Lomefloxacinium picrate

Jasinski, J.P.; Butcher, R.J.; Siddegowda, M.S.; Yathirajan, H.S.; Hakim Al-arique, Q.N.M.

doi:10.1107/S1600536811002534

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages o483-o484

doi:10.1107/S1600536811002534

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Lomefloxacinium picrate

Jerry P. Jasinski,^a ^* Ray J. Butcher,^b M. S. Siddegowda,^c H. S. Yathirajan ^c and Q. N. M. Hakim Al-arique ^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 28 December 2010; accepted 18 January 2011; online 26 January 2011)

In the cation of the title compound [systematic name: (RS)-4-(3-carboxy-1-ethyl-6,8-difluoro-4-oxo-1,4-dihydroquinolin-7-yl)-2-methylpiperazin-1-ium 2,4,6-trinitrophenolate], C₁₇H₂₀F₂N₃O₃⁺·C₆H₂N₃O₇⁻, the piperazine ring adopts a slightly distorted chair conformation and contains a protonated N atom. An intramolecular O—H⋯O hydrogen bond occurs in the cation. The dihedral angles between the mean planes of the six-atom piperazine ring and the 10-atom fused ring system is 43.3 (5)°. The picrate anion interacts with the protonated N atom of an adjacent cation through a bifurcated N—H⋯(O,O) three-center hydrogen bond. Strong N—H⋯O hydrogen bonds in concert with weak π–π stacking interactions [centroid–centroid distance = 3.6460 (14) Å] dominate the crystal packing, creating a two-dimensional network structure along [011].

Related literature

For background to lomefloxacin, see: Rubinstein et al. (2001 ). For related structures, see: Jasinski et al. (2009 , 2010a ,b ). For puckering parameters, see: Cremer & Pople (1975 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₇H₂₀F₂N₃O₃⁺·C₆H₂N₃O₇⁻
M_r = 580.47
Triclinic, $[P \overline 1]$
a = 10.9314 (4) Å
b = 11.6748 (4) Å
c = 12.0530 (4) Å
α = 92.969 (3)°
β = 115.555 (3)°
γ = 109.852 (3)°
V = 1269.14 (8) Å³
Z = 2
Cu Kα radiation
μ = 1.13 mm⁻¹
T = 123 K
0.44 × 0.33 × 0.19 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 = 0.838, T_max = 1.000
8890 measured reflections
5002 independent reflections
4423 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.198
S = 1.06
5002 reflections
373 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.84	1.74	2.520 (3)	153
N3—H3A⋯O2ⁱ	0.92	2.09	2.984 (3)	164
N3—H3B⋯O1B	0.92	1.81	2.714 (3)	166
N3—H3B⋯O2B	0.92	2.52	2.993 (3)	113
Symmetry code: (i) x+1, y+1, 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/S1600536811002534/fl2332sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002534/fl2332Isup2.hkl

checkCIF report

Comment top

Lomefloxacin hydrochloride is a fluoroquinolone antibiotic used to treat bacterial infections including bronchitis and urinary tract infections. It is also used to prevent urinary tract infections prior to surgery. Lomefloxacin, chemically (RS)-1-ethyl-6,8-difluoro-7-(3-methylpiperazin- 1-yl)-4-oxo-quinoline-3-carboxylic acid, is associated with phototoxicity and adverse central nervous system adverse effects (Rubinstein et al., 2001). 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 (I), obtained by the interaction of picric acid and lomefloxacin.

In the crystal structure of the title compound, there is one cation-anion pair in the asymmetric unit (Fig. 1). One N atom in the 6-membered piperazine ring (N2/C10/C11/N3/C13/C14) in the lomefloxacinium cation is protonated which adopts a slightly distorted chair conformation with puckering parameters Q, θ and ϕ of 0.565 (3) Å, 178.0 (3)° and 109 (58)° (Cremer & Pople, 1975). The dihedral angle between the mean planes of the piperazine ring (N2/C10/C11/N3/C13/C14) and the 10-atom ring system of the quinolone group is 43.3 (5)°. The picrate anion interacts with the protonated N atom of an adjacent cation through a bifurcated N—H···O three-center hydrogen bond. The dihedral angle between the mean planes of the anion benzene and cation piperizine and quinoline rings is 46.2 (9)° and 7.2 (2)°, respectively. The mean planes of the two o-NO₂ and single p-NO₂ groups in the picrate anion are twisted by, 37.9 (5)°, 57.0 (8)° [using predominant component (0.743 (4), O6A & O7A, of disordered O atoms] and 2.5 (1)° with respect to the mean planes of the 6-membered benzene ring. Bond distances (Allen et al., 1987) and angles are in normal ranges. Strong N—H···O hydrogen bonds in concert with weak π–π stacking interactions (Table 2) dominate the crystal packing creating a 2-D network along [011] (Fig. 2).

