Syntheses and crystal structures of three salts of sparfloxacin, one incorporating extended tapes of fused penta­gonal water assemblies

Shankara Prasad, H.J.; Devaraju; Vinaya; Basavaraju, Y.B.; Yathirajan, H.S.; Parkin, S.

doi:10.1107/S2056989022011239

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 78| Part 12| December 2022| Pages 1257-1264

https://doi.org/10.1107/S2056989022011239

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Syntheses and crystal structures of three salts of sparfloxacin, one incorporating extended tapes of fused pentagonal water assemblies

Holehundi J. Shankara Prasad,^a Devaraju,^a ^* Vinaya,^b Yeriyur B. Basavaraju,^b Hemmige S. Yathirajan ^b ^* and Sean Parkin ^c

^aDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysore-570 005, India, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, and ^cDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
^*Correspondence e-mail: Passion49432005@gmail.com, yathirajan@hotmail.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 8 November 2022; accepted 22 November 2022; online 30 November 2022)

Three organic salts of sparfloxacin, a difluorinated third-generation fluoroquinolone antibiotic, have been synthesized and their crystal structures determined. The salts, sparfloxacinium 4-nitrobenzoate dihydrate, C₁₉H₂₃F₂N₄O₃⁺·C₇H₄NO₄⁻·2H₂O (I), sparfloxacinium 2-phenylacetate, C₁₉H₂₃F₂N₄O₃⁺·C₈H₇O₂⁻ (II), and sparfloxacinium 4-methylbenzoate trihydrate, C₁₉H₂₃F₂N₄O₃⁺·C₈H₇O₂⁻·3H₂O (III), exhibit similar inter-species packing interactions. The overall crystal structures each, however, have their own distinct characteristics, which are described here along with a Hirshfeld surface analysis of the various atom–atom contacts involving the sparfloxacinium cations. In the crystal structure of III, an extended supramolecular tape of edge-fused hydrogen-bonded water pentagons was found. These pentagonal water and tape motifs are compared to related constructs in a broad selection of structure types, ranging from macromolecules to small molecules, clathrates, and exotic `ice' formations on clean metal surfaces.

Keywords: sparfloxacin; sparfloxacinium salt; hydrogen bonding; water pentagons; π–π stacking; crystal structure.

CCDC references: 2221478; 2221477; 2221476

1. Chemical context

Fluoroquinolones are highly effective antibiotics that have many advantageous pharmacokinetic properties, including high oral bioavailability, large volume of distribution, and broad-spectrum antimicrobial activity (Jain et al., 2002 ; Marona et al., 2001 ; Faria et al., 2006 ). A critical review of fluoroquinolones was given by Zhanel et al., 2002 . Sparfloxacin, systematic name: 5-amino-1-cyclopropyl-7-(cis-3,5-dimethyl-1-piperazinyl)-6,8-difluoro-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, C₁₉H₂₂F₂N₄O₃, is a difluorinated third-generation fluoroquinolone antibiotic and is one of the most important and successful classes of man-made antibacterials used in the treatment of lung infections, urinary tract infections, and cutaneous allergy. A structural investigation of sparfloxacin using mass spectrometry and MNDO semi-empirical molecular orbital calculations was published by Abd El-Kareem et al. (2018 ). The photodegradation of sparfloxacin and isolation of its degradation products by preparative HPLC was published by Salgado et al. (2005 ). Nanoparticles of Ag–TiO₂ for photocatalytic degradation of sparfloxacin was reported by Kulkarni et al. (2018 ). Newly validated UV spectrophotometric methods for the determination of sparfloxacin in tablets was described by Sowjanya et al. (2020 ). The electrostatic properties of nine fluoroquinolone antibiotics derived directly from their crystal structures was given by Holstein et al. (2012 ). Reviews of sparfloxacin (Schentag, 2000 ), its antibacterial activity, pharmacokinetic properties, clinical efficacy, and tolerability in lower respiratory tract infections (Goa et al., 1997 ), as well as a review of its penetration into the lower respiratory tract and sinuses (Wise & Honeybourne, 1996 ) have also been published.

In view of the importance of floxacin drugs, particularly sparfloxacin, the present paper reports the crystal structures of three sparfloxacin salts with organic anions: sparfloxacinium 4-nitrobenzoate dihydrate (I), sparfloxacinium 2-phenylacetate (II) and sparfloxacinium 4-methylbenzoate trihydrate (III). A serendipitous extended tape of fused water pentagons in III is also described.

2. Structural commentary

Reactions between sparfloxacin and 4-nitrobenzoic acid, phenylacetic acid, and 4-methylbenzoic acid yielded the three salts sparfloxacinium 4-nitrobenzoate (I), sparfloxacinium 2-phenylacetate (II), and sparfloxacinium 4-methylbenzoate (III) (see Scheme). Crystals of I (Fig. 1) form as a dihydrate, with a chain of disordered water molecules occupying channels parallel to the a-axis. In II (Fig. 2), the crystals are solvent free. Compound III (Fig. 3) crystallizes as a trihydrate, with the water molecules in channels parallel to the b-axis (section 3, Supramolecular details). Within each salt, the sparfloxacinium cations are structurally similar and have no unusual bond lengths or angles. The dihydroquinoline ring system plus the attached amino, carboxyl, and fluorine atoms are essentially planar (r.m.s. deviations are: I = 0.0744 Å, II = 0.0505 Å and III = 0.0496 Å), with the largest deviations being 0.1901 (8) Å for F1 in I, 0.1392 (8) Å for O2 in II, and 0.1343 (8) for F1 in III. A pair of intramolecular hydrogen bonds (Tables 1–3 ), O2—H2O⋯O3 and N2—H2NB⋯O3, each form S(6) ring motifs that are preserved in all three structures. The main differences in the cations result from variations in the orientation of the dimethyl piperazine rings, the C6—C7—N3—C10 torsion angles being 60.12 (16)° in I, 39.09 (16)° in II, and −30.9 (2)° in III. By contrast, there is much less variation of the cyclopropyl orientations: C1—N1—C16—C17 torsion angles are 105.99 (15)°, 103.20 (12)°, and 102.71 (15)° for I, II, and III, respectively. The similarities and differences are highlighted in a least-squares-fit overlay of the three cations (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O3	0.97 (3)	1.60 (3)	2.5257 (15)	157 (2)
N2—H2NB⋯O3	0.92 (2)	1.901 (19)	2.6343 (17)	135.0 (16)
N4—H4NA⋯O4	0.960 (18)	1.824 (18)	2.7666 (15)	166.4 (15)
O1W—H1W1⋯O5	0.81	2.00	2.806 (2)	173
O2W—H1W2⋯O1W	0.82	2.12	2.811 (5)	141
O1W—H2W1⋯O2Wⁱ	0.80	2.01	2.803 (5)	172
O2W—H2W2⋯O1ⁱⁱ	0.82	2.02	2.807 (3)	161
N2—H2NA⋯O1Wⁱⁱⁱ	0.89 (2)	2.07 (2)	2.947 (2)	167.8 (19)
N4—H4NB⋯O4^iv	0.913 (18)	1.957 (18)	2.8405 (16)	162.5 (15)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Table 2
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O3	0.95 (2)	1.61 (2)	2.5162 (12)	157.3 (18)
N2—H2NB⋯O3	0.900 (17)	1.917 (16)	2.6200 (13)	133.6 (14)
N4—H4NB⋯O4	0.949 (16)	1.781 (16)	2.7122 (12)	166.3 (13)
N2—H2NA⋯O5ⁱ	0.869 (17)	2.232 (17)	2.9958 (13)	146.5 (14)
N4—H4NA⋯O4ⁱⁱ	0.956 (16)	1.834 (16)	2.7580 (12)	161.8 (14)
Symmetry codes: (i) ; (ii) .

Table 3
Hydrogen-bond geometry (Å, °) for III

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O3	0.92 (2)	1.64 (2)	2.5014 (14)	155 (2)
N2—H2NB⋯O3	0.91 (2)	1.93 (2)	2.6367 (17)	133.4 (18)
N4—H4NA⋯O4	0.967 (19)	1.73 (2)	2.6722 (16)	164.1 (17)
N4—H4NB⋯O5ⁱ	0.91 (2)	1.86 (2)	2.7473 (16)	163.0 (18)
N2—H2NA⋯O2Wⁱⁱ	0.91 (2)	2.12 (2)	2.9664 (17)	153.9 (17)
O2W—H2W2⋯O4	0.94 (3)	1.80 (3)	2.7371 (16)	171 (2)
O1W—H1W1⋯O2W	1.04 (3)	1.71 (3)	2.7503 (17)	175 (2)
O2W—H1W2⋯O3W	0.93 (3)	1.83 (3)	2.7546 (18)	171 (2)
O1W—H2W1⋯O1ⁱⁱⁱ	0.96 (3)	1.89 (3)	2.8434 (16)	171 (2)
O3W—H1W3⋯O1Wⁱⁱ	1.02 (3)	1.82 (3)	2.8362 (17)	173 (2)
O3W—H2W3⋯O1W^iv	1.00 (4)	1.88 (4)	2.8798 (18)	178 (3)
Symmetry codes: (i) ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) ; (iv) x, y+1, z.

Figure 1
An ellipsoid (30% probability) plot of I. Intramolecular hydrogen bonds are drawn as thick dashed lines while intermolecular hydrogen bonds are drawn as open dashed lines. Minor disorder components of water molecules are omitted to enhance clarity.

Figure 2
An ellipsoid (50% probability) plot of II. Intramolecular hydrogen bonds are drawn as thick dashed lines while intermolecular hydrogen bonds are drawn as open dashed lines.

Figure 3
An ellipsoid (50% probability) plot of III. Intramolecular hydrogen bonds are drawn as thick dashed lines while intermolecular hydrogen bonds are drawn as open dashed lines.

Figure 4
A least-squares-fit overlay of the sparfloxacinium cations in I (red), II (green), and III (blue).

In the chosen asymmetric units for each structure, anion placement was selected (amongst symmetry equivalents) so as to form the shortest hydrogen bond between the cationic N4 and the carboxylate O4 of their respective anions (Tables 1–3 ). In I and III, these involve the equatorial hydrogen (H4NA), i.e., N4—H4NA⋯O4, having donor—acceptor distances of 2.7666 (15) Å in I and 2.6722 (16) Å in III. By contrast, in II, the shortest hydrogen bond for N4 involves the axial hydrogen (H4NB), i.e., N4—H4NB⋯O4 at 2.7122 (12) Å.

3. Supramolecular features

The crystal packing in I, II, and III share a few of types of supramolecular features, including extensive hydrogen bonding and π–π stacking of their quinoline ring systems. Nevertheless, within each structure, the specific interactions lead to distinct structural motifs.

In I, pairs of N4—H4NA⋯O4 and N4—H4NB⋯O4^inv (inv = −x + 1, −y + 1, −z + 1) hydrogen bonds (Table 1) form R₄²(8) ring motifs (Fig. 5) with their inversion-related counterparts, in which the anion O4 atom is a bifurcated acceptor. Hydrogen bonding to the water channel is complicated by the inherent disorder within the water chains, but there is clear evidence of an O1W—H1W1⋯O5 hydrogen bond to the 4-nitrobenzoate anion (Table 1, Fig. 5). In II, a similar R₄²(8) ring motif (Fig. 6), to that in I, with bifurcated acceptor O4, is built from N4—H4NB⋯O4 and N4—H4NA⋯O4^inv hydrogen bonds (Table 2). Structure III features a hydrogen-bonded R₄⁴(12) ring motif formed from N4—H4NA⋯O4 and N4—H4NB⋯O5^inv hydrogen bonds of cation/anion pairs (Table 3, Fig. 7). For each structure, additional strong intermolecular N—H⋯O hydrogen bonds connect the NH₂ amine group to a water molecule (in I and III) or to an anion (in II) (Tables 1–3 ). The hydrogen-bonded water structure in III is especially intricate, and will be described separately (vide infra).

Figure 5
A partial packing plot of I viewed approximately down the a-axis. Intramolecular hydrogen bonds are drawn as thick dashed lines while intermolecular hydrogen bonds are drawn as open dashed lines. Minor disorder components of water molecules and H atoms on groups not involved in hydrogen bonding are omitted.

Figure 6
A partial packing plot of II viewed down the a-axis. Intramolecular hydrogen bonds are drawn as thick dashed lines and intermolecular hydrogen bonds are drawn as open dashed lines. H atoms on groups not involved in hydrogen bonding are omitted.

Figure 7
A partial packing plot of III viewed down the b-axis. Intramolecular hydrogen bonds are drawn as thick dashed lines, intermolecular hydrogen bonds are drawn as open dashed lines, and hydrogen bonds to and between water molecules are drawn as thin dashed lines. The water molecules form hydrogen-bonded pentagons (see also Fig. 11

). H atoms on groups not involved in hydrogen bonding are omitted.

Inversion-related quinoline ring systems in I π–π stack to give two different interplanar spacings: 3.3789 (14) Å (via −x, −y, −z + 2) and 3.3901 (14) Å (via −x + 1, −y, −z + 2) for the mean planes through N1,C1–C9,O3, leading to columns of cations along the a-axis (Fig. 8). In II, stacking of inversion-related (−x + 2, −y, −z + 2) cations gives an interplanar spacing of 3.3413 (11) Å, but does not lead to extended columns because the offset to adjacent pairs is too great (Fig. 9). In III, π–π stacking again leads to extended columns, this time parallel to the b-axis (Fig. 10), with interplanar spacings of 3.3452 (15) Å (via −x, −y + 2, −z + 1) and 3.4677 (14) Å (via −x, −y + 1, −z + 1).

