4-(3-Carb-oxy-1-ethyl-6-fluoro-4-oxo-1,4-dihydro-7-quinol-yl)-1-methyl-piper-azin-ium picrate.

The pefloxacinium cation of the title salt, C(17)H(21)FN(3)O(3) (+)·C(6)H(2)N(3)O(7) (-), is composed of an essentially planar quinoline ring system [maximum deviation = 0.021 (2) Å] and a piperazine ring, which adopts a chair conformation. In the picrate anion, the two O atoms of one of the o-NO(2) groups are disordered over two positions, with an occupancy ratio of 0.56 (4):0.44 (4). In the crystal structure, cations and anions are connected by inter-molecular N-H⋯O, O-H⋯O, C-H⋯O and C-H⋯F hydrogen bonds, forming a three-dimensional network. In addition, π-π inter-actions between the pyridine rings and between the benzene rings of the anions, with centroid-centroid distances of 3.6103 (12) and 3.5298 (11) Å, respectively, are observed.

Related literature

For background to the biological activity, pharmacokinetic properties and therapeutic use of pefloxacin, a synthetic chemotherapeutic agent used to treat severe bacterial infections, see: Mizuki et al. (1996 ▶); Gonzalez & Henwood (1989 ▶); Tripathi (1995 ▶); Ross & Riley (1990 ▶); Burkhardt et al. (1997 ▶). For the silver(I), manganese(II) and cobalt(II) derivatives of the pefloxacin anion, see: Baenziger et al. (1986 ▶); An, Huang & Qi (2007 ▶); An, Qi & Huang (2007 ▶). For related structures, see; An & Liang (2008 ▶); Florence et al. (2000 ▶); Hu & Yu (2005 ▶); Parvez et al. (2000 ▶). For hydrogen-bonding motifs see: Bernstein et al. (1995 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C17H21FN3O3 +·C6H2N3O7 −

M = 562.47

Triclinic,

a = 7.2645 (1) Å

b = 9.1987 (2) Å

c = 20.2253 (4) Å

α = 77.116 (1)°

β = 81.315 (1)°

γ = 67.124 (1)°

V = 1210.77 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 296 K

0.36 × 0.13 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.955, T max = 0.984

23708 measured reflections

5523 independent reflections

3682 reflections with I > 2s(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.123

S = 1.03

5523 reflections

472 parameters

All H-atom parameters refined

Δρmax = 0.21 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006835/tk2633sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006835/tk2633Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H21FN3O3+·C6H2N3O7−	Z = 2
Mr = 562.47	F(000) = 584
Triclinic, P1	Dx = 1.543 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2645 (1) Å	Cell parameters from 4949 reflections
b = 9.1987 (2) Å	θ = 2.5–31.8°
c = 20.2253 (4) Å	µ = 0.13 mm−1
α = 77.116 (1)°	T = 296 K
β = 81.315 (1)°	Block, yellow
γ = 67.124 (1)°	0.36 × 0.13 × 0.13 mm
V = 1210.77 (4) Å3

Bruker SMART APEXII CCD area-detector diffractometer	5523 independent reflections
Radiation source: fine-focus sealed tube	3682 reflections with I > 2s(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.955, Tmax = 0.984	k = −11→11
23708 measured reflections	l = −26→26