Related literature top

For background to lomefloxacin [systematic name: (RS)-1-ethyl-6,8-difluoro-7-(3-methylpiperazin-1-yl)-4-oxo-quinoline-3-carboxylic acid], see: Rubinstein et al. (2001). For related structures, see: Jasinski et al. (2009, 2010a,b). For puckering parameters, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

Lomefloxacin hydrochloride (3.87 g, 0.01 mol) of picric acid (2.99 g, 0.01 mol) was dissolved in 15 ml of dimethyl formamide. The solution was stirred for 15 min over a heating magnetic stirrer at 335 K. The resulting solution was kept aside at room temperature. X-ray quality crystals were grown from slow evaporation of dimethyl formamide solution (m.p.: 489 – 491 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 an intramolecular O—H···O hydrogen bond in the cation. and a bifurcated N—H···(O,O) intermolecular three-centered hydrogen bond formed between the protonated N atom from the lomefloxacinium cation and the picrate anion. In the picrate anion only the predominate disordered O6A and O7A (0.762 (4)) atoms are displayed.

Fig. 2. Packing diagram of the title compound viewed down the a axis. Dashed lines indicate N—H···O hydrogen bonds creating a 2-D network along [011].

(RS)-4-(3-carboxy-1-ethyl-6,8-difluoro-4-oxo-1,4-dihydroquinolin-7-yl)- 2-methylpiperazin-1-ium 2,4,6-trinitrophenolate top

Crystal data top

C₁₇H₂₀F₂N₃O₃⁺·C₆H₂N₃O₇⁻	Z = 2
M_r = 580.47	F(000) = 600
Triclinic, P1	D_x = 1.519 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 10.9314 (4) Å	Cell parameters from 6216 reflections
b = 11.6748 (4) Å	θ = 4.7–73.8°
c = 12.0530 (4) Å	µ = 1.13 mm⁻¹
α = 92.969 (3)°	T = 123 K
β = 115.555 (3)°	Prism, pale yellow
γ = 109.852 (3)°	0.44 × 0.33 × 0.19 mm
V = 1269.14 (8) Å³

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5002 independent reflections
Radiation source: Enhance (Cu) X-ray Source	4423 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 10.5081 pixels mm^-1	θ_max = 74.0°, θ_min = 4.7°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −14→14
T_min = 0.838, T_max = 1.000	l = −15→11
8890 measured reflections