Figure 8
A partial packing plot of I viewed approximately along [0 $[\overline{1}]$ $[\overline{1}]$ ] showing π–π stacking of inversion-related sparfloxacinium cations into columns that extend parallel to the a-axis. Dotted lines connect the centroids of overlapping rings.

Figure 9
A partial packing plot of II viewed down the c-axis. Pairs of inversion-related sparfloxacinium cations form π–π-stacked dimers. Dotted lines connect the centroids of overlapping rings.

Figure 10
A partial packing plot of III viewed down the c-axis showing π–π stacking of inversion-related sparfloxacinium cations into columns that extend parallel to the b-axis. Dotted lines connect the centroids of overlapping rings.

Atom–atom contact coverages obtained from Hirshfeld surface 2D fingerprint plots calculated using CrystalExplorer (Spackman et al., 2021 ) for the sparfloxacinium cations in I, II, and III are given in the supporting information (Figs. S1–S3) and summarized in Table 4. In all three salts, the predominant contacts are between H⋯H, H⋯O/O⋯H, and H⋯C/C⋯H.

Table 4
Atom-atom contact coverages (%) in I, II, and III

Atom contacts	I	II	III
H⋯H	41.2	40.3	48.0
H⋯O	28.8	25.5	23.4
H⋯C	10.0	15.5	7.9
C⋯C	6.0	4.6	7.7
H⋯F	3.5	7.7	5.7
O⋯F	2.6	0.2	1.3
C⋯O	2.3	1.4	2.5
H⋯N	1.6	3.0	1.5
Heterogeneous contact types here include the reciprocal interactions, e.g., "H⋯O" represents "H⋯O/O⋯H". All other fractions of atom-contact coverages were negligible.

In the structure of III, the three water molecules hydrogen bond to n-glide-related copies (Table 3) to form cyclic five-membered slightly puckered pentagonal ring structures. These water pentagons are edge-fused to form extended ribbon- or tape-like chains that propagate parallel to the b-axis by further hydrogen bonding to n-glide- and translation-related water molecules. The tapes hydrogen bond to the sparfloxacinium cation as both donor (O1W—H2W1⋯O1ⁱⁱⁱ) and acceptor (N2—H2NA⋯O2Wⁱⁱ) and to the anion as a donor (O2W—H2W2⋯O4) (symmetry codes as per Table 3). Two views of these supramolecular water-tape structures are shown in Fig. 11. A few other instances of similar pentagonal water assemblies are known. These are compared to those of III, along with some additional background information, in section 4 (Database survey and related literature).

Figure 11
Two views of the extended chains of water-molecule pentagons observed in the crystal packing of III. Hydrogen bonds are depicted as dashed lines. For the sake of clarity, the cations and anions are omitted.

4. Database survey and related literature

A search of the Cambridge Structure Database (CSD version 5.43 with all updates through September 2022; Groom et al., 2016 ) for the keyword `sparfloxacin' returned (ignoring duplicates) 29 records. Of these, 11 are complexes with metals and have few structural characteristics in common with I, II, or III other than the presence of ligated sparfloxacin molecules. Of the remaining 18 entries, 12 are salts and all but one are co-crystals, hydrates and/or solvates. CSD entry JEKMOB (Miyamoto et al., 1990 ) corresponds to pure sparfloxacin, while COQWOU (Sivalakshmidevi et al., 2000 ) is a trihydrate of sparfloxacin. Four entries, UXEPUK, UXEQEV, UXEQAR, and UXEQIZ (Gunnam et al., 2016 ) are sparfloxacin co-crystallized with methyl, ethyl, propyl, and isobutyl para-hydroxybenzoic acids, respectively. The remaining 12 structures are sparfloxacinium salts, five of which have inorganic counter-anions [CIBYIW (BF₄⁻; Shingnapurkar et al., 2007 ), GALFEH (Br⁻; Golovnev & Vasil'ev, 2016 ), JADGON and JADGUT (CdBr₄²⁻ and ZnBr₄²⁻; Vasil'ev & Golovnev, 2015 ), and YOBCUP (CuBr₄⁻; Vasil'ev & Golovnev, 2014 )]. Of the seven entries with organic counter-anions, GAPCUZ and GAPDAG (Zhang et al., 2022 ) are salts with pyrocatechuic acid that differ in their occluded solvent, while IJEBIL, IJEBOR, IJEBUX, IJECAE, and IJEDIN (Djalò et al., 2021 ) have 2-(carboxymethyl)-2-hydroxybutanedioate, pyridine-3-carboxylate, 3-carboxybenzoate, 3-carboxyprop-2-enoate, and 2-aminobenzoate anions respectively. The crystal structures of some closely related compounds, viz., bis(lomefloxacin) 1,4-benzenedicarboxylate dihydrate (XEWSOI; Zhou et al., 2006 ), gatifloxacin hydrochloride (HOTTOA; Yu et al., 2009 ), lomefloxacinium picrate (IKAPIU; Jasinski et al., 2011 ) and lomefloxacin chloride dihydrate (LATPON; Holstein et al., 2012) have also been reported.

Assemblies of water having pentagonal structural units are not uncommon. They are ubiquitous in the clathrate hydrates (see e.g., Englezos, 1993 ), but are far less common in other structure types. They have been reported in studies of small proteins [e.g., crambin (refcode 1CRN in PDB; Teeter, 1984 ), BPTI (refcode 1BPI; Parkin et al., 1996 ); PDB = Protein Data Bank (Berman et al., 2000 )] and collagen peptides (Bella et al., 1995 ), and in small molecules, including a hexahydrate of pinacol (CSD code PINOLH01; Hao et al., 2005 ), amongst others. A few extended linear water–pentagon tapes similar to those in III have also been reported, e.g., L-leucyl-L-alanine tetrahydrate (CSD code RAVMOQ; Görbitz, 1997 ); trans-4,4′-azopyridine dioxide tetrahydrate (WAGMOH; Ma et al., 2004 ), a Cu^II-based MOF (OFUYOE02; Mukherjee et al., 2011 ), and a Co(cyclam)Cl₂ complex (REFDUD; Jana et al., 2012 ). In RAVMOQ, the pentagons have similar regularity to those in III but the tapes are considerably more buckled, while in WAGMOH and OFUYOE02 the pentagons/tapes are both severely distorted/buckled relative to those in III. In REFDUD, the tapes of pentagons are further linked into extended layers. Water pentagons are also believed to play a role in ice nucleation (see e.g. Pirzadeh et al., 2011 and references therein). Indeed, an exotic mono-periodic form of `ice' consisting of a linear array of fused water pentagons, reported to nucleate on the (110) surface of copper at temperatures between 100 and 140 K (Carrasco et al., 2009 ), bears a striking resemblance to the water-pentagon tape in III.

5. Synthesis and crystallization

Sparfloxacin (a gift from Recon Healthcare, Bengaluru) (100 mg, 0.255 mmol) was dissolved in methanol (10 ml) and water (1 ml) under constant stirring at 333 K for 30 min. Equimolar solutions of either 4-nitrobenzoic acid (43 mg, 0.255 mmol), phenylacetic acid (35 mg, 0.255 mmol), or 4-methylbenzoic acid (35 mg, 0.255 mmol) in methanol (10 ml) and acetonitrile (10 ml) were added separately to the solutions of sparfloxacin and stirring was continued for 60 min at 333 K. The mixtures were then cooled to room temperature. X-ray quality crystals were formed by slow evaporation over fifteen days. The melting points were 511–514 K (I), 485–488 K (II) and 498–503 K (III). A generalized reaction scheme for the three salts of sparfloxacin is given in Fig. 12.

Figure 12
Synthetic routes to the formation of I, II, and III.

6. Data collection and structure refinement

Crystal data, data collection, and structure refinement details are given in Table 5. At 90 K, crystals of I gave diffraction with satellite reflections, suggesting modulation of the structure. On warming, the satellites diminished, and were absent at the data collection temperature of 250 (1) K. The water molecules in I were extensively disordered. The SQUEEZE routine in PLATON (Spek, 2015 ) suggested the presence of ∼40e⁻ in the cell `voids', corresponding to two water molecules per asymmetric unit. Thus, a hydrate model consisting of two major components [occupancies 0.688 (3) for O1W and 0.608 (3) for O2W] and two minor parts for each major [occupancies 0.185 (3), 0.127 (3), 0.265 (3), and 0.128 (3) for O1W′, O1W", O2W′, and O2W", respectively] was built from difference-map peaks. Hydrogen atoms on these partial-occupancy fragments were placed so as to make reasonable hydrogen bonds, but other than H1W1 and H1W2, their presence is solely to ensure a correct atom count. Occupancies for these disordered waters were restrained using SUMP and their U^ij restrained with SIMU in SHELXL (Sheldrick, 2015b ). Crystals of II and III presented no such problems. All non-disordered hydrogen atoms were found in difference-Fourier maps, but those bound to carbon were subsequently included in the refinement using riding models, with constrained distances set to SHELXL defaults [0.99 Å (R₃CH), 0.94 Å (Csp²H), 0.98 Å (R₂CH₂), 0.97 Å (RCH₃) in I and 1.00 Å (R₃CH), 0.95 Å (Csp²H), 0.99 Å (R₂CH₂), 0.98 Å (RCH₃) in II and III]. U_iso(H) values for carbon-bound hydrogens were set to 1.2U_eq or 1.5U_eq (CH₃) of the parent atom. The OH and NH hydrogen atoms were refined freely (as per Fábry, 2018 ), aside from the minor-component water hydrogens of I, which were fixed and had U_iso(H) set to 1.5U_eq of their water oxygen.

Table 5
Experimental details

	I	II	III
Crystal data
Chemical formula	C₁₉H₂₃F₂N₄O₃⁺·C₇H₄NO₄⁻·2H₂O	C₁₉H₂₃F₂N₄O₃⁺·C₈H₇O₂⁻	C₁₉H₂₃F₂N₄O₃⁺·C₈H₇O₂⁻·3H₂O
M_r	595.56	528.55	582.60
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n
Temperature (K)	250	90	90
a, b, c (Å)	7.5736 (4), 13.1809 (9), 13.8947 (9)	10.0222 (4), 10.1145 (4), 13.5255 (5)	18.4423 (9), 7.0694 (3), 21.0669 (10)
α, β, γ (°)	85.658 (2), 82.316 (2), 81.108 (2)	69.606 (2), 73.032 (2), 83.747 (2)	90, 93.252 (2), 90
V (Å³)	1355.94 (15)	1229.15 (9)	2742.2 (2)
Z	2	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.12	0.11	0.11
Crystal size (mm)	0.33 × 0.31 × 0.27	0.34 × 0.28 × 0.26	0.19 × 0.15 × 0.04

Data collection
Diffractometer	Bruker D8 Venture dual source	Bruker D8 Venture dual source	Bruker D8 Venture dual source
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.930, 0.971	0.914, 0.959	0.894, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	45287, 6210, 4944	41293, 5639, 5029	44990, 6296, 5086
R_int	0.033	0.038	0.043
(sin θ/λ)_max (Å⁻¹)	0.653	0.650	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.04	0.034, 0.092, 1.02	0.040, 0.100, 1.04
No. of reflections	6210	5639	6296
No. of parameters	443	365	418
No. of restraints	46	0	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.22	0.37, −0.20	0.31, −0.23
Computer programs: APEX3 (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b), SHELXTL and XP in SHELXTL (Sheldrick, 2008 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2221478; 2221477; 2221476

Crystal structure: contains datablocks I, II, III, global. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022011239/vm2274Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022011239/vm2274IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989022011239/vm2274IIIsup4.hkl

Hirshfeld surface fingerprint plots for I. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup5.png

Hirshfeld surface fingerprint plots for II. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup6.png

Hirshfeld surface fingerprint plots for III. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup7.png

checkCIF report

Computing details top

For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

4-(5-Amino-3-carboxy-1-cyclopropyl-6,8-difluoro-4-oxo-1,4-dihydroquinolin-7-yl)-2,6-dimethylpiperazin-1-ium 4-nitrobenzoate dihydrate (I) top

Crystal data top

C₁₉H₂₃F₂N₄O₃⁺·C₇H₄NO₄⁻·2H₂O	Z = 2
M_r = 595.56	F(000) = 624
Triclinic, P1	D_x = 1.459 Mg m⁻³
a = 7.5736 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.1809 (9) Å	Cell parameters from 9803 reflections
c = 13.8947 (9) Å	θ = 2.8–27.5°
α = 85.658 (2)°	µ = 0.12 mm⁻¹
β = 82.316 (2)°	T = 250 K
γ = 81.108 (2)°	Cut block, yellow
V = 1355.94 (15) Å³	0.33 × 0.31 × 0.27 mm

Data collection top

Bruker D8 Venture dual source diffractometer	6210 independent reflections
Radiation source: microsource	4944 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm^-1	R_int = 0.033
φ and ω scans	θ_max = 27.6°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.930, T_max = 0.971	k = −17→17
45287 measured reflections	l = −17→18

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)] = 0.039	Hydrogen site location: mixed
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0419P)² + 0.4829P] where P = (F_o² + 2F_c²)/3
6210 reflections	(Δ/σ)_max = 0.001
443 parameters	Δρ_max = 0.27 e Å⁻³
46 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998).