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	All H-atom parameters refined
S = 1.03	w = 1/[σ2(Fo2) + (0.0539P)2 + 0.1877P] where P = (Fo2 + 2Fc2)/3
5523 reflections	(Δ/σ)max = 0.001
472 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.4979 (2)	0.79508 (17)	0.88294 (6)	0.0614 (4)
O2	0.7151 (13)	0.5178 (13)	0.8445 (5)	0.067 (2)	0.56 (4)
O3	0.9703 (16)	0.3754 (18)	0.9011 (8)	0.075 (3)	0.56 (4)
O2B	0.768 (5)	0.546 (3)	0.8376 (7)	0.120 (6)	0.44 (4)
O3B	0.934 (4)	0.357 (3)	0.9074 (10)	0.103 (5)	0.44 (4)
O4	0.8735 (3)	0.32881 (19)	1.14260 (8)	0.0788 (5)
O5	0.6553 (3)	0.5215 (2)	1.18879 (7)	0.0730 (5)
O6	0.2844 (2)	1.00907 (18)	1.04797 (8)	0.0663 (4)
O7	0.2049 (3)	0.9961 (2)	0.95255 (9)	0.0994 (7)
N1	0.8047 (2)	0.4832 (2)	0.89513 (8)	0.0473 (4)
N2	0.7383 (3)	0.4603 (2)	1.13878 (9)	0.0543 (4)
N3	0.3077 (3)	0.9389 (2)	1.00085 (9)	0.0531 (4)
C1	0.7049 (2)	0.5634 (2)	0.95257 (8)	0.0367 (4)
C2	0.5487 (2)	0.7206 (2)	0.94034 (8)	0.0388 (4)
C3	0.4645 (3)	0.7803 (2)	1.00324 (9)	0.0391 (4)
C4	0.5270 (3)	0.6985 (2)	1.06618 (10)	0.0422 (4)
C5	0.6760 (3)	0.5484 (2)	1.07199 (9)	0.0425 (4)
C6	0.7669 (3)	0.4806 (2)	1.01542 (9)	0.0404 (4)
F1	0.63677 (18)	−0.03326 (12)	0.57808 (5)	0.0561 (3)
O8	−0.0325 (3)	0.9171 (2)	0.40639 (8)	0.0782 (5)
O9	0.0924 (3)	0.7207 (2)	0.34701 (8)	0.0711 (5)
O10	0.2917 (2)	0.43985 (18)	0.40332 (7)	0.0611 (4)
N4	0.2108 (2)	0.60713 (17)	0.58140 (7)	0.0395 (3)
N5	0.5335 (2)	0.06173 (16)	0.70402 (7)	0.0355 (3)
N6	0.2153 (2)	0.01715 (17)	0.80261 (7)	0.0381 (3)
C7	0.1335 (3)	0.7054 (2)	0.52424 (10)	0.0452 (5)
C8	0.1526 (3)	0.6553 (2)	0.46406 (9)	0.0456 (5)
C9	0.2625 (3)	0.4915 (2)	0.45840 (9)	0.0440 (5)
C10	0.3409 (3)	0.3855 (2)	0.52080 (8)	0.0375 (4)
C11	0.4521 (3)	0.2212 (2)	0.52173 (9)	0.0419 (4)
C12	0.5179 (3)	0.1222 (2)	0.58059 (9)	0.0386 (4)
C13	0.4736 (2)	0.1723 (2)	0.64432 (8)	0.0329 (4)
C14	0.3771 (2)	0.3363 (2)	0.64216 (9)	0.0341 (4)
C15	0.3112 (2)	0.4432 (2)	0.58177 (8)	0.0343 (4)
C16	0.4921 (3)	−0.0875 (2)	0.71661 (10)	0.0403 (4)
C17	0.2763 (3)	−0.0593 (2)	0.74081 (9)	0.0403 (4)
C18	0.2690 (3)	0.1625 (2)	0.79291 (10)	0.0409 (4)
C19	0.4868 (3)	0.1236 (2)	0.76759 (9)	0.0386 (4)
C20	−0.0031 (3)	0.0581 (3)	0.82167 (14)	0.0571 (6)
