—N2—C1—C2	−137.6 (3)	N1—C11—C12—C13	108.3 (3)
C17—N2—C1—C10	−176.1 (2)	N1—C11—C13—C12	−111.2 (3)
C14—N2—C1—C10	46.0 (3)	C1—N2—C14—C15	82.1 (3)
N2—C1—C2—C3	179.7 (2)	C17—N2—C14—C15	−59.7 (3)
C10—C1—C2—C3	−3.8 (3)	C16—N3—C15—C14	−52.8 (3)
C4—N1—C3—C2	178.3 (2)	C18—N3—C15—C14	−177.9 (2)
C11—N1—C3—C2	−8.4 (3)	N2—C14—C15—N3	57.1 (3)
C4—N1—C3—C8	−1.5 (3)	C15—N3—C16—C17	52.0 (3)
C11—N1—C3—C8	171.75 (19)	C18—N3—C16—C17	175.7 (2)
C1—C2—C3—N1	−178.5 (2)	C1—N2—C17—C16	−82.7 (3)
C1—C2—C3—C8	1.3 (3)	C14—N2—C17—C16	59.7 (3)
C3—N1—C4—C5	−0.1 (3)	N3—C16—C17—N2	−57.0 (3)
C11—N1—C4—C5	−173.4 (2)	C15—N3—C18—C19	−163.2 (3)
N1—C4—C5—C7	2.5 (3)	C16—N3—C18—C19	72.6 (4)
N1—C4—C5—C6	−179.3 (2)	O1A—C1A—C2A—C3A	171.7 (3)
C4—C5—C6—O1	7.0 (4)	C6A—C1A—C2A—C3A	−5.5 (4)
C7—C5—C6—O1	−174.8 (3)	O1A—C1A—C2A—N1A	−8.2 (4)
C4—C5—C6—O2	−174.1 (2)	C6A—C1A—C2A—N1A	174.5 (2)
C7—C5—C6—O2	4.1 (4)	O2A—N1A—C2A—C3A	140.3 (3)
C4—C5—C7—O3	176.0 (2)	O3A—N1A—C2A—C3A	−38.2 (4)
C6—C5—C7—O3	−2.2 (3)	O2A—N1A—C2A—C1A	−39.8 (4)
C4—C5—C7—C8	−3.0 (3)	O3A—N1A—C2A—C1A	141.7 (3)
C6—C5—C7—C8	178.8 (2)	C1A—C2A—C3A—C4A	2.8 (4)
N1—C3—C8—C9	−178.78 (19)	N1A—C2A—C3A—C4A	−177.3 (2)
C2—C3—C8—C9	1.4 (3)	C2A—C3A—C4A—C5A	1.4 (4)
N1—C3—C8—C7	0.7 (3)	C2A—C3A—C4A—N2A	179.8 (2)
C2—C3—C8—C7	−179.07 (19)	O4A—N2A—C4A—C5A	−173.7 (3)
O3—C7—C8—C9	2.0 (3)	O5A—N2A—C4A—C5A	5.2 (4)
C5—C7—C8—C9	−179.0 (2)	O4A—N2A—C4A—C3A	7.9 (4)
O3—C7—C8—C3	−177.5 (2)	O5A—N2A—C4A—C3A	−173.2 (3)
C5—C7—C8—C3	1.5 (3)	C3A—C4A—C5A—C6A	−2.1 (4)
C3—C8—C9—C10	−1.4 (3)	N2A—C4A—C5A—C6A	179.5 (2)
C7—C8—C9—C10	179.1 (2)	C4A—C5A—C6A—C1A	−1.3 (4)
C8—C9—C10—F1	176.6 (2)	C4A—C5A—C6A—N3A	−180.0 (2)
C8—C9—C10—C1	−1.4 (4)	O1A—C1A—C6A—C5A	−172.4 (3)
C2—C1—C10—C9	3.9 (4)	C2A—C1A—C6A—C5A	4.7 (3)
N2—C1—C10—C9	−179.4 (2)	O1A—C1A—C6A—N3A	6.3 (4)
C2—C1—C10—F1	−174.0 (2)	C2A—C1A—C6A—N3A	−176.6 (2)
N2—C1—C10—F1	2.6 (4)	O7A—N3A—C6A—C5A	−165.8 (3)
C4—N1—C11—C13	−41.8 (3)	O6A—N3A—C6A—C5A	11.8 (3)
C3—N1—C11—C13	145.0 (2)	O7A—N3A—C6A—C1A	15.4 (4)
C4—N1—C11—C12	−112.3 (3)	O6A—N3A—C6A—C1A	−167.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	1.78	2.536 (3)	151
N3—H3A···O1A	0.91	1.87	2.724 (3)	155
N3—H3A···O7A	0.91	2.38	3.024 (3)	128
C11—H11A···O3ⁱ	0.98	2.55	3.385 (3)	144
C15—H15B···O1ⁱⁱ	0.97	2.35	3.312 (3)	169
C17—H17B···O3Aⁱⁱⁱ	0.97	2.56	3.458 (4)	154
C3A—H3AA···O3^iv	0.93	2.55	3.331 (3)	142
C9—H9A···O4A^v	0.93	2.58	3.495 (3)	170
C14—H14B···O5A^vi	0.97	2.60	3.517 (4)	157
C18—H18A···O5A^vii	0.97	2.50	3.451 (5)	167

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

Experimental details

Crystal data
Chemical formula	C₁₉H₂₃FN₃O₃⁺·C₆H₂N₃O₇⁻
M_r	588.51
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.2111 (7), 12.5766 (7), 16.2362 (4)
α, β, γ (°)	105.556 (2), 96.367 (6), 96.223 (7)
V (Å³)	1395.04 (16)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.44 × 0.31 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.896, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9440, 5437, 3425
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.177, 1.00
No. of reflections	5437
No. of parameters	382
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	1.78	2.536 (3)	151
N3—H3A···O1A	0.91	1.87	2.724 (3)	155
N3—H3A···O7A	0.91	2.38	3.024 (3)	128
C11—H11A···O3ⁱ	0.98	2.55	3.385 (3)	144
C15—H15B···O1ⁱⁱ	0.97	2.35	3.312 (3)	169
C17—H17B···O3Aⁱⁱⁱ	0.97	2.56	3.458 (4)	154
C3A—H3AA···O3^iv	0.93	2.55	3.331 (3)	142
C9—H9A···O4A^v	0.93	2.58	3.495 (3)	170
C14—H14B···O5A^vi	0.97	2.60	3.517 (4)	157
C18—H18A···O5A^vii	0.97	2.50	3.451 (5)	167

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

Cg···Cg π stacking interactions, Cg2 and Cg4 are the centroids of rings N1/C3/C8/C7/C5/C4 and C1/C2/C3/C8/C9/C10; [Symmetry codes: (i) -x, 1-y, -z; (ii) 1-x, 1-y, -z;] top

CgI···CgJ	Cg···Cg (Å)	CgI Perp (Å)	Cgj Perp (Å)	Slippage (Å)
Cg2···Cg2ⁱ	3.5785 (13)	-3.3834 (9)	-3.3834 (9)	1.16 (5)
Cg2···Cg2ⁱⁱ	3.7451 (12)	-3.6091 (9)	3.6090 (9)	1.00 (0)
Cg2···Cg4ⁱⁱ	3.6587 (13)	-3.3748 (9)	-3.4114 (10)

Acknowledgements

MSS thanks the University of Mysore for the research facilities and HSY thanks the UOM for sabbatical leave. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

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