The crystals appeared to become modulated (doubled cell, some satellite reflections) when cooled to 90K. Visual inspection of crystal integrity and diffraction quality vs temperature established a safe temperature for data collection of -23° C.

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

Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1W	1.0080 (5)	0.43691 (14)	0.13115 (13)	0.0767 (9)	0.688 (3)
H1W1	0.989672	0.457266	0.185755	0.115*	0.688 (3)
H2W1	1.079647	0.467749	0.098119	0.115*	0.688 (3)
O1W'	0.8676 (14)	0.4128 (5)	0.1178 (6)	0.070 (3)	0.185 (3)
H5W1	0.868139	0.425647	0.174506	0.105*	0.185 (3)
H6W1	0.860698	0.433812	0.056840	0.105*	0.185 (3)
O2W	0.7704 (6)	0.4430 (2)	−0.0090 (2)	0.0987 (12)	0.607 (3)
H1W2	0.795334	0.431906	0.047015	0.148*	0.607 (3)
H2W2	0.794277	0.387475	−0.034142	0.148*	0.607 (3)
O2W'	0.6241 (18)	0.4587 (10)	0.0029 (7)	0.148 (4)	0.265 (3)
H3W2	0.591257	0.540477	−0.008066	0.222*	0.265 (3)
H4W2	0.611625	0.429007	0.056105	0.222*	0.265 (3)
O1W"	1.1155 (10)	0.5163 (6)	0.1538 (6)	0.035 (2)	0.127 (2)
H3W1	1.079941	0.501309	0.210951	0.053*	0.127 (2)
H4W1	1.058065	0.486154	0.122076	0.053*	0.127 (2)
O2W"	0.4728 (18)	0.3998 (9)	0.0386 (7)	0.071 (4)	0.128 (3)
H5W2	0.458449	0.355478	0.002884	0.107*	0.128 (3)
H6W2	0.421442	0.383063	0.092059	0.107*	0.128 (3)
F1	0.52757 (11)	0.05643 (6)	0.77813 (6)	0.0371 (2)
F2	0.18695 (13)	0.33665 (6)	0.93914 (6)	0.0439 (2)
O1	0.17039 (17)	−0.28135 (8)	1.13520 (8)	0.0491 (3)
O2	0.04706 (18)	−0.15414 (10)	1.22784 (8)	0.0531 (3)
H2O	0.038 (3)	−0.080 (2)	1.2189 (18)	0.092 (8)*
O3	0.05728 (15)	0.02882 (8)	1.16122 (7)	0.0410 (2)
N1	0.36989 (15)	−0.08370 (8)	0.91686 (8)	0.0278 (2)
N2	0.06988 (19)	0.21803 (10)	1.08748 (9)	0.0408 (3)
H2NA	0.054 (3)	0.2860 (17)	1.0912 (15)	0.068 (6)*
H2NB	0.028 (3)	0.1740 (15)	1.1371 (14)	0.056 (5)*
N3	0.42835 (16)	0.25859 (8)	0.77468 (8)	0.0312 (2)
N4	0.53893 (17)	0.38569 (8)	0.61030 (8)	0.0302 (2)
H4NA	0.627 (2)	0.4111 (13)	0.5620 (13)	0.047 (5)*
H4NB	0.433 (2)	0.4245 (13)	0.5980 (12)	0.045 (5)*
C1	0.30722 (18)	−0.14548 (10)	0.99045 (9)	0.0299 (3)
H1	0.337777	−0.216882	0.985064	0.036*
C2	0.20213 (18)	−0.11166 (10)	1.07257 (9)	0.0304 (3)
C3	0.15347 (17)	−0.00419 (10)	1.08473 (9)	0.0292 (3)
C4	0.22010 (17)	0.06439 (10)	1.00629 (9)	0.0266 (3)
C5	0.33138 (16)	0.02359 (9)	0.92265 (9)	0.0250 (2)
C6	0.40038 (17)	0.0912 (1)	0.85124 (9)	0.0269 (3)
C7	0.35467 (17)	0.1980 (1)	0.85219 (9)	0.0275 (3)
C8	0.24335 (18)	0.23468 (10)	0.93348 (10)	0.0305 (3)
C9	0.17783 (18)	0.17274 (10)	1.01162 (9)	0.0292 (3)
C10	0.38665 (19)	0.24164 (10)	0.67695 (9)	0.0313 (3)
H10A	0.270121	0.281690	0.666003	0.038*
H10B	0.378584	0.168737	0.672166	0.038*
C11	0.53265 (18)	0.27401 (9)	0.60029 (9)	0.0297 (3)
H11	0.649781	0.234195	0.613369	0.036*
C12	0.5777 (2)	0.40582 (10)	0.71004 (10)	0.0333 (3)
H12	0.697490	0.367927	0.720892	0.040*
C13	0.4360 (2)	0.36726 (10)	0.78632 (10)	0.0336 (3)
H13A	0.465625	0.375773	0.851484	0.040*
H13B	0.318020	0.407835	0.779453	0.040*
C14	0.5807 (3)	0.51991 (11)	0.71586 (12)	0.0502 (4)
H14A	0.608301	0.532920	0.779579	0.075*
H14B	0.463712	0.557707	0.705381	0.075*
H14C	0.671827	0.542109	0.666327	0.075*
C15	0.5023 (2)	0.25721 (12)	0.49722 (10)	0.0389 (3)
H15A	0.498785	0.184777	0.490906	0.058*
H15B	0.599751	0.279189	0.451824	0.058*
H15C	0.388849	0.296912	0.483088	0.058*
C16	0.4737 (2)	−0.12999 (10)	0.83077 (10)	0.0334 (3)
H16	0.603900	−0.124621	0.821780	0.040*
C17	0.3878 (2)	−0.12486 (13)	0.73970 (11)	0.0475 (4)
H17A	0.262288	−0.091945	0.741442	0.057*
H17B	0.463252	−0.114810	0.677711	0.057*
C18	0.4245 (3)	−0.22495 (13)	0.79618 (13)	0.0575 (5)
H18A	0.321508	−0.253376	0.832512	0.069*
H18B	0.522463	−0.276239	0.768785	0.069*
C19	0.1399 (2)	−0.18977 (11)	1.14682 (10)	0.0378 (3)
O4	0.75064 (14)	0.48408 (8)	0.46618 (8)	0.0416 (3)
O5	0.9197 (2)	0.49587 (10)	0.32356 (9)	0.0704 (4)
O6	1.2405 (3)	−0.02164 (11)	0.40432 (12)	0.0886 (5)
O7	1.2235 (3)	0.00344 (12)	0.55450 (12)	0.0933 (6)
N5	1.20030 (19)	0.03305 (10)	0.47204 (11)	0.0486 (3)
C20	1.11515 (19)	0.13962 (10)	0.45442 (11)	0.0349 (3)
C21	1.1012 (2)	0.17648 (12)	0.35967 (11)	0.0441 (4)
H21	1.140867	0.133723	0.307551	0.053*
C22	1.0273 (2)	0.27779 (12)	0.34355 (11)	0.0431 (4)
H22	1.018655	0.304761	0.279485	0.052*
C23	0.96571 (18)	0.34046 (11)	0.42053 (10)	0.0328 (3)
C24	0.98225 (19)	0.30048 (11)	0.51504 (10)	0.0338 (3)
H24	0.942055	0.342696	0.567518	0.041*
C25	1.05718 (19)	0.19935 (11)	0.53262 (10)	0.0355 (3)
H25	1.068158	0.172163	0.596423	0.043*
C26	0.8742 (2)	0.44884 (11)	0.40125 (11)	0.0384 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1W	0.150 (3)	0.0352 (10)	0.035 (1)	0.0000 (13)	0.0110 (12)	−0.0034 (7)
O1W'	0.089 (6)	0.032 (4)	0.074 (5)	0.014 (4)	0.023 (5)	−0.007 (3)
O2W	0.138 (3)	0.0614 (17)	0.093 (2)	0.0114 (19)	−0.015 (2)	−0.0300 (15)
O2W'	0.152 (9)	0.198 (11)	0.103 (6)	−0.014 (9)	−0.021 (7)	−0.076 (7)
O1W"	0.035 (4)	0.035 (4)	0.034 (4)	−0.003 (3)	−0.005 (3)	0.009 (3)
O2W"	0.107 (10)	0.067 (7)	0.043 (6)	−0.021 (7)	−0.003 (6)	−0.022 (5)
F1	0.0448 (5)	0.0298 (4)	0.0315 (4)	−0.0027 (3)	0.0113 (3)	−0.0035 (3)
F2	0.0602 (6)	0.0226 (4)	0.0418 (5)	0.0027 (4)	0.0092 (4)	−0.0022 (3)
O1	0.0692 (8)	0.0342 (6)	0.0456 (6)	−0.0145 (5)	−0.0130 (6)	0.0113 (5)
O2	0.0740 (8)	0.0489 (7)	0.0341 (6)	−0.0190 (6)	0.0073 (5)	0.0082 (5)
O3	0.0515 (6)	0.0395 (6)	0.0280 (5)	−0.0064 (5)	0.0082 (4)	−0.0004 (4)
N1	0.0335 (6)	0.0228 (5)	0.0262 (5)	−0.0020 (4)	−0.0033 (4)	−0.0010 (4)
N2	0.0544 (8)	0.0304 (7)	0.0321 (6)	−0.0001 (6)	0.0092 (6)	−0.0048 (5)
N3	0.0459 (7)	0.0243 (5)	0.0237 (5)	−0.0093 (5)	−0.0011 (5)	0.0003 (4)
N4	0.0354 (6)	0.0231 (5)	0.0296 (6)	−0.0018 (5)	0.0000 (5)	0.0031 (4)
C1	0.0362 (7)	0.0242 (6)	0.0301 (7)	−0.0048 (5)	−0.0095 (5)	0.0028 (5)
C2	0.0346 (7)	0.0310 (7)	0.0271 (6)	−0.0078 (5)	−0.0085 (5)	0.0046 (5)
C3	0.0298 (6)	0.0341 (7)	0.0241 (6)	−0.0052 (5)	−0.0050 (5)	0.0006 (5)
C4	0.0286 (6)	0.0270 (6)	0.0240 (6)	−0.0032 (5)	−0.0048 (5)	−0.0003 (5)
C5	0.0272 (6)	0.0227 (6)	0.0252 (6)	−0.0024 (5)	−0.0056 (5)	−0.0009 (5)
C6	0.0299 (6)	0.0271 (6)	0.0225 (6)	−0.0023 (5)	0.0001 (5)	−0.0034 (5)
C7	0.0323 (6)	0.0259 (6)	0.0241 (6)	−0.0049 (5)	−0.0037 (5)	0.0008 (5)
C8	0.0373 (7)	0.0215 (6)	0.0311 (7)	−0.0002 (5)	−0.0023 (5)	−0.0018 (5)
C9	0.0329 (7)	0.0292 (6)	0.0244 (6)	−0.0012 (5)	−0.0028 (5)	−0.0027 (5)
C10	0.0409 (7)	0.0279 (6)	0.0252 (6)	−0.0075 (5)	−0.0032 (5)	0.0005 (5)
C11	0.0369 (7)	0.0224 (6)	0.0278 (6)	−0.0015 (5)	−0.0011 (5)	0.0003 (5)
C12	0.0443 (8)	0.0249 (6)	0.0306 (7)	−0.0076 (6)	−0.0030 (6)	0.0001 (5)
C13	0.0468 (8)	0.0234 (6)	0.0298 (7)	−0.0060 (6)	−0.0001 (6)	−0.0013 (5)
C14	0.0772 (12)	0.0299 (8)	0.0452 (9)	−0.0202 (8)	0.0012 (8)	−0.0020 (6)
C15	0.0495 (9)	0.0399 (8)	0.0272 (7)	−0.0107 (7)	0.0000 (6)	−0.0014 (6)
C16	0.0397 (7)	0.0263 (6)	0.0318 (7)	−0.0006 (5)	0.0011 (6)	−0.0050 (5)
C17	0.0602 (10)	0.0509 (9)	0.0329 (8)	−0.0105 (8)	−0.0027 (7)	−0.0126 (7)
C18	0.0856 (13)	0.0344 (8)	0.0513 (10)	−0.0160 (8)	0.0122 (9)	−0.0163 (7)
C19	0.0442 (8)	0.0379 (8)	0.0332 (7)	−0.0117 (6)	−0.0110 (6)	0.0085 (6)
O4	0.0427 (6)	0.0327 (5)	0.0423 (6)	0.0030 (4)	0.0069 (5)	0.0031 (4)
O5	0.0889 (10)	0.0538 (8)	0.0475 (7)	0.0188 (7)	0.0197 (7)	0.0213 (6)
O6	0.1316 (15)	0.0443 (8)	0.0737 (10)	0.0239 (8)	0.0071 (10)	−0.0100 (7)
O7	0.1428 (16)	0.0572 (9)	0.0674 (10)	0.0305 (9)	−0.0285 (10)	0.0123 (7)
N5	0.0492 (8)	0.0353 (7)	0.0557 (9)	0.0007 (6)	0.0019 (6)	0.0043 (6)
C20	0.0325 (7)	0.0303 (7)	0.0399 (8)	−0.0023 (5)	−0.0014 (6)	0.0016 (6)
C21	0.0546 (9)	0.0396 (8)	0.0343 (8)	0.0008 (7)	0.0020 (7)	−0.0066 (6)
C22	0.0552 (9)	0.0434 (8)	0.0261 (7)	0.0026 (7)	−0.0018 (6)	0.0017 (6)
C23	0.0307 (7)	0.0337 (7)	0.0315 (7)	−0.0016 (5)	0.0001 (5)	0.0017 (5)
C24	0.0347 (7)	0.0374 (7)	0.0274 (7)	−0.0014 (6)	−0.0011 (5)	−0.0030 (5)
C25	0.0352 (7)	0.0390 (8)	0.0308 (7)	−0.0037 (6)	−0.0045 (6)	0.0042 (6)
C26	0.0412 (8)	0.0357 (8)	0.0342 (7)	0.0012 (6)	−0.0004 (6)	0.0036 (6)