Refinement top

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.198	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0848P)² + 0.7775P] where P = (F_o² + 2F_c²)/3
5002 reflections	(Δ/σ)_max = 0.011
373 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₇H₂₀F₂N₃O₃⁺·C₆H₂N₃O₇⁻	γ = 109.852 (3)°
M_r = 580.47	V = 1269.14 (8) Å³
Triclinic, P1	Z = 2
a = 10.9314 (4) Å	Cu Kα radiation
b = 11.6748 (4) Å	µ = 1.13 mm⁻¹
c = 12.0530 (4) Å	T = 123 K
α = 92.969 (3)°	0.44 × 0.33 × 0.19 mm
β = 115.555 (3)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5002 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	4423 reflections with I > 2σ(I)
T_min = 0.838, T_max = 1.000	R_int = 0.018
8890 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.198	H-atom parameters constrained
S = 1.06	Δρ_max = 0.54 e Å⁻³
5002 reflections	Δρ_min = −0.59 e Å⁻³
373 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	Occ. (<1)
F1	0.6041 (2)	0.51552 (14)	0.14890 (17)	0.0702 (5)
F2	0.5633 (2)	0.21345 (13)	0.38653 (13)	0.0626 (5)
O1	0.1693 (3)	−0.2597 (2)	−0.1643 (2)	0.0873 (8)
O2	0.1665 (3)	−0.1195 (2)	−0.2795 (2)	0.0762 (7)
H2	0.1948	−0.0413	−0.2670	0.114*
O3	0.3100 (2)	0.1106 (2)	−0.17445 (17)	0.0677 (6)
N1	0.4330 (2)	0.01780 (17)	0.16877 (19)	0.0436 (5)
N2	0.6695 (3)	0.46292 (19)	0.3820 (2)	0.0533 (6)
N3	0.8631 (2)	0.67661 (19)	0.58301 (19)	0.0496 (5)
H3A	0.9470	0.7498	0.6208	0.060*
H3B	0.8207	0.6649	0.6352	0.060*
C1	0.3493 (3)	−0.0691 (2)	0.0590 (2)	0.0482 (6)
H1A	0.3202	−0.1545	0.0631	0.058*
C2	0.3035 (3)	−0.0441 (2)	−0.0569 (2)	0.0495 (6)
C3	0.3465 (3)	0.0821 (3)	−0.0690 (2)	0.0485 (6)
C4	0.4355 (2)	0.1778 (2)	0.0492 (2)	0.0418 (5)
C5	0.4789 (3)	0.3043 (2)	0.0451 (2)	0.0478 (6)
H5A	0.4542	0.3271	−0.0338	0.057*
C6	0.5558 (3)	0.3938 (2)	0.1536 (2)	0.0484 (6)
C7	0.5904 (3)	0.3680 (2)	0.2737 (2)	0.0435 (5)
C8	0.5437 (3)	0.2414 (2)	0.2746 (2)	0.0430 (5)
C9	0.4727 (2)	0.1443 (2)	0.1660 (2)	0.0391 (5)
C10	0.6250 (3)	0.5649 (3)	0.3947 (3)	0.0626 (8)
H10A	0.5717	0.5482	0.4448	0.075*
H10B	0.5562	0.5690	0.3098	0.075*
C11	0.7563 (3)	0.6884 (2)	0.4582 (3)	0.0592 (7)
H11A	0.8060	0.7051	0.4044	0.071*
C12	0.7179 (5)	0.7965 (3)	0.4768 (4)	0.0860 (12)
H12A	0.8083	0.8737	0.5171	0.129*
H12B	0.6708	0.7830	0.5309	0.129*
H12C	0.6495	0.8038	0.3946	0.129*
C13	0.9051 (3)	0.5702 (3)	0.5682 (3)	0.0572 (7)
H13A	0.9588	0.5861	0.5184	0.069*
