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

The syntheses and crystal structures of three organic salts of sparfloxacin are described. Crystals of the salt with 4-methyl­benzoate incorporate extended chains of fused water penta­gons, reminiscent of an exotic form of linear `ice' that forms of the Cu(110) surface at low temperature.

Computing details

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)

Crystal data

C19H23F2N4O3^+·C7H4NO4^−·2H2O	Z = 2
Mr = 595.56	F(000) = 624
Triclinic, P1	Dx = 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) Å^3	0.33 × 0.31 × 0.27 mm

Data collection

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	Rint = 0.033
φ and ω scans	θmax = 27.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
Tmin = 0.930, Tmax = 0.971	k = −17→17
45287 measured reflections	l = −17→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: mixed
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.4829P] where P = (Fo^2 + 2Fc^2)/3
6210 reflections	(Δ/σ)max = 0.001
443 parameters	Δρmax = 0.27 e Å^−3
46 restraints	Δρmin = −0.22 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O2W^i	0.80	2.01	2.803 (5)	172
O2W—H2W2···O1^ii	0.82	2.02	2.807 (3)	161
N2—H2NA···O1W^iii	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)

Crystal data

C19H23F2N4O3^+·C8H7O2^−	Z = 2
Mr = 528.55	F(000) = 556
Triclinic, P1	Dx = 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) Å^3	0.34 × 0.28 × 0.26 mm

Data collection

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	Rint = 0.038
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
Tmin = 0.914, Tmax = 0.959	k = −12→13
41293 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: mixed
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 0.5792P] where P = (Fo^2 + 2Fc^2)/3
5639 reflections	(Δ/σ)max = 0.002
365 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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).

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

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O5^i	0.869 (17)	2.232 (17)	2.9958 (13)	146.5 (14)
N4—H4NA···O4^ii	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)

Crystal data

C19H23F2N4O3^+·C8H7O2^−·3H2O	F(000) = 1232
Mr = 582.60	Dx = 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) Å^3	Tablet, pale yellow
Z = 4	0.19 × 0.15 × 0.04 mm

Data collection

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	Rint = 0.043
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −23→23
Tmin = 0.894, Tmax = 0.959	k = −9→9
44990 measured reflections	l = −27→27

Refinement

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

Special details

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).

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

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O5^i	0.91 (2)	1.86 (2)	2.7473 (16)	163.0 (18)
N2—H2NA···O2W^ii	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···O1^iii	0.96 (3)	1.89 (3)	2.8434 (16)	171 (2)
O3W—H1W3···O1W^ii	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.