Geometric parameters (Å, º) top

O1W—O1W'	1.196 (10)	C6—C7	1.3973 (18)
O1W—H1W1	0.8112	C7—C8	1.3865 (18)
O1W—H2W1	0.8024	C8—C9	1.3923 (18)
O1W—H5W1	1.1709	C10—C11	1.5170 (18)
O1W'—H5W1	0.8189	C10—H10A	0.9800
O1W'—H6W1	0.8767	C10—H10B	0.9800
O1W'—H1W2	1.1808	C11—C15	1.5182 (19)
O2W—H6W1	1.2013	C11—H11	0.9900
O2W—H1W2	0.8218	C12—C14	1.5157 (19)
O2W—H2W2	0.8195	C12—C13	1.5223 (19)
O2W'—H3W2	1.0717	C12—H12	0.9900
O2W'—H4W2	0.8116	C13—H13A	0.9800
O1W"—H3W1	0.8237	C13—H13B	0.9800
O1W"—H4W1	0.8198	C14—H14A	0.9700
O2W"—H5W2	0.8223	C14—H14B	0.9700
O2W"—H6W2	0.8224	C14—H14C	0.9700
F1—C6	1.3573 (14)	C15—H15A	0.9700
F2—C8	1.3508 (14)	C15—H15B	0.9700
O1—C19	1.2124 (18)	C15—H15C	0.9700
O2—C19	1.3224 (19)	C16—C18	1.490 (2)
O2—H2O	0.97 (3)	C16—C17	1.491 (2)
O3—C3	1.2705 (16)	C16—H16	0.9900
N1—C1	1.3408 (16)	C17—C18	1.491 (2)
N1—C5	1.4053 (16)	C17—H17A	0.9800
N1—C16	1.4601 (16)	C17—H17B	0.9800
N2—C9	1.3601 (17)	C18—H18A	0.9800
N2—H2NA	0.89 (2)	C18—H18B	0.9800
N2—H2NB	0.92 (2)	O4—C26	1.2682 (17)
N3—C7	1.3986 (16)	O5—C26	1.2384 (18)
N3—C13	1.4644 (16)	O6—N5	1.207 (2)
N3—C10	1.4751 (17)	O7—N5	1.209 (2)
N4—C11	1.4975 (16)	N5—C20	1.4694 (18)
N4—C12	1.5053 (18)	C20—C25	1.374 (2)
N4—H4NA	0.960 (18)	C20—C21	1.380 (2)
N4—H4NB	0.913 (18)	C21—C22	1.380 (2)
C1—C2	1.3633 (19)	C21—H21	0.9400
C1—H1	0.9400	C22—C23	1.388 (2)
C2—C3	1.4245 (19)	C22—H22	0.9400
C2—C19	1.4852 (18)	C23—C24	1.3916 (19)
C3—C4	1.4506 (17)	C23—C26	1.5095 (19)
C4—C9	1.4199 (18)	C24—C25	1.383 (2)
C4—C5	1.4292 (17)	C24—H24	0.9400
C5—C6	1.3867 (17)	C25—H25	0.9400

O1W'—O1W—H1W1	104.5	C10—C11—H11	108.7
O1W'—O1W—H2W1	133.2	C15—C11—H11	108.7
H1W1—O1W—H2W1	110.0	N4—C12—C14	109.29 (11)
O1W'—O1W—H5W1	40.5	N4—C12—C13	109.42 (11)
H1W1—O1W—H5W1	64.5	C14—C12—C13	111.47 (12)
H2W1—O1W—H5W1	156.0	N4—C12—H12	108.9
O1W—O1W'—H5W1	68.1	C14—C12—H12	108.9
O1W—O1W'—H6W1	102.1	C13—C12—H12	108.9
H5W1—O1W'—H6W1	150.1	N3—C13—C12	110.13 (11)
O1W—O1W'—H1W2	126.7	N3—C13—H13A	109.6
H5W1—O1W'—H1W2	146.3	C12—C13—H13A	109.6
H6W1—O1W'—H1W2	25.0	N3—C13—H13B	109.6
H6W1—O2W—H1W2	21.9	C12—C13—H13B	109.6
H6W1—O2W—H2W2	104.5	H13A—C13—H13B	108.1
H1W2—O2W—H2W2	106.0	C12—C14—H14A	109.5
H3W2—O2W'—H4W2	122.7	C12—C14—H14B	109.5
H3W1—O1W"—H4W1	104.8	H14A—C14—H14B	109.5
H5W2—O2W"—H6W2	104.4	C12—C14—H14C	109.5
C19—O2—H2O	105.3 (14)	H14A—C14—H14C	109.5
C1—N1—C5	119.87 (11)	H14B—C14—H14C	109.5
C1—N1—C16	118.82 (11)	C11—C15—H15A	109.5
C5—N1—C16	121.29 (10)	C11—C15—H15B	109.5
C9—N2—H2NA	120.4 (14)	H15A—C15—H15B	109.5
C9—N2—H2NB	115.8 (12)	C11—C15—H15C	109.5
H2NA—N2—H2NB	123.3 (18)	H15A—C15—H15C	109.5
C7—N3—C13	120.17 (11)	H15B—C15—H15C	109.5
C7—N3—C10	116.79 (11)	N1—C16—C18	119.56 (13)
C13—N3—C10	111.65 (10)	N1—C16—C17	118.95 (12)
C11—N4—C12	111.82 (10)	C18—C16—C17	60.01 (11)
C11—N4—H4NA	111.3 (10)	N1—C16—H16	115.6
C12—N4—H4NA	109.6 (11)	C18—C16—H16	115.6
C11—N4—H4NB	110.7 (11)	C17—C16—H16	115.6
C12—N4—H4NB	109.2 (11)	C18—C17—C16	59.96 (11)
H4NA—N4—H4NB	104.0 (14)	C18—C17—H17A	117.8
N1—C1—C2	124.37 (12)	C16—C17—H17A	117.8
N1—C1—H1	117.8	C18—C17—H17B	117.8
C2—C1—H1	117.8	C16—C17—H17B	117.8
C1—C2—C3	120.03 (12)	H17A—C17—H17B	114.9
C1—C2—C19	118.03 (12)	C16—C18—C17	60.03 (10)
C3—C2—C19	121.93 (12)	C16—C18—H18A	117.8
O3—C3—C2	120.95 (12)	C17—C18—H18A	117.8
O3—C3—C4	122.34 (12)	C16—C18—H18B	117.8
C2—C3—C4	116.71 (11)	C17—C18—H18B	117.8
C9—C4—C5	118.93 (11)	H18A—C18—H18B	114.9
C9—C4—C3	120.79 (11)	O1—C19—O2	120.84 (13)
C5—C4—C3	120.28 (11)	O1—C19—C2	122.93 (14)
C6—C5—N1	122.45 (11)	O2—C19—C2	116.23 (13)
C6—C5—C4	118.84 (11)	O6—N5—O7	122.86 (15)
N1—C5—C4	118.70 (11)	O6—N5—C20	118.87 (15)
F1—C6—C5	120.87 (11)	O7—N5—C20	118.25 (14)
F1—C6—C7	115.55 (11)	C25—C20—C21	122.68 (13)
C5—C6—C7	123.46 (11)	C25—C20—N5	118.74 (13)
C8—C7—C6	115.87 (11)	C21—C20—N5	118.56 (13)
C8—C7—N3	125.60 (12)	C22—C21—C20	118.18 (14)
C6—C7—N3	118.49 (11)	C22—C21—H21	120.9
F2—C8—C7	119.99 (11)	C20—C21—H21	120.9
F2—C8—C9	115.54 (11)	C21—C22—C23	120.96 (14)
C7—C8—C9	124.44 (12)	C21—C22—H22	119.5
N2—C9—C8	118.91 (12)	C23—C22—H22	119.5
N2—C9—C4	122.81 (12)	C22—C23—C24	119.14 (13)
C8—C9—C4	118.21 (11)	C22—C23—C26	119.83 (13)
N3—C10—C11	109.88 (11)	C24—C23—C26	120.96 (13)
N3—C10—H10A	109.7	C25—C24—C23	120.74 (13)
C11—C10—H10A	109.7	C25—C24—H24	119.6
N3—C10—H10B	109.7	C23—C24—H24	119.6
C11—C10—H10B	109.7	C20—C25—C24	118.29 (13)
H10A—C10—H10B	108.2	C20—C25—H25	120.9
N4—C11—C10	107.6 (1)	C24—C25—H25	120.9
N4—C11—C15	109.68 (11)	O5—C26—O4	124.62 (14)
C10—C11—C15	113.43 (12)	O5—C26—C23	118.92 (13)
N4—C11—H11	108.7	O4—C26—C23	116.44 (12)

C5—N1—C1—C2	1.5 (2)	C5—C4—C9—C8	1.62 (18)
C16—N1—C1—C2	−176.94 (13)	C3—C4—C9—C8	−179.06 (12)
N1—C1—C2—C3	−0.6 (2)	C7—N3—C10—C11	−155.08 (11)
N1—C1—C2—C19	178.70 (12)	C13—N3—C10—C11	61.19 (14)
C1—C2—C3—O3	−179.23 (13)	C12—N4—C11—C10	58.92 (14)
C19—C2—C3—O3	1.5 (2)	C12—N4—C11—C15	−177.27 (11)
C1—C2—C3—C4	0.35 (18)	N3—C10—C11—N4	−59.62 (14)
C19—C2—C3—C4	−178.93 (12)	N3—C10—C11—C15	178.88 (11)
O3—C3—C4—C9	−0.8 (2)	C11—N4—C12—C14	−179.49 (12)
C2—C3—C4—C9	179.66 (12)	C11—N4—C12—C13	−57.18 (14)
O3—C3—C4—C5	178.54 (12)	C7—N3—C13—C12	159.20 (12)
C2—C3—C4—C5	−1.03 (18)	C10—N3—C13—C12	−58.45 (15)
C1—N1—C5—C6	176.48 (12)	N4—C12—C13—N3	55.29 (15)
C16—N1—C5—C6	−5.09 (19)	C14—C12—C13—N3	176.29 (13)
C1—N1—C5—C4	−2.13 (17)	C1—N1—C16—C18	36.0 (2)
C16—N1—C5—C4	176.30 (12)	C5—N1—C16—C18	−142.40 (14)
C9—C4—C5—C6	2.57 (18)	C1—N1—C16—C17	105.99 (15)
C3—C4—C5—C6	−176.75 (12)	C5—N1—C16—C17	−72.46 (17)
C9—C4—C5—N1	−178.76 (11)	N1—C16—C17—C18	−109.38 (15)
C3—C4—C5—N1	1.92 (18)	N1—C16—C18—C17	108.37 (15)
N1—C5—C6—F1	−8.58 (19)	C1—C2—C19—O1	−4.0 (2)
C4—C5—C6—F1	170.03 (11)	C3—C2—C19—O1	175.27 (14)
N1—C5—C6—C7	175.64 (12)	C1—C2—C19—O2	176.23 (13)
C4—C5—C6—C7	−5.75 (19)	C3—C2—C19—O2	−4.5 (2)
F1—C6—C7—C8	−171.68 (11)	O6—N5—C20—C25	175.16 (17)
C5—C6—C7—C8	4.30 (19)	O7—N5—C20—C25	−3.3 (2)
F1—C6—C7—N3	5.98 (18)	O6—N5—C20—C21	−6.6 (2)
C5—C6—C7—N3	−178.03 (12)	O7—N5—C20—C21	174.94 (18)
C13—N3—C7—C8	18.0 (2)	C25—C20—C21—C22	0.6 (2)
C10—N3—C7—C8	−122.47 (14)	N5—C20—C21—C22	−177.55 (15)
C13—N3—C7—C6	−159.38 (12)	C20—C21—C22—C23	−1.2 (3)
C10—N3—C7—C6	60.12 (16)	C21—C22—C23—C24	1.2 (2)
C6—C7—C8—F2	−177.64 (12)	C21—C22—C23—C26	−175.88 (15)
N3—C7—C8—F2	4.9 (2)	C22—C23—C24—C25	−0.7 (2)
C6—C7—C8—C9	0.3 (2)	C26—C23—C24—C25	176.36 (13)
N3—C7—C8—C9	−177.18 (13)	C21—C20—C25—C24	−0.1 (2)
F2—C8—C9—N2	−2.18 (19)	N5—C20—C25—C24	178.04 (13)
C7—C8—C9—N2	179.79 (13)	C23—C24—C25—C20	0.2 (2)
F2—C8—C9—C4	174.87 (11)	C22—C23—C26—O5	−31.0 (2)
C7—C8—C9—C4	−3.2 (2)	C24—C23—C26—O5	151.92 (17)
C5—C4—C9—N2	178.55 (13)	C22—C23—C26—O4	147.01 (15)
C3—C4—C9—N2	−2.1 (2)	C24—C23—C26—O4	−30.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.97 (3)	1.60 (3)	2.5257 (15)	157 (2)
N2—H2NB···O3	0.92 (2)	1.901 (19)	2.6343 (17)	135.0 (16)
N4—H4NA···O4	0.960 (18)	1.824 (18)	2.7666 (15)	166.4 (15)
O1W—H1W1···O5	0.81	2.00	2.806 (2)	173
O2W—H1W2···O1W	0.82	2.12	2.811 (5)	141
O1W—H2W1···O2Wⁱ	0.80	2.01	2.803 (5)	172
O2W—H2W2···O1ⁱⁱ	0.82	2.02	2.807 (3)	161
N2—H2NA···O1Wⁱⁱⁱ	0.89 (2)	2.07 (2)	2.947 (2)	167.8 (19)
N4—H4NB···O4^iv	0.913 (18)	1.957 (18)	2.8405 (16)	162.5 (15)