H13B	0.9723	0.5637	0.6526	0.069*
C14	0.7718 (3)	0.4506 (2)	0.5035 (3)	0.0604 (8)
H14A	0.8010	0.3818	0.4899	0.072*
H14B	0.7229	0.4303	0.5567	0.072*
C15	0.4738 (3)	−0.0307 (2)	0.2860 (3)	0.0547 (6)
H15A	0.5682	0.0326	0.3549	0.066*
H15B	0.4897	−0.1073	0.2707	0.066*
C16	0.3574 (4)	−0.0604 (3)	0.3270 (3)	0.0721 (9)
H16A	0.3826	−0.1023	0.3970	0.108*
H16B	0.2612	−0.1157	0.2559	0.108*
H16C	0.3522	0.0173	0.3550	0.108*
C17	0.2083 (3)	−0.1516 (3)	−0.1695 (3)	0.0635 (8)
O1B	0.7431 (2)	0.60714 (18)	0.73716 (18)	0.0620 (5)
O2B	0.9064 (3)	0.8637 (2)	0.7905 (2)	0.0755 (7)
O3B	0.8490 (2)	0.94720 (17)	0.9138 (2)	0.0563 (5)
O4B	1.0085 (4)	0.8183 (3)	1.3141 (2)	0.0968 (9)
O5B	0.9630 (4)	0.6231 (3)	1.3095 (2)	0.0926 (8)
O6A	0.6327 (5)	0.3366 (3)	0.8566 (5)	0.1035 (10)	0.762 (4)
O7A	0.7909 (5)	0.3882 (3)	0.7890 (4)	0.1035 (10)	0.762 (4)
O6B	0.6273 (9)	0.3566 (9)	0.7639 (9)	0.1035 (10)	0.238 (4)
O7B	0.8257 (10)	0.3560 (9)	0.9080 (10)	0.1035 (10)	0.238 (4)
N1B	0.8724 (2)	0.86209 (18)	0.8747 (2)	0.0466 (5)
N2B	0.9639 (3)	0.7109 (3)	1.2577 (3)	0.0683 (7)
N3B	0.7447 (3)	0.4116 (2)	0.8604 (3)	0.0675 (7)
C1B	0.7998 (3)	0.6332 (2)	0.8548 (2)	0.0476 (6)
C2B	0.8633 (3)	0.7566 (2)	0.9345 (2)	0.0443 (5)
C3B	0.9121 (3)	0.7818 (2)	1.0621 (2)	0.0482 (6)
H3BA	0.9482	0.8649	1.1084	0.058*
C4B	0.9077 (3)	0.6843 (3)	1.1220 (3)	0.0544 (6)
C5B	0.8520 (3)	0.5620 (3)	1.0552 (3)	0.0593 (7)
H5BA	0.8492	0.4953	1.0972	0.071*
C6B	0.8019 (3)	0.5399 (2)	0.9289 (3)	0.0544 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0779 (11)	0.0377 (8)	0.0661 (10)	0.0129 (8)	0.0173 (9)	0.0181 (7)
F2	0.0898 (12)	0.0390 (8)	0.0360 (7)	0.0139 (8)	0.0201 (7)	0.0050 (6)
O1	0.0778 (16)	0.0513 (13)	0.0785 (16)	0.0096 (11)	0.0083 (12)	−0.0238 (11)
O2	0.0637 (13)	0.0804 (15)	0.0460 (11)	0.0075 (12)	0.0134 (10)	−0.0153 (10)
O3	0.0677 (13)	0.0764 (14)	0.0347 (9)	0.0175 (11)	0.0137 (9)	0.0042 (9)
N1	0.0435 (10)	0.0321 (9)	0.0418 (10)	0.0140 (8)	0.0110 (8)	0.0012 (8)
N2	0.0547 (12)	0.0340 (10)	0.0436 (11)	0.0187 (9)	0.0010 (9)	−0.0036 (8)
N3	0.0522 (12)	0.0372 (10)	0.0396 (10)	0.0137 (9)	0.0098 (9)	−0.0036 (8)
C1	0.0421 (12)	0.0350 (11)	0.0525 (14)	0.0124 (10)	0.0141 (11)	−0.0045 (10)
C2	0.0391 (12)	0.0476 (14)	0.0442 (13)	0.0125 (10)	0.0111 (10)	−0.0091 (10)
C3	0.0392 (12)	0.0571 (15)	0.0373 (12)	0.0158 (11)	0.0123 (10)	−0.0010 (10)