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

4-(5-Amino-3-carboxy-1-cyclopropyl-6,8-difluoro-4-oxo-1,4-dihydroquinolin-7-yl)-2,6-dimethylpiperazin-1-ium 2-phenylacetate (II) top

Crystal data top

C₁₉H₂₃F₂N₄O₃⁺·C₈H₇O₂⁻	Z = 2
M_r = 528.55	F(000) = 556
Triclinic, P1	D_x = 1.428 Mg m⁻³
a = 10.0222 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1145 (4) Å	Cell parameters from 9186 reflections
c = 13.5255 (5) Å	θ = 3.0–27.5°
α = 69.606 (2)°	µ = 0.11 mm⁻¹
β = 73.032 (2)°	T = 90 K
γ = 83.747 (2)°	Irregular block, pale yellow
V = 1229.15 (9) Å³	0.34 × 0.28 × 0.26 mm

Data collection top

Bruker D8 Venture dual source diffractometer	5639 independent reflections
Radiation source: microsource	5029 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm^-1	R_int = 0.038
φ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
T_min = 0.914, T_max = 0.959	k = −12→13
41293 measured reflections	l = −17→17

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)] = 0.034	Hydrogen site location: mixed
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0413P)² + 0.5792P] where P = (F_o² + 2F_c²)/3
5639 reflections	(Δ/σ)_max = 0.002
365 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Special details top

Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

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

	x	y	z	U_iso*/U_eq
F1	0.70792 (7)	0.00637 (7)	0.83721 (5)	0.01777 (15)
F2	0.63127 (7)	0.35650 (7)	1.00282 (5)	0.01665 (14)
O1	1.05409 (8)	−0.41085 (8)	1.22035 (7)	0.01857 (17)
O2	1.00723 (10)	−0.25755 (9)	1.31012 (7)	0.02240 (19)
H2O	0.970 (2)	−0.164 (2)	1.2943 (16)	0.051 (5)*
O3	0.89918 (9)	−0.02316 (8)	1.22819 (6)	0.01721 (17)
N1	0.84402 (9)	−0.17056 (9)	0.99535 (7)	0.01228 (18)
N2	0.77272 (12)	0.21351 (11)	1.14682 (8)	0.0201 (2)
H2NA	0.7380 (17)	0.2964 (18)	1.1458 (13)	0.029 (4)*
H2NB	0.8144 (17)	0.1606 (17)	1.1985 (13)	0.027 (4)*
N3	0.59393 (10)	0.26309 (10)	0.84423 (7)	0.01448 (19)
N4	0.58386 (10)	0.38019 (10)	0.62261 (7)	0.01321 (18)
H4NA	0.6191 (17)	0.3897 (17)	0.5467 (13)	0.029 (4)*
H4NB	0.5030 (16)	0.4386 (16)	0.6268 (12)	0.023 (4)*
C1	0.91214 (11)	−0.24536 (11)	1.06947 (9)	0.0133 (2)
H1	0.950209	−0.334367	1.065994	0.016*
C2	0.93024 (11)	−0.20187 (11)	1.14943 (8)	0.0134 (2)
C3	0.88013 (11)	−0.06613 (11)	1.15534 (8)	0.0129 (2)
C4	0.80895 (11)	0.01794 (11)	1.07502 (8)	0.0123 (2)
C5	0.78917 (11)	−0.03613 (11)	0.99549 (8)	0.0119 (2)
C6	0.71912 (11)	0.04728 (11)	0.91986 (8)	0.0131 (2)
C7	0.66418 (11)	0.18133 (11)	0.91898 (8)	0.0128 (2)
C8	0.68554 (11)	0.22948 (11)	0.99773 (9)	0.0135 (2)
C9	0.75685 (11)	0.15531 (11)	1.07451 (8)	0.0131 (2)
C10	0.49686 (11)	0.20780 (11)	0.80689 (8)	0.0137 (2)
H10A	0.405327	0.255422	0.822658	0.016*
H10B	0.483568	0.105862	0.848679	0.016*
C11	0.54638 (11)	0.22823 (11)	0.68460 (8)	0.0132 (2)
H11	0.630826	0.167958	0.670230	0.016*
C12	0.68765 (11)	0.43180 (11)	0.66142 (9)	0.0149 (2)
H12	0.775319	0.374507	0.651603	0.018*
C13	0.62643 (12)	0.41177 (11)	0.78307 (9)	0.0145 (2)
H13A	0.694316	0.443183	0.810613	0.017*
H13B	0.540560	0.469619	0.793619	0.017*
C14	0.72062 (14)	0.58531 (13)	0.59395 (10)	0.0242 (3)
H14A	0.755513	0.594990	0.516135	0.036*
H14B	0.791838	0.617518	0.616781	0.036*
H14C	0.635807	0.642584	0.605345	0.036*
C15	0.43375 (12)	0.18919 (12)	0.64521 (9)	0.0176 (2)
H15A	0.466770	0.208543	0.565850	0.026*
H15B	0.349399	0.245187	0.662023	0.026*
H15C	0.412447	0.088674	0.682358	0.026*
C16	0.83214 (11)	−0.23184 (11)	0.91487 (8)	0.0139 (2)
H16	0.885555	−0.182759	0.837347	0.017*
C17	0.69701 (12)	−0.29534 (12)	0.92921 (9)	0.0190 (2)
H17A	0.668119	−0.282994	0.862478	0.023*
H17B	0.619520	−0.295690	0.994438	0.023*
C18	0.82133 (13)	−0.38861 (12)	0.94729 (9)	0.0189 (2)
H18A	0.820179	−0.446110	1.023612	0.023*
H18B	0.868786	−0.433412	0.891632	0.023*
C19	1.00275 (11)	−0.29946 (12)	1.22819 (9)	0.0153 (2)
O4	0.35788 (9)	0.55031 (9)	0.60167 (6)	0.01934 (18)
O5	0.29414 (9)	0.53584 (9)	0.77723 (7)	0.02231 (19)
C20	0.18020 (11)	0.80365 (11)	0.56629 (9)	0.0143 (2)
C21	0.27729 (12)	0.89939 (12)	0.55673 (9)	0.0183 (2)
H21	0.327649	0.877691	0.610123	0.022*
C22	0.30119 (13)	1.02595 (13)	0.47016 (10)	0.0221 (2)
H22	0.367933	1.090038	0.464389	0.026*
C23	0.22759 (13)	1.05909 (12)	0.39183 (9)	0.0213 (2)
H23	0.243173	1.146127	0.332936	0.026*
C24	0.13151 (12)	0.96463 (12)	0.40009 (9)	0.0194 (2)
H24	0.081044	0.986744	0.346737	0.023*
C25	0.10881 (12)	0.83743 (12)	0.48642 (9)	0.0164 (2)
H25	0.043610	0.772607	0.490962	0.020*
C26	0.14869 (11)	0.66952 (12)	0.66354 (9)	0.0157 (2)
H26A	0.083521	0.612589	0.652443	0.019*
H26B	0.100571	0.694457	0.729885	0.019*
C27	0.27658 (11)	0.57882 (11)	0.68409 (9)	0.0142 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0263 (4)	0.0183 (3)	0.0142 (3)	0.0045 (3)	−0.0104 (3)	−0.0093 (3)
F2	0.0211 (3)	0.0131 (3)	0.0188 (3)	0.0042 (2)	−0.0083 (3)	−0.0079 (3)
O1	0.0188 (4)	0.0148 (4)	0.0223 (4)	0.0014 (3)	−0.0083 (3)	−0.0047 (3)
O2	0.0312 (5)	0.0204 (4)	0.0215 (4)	0.0064 (4)	−0.0166 (4)	−0.0083 (3)
O3	0.0221 (4)	0.0179 (4)	0.0160 (4)	0.0021 (3)	−0.0099 (3)	−0.0077 (3)
N1	0.0138 (4)	0.0119 (4)	0.0115 (4)	−0.0007 (3)	−0.0029 (3)	−0.0045 (3)
N2	0.0308 (6)	0.0160 (5)	0.0210 (5)	0.0070 (4)	−0.0152 (4)	−0.0106 (4)
N3	0.0179 (5)	0.0123 (4)	0.0139 (4)	−0.0017 (3)	−0.0078 (4)	−0.0020 (3)
N4	0.0144 (4)	0.0134 (4)	0.0109 (4)	0.0004 (3)	−0.0036 (3)	−0.0031 (3)
C1	0.0114 (5)	0.0126 (5)	0.0139 (5)	−0.0008 (4)	−0.0016 (4)	−0.0032 (4)
C2	0.0127 (5)	0.0135 (5)	0.0127 (5)	−0.0013 (4)	−0.0031 (4)	−0.0027 (4)
C3	0.0116 (5)	0.0147 (5)	0.0117 (5)	−0.0026 (4)	−0.0016 (4)	−0.0038 (4)
C4	0.0123 (5)	0.0134 (5)	0.0107 (5)	−0.0015 (4)	−0.0023 (4)	−0.0038 (4)
C5	0.0120 (5)	0.0115 (5)	0.0109 (5)	−0.0014 (4)	−0.0011 (4)	−0.0036 (4)
C6	0.0151 (5)	0.0157 (5)	0.0100 (5)	−0.0015 (4)	−0.0031 (4)	−0.0059 (4)
C7	0.0117 (5)	0.0141 (5)	0.0108 (5)	−0.0018 (4)	−0.0020 (4)	−0.0025 (4)
C8	0.0146 (5)	0.0112 (5)	0.0142 (5)	0.0008 (4)	−0.0026 (4)	−0.0048 (4)
C9	0.0140 (5)	0.0141 (5)	0.0113 (5)	−0.0013 (4)	−0.0026 (4)	−0.0047 (4)
C10	0.0132 (5)	0.0157 (5)	0.0125 (5)	−0.0012 (4)	−0.0038 (4)	−0.0042 (4)
C11	0.0142 (5)	0.0124 (5)	0.0126 (5)	0.0002 (4)	−0.0035 (4)	−0.0040 (4)
C12	0.0147 (5)	0.0151 (5)	0.0145 (5)	−0.0014 (4)	−0.0056 (4)	−0.0028 (4)
C13	0.0173 (5)	0.0120 (5)	0.0145 (5)	0.0002 (4)	−0.0063 (4)	−0.0033 (4)
C14	0.0316 (7)	0.0180 (6)	0.0206 (6)	−0.0087 (5)	−0.0097 (5)	0.0011 (5)
C15	0.0189 (5)	0.0206 (6)	0.0152 (5)	−0.0025 (4)	−0.0057 (4)	−0.0068 (4)
C16	0.0179 (5)	0.0135 (5)	0.0114 (5)	−0.0007 (4)	−0.0032 (4)	−0.0058 (4)
C17	0.0203 (6)	0.0218 (6)	0.0178 (5)	−0.0047 (4)	−0.0043 (4)	−0.0093 (4)
C18	0.0276 (6)	0.0138 (5)	0.0169 (5)	−0.0023 (4)	−0.0063 (4)	−0.0062 (4)
C19	0.0133 (5)	0.0157 (5)	0.0156 (5)	−0.0021 (4)	−0.0047 (4)	−0.0026 (4)
O4	0.0206 (4)	0.0220 (4)	0.0134 (4)	0.0070 (3)	−0.0039 (3)	−0.0063 (3)
O5	0.0283 (5)	0.0249 (4)	0.0148 (4)	0.0089 (4)	−0.0089 (3)	−0.0082 (3)
C20	0.0147 (5)	0.0138 (5)	0.0140 (5)	0.0033 (4)	−0.0021 (4)	−0.0065 (4)
C21	0.0213 (6)	0.0183 (5)	0.0170 (5)	−0.0004 (4)	−0.0063 (4)	−0.0070 (4)
C22	0.0279 (6)	0.0171 (5)	0.0217 (6)	−0.0041 (5)	−0.0044 (5)	−0.0078 (5)
C23	0.0303 (6)	0.0140 (5)	0.0159 (5)	0.0031 (5)	−0.0031 (5)	−0.0038 (4)
C24	0.0217 (6)	0.0215 (6)	0.0149 (5)	0.0076 (4)	−0.0064 (4)	−0.0071 (4)
C25	0.0149 (5)	0.0186 (5)	0.0166 (5)	0.0023 (4)	−0.0033 (4)	−0.0085 (4)
C26	0.0144 (5)	0.0163 (5)	0.0147 (5)	0.0009 (4)	−0.0030 (4)	−0.0041 (4)
C27	0.0158 (5)	0.0117 (5)	0.0144 (5)	−0.0006 (4)	−0.0033 (4)	−0.0041 (4)