C4	0.0376 (11)	0.0427 (12)	0.0350 (11)	0.0142 (9)	0.0111 (9)	0.0023 (9)
C5	0.0461 (13)	0.0479 (13)	0.0395 (12)	0.0169 (11)	0.0133 (10)	0.0124 (10)
C6	0.0460 (13)	0.0344 (11)	0.0507 (14)	0.0123 (10)	0.0139 (11)	0.0123 (10)
C7	0.0384 (11)	0.0345 (11)	0.0399 (12)	0.0117 (9)	0.0069 (9)	0.0007 (9)
C8	0.0448 (12)	0.0368 (11)	0.0331 (11)	0.0127 (9)	0.0098 (9)	0.0037 (9)
C9	0.0371 (11)	0.0337 (11)	0.0377 (11)	0.0129 (9)	0.0120 (9)	0.0033 (9)
C10	0.0559 (15)	0.0452 (14)	0.0604 (16)	0.0235 (12)	0.0049 (13)	−0.0038 (12)
C11	0.0684 (17)	0.0419 (13)	0.0485 (14)	0.0221 (13)	0.0131 (13)	0.0025 (11)
C12	0.109 (3)	0.0548 (18)	0.071 (2)	0.046 (2)	0.015 (2)	0.0017 (15)
C13	0.0565 (15)	0.0496 (14)	0.0442 (13)	0.0240 (12)	0.0056 (11)	−0.0034 (11)
C14	0.0648 (17)	0.0407 (13)	0.0462 (14)	0.0229 (12)	0.0017 (12)	−0.0015 (11)
C15	0.0656 (16)	0.0363 (12)	0.0500 (14)	0.0222 (12)	0.0160 (12)	0.0106 (10)
C16	0.082 (2)	0.0591 (17)	0.0626 (18)	0.0180 (16)	0.0319 (17)	0.0185 (14)
C17	0.0458 (14)	0.0654 (19)	0.0528 (16)	0.0132 (13)	0.0113 (12)	−0.0158 (13)
O1B	0.0670 (12)	0.0486 (10)	0.0480 (10)	0.0090 (9)	0.0207 (9)	0.0009 (8)
O2B	0.128 (2)	0.0528 (12)	0.0654 (13)	0.0362 (13)	0.0615 (14)	0.0211 (10)
O3B	0.0553 (10)	0.0428 (9)	0.0721 (12)	0.0245 (8)	0.0280 (9)	0.0123 (8)
O4B	0.126 (2)	0.100 (2)	0.0534 (13)	0.0370 (18)	0.0404 (15)	0.0133 (13)
O5B	0.122 (2)	0.119 (2)	0.0731 (15)	0.0732 (19)	0.0545 (16)	0.0567 (16)
O6A	0.123 (2)	0.0541 (13)	0.137 (3)	0.0198 (13)	0.080 (2)	0.0015 (14)
O7A	0.123 (2)	0.0541 (13)	0.137 (3)	0.0198 (13)	0.080 (2)	0.0015 (14)
O6B	0.123 (2)	0.0541 (13)	0.137 (3)	0.0198 (13)	0.080 (2)	0.0015 (14)
O7B	0.123 (2)	0.0541 (13)	0.137 (3)	0.0198 (13)	0.080 (2)	0.0015 (14)
N1B	0.0487 (11)	0.0368 (10)	0.0450 (11)	0.0152 (9)	0.0163 (9)	0.0070 (8)
N2B	0.0743 (17)	0.087 (2)	0.0550 (14)	0.0398 (15)	0.0343 (13)	0.0262 (14)
N3B	0.0766 (17)	0.0369 (12)	0.0908 (19)	0.0209 (12)	0.0430 (15)	0.0145 (12)
C1B	0.0467 (13)	0.0384 (12)	0.0545 (14)	0.0144 (10)	0.0239 (11)	0.0086 (10)
C2B	0.0450 (12)	0.0389 (12)	0.0475 (13)	0.0167 (10)	0.0208 (10)	0.0114 (10)
C3B	0.0479 (13)	0.0458 (13)	0.0495 (13)	0.0180 (11)	0.0229 (11)	0.0088 (10)
C4B	0.0588 (15)	0.0616 (16)	0.0507 (14)	0.0279 (13)	0.0291 (13)	0.0209 (12)
C5B	0.0689 (17)	0.0520 (15)	0.0729 (19)	0.0294 (14)	0.0420 (15)	0.0291 (14)
C6B	0.0562 (15)	0.0409 (13)	0.0667 (17)	0.0184 (11)	0.0306 (13)	0.0138 (12)