Geometric parameters (Å, º) top

F1—C6	1.3562 (11)	C12—C13	1.5266 (15)
F2—C8	1.3560 (12)	C12—H12	1.0000
O1—C19	1.2126 (14)	C13—H13A	0.9900
O2—C19	1.3304 (14)	C13—H13B	0.9900
O2—H2O	0.95 (2)	C14—H14A	0.9800
O3—C3	1.2738 (13)	C14—H14B	0.9800
N1—C1	1.3423 (14)	C14—H14C	0.9800
N1—C5	1.4104 (13)	C15—H15A	0.9800
N1—C16	1.4646 (13)	C15—H15B	0.9800
N2—C9	1.3567 (14)	C15—H15C	0.9800
N2—H2NA	0.869 (17)	C16—C17	1.4945 (15)
N2—H2NB	0.900 (17)	C16—C18	1.4978 (15)
N3—C7	1.3812 (14)	C16—H16	1.0000
N3—C10	1.4548 (13)	C17—C18	1.5044 (17)
N3—C13	1.4609 (13)	C17—H17A	0.9900
N4—C11	1.5000 (13)	C17—H17B	0.9900
N4—C12	1.5026 (13)	C18—H18A	0.9900
N4—H4NA	0.956 (16)	C18—H18B	0.9900
N4—H4NB	0.949 (16)	O4—C27	1.2777 (13)
C1—C2	1.3636 (15)	O5—C27	1.2401 (13)
C1—H1	0.9500	C20—C25	1.3916 (15)
C2—C3	1.4305 (15)	C20—C21	1.3949 (16)
C2—C19	1.4833 (15)	C20—C26	1.5091 (15)
C3—C4	1.4452 (14)	C21—C22	1.3876 (17)
C4—C9	1.4285 (15)	C21—H21	0.9500
C4—C5	1.4329 (14)	C22—C23	1.3906 (18)
C5—C6	1.3927 (15)	C22—H22	0.9500
C6—C7	1.4041 (15)	C23—C24	1.3841 (18)
C7—C8	1.3910 (14)	C23—H23	0.9500
C8—C9	1.3877 (15)	C24—C25	1.3900 (16)
C10—C11	1.5264 (14)	C24—H24	0.9500
C10—H10A	0.9900	C25—H25	0.9500
C10—H10B	0.9900	C26—C27	1.5283 (15)
C11—C15	1.5194 (15)	C26—H26A	0.9900
C11—H11	1.0000	C26—H26B	0.9900
C12—C14	1.5169 (15)

C19—O2—H2O	105.6 (12)	N3—C13—H13B	109.8
C1—N1—C5	119.83 (9)	C12—C13—H13B	109.8
C1—N1—C16	117.94 (9)	H13A—C13—H13B	108.2
C5—N1—C16	122.22 (9)	C12—C14—H14A	109.5
C9—N2—H2NA	120.6 (11)	C12—C14—H14B	109.5
C9—N2—H2NB	117.6 (10)	H14A—C14—H14B	109.5
H2NA—N2—H2NB	121.7 (14)	C12—C14—H14C	109.5
C7—N3—C10	124.24 (9)	H14A—C14—H14C	109.5
C7—N3—C13	122.03 (9)	H14B—C14—H14C	109.5
C10—N3—C13	113.16 (8)	C11—C15—H15A	109.5
C11—N4—C12	112.99 (8)	C11—C15—H15B	109.5
C11—N4—H4NA	107.3 (10)	H15A—C15—H15B	109.5
C12—N4—H4NA	111.1 (10)	C11—C15—H15C	109.5
C11—N4—H4NB	110.9 (9)	H15A—C15—H15C	109.5
C12—N4—H4NB	109.4 (9)	H15B—C15—H15C	109.5
H4NA—N4—H4NB	104.9 (13)	N1—C16—C17	119.36 (9)
N1—C1—C2	124.25 (10)	N1—C16—C18	119.26 (9)
N1—C1—H1	117.9	C17—C16—C18	60.36 (8)
C2—C1—H1	117.9	N1—C16—H16	115.6
C1—C2—C3	120.08 (10)	C17—C16—H16	115.6
C1—C2—C19	117.76 (10)	C18—C16—H16	115.6
C3—C2—C19	122.16 (10)	C16—C17—C18	59.93 (7)
O3—C3—C2	120.62 (10)	C16—C17—H17A	117.8
O3—C3—C4	122.58 (10)	C18—C17—H17A	117.8
C2—C3—C4	116.80 (9)	C16—C17—H17B	117.8
C9—C4—C5	119.35 (9)	C18—C17—H17B	117.8
C9—C4—C3	120.38 (9)	H17A—C17—H17B	114.9
C5—C4—C3	120.28 (9)	C16—C18—C17	59.71 (7)
C6—C5—N1	122.53 (9)	C16—C18—H18A	117.8
C6—C5—C4	118.75 (9)	C17—C18—H18A	117.8
N1—C5—C4	118.71 (9)	C16—C18—H18B	117.8
F1—C6—C5	121.11 (9)	C17—C18—H18B	117.8
F1—C6—C7	115.64 (9)	H18A—C18—H18B	114.9
C5—C6—C7	123.12 (9)	O1—C19—O2	121.36 (10)
N3—C7—C8	121.0 (1)	O1—C19—C2	123.17 (10)
N3—C7—C6	122.83 (9)	O2—C19—C2	115.47 (10)
C8—C7—C6	116.17 (9)	C25—C20—C21	118.45 (10)
F2—C8—C9	116.52 (9)	C25—C20—C26	120.7 (1)
F2—C8—C7	118.76 (9)	C21—C20—C26	120.8 (1)
C9—C8—C7	124.71 (10)	C22—C21—C20	120.78 (11)
N2—C9—C8	119.61 (10)	C22—C21—H21	119.6
N2—C9—C4	122.51 (10)	C20—C21—H21	119.6
C8—C9—C4	117.87 (9)	C21—C22—C23	120.09 (11)
N3—C10—C11	112.99 (9)	C21—C22—H22	120.0
N3—C10—H10A	109.0	C23—C22—H22	120.0
C11—C10—H10A	109.0	C24—C23—C22	119.67 (11)
N3—C10—H10B	109.0	C24—C23—H23	120.2
C11—C10—H10B	109.0	C22—C23—H23	120.2
H10A—C10—H10B	107.8	C23—C24—C25	120.03 (11)
N4—C11—C15	108.99 (9)	C23—C24—H24	120.0
N4—C11—C10	108.68 (8)	C25—C24—H24	120.0
C15—C11—C10	111.49 (9)	C24—C25—C20	120.96 (11)
N4—C11—H11	109.2	C24—C25—H25	119.5
C15—C11—H11	109.2	C20—C25—H25	119.5
C10—C11—H11	109.2	C20—C26—C27	114.65 (9)
N4—C12—C14	109.52 (9)	C20—C26—H26A	108.6
N4—C12—C13	108.54 (9)	C27—C26—H26A	108.6
C14—C12—C13	111.62 (9)	C20—C26—H26B	108.6
N4—C12—H12	109.0	C27—C26—H26B	108.6
C14—C12—H12	109.0	H26A—C26—H26B	107.6
C13—C12—H12	109.0	O5—C27—O4	124.4 (1)
N3—C13—C12	109.59 (9)	O5—C27—C26	119.62 (10)
N3—C13—H13A	109.8	O4—C27—C26	115.97 (9)
C12—C13—H13A	109.8

C5—N1—C1—C2	1.77 (16)	C7—C8—C9—C4	−1.82 (16)
C16—N1—C1—C2	−179.51 (10)	C5—C4—C9—N2	−179.51 (10)
N1—C1—C2—C3	−2.65 (17)	C3—C4—C9—N2	0.89 (16)
N1—C1—C2—C19	177.40 (9)	C5—C4—C9—C8	1.59 (15)
C1—C2—C3—O3	−178.44 (10)	C3—C4—C9—C8	−178.01 (9)
C19—C2—C3—O3	1.50 (16)	C7—N3—C10—C11	−116.00 (11)
C1—C2—C3—C4	1.16 (15)	C13—N3—C10—C11	55.53 (12)
C19—C2—C3—C4	−178.89 (9)	C12—N4—C11—C15	175.95 (9)
O3—C3—C4—C9	0.20 (16)	C12—N4—C11—C10	54.26 (11)
C2—C3—C4—C9	−179.39 (9)	N3—C10—C11—N4	−51.50 (11)
O3—C3—C4—C5	−179.40 (9)	N3—C10—C11—C15	−171.65 (9)
C2—C3—C4—C5	1.01 (15)	C11—N4—C12—C14	179.47 (9)
C1—N1—C5—C6	179.14 (10)	C11—N4—C12—C13	−58.45 (11)
C16—N1—C5—C6	0.48 (15)	C7—N3—C13—C12	113.64 (11)
C1—N1—C5—C4	0.54 (14)	C10—N3—C13—C12	−58.10 (12)
C16—N1—C5—C4	−178.13 (9)	N4—C12—C13—N3	58.10 (11)
C9—C4—C5—C6	−0.12 (15)	C14—C12—C13—N3	178.90 (9)
C3—C4—C5—C6	179.48 (9)	C1—N1—C16—C17	103.20 (12)
C9—C4—C5—N1	178.54 (9)	C5—N1—C16—C17	−78.11 (13)
C3—C4—C5—N1	−1.86 (15)	C1—N1—C16—C18	32.78 (14)
N1—C5—C6—F1	−4.25 (16)	C5—N1—C16—C18	−148.53 (10)
C4—C5—C6—F1	174.35 (9)	N1—C16—C17—C18	−108.97 (11)
N1—C5—C6—C7	−179.91 (9)	N1—C16—C18—C17	109.14 (11)
C4—C5—C6—C7	−1.31 (16)	C1—C2—C19—O1	4.97 (16)
C10—N3—C7—C8	−141.61 (11)	C3—C2—C19—O1	−174.97 (10)
C13—N3—C7—C8	47.59 (15)	C1—C2—C19—O2	−174.44 (10)
C10—N3—C7—C6	39.09 (16)	C3—C2—C19—O2	5.62 (15)
C13—N3—C7—C6	−131.71 (11)	C25—C20—C21—C22	0.59 (17)
F1—C6—C7—N3	4.61 (15)	C26—C20—C21—C22	−176.77 (10)
C5—C6—C7—N3	−179.52 (10)	C20—C21—C22—C23	0.31 (18)
F1—C6—C7—C8	−174.73 (9)	C21—C22—C23—C24	−0.65 (18)
C5—C6—C7—C8	1.15 (16)	C22—C23—C24—C25	0.07 (17)
N3—C7—C8—F2	2.55 (15)	C23—C24—C25—C20	0.85 (17)
C6—C7—C8—F2	−178.11 (9)	C21—C20—C25—C24	−1.17 (16)
N3—C7—C8—C9	−178.87 (10)	C26—C20—C25—C24	176.2 (1)
C6—C7—C8—C9	0.47 (16)	C25—C20—C26—C27	128.84 (11)
F2—C8—C9—N2	−2.14 (15)	C21—C20—C26—C27	−53.85 (14)
C7—C8—C9—N2	179.25 (10)	C20—C26—C27—O5	130.02 (11)
F2—C8—C9—C4	176.79 (9)	C20—C26—C27—O4	−51.32 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.95 (2)	1.61 (2)	2.5162 (12)	157.3 (18)
N2—H2NB···O3	0.900 (17)	1.917 (16)	2.6200 (13)	133.6 (14)
N4—H4NB···O4	0.949 (16)	1.781 (16)	2.7122 (12)	166.3 (13)
N2—H2NA···O5ⁱ	0.869 (17)	2.232 (17)	2.9958 (13)	146.5 (14)
N4—H4NA···O4ⁱⁱ	0.956 (16)	1.834 (16)	2.7580 (12)	161.8 (14)

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

4-(5-Amino-3-carboxy-1-cyclopropyl-6,8-difluoro-4-oxo-1,4-dihydroquinolin-7-yl)-2,6-dimethylpiperazin-1-ium 4-methylbenzoate trihydrate (III) top

Crystal data top

C₁₉H₂₃F₂N₄O₃⁺·C₈H₇O₂⁻·3H₂O	F(000) = 1232
M_r = 582.60	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 18.4423 (9) Å	Cell parameters from 9800 reflections
b = 7.0694 (3) Å	θ = 2.9–27.5°
c = 21.0669 (10) Å	µ = 0.11 mm⁻¹
β = 93.252 (2)°	T = 90 K
V = 2742.2 (2) Å³	Tablet, pale yellow
Z = 4	0.19 × 0.15 × 0.04 mm

Data collection top

Bruker D8 Venture dual source diffractometer	6296 independent reflections
Radiation source: microsource	5086 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm^-1	R_int = 0.043
φ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −23→23
T_min = 0.894, T_max = 0.959	k = −9→9
44990 measured reflections	l = −27→27

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.040P)² + 1.6577P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
6296 reflections	Δρ_max = 0.31 e Å⁻³
418 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL-2019/2 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (5)

Special details top

Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

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

	x	y	z	U_iso*/U_eq
F1	0.16930 (4)	0.64545 (14)	0.41384 (4)	0.0232 (2)
F2	0.19188 (4)	0.74700 (13)	0.63429 (4)	0.0213 (2)
O1	−0.20441 (5)	0.79723 (16)	0.41468 (5)	0.0235 (2)
O2	−0.19618 (5)	0.87221 (15)	0.51703 (5)	0.0202 (2)
H2O	−0.1594 (12)	0.877 (3)	0.5482 (10)	0.044 (6)*
O3	−0.07638 (5)	0.84435 (15)	0.57818 (5)	0.0189 (2)
N1	0.01575 (6)	0.68755 (17)	0.41300 (5)	0.0142 (2)
N2	0.05167 (7)	0.8265 (2)	0.64025 (6)	0.0213 (3)
H2NA	0.0811 (11)	0.828 (3)	0.6762 (10)	0.034 (5)*
H2NB	0.0031 (12)	0.843 (3)	0.6419 (10)	0.042 (6)*
N3	0.25676 (6)	0.66015 (18)	0.52407 (6)	0.0177 (3)
N4	0.40460 (6)	0.56168 (18)	0.54358 (6)	0.0147 (2)
H4NA	0.4412 (10)	0.495 (3)	0.5696 (9)	0.029 (5)*
H4NB	0.4268 (10)	0.618 (3)	0.5108 (10)	0.034 (5)*
C1	−0.05565 (7)	0.7201 (2)	0.41541 (7)	0.0152 (3)
H1	−0.085398	0.704074	0.377484	0.018*
C2	−0.08820 (7)	0.7749 (2)	0.46899 (7)	0.0151 (3)
C3	−0.04622 (7)	0.79463 (19)	0.52777 (7)	0.0147 (3)
C4	0.03060 (7)	0.75619 (19)	0.52685 (7)	0.0140 (3)
C5	0.06170 (7)	0.70427 (19)	0.46870 (6)	0.0138 (3)
C6	0.13643 (7)	0.6767 (2)	0.46875 (7)	0.0152 (3)
C7	0.18246 (7)	0.6910 (2)	0.52359 (7)	0.0152 (3)
C8	0.15010 (7)	0.7376 (2)	0.57941 (7)	0.0161 (3)
C9	0.07665 (7)	0.7750 (2)	0.58355 (7)	0.0151 (3)
C10	0.28872 (7)	0.5277 (2)	0.48072 (7)	0.0161 (3)
H10A	0.307178	0.597178	0.444152	0.019*
H10B	0.251383	0.436797	0.464287	0.019*
C11	0.35064 (7)	0.4220 (2)	0.51562 (7)	0.0155 (3)
H11	0.330677	0.346821	0.550866	0.019*
C12	0.37170 (7)	0.7063 (2)	0.58566 (7)	0.0156 (3)
H12	0.353367	0.640709	0.623632	0.019*
C13	0.30834 (7)	0.8012 (2)	0.54943 (7)	0.0160 (3)
H13A	0.283667	0.887997	0.578133	0.019*
H13B	0.326437	0.876885	0.514093	0.019*
C14	0.43038 (8)	0.8463 (2)	0.60792 (7)	0.0209 (3)
H14A	0.449360	0.909818	0.570983	0.031*
H14B	0.469877	0.778736	0.631283	0.031*
H14C	0.409720	0.940576	0.635826	0.031*
C15	0.38846 (8)	0.2884 (2)	0.47176 (7)	0.0206 (3)
H15A	0.353957	0.192234	0.455446	0.031*
H15B	0.429211	0.226688	0.495390	0.031*
H15C	0.406627	0.360047	0.436145	0.031*
C16	0.04298 (7)	0.6192 (2)	0.35325 (7)	0.0163 (3)
H16	0.062144	0.486827	0.354403	0.020*
C17	0.08061 (8)	0.7518 (2)	0.31081 (7)	0.0218 (3)
H17A	0.122153	0.702225	0.288103	0.026*
H17B	0.085039	0.885832	0.324048	0.026*
C18	0.00625 (8)	0.6788 (3)	0.29126 (7)	0.0264 (4)
H18A	−0.035058	0.767882	0.292530	0.032*
H18B	0.002063	0.584243	0.256578	0.032*
C19	−0.16741 (7)	0.8147 (2)	0.46384 (7)	0.0173 (3)
O4	0.48721 (6)	0.37218 (16)	0.63034 (5)	0.0225 (2)
O5	0.55454 (5)	0.23301 (15)	0.55920 (5)	0.0191 (2)
C20	0.59698 (7)	0.2240 (2)	0.66740 (7)	0.0146 (3)
C21	0.58790 (8)	0.2764 (2)	0.73007 (7)	0.0169 (3)
H21	0.544617	0.338837	0.740721	0.020*
C22	0.64159 (8)	0.2383 (2)	0.77720 (7)	0.0171 (3)
H22	0.634344	0.274197	0.819832	0.021*
C23	0.70593 (8)	0.1483 (2)	0.76303 (7)	0.0166 (3)
C24	0.71450 (8)	0.0948 (2)	0.70020 (7)	0.0173 (3)
H24	0.757892	0.033059	0.689484	0.021*
C25	0.66076 (8)	0.1303 (2)	0.65326 (7)	0.0172 (3)
H25	0.667292	0.090469	0.610891	0.021*
C26	0.54199 (7)	0.2778 (2)	0.61474 (7)	0.0159 (3)
C27	0.76456 (8)	0.1112 (2)	0.81411 (7)	0.0209 (3)
H27A	0.765320	−0.023819	0.824717	0.031*
H27B	0.754839	0.184994	0.852067	0.031*
H27C	0.811717	0.148138	0.798799	0.031*
O1W	0.29379 (6)	0.11084 (17)	0.69541 (6)	0.0268 (3)
H1W1	0.3314 (14)	0.219 (4)	0.7047 (12)	0.064 (7)*
H2W1	0.2678 (15)	0.150 (4)	0.6565 (14)	0.077 (9)*
O2W	0.39349 (6)	0.39000 (18)	0.72635 (5)	0.0236 (2)
H1W2	0.3732 (13)	0.510 (4)	0.7276 (11)	0.060 (7)*
H2W2	0.4297 (13)	0.386 (4)	0.6967 (12)	0.058 (7)*
O3W	0.32955 (6)	0.73767 (19)	0.74222 (6)	0.0302 (3)
H1W3	0.2830 (13)	0.702 (4)	0.7636 (11)	0.057 (7)*
H2W3	0.3180 (17)	0.868 (5)	0.7265 (15)	0.100 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0146 (4)	0.0418 (6)	0.0133 (4)	0.0048 (4)	0.0013 (3)	−0.0019 (4)
F2	0.0176 (4)	0.0310 (5)	0.0147 (4)	0.0010 (4)	−0.0054 (3)	−0.0021 (4)
O1	0.0155 (5)	0.0304 (6)	0.0241 (6)	0.0022 (5)	−0.0036 (4)	−0.0007 (5)
O2	0.0143 (5)	0.0240 (6)	0.0224 (6)	0.0014 (4)	0.0015 (4)	0.0000 (4)
O3	0.0168 (5)	0.0245 (6)	0.0157 (5)	0.0019 (4)	0.0030 (4)	0.0003 (4)
N1	0.0139 (5)	0.0158 (6)	0.0127 (6)	0.0002 (5)	−0.0002 (4)	0.0003 (5)
N2	0.0174 (6)	0.0331 (8)	0.0132 (6)	0.0015 (6)	0.0001 (5)	−0.0029 (5)
N3	0.0124 (5)	0.0200 (6)	0.0204 (6)	0.0009 (5)	−0.0019 (5)	−0.0050 (5)
N4	0.0131 (5)	0.0173 (6)	0.0136 (6)	0.0009 (5)	−0.0008 (5)	−0.0009 (5)
C1	0.0140 (6)	0.0134 (6)	0.0176 (7)	−0.0004 (5)	−0.0028 (5)	0.0021 (5)
C2	0.0130 (6)	0.0147 (7)	0.0174 (7)	0.0001 (5)	−0.0002 (5)	0.0024 (5)
C3	0.0160 (6)	0.0111 (6)	0.0171 (7)	−0.0008 (5)	0.0006 (5)	0.0031 (5)
C4	0.0145 (6)	0.0122 (6)	0.0152 (7)	−0.0007 (5)	0.0001 (5)	0.0012 (5)
C5	0.0144 (6)	0.0127 (6)	0.0139 (7)	−0.0013 (5)	−0.0015 (5)	0.0016 (5)
C6	0.0158 (6)	0.0172 (7)	0.0127 (6)	0.0003 (5)	0.0024 (5)	0.0001 (5)
C7	0.0130 (6)	0.0141 (7)	0.0182 (7)	0.0004 (5)	−0.0010 (5)	0.0010 (5)
C8	0.0166 (7)	0.0180 (7)	0.0132 (7)	−0.0010 (5)	−0.0047 (5)	0.0011 (5)
C9	0.0168 (7)	0.0143 (7)	0.0142 (7)	−0.0012 (5)	0.0003 (5)	0.0012 (5)
C10	0.0147 (6)	0.0175 (7)	0.0160 (7)	−0.0004 (5)	−0.0013 (5)	−0.0029 (6)
C11	0.0143 (6)	0.0149 (7)	0.0171 (7)	−0.0013 (5)	−0.0007 (5)	−0.0003 (5)
C12	0.0148 (6)	0.0191 (7)	0.0127 (6)	0.0007 (6)	0.0003 (5)	−0.0021 (6)
C13	0.0143 (6)	0.0164 (7)	0.0171 (7)	−0.0002 (5)	−0.0009 (5)	−0.0022 (6)
C14	0.0158 (7)	0.0251 (8)	0.0215 (8)	−0.0008 (6)	−0.0019 (6)	−0.0067 (6)
C15	0.0199 (7)	0.0189 (7)	0.0229 (8)	0.0025 (6)	−0.0007 (6)	−0.0042 (6)
C16	0.0163 (6)	0.0177 (7)	0.0147 (7)	0.0017 (5)	−0.0008 (5)	−0.0020 (5)
C17	0.0234 (7)	0.0245 (8)	0.0180 (7)	0.0036 (6)	0.0040 (6)	0.0041 (6)
C18	0.0223 (7)	0.0419 (10)	0.0148 (7)	0.0071 (7)	−0.0009 (6)	0.0002 (7)
C19	0.0154 (7)	0.0166 (7)	0.0200 (7)	−0.0004 (6)	0.0015 (5)	0.0021 (6)
O4	0.0197 (5)	0.0300 (6)	0.0174 (5)	0.0076 (5)	−0.0009 (4)	0.0015 (5)
O5	0.0201 (5)	0.0236 (6)	0.0135 (5)	−0.0011 (4)	−0.0011 (4)	0.0008 (4)
C20	0.0158 (6)	0.0138 (6)	0.0139 (7)	−0.0016 (5)	−0.0008 (5)	0.0012 (5)
C21	0.0153 (6)	0.0191 (7)	0.0164 (7)	0.0003 (6)	0.0013 (5)	0.0005 (6)
C22	0.0199 (7)	0.0180 (7)	0.0135 (7)	−0.0009 (6)	0.0010 (5)	0.0003 (6)
C23	0.0185 (7)	0.0137 (7)	0.0172 (7)	−0.0014 (5)	−0.0015 (5)	0.0032 (5)
C24	0.0176 (7)	0.0149 (7)	0.0194 (7)	0.0030 (6)	0.0007 (6)	0.0010 (6)
C25	0.0211 (7)	0.0151 (7)	0.0152 (7)	−0.0003 (6)	0.0012 (5)	−0.0004 (6)
C26	0.0160 (6)	0.0158 (7)	0.0159 (7)	−0.0024 (5)	−0.0002 (5)	0.0027 (5)
C27	0.0225 (7)	0.0212 (7)	0.0184 (7)	0.0025 (6)	−0.0041 (6)	0.0018 (6)
O1W	0.0254 (6)	0.0285 (6)	0.0262 (6)	0.0007 (5)	−0.0017 (5)	−0.0008 (5)
O2W	0.0219 (5)	0.0287 (6)	0.0201 (6)	0.0018 (5)	0.0008 (4)	0.0019 (5)
O3W	0.0257 (6)	0.0307 (7)	0.0349 (7)	0.0040 (5)	0.0072 (5)	0.0039 (5)