Geometric parameters (Å, º) top

F1—C6	1.351 (3)	C12—H12B	0.9800
F2—C8	1.348 (3)	C12—H12C	0.9800
O1—C17	1.202 (4)	C13—C14	1.485 (4)
O2—C17	1.323 (4)	C13—H13A	0.9900
O2—H2	0.8400	C13—H13B	0.9900
O3—C3	1.258 (3)	C14—H14A	0.9900
N1—C1	1.343 (3)	C14—H14B	0.9900
N1—C9	1.397 (3)	C15—C16	1.499 (5)
N1—C15	1.492 (3)	C15—H15A	0.9900
N2—C7	1.381 (3)	C15—H15B	0.9900
N2—C10	1.455 (3)	C16—H16A	0.9800
N2—C14	1.460 (3)	C16—H16B	0.9800
N3—C13	1.490 (3)	C16—H16C	0.9800
N3—C11	1.504 (3)	O1B—C1B	1.248 (3)
N3—H3A	0.9200	O2B—N1B	1.221 (3)
N3—H3B	0.9200	O3B—N1B	1.226 (3)
C1—C2	1.351 (4)	O4B—N2B	1.218 (4)
C1—H1A	0.9500	O5B—N2B	1.227 (4)
C2—C3	1.422 (4)	O6A—N3B	1.219 (3)
C2—C17	1.489 (3)	O7A—N3B	1.2298 (19)
C3—C4	1.459 (3)	O6B—N3B	1.219 (5)
C4—C5	1.400 (4)	O7B—N3B	1.234 (2)
C4—C9	1.405 (3)	N1B—C2B	1.455 (3)
C5—C6	1.350 (4)	N2B—C4B	1.449 (4)
C5—H5A	0.9500	N3B—C6B	1.451 (3)
C6—C7	1.407 (4)	C1B—C2B	1.443 (3)
C7—C8	1.392 (3)	C1B—C6B	1.444 (4)
C8—C9	1.405 (3)	C2B—C3B	1.370 (4)
C10—C11	1.503 (4)	C3B—C4B	1.377 (4)
C10—H10A	0.9900	C3B—H3BA	0.9500
C10—H10B	0.9900	C4B—C5B	1.388 (4)
C11—C12	1.493 (4)	C5B—C6B	1.351 (4)
C11—H11A	1.0000	C5B—H5BA	0.9500
C12—H12A	0.9800

C17—O2—H2	109.5	C14—C13—N3	110.8 (2)
C1—N1—C9	119.0 (2)	C14—C13—H13A	109.5
C1—N1—C15	116.0 (2)	N3—C13—H13A	109.5
C9—N1—C15	125.02 (19)	C14—C13—H13B	109.5
C7—N2—C10	121.8 (2)	N3—C13—H13B	109.5
C7—N2—C14	122.7 (2)	H13A—C13—H13B	108.1
C10—N2—C14	112.8 (2)	N2—C14—C13	109.3 (2)
C13—N3—C11	112.07 (19)	N2—C14—H14A	109.8
C13—N3—H3A	109.2	C13—C14—H14A	109.8
C11—N3—H3A	109.2	N2—C14—H14B	109.8
C13—N3—H3B	109.2	C13—C14—H14B	109.8
C11—N3—H3B	109.2	H14A—C14—H14B	108.3
H3A—N3—H3B	107.9	N1—C15—C16	112.5 (2)
N1—C1—C2	124.9 (2)	N1—C15—H15A	109.1
N1—C1—H1A	117.5	C16—C15—H15A	109.1