Geometric parameters (Å, º) top

F1—C6	1.3541 (16)	C13—H13B	0.9900
F2—C8	1.3540 (15)	C14—H14A	0.9800
O1—C19	1.2138 (18)	C14—H14B	0.9800
O2—C19	1.3305 (18)	C14—H14C	0.9800
O2—H2O	0.92 (2)	C15—H15A	0.9800
O3—C3	1.2758 (17)	C15—H15B	0.9800
N1—C1	1.3404 (17)	C15—H15C	0.9800
N1—C5	1.4129 (17)	C16—C17	1.493 (2)
N1—C16	1.4636 (18)	C16—C18	1.497 (2)
N2—C9	1.3542 (19)	C16—H16	1.0000
N2—H2NA	0.91 (2)	C17—C18	1.501 (2)
N2—H2NB	0.91 (2)	C17—H17A	0.9900
N3—C7	1.3870 (17)	C17—H17B	0.9900
N3—C10	1.4558 (18)	C18—H18A	0.9900
N3—C13	1.4585 (18)	C18—H18B	0.9900
N4—C11	1.4987 (18)	O4—C26	1.2692 (18)
N4—C12	1.5036 (18)	O5—C26	1.2465 (17)
N4—H4NA	0.967 (19)	C20—C21	1.391 (2)
N4—H4NB	0.91 (2)	C20—C25	1.397 (2)
C1—C2	1.364 (2)	C20—C26	1.5089 (19)
C1—H1	0.9500	C21—C22	1.388 (2)
C2—C3	1.4296 (19)	C21—H21	0.9500
C2—C19	1.4855 (19)	C22—C23	1.394 (2)
C3—C4	1.4438 (19)	C22—H22	0.9500
C4—C5	1.4298 (19)	C23—C24	1.394 (2)
C4—C9	1.4321 (19)	C23—C27	1.5045 (19)
C5—C6	1.3920 (19)	C24—C25	1.383 (2)
C6—C7	1.3980 (19)	C24—H24	0.9500
C7—C8	1.388 (2)	C25—H25	0.9500
C8—C9	1.3877 (19)	C27—H27A	0.9800
C10—C11	1.5193 (19)	C27—H27B	0.9800
C10—H10A	0.9900	C27—H27C	0.9800
C10—H10B	0.9900	O1W—H1W1	1.04 (3)
C11—C15	1.518 (2)	O1W—H2W1	0.96 (3)
C11—H11	1.0000	O2W—H1W2	0.93 (3)
C12—C13	1.5155 (19)	O2W—H2W2	0.94 (3)
C12—C14	1.521 (2)	O3W—H1W3	1.02 (3)
C12—H12	1.0000	O3W—H2W3	1.00 (4)
C13—H13A	0.9900

C19—O2—H2O	107.5 (14)	C12—C13—H13B	109.6
C1—N1—C5	119.89 (12)	H13A—C13—H13B	108.1
C1—N1—C16	118.36 (11)	C12—C14—H14A	109.5
C5—N1—C16	121.53 (11)	C12—C14—H14B	109.5
C9—N2—H2NA	121.5 (12)	H14A—C14—H14B	109.5
C9—N2—H2NB	117.1 (13)	C12—C14—H14C	109.5
H2NA—N2—H2NB	120.8 (18)	H14A—C14—H14C	109.5
C7—N3—C10	122.11 (12)	H14B—C14—H14C	109.5
C7—N3—C13	121.25 (12)	C11—C15—H15A	109.5
C10—N3—C13	113.00 (11)	C11—C15—H15B	109.5
C11—N4—C12	113.50 (11)	H15A—C15—H15B	109.5
C11—N4—H4NA	109.2 (11)	C11—C15—H15C	109.5
C12—N4—H4NA	106.8 (11)	H15A—C15—H15C	109.5
C11—N4—H4NB	107.8 (12)	H15B—C15—H15C	109.5
C12—N4—H4NB	111.4 (13)	N1—C16—C17	120.10 (13)
H4NA—N4—H4NB	108.1 (16)	N1—C16—C18	119.79 (12)
N1—C1—C2	124.01 (13)	C17—C16—C18	60.25 (10)
N1—C1—H1	118.0	N1—C16—H16	115.2
C2—C1—H1	118.0	C17—C16—H16	115.2
C1—C2—C3	120.15 (12)	C18—C16—H16	115.2
C1—C2—C19	118.06 (13)	C16—C17—C18	60.0 (1)
C3—C2—C19	121.78 (13)	C16—C17—H17A	117.8
O3—C3—C2	120.51 (12)	C18—C17—H17A	117.8
O3—C3—C4	122.51 (13)	C16—C17—H17B	117.8
C2—C3—C4	116.98 (12)	C18—C17—H17B	117.8
C5—C4—C9	119.40 (12)	H17A—C17—H17B	114.9
C5—C4—C3	120.09 (12)	C16—C18—C17	59.75 (10)
C9—C4—C3	120.49 (13)	C16—C18—H18A	117.8
C6—C5—N1	122.42 (12)	C17—C18—H18A	117.8
C6—C5—C4	118.73 (12)	C16—C18—H18B	117.8
N1—C5—C4	118.83 (12)	C17—C18—H18B	117.8
F1—C6—C5	120.90 (12)	H18A—C18—H18B	114.9
F1—C6—C7	115.95 (12)	O1—C19—O2	121.19 (13)
C5—C6—C7	123.03 (13)	O1—C19—C2	123.08 (13)
N3—C7—C8	120.21 (12)	O2—C19—C2	115.72 (12)
N3—C7—C6	123.22 (13)	C21—C20—C25	118.51 (13)
C8—C7—C6	116.57 (12)	C21—C20—C26	121.24 (13)
F2—C8—C9	116.56 (12)	C25—C20—C26	120.12 (13)
F2—C8—C7	118.93 (12)	C22—C21—C20	120.52 (13)
C9—C8—C7	124.51 (13)	C22—C21—H21	119.7
N2—C9—C8	119.27 (13)	C20—C21—H21	119.7
N2—C9—C4	123.04 (13)	C21—C22—C23	121.13 (13)
C8—C9—C4	117.69 (13)	C21—C22—H22	119.4
N3—C10—C11	109.43 (11)	C23—C22—H22	119.4
N3—C10—H10A	109.8	C22—C23—C24	118.09 (13)
C11—C10—H10A	109.8	C22—C23—C27	120.84 (13)
N3—C10—H10B	109.8	C24—C23—C27	121.07 (13)
C11—C10—H10B	109.8	C25—C24—C23	120.97 (13)
H10A—C10—H10B	108.2	C25—C24—H24	119.5
N4—C11—C15	109.35 (11)	C23—C24—H24	119.5
N4—C11—C10	109.27 (11)	C24—C25—C20	120.76 (13)
C15—C11—C10	111.72 (12)	C24—C25—H25	119.6
N4—C11—H11	108.8	C20—C25—H25	119.6
C15—C11—H11	108.8	O5—C26—O4	124.71 (13)
C10—C11—H11	108.8	O5—C26—C20	118.24 (13)
N4—C12—C13	109.24 (11)	O4—C26—C20	117.00 (12)
N4—C12—C14	108.69 (11)	C23—C27—H27A	109.5
C13—C12—C14	112.46 (12)	C23—C27—H27B	109.5
N4—C12—H12	108.8	H27A—C27—H27B	109.5
C13—C12—H12	108.8	C23—C27—H27C	109.5
C14—C12—H12	108.8	H27A—C27—H27C	109.5
N3—C13—C12	110.49 (12)	H27B—C27—H27C	109.5
N3—C13—H13A	109.6	H1W1—O1W—H2W1	104 (2)
C12—C13—H13A	109.6	H1W2—O2W—H2W2	110 (2)
N3—C13—H13B	109.6	H1W3—O3W—H2W3	102 (2)

C5—N1—C1—C2	1.9 (2)	C5—C4—C9—N2	178.94 (13)
C16—N1—C1—C2	176.62 (13)	C3—C4—C9—N2	0.8 (2)
N1—C1—C2—C3	−2.2 (2)	C5—C4—C9—C8	−1.3 (2)
N1—C1—C2—C19	177.15 (13)	C3—C4—C9—C8	−179.45 (13)
C1—C2—C3—O3	−179.45 (13)	C7—N3—C10—C11	−140.81 (13)
C19—C2—C3—O3	1.3 (2)	C13—N3—C10—C11	60.49 (15)
C1—C2—C3—C4	0.6 (2)	C12—N4—C11—C15	177.44 (12)
C19—C2—C3—C4	−178.66 (12)	C12—N4—C11—C10	54.87 (15)
O3—C3—C4—C5	−178.86 (13)	N3—C10—C11—N4	−56.09 (15)
C2—C3—C4—C5	1.06 (19)	N3—C10—C11—C15	−177.22 (12)
O3—C3—C4—C9	−0.7 (2)	C11—N4—C12—C13	−53.64 (15)
C2—C3—C4—C9	179.20 (13)	C11—N4—C12—C14	−176.68 (12)
C1—N1—C5—C6	−178.40 (13)	C7—N3—C13—C12	141.28 (13)
C16—N1—C5—C6	7.0 (2)	C10—N3—C13—C12	−59.81 (16)
C1—N1—C5—C4	−0.05 (19)	N4—C12—C13—N3	54.01 (15)
C16—N1—C5—C4	−174.64 (12)	C14—C12—C13—N3	174.77 (12)
C9—C4—C5—C6	−1.1 (2)	C1—N1—C16—C17	102.71 (15)
C3—C4—C5—C6	177.05 (13)	C5—N1—C16—C17	−82.62 (17)
C9—C4—C5—N1	−179.52 (12)	C1—N1—C16—C18	31.9 (2)
C3—C4—C5—N1	−1.36 (19)	C5—N1—C16—C18	−153.41 (14)
N1—C5—C6—F1	4.8 (2)	N1—C16—C17—C18	−109.28 (15)
C4—C5—C6—F1	−173.55 (12)	N1—C16—C18—C17	109.78 (15)
N1—C5—C6—C7	−179.38 (13)	C1—C2—C19—O1	1.4 (2)
C4—C5—C6—C7	2.3 (2)	C3—C2—C19—O1	−179.26 (14)
C10—N3—C7—C8	148.72 (14)	C1—C2—C19—O2	−178.35 (13)
C13—N3—C7—C8	−54.31 (19)	C3—C2—C19—O2	1.0 (2)
C10—N3—C7—C6	−30.9 (2)	C25—C20—C21—C22	0.8 (2)
C13—N3—C7—C6	126.05 (15)	C26—C20—C21—C22	−175.08 (13)
F1—C6—C7—N3	−5.2 (2)	C20—C21—C22—C23	0.5 (2)
C5—C6—C7—N3	178.76 (13)	C21—C22—C23—C24	−1.0 (2)
F1—C6—C7—C8	175.12 (12)	C21—C22—C23—C27	178.68 (14)
C5—C6—C7—C8	−0.9 (2)	C22—C23—C24—C25	0.1 (2)
N3—C7—C8—F2	−1.9 (2)	C27—C23—C24—C25	−179.53 (14)
C6—C7—C8—F2	177.78 (12)	C23—C24—C25—C20	1.2 (2)
N3—C7—C8—C9	178.56 (13)	C21—C20—C25—C24	−1.6 (2)
C6—C7—C8—C9	−1.8 (2)	C26—C20—C25—C24	174.28 (13)
F2—C8—C9—N2	3.0 (2)	C21—C20—C26—O5	177.27 (13)
C7—C8—C9—N2	−177.39 (14)	C25—C20—C26—O5	1.5 (2)
F2—C8—C9—C4	−176.72 (12)	C21—C20—C26—O4	−0.3 (2)
C7—C8—C9—C4	2.8 (2)	C25—C20—C26—O4	−176.07 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.92 (2)	1.64 (2)	2.5014 (14)	155 (2)
N2—H2NB···O3	0.91 (2)	1.93 (2)	2.6367 (17)	133.4 (18)
N4—H4NA···O4	0.967 (19)	1.73 (2)	2.6722 (16)	164.1 (17)
N4—H4NB···O5ⁱ	0.91 (2)	1.86 (2)	2.7473 (16)	163.0 (18)
N2—H2NA···O2Wⁱⁱ	0.91 (2)	2.12 (2)	2.9664 (17)	153.9 (17)
O2W—H2W2···O4	0.94 (3)	1.80 (3)	2.7371 (16)	171 (2)
O1W—H1W1···O2W	1.04 (3)	1.71 (3)	2.7503 (17)	175 (2)
O2W—H1W2···O3W	0.93 (3)	1.83 (3)	2.7546 (18)	171 (2)
O1W—H2W1···O1ⁱⁱⁱ	0.96 (3)	1.89 (3)	2.8434 (16)	171 (2)
O3W—H1W3···O1Wⁱⁱ	1.02 (3)	1.82 (3)	2.8362 (17)	173 (2)
O3W—H2W3···O1W^iv	1.00 (4)	1.88 (4)	2.8798 (18)	178 (3)

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

Atom-atom contact coverages (%) in I, II, and III top

Atom contacts	I	II	III
H···H	41.2	40.3	48.0
H···O	28.8	25.5	23.4
H···C	10.0	15.5	7.9
C···C	6.0	4.6	7.7
H···F	3.5	7.7	5.7
O···F	2.6	0.2	1.3
C···O	2.3	1.4	2.5
H···N	1.6	3.0	1.5

Heterogeneous contact types here include the reciprocal interactions, e.g., "H···O" represents "H···O/O···H". All other fractions of atom-contact coverages were negligible.

Acknowledgements

One of the authors (HJS) is grateful to the University of Mysore for research facilities. HSY also thanks UGC for a BSR Faculty fellowship for three years.

Funding information

Funding for this research was provided by: NSF (MRI CHE1625732) and the University of Kentucky (Bruker D8 Venture diffractometer) to SP.

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Volume 78| Part 12| December 2022| Pages 1257-1264

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Syntheses and crystal structures of three salts of sparfloxacin, one incorporating extended tapes of fused penta­gonal water assemblies

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey and related literature

5. Synthesis and crystallization

6. Data collection and structure refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Syntheses and crystal structures of three salts of sparfloxacin, one incorporating extended tapes of fused pentagonal water assemblies

3. Supramolecular features