C2—C1—H1A	117.5	N1—C15—H15B	109.1
C1—C2—C3	120.0 (2)	C16—C15—H15B	109.1
C1—C2—C17	118.2 (3)	H15A—C15—H15B	107.8
C3—C2—C17	121.8 (3)	C15—C16—H16A	109.5
O3—C3—C2	122.7 (2)	C15—C16—H16B	109.5
O3—C3—C4	121.5 (3)	H16A—C16—H16B	109.5
C2—C3—C4	115.8 (2)	C15—C16—H16C	109.5
C5—C4—C9	120.0 (2)	H16A—C16—H16C	109.5
C5—C4—C3	119.2 (2)	H16B—C16—H16C	109.5
C9—C4—C3	120.7 (2)	O1—C17—O2	121.1 (3)
C6—C5—C4	119.9 (2)	O1—C17—C2	124.3 (3)
C6—C5—H5A	120.1	O2—C17—C2	114.5 (3)
C4—C5—H5A	120.1	O2B—N1B—O3B	122.9 (2)
C5—C6—F1	119.3 (2)	O2B—N1B—C2B	118.9 (2)
C5—C6—C7	123.6 (2)	O3B—N1B—C2B	118.1 (2)
F1—C6—C7	117.2 (2)	O4B—N2B—O5B	123.5 (3)
N2—C7—C8	123.3 (2)	O4B—N2B—C4B	118.7 (3)
N2—C7—C6	121.4 (2)	O5B—N2B—C4B	117.9 (3)
C8—C7—C6	115.2 (2)	O6A—N3B—O7A	121.6 (3)
F2—C8—C7	116.6 (2)	O6B—N3B—O7B	119.2 (6)
F2—C8—C9	119.6 (2)	O6B—N3B—C6B	126.3 (5)
C7—C8—C9	123.8 (2)	O6A—N3B—C6B	117.5 (3)
N1—C9—C4	119.3 (2)	O7A—N3B—C6B	119.2 (3)
N1—C9—C8	123.4 (2)	O7B—N3B—C6B	114.5 (5)
C4—C9—C8	117.2 (2)	O1B—C1B—C2B	125.8 (2)
N2—C10—C11	111.5 (2)	O1B—C1B—C6B	123.3 (2)
N2—C10—H10A	109.3	C2B—C1B—C6B	110.8 (2)
C11—C10—H10A	109.3	C3B—C2B—C1B	124.9 (2)
N2—C10—H10B	109.3	C3B—C2B—N1B	117.3 (2)
C11—C10—H10B	109.3	C1B—C2B—N1B	117.8 (2)
H10A—C10—H10B	108.0	C2B—C3B—C4B	118.7 (2)
C12—C11—C10	114.0 (3)	C2B—C3B—H3BA	120.7
C12—C11—N3	110.5 (2)	C4B—C3B—H3BA	120.7
C10—C11—N3	108.1 (2)	C3B—C4B—C5B	121.3 (3)
C12—C11—H11A	108.0	C3B—C4B—N2B	119.0 (3)
C10—C11—H11A	108.0	C5B—C4B—N2B	119.7 (3)
N3—C11—H11A	108.0	C6B—C5B—C4B	118.5 (3)
C11—C12—H12A	109.5	C6B—C5B—H5BA	120.7
C11—C12—H12B	109.5	C4B—C5B—H5BA	120.7
H12A—C12—H12B	109.5	C5B—C6B—C1B	125.7 (3)
C11—C12—H12C	109.5	C5B—C6B—N3B	117.9 (3)
H12A—C12—H12C	109.5	C1B—C6B—N3B	116.4 (3)
H12B—C12—H12C	109.5

C9—N1—C1—C2	2.6 (4)	C13—N3—C11—C12	−179.5 (3)
C15—N1—C1—C2	−178.6 (2)	C13—N3—C11—C10	55.1 (3)
N1—C1—C2—C3	1.4 (4)	C11—N3—C13—C14	−57.0 (3)
N1—C1—C2—C17	−178.7 (2)	C7—N2—C14—C13	140.2 (3)
C1—C2—C3—O3	178.3 (2)	C10—N2—C14—C13	−57.9 (4)
C17—C2—C3—O3	−1.6 (4)	N3—C13—C14—N2	56.2 (3)
C1—C2—C3—C4	−2.2 (4)	C1—N1—C15—C16	−85.8 (3)
C17—C2—C3—C4	177.9 (2)	C9—N1—C15—C16	92.9 (3)
O3—C3—C4—C5	1.2 (4)	C1—C2—C17—O1	−0.1 (4)
C2—C3—C4—C5	−178.3 (2)	C3—C2—C17—O1	179.8 (3)
O3—C3—C4—C9	178.6 (2)	C1—C2—C17—O2	179.2 (3)
C2—C3—C4—C9	−0.9 (3)	C3—C2—C17—O2	−0.9 (4)
C9—C4—C5—C6	−0.3 (4)	O1B—C1B—C2B—C3B	173.3 (3)
C3—C4—C5—C6	177.1 (2)	C6B—C1B—C2B—C3B	−3.2 (4)
C4—C5—C6—F1	176.3 (2)	O1B—C1B—C2B—N1B	−4.6 (4)
C4—C5—C6—C7	−3.2 (4)	C6B—C1B—C2B—N1B	178.8 (2)
C10—N2—C7—C8	−129.4 (3)	O2B—N1B—C2B—C3B	142.1 (3)
C14—N2—C7—C8	30.8 (4)	O3B—N1B—C2B—C3B	−36.0 (3)
C10—N2—C7—C6	52.8 (4)	O2B—N1B—C2B—C1B	−39.8 (3)
C14—N2—C7—C6	−146.9 (3)	O3B—N1B—C2B—C1B	142.1 (2)
C5—C6—C7—N2	180.0 (2)	C1B—C2B—C3B—C4B	3.3 (4)
F1—C6—C7—N2	0.4 (4)	N1B—C2B—C3B—C4B	−178.8 (2)
C5—C6—C7—C8	2.0 (4)	C2B—C3B—C4B—C5B	−1.6 (4)
F1—C6—C7—C8	−177.5 (2)	C2B—C3B—C4B—N2B	177.8 (2)
N2—C7—C8—F2	8.0 (4)	O4B—N2B—C4B—C3B	2.6 (4)
C6—C7—C8—F2	−174.1 (2)	O5B—N2B—C4B—C3B	−177.9 (3)
N2—C7—C8—C9	−175.2 (2)	O4B—N2B—C4B—C5B	−178.0 (3)
C6—C7—C8—C9	2.7 (4)	O5B—N2B—C4B—C5B	1.6 (4)
C1—N1—C9—C4	−5.6 (3)	C3B—C4B—C5B—C6B	0.2 (4)
C15—N1—C9—C4	175.7 (2)	N2B—C4B—C5B—C6B	−179.2 (3)
C1—N1—C9—C8	171.8 (2)	C4B—C5B—C6B—C1B	−0.4 (5)
C15—N1—C9—C8	−6.9 (4)	C4B—C5B—C6B—N3B	179.7 (3)
C5—C4—C9—N1	−177.8 (2)	O1B—C1B—C6B—C5B	−174.9 (3)
C3—C4—C9—N1	4.8 (3)	C2B—C1B—C6B—C5B	1.8 (4)
C5—C4—C9—C8	4.6 (3)	O1B—C1B—C6B—N3B	5.0 (4)
C3—C4—C9—C8	−172.8 (2)	C2B—C1B—C6B—N3B	−178.3 (2)
F2—C8—C9—N1	−6.6 (4)	O6B—N3B—C6B—C5B	130.8 (9)
C7—C8—C9—N1	176.6 (2)	O6A—N3B—C6B—C5B	65.1 (5)
F2—C8—C9—C4	170.8 (2)	O7A—N3B—C6B—C5B	−129.3 (4)
C7—C8—C9—C4	−5.9 (4)	O7B—N3B—C6B—C5B	−48.8 (7)
C7—N2—C10—C11	−139.1 (3)	O6B—N3B—C6B—C1B	−49.1 (9)
C14—N2—C10—C11	58.8 (4)	O6A—N3B—C6B—C1B	−114.8 (4)
N2—C10—C11—C12	−178.6 (3)	O7A—N3B—C6B—C1B	50.8 (5)
N2—C10—C11—N3	−55.3 (3)	O7B—N3B—C6B—C1B	131.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.74	2.520 (3)	153
N3—H3A···O2ⁱ	0.92	2.09	2.984 (3)	164
N3—H3B···O1B	0.92	1.81	2.714 (3)	166
N3—H3B···O2B	0.92	2.52	2.993 (3)	113

Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₀F₂N₃O₃⁺·C₆H₂N₃O₇⁻
M_r	580.47
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	10.9314 (4), 11.6748 (4), 12.0530 (4)
α, β, γ (°)	92.969 (3), 115.555 (3), 109.852 (3)
V (Å³)	1269.14 (8)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.13
Crystal size (mm)	0.44 × 0.33 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.838, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8890, 5002, 4423
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.198, 1.06
No. of reflections	5002
No. of parameters	373
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.59

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	0.84	1.74	2.520 (3)	153
N3—H3A···O2ⁱ	0.92	2.09	2.984 (3)	164
N3—H3B···O1B	0.92	1.81	2.714 (3)	166
N3—H3B···O2B	0.92	2.52	2.993 (3)	113

Symmetry code: (i) x+1, y+1, z+1.

Cg···Cg π stacking interactions, Cg1 is the centroid of ring N1/C1/C2/C3/C4/C9; [Symmetry code: (i) 1-x, -y, -z] top

CgI···CgJ	Cg···Cg (Å)	CgI Perp (Å)	Cgj Perp (Å)	Slippage (Å)
Cg1···Cg1ⁱ	3.6460 (14)	3.3385 (10)	3.3385 (10)	1.46 (6)

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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