C21	0.1823 (3)	0.6765 (3)	0.64328 (11)	0.0493 (5)
C22	0.0028 (4)	0.6633 (4)	0.68827 (13)	0.0664 (7)
C23	0.0618 (3)	0.7773 (3)	0.40435 (11)	0.0563 (6)
H4	0.468 (3)	0.743 (2)	1.1031 (11)	0.055 (6)*
H6	0.864 (3)	0.386 (2)	1.0177 (9)	0.046 (5)*
H7	0.066 (3)	0.813 (3)	0.5297 (10)	0.055 (6)*
H11	0.485 (3)	0.181 (2)	0.4813 (10)	0.047 (5)*
H14	0.349 (2)	0.379 (2)	0.6821 (9)	0.036 (5)*
H16A	0.526 (3)	−0.136 (2)	0.6761 (11)	0.057 (6)*
H16B	0.583 (3)	−0.163 (2)	0.7505 (10)	0.053 (5)*
H17A	0.193 (3)	0.012 (2)	0.7078 (9)	0.044 (5)*
H17B	0.251 (3)	−0.164 (3)	0.7550 (10)	0.059 (6)*
H18A	0.245 (3)	0.196 (2)	0.8351 (10)	0.043 (5)*
H18B	0.182 (3)	0.241 (2)	0.7603 (10)	0.045 (5)*
H19A	0.569 (3)	0.039 (2)	0.8001 (9)	0.040 (5)*
H19B	0.521 (2)	0.220 (2)	0.7621 (9)	0.040 (5)*
H20A	−0.038 (3)	0.107 (3)	0.8617 (12)	0.072 (7)*
H20B	−0.079 (4)	0.131 (3)	0.7848 (13)	0.081 (8)*
H20C	−0.033 (3)	−0.043 (3)	0.8318 (12)	0.080 (8)*
H21A	0.303 (3)	0.623 (2)	0.6670 (9)	0.046 (5)*
H21B	0.161 (3)	0.781 (3)	0.6285 (10)	0.055 (6)*
H22A	−0.106 (4)	0.710 (3)	0.6634 (14)	0.096 (9)*
H22B	0.022 (4)	0.552 (4)	0.7065 (13)	0.092 (9)*
H22C	−0.013 (4)	0.715 (3)	0.7274 (15)	0.103 (9)*
H1O9	0.179 (4)	0.610 (4)	0.3556 (15)	0.110 (11)*
H1N6	0.284 (3)	−0.055 (2)	0.8372 (10)	0.044 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0640 (9)	0.0613 (9)	0.0329 (7)	−0.0004 (7)	−0.0099 (6)	0.0052 (6)
O2	0.075 (3)	0.091 (4)	0.032 (3)	−0.022 (3)	−0.008 (2)	−0.019 (3)
O3	0.046 (3)	0.075 (4)	0.094 (7)	−0.001 (3)	−0.005 (3)	−0.037 (4)
O2B	0.146 (11)	0.093 (7)	0.041 (3)	0.026 (7)	0.016 (6)	0.001 (4)
O3B	0.114 (10)	0.072 (7)	0.058 (5)	0.034 (7)	0.006 (7)	−0.015 (4)
O4	0.1096 (14)	0.0488 (10)	0.0600 (10)	−0.0117 (9)	−0.0349 (9)	0.0128 (8)
O5	0.1082 (13)	0.0755 (11)	0.0342 (8)	−0.0327 (10)	−0.0172 (8)	−0.0017 (8)
O6	0.0818 (10)	0.0514 (9)	0.0601 (10)	−0.0210 (8)	0.0176 (8)	−0.0208 (8)
O7	0.0998 (13)	0.0821 (13)	0.0596 (11)	0.0313 (10)	−0.0219 (10)	−0.0093 (9)
N1	0.0471 (9)	0.0478 (11)	0.0434 (10)	−0.0148 (8)	0.0000 (8)	−0.0083 (8)
N2	0.0789 (12)	0.0483 (11)	0.0388 (10)	−0.0286 (9)	−0.0205 (9)	0.0067 (8)
N3	0.0613 (10)	0.0434 (10)	0.0418 (10)	−0.0125 (8)	0.0051 (8)	−0.0009 (8)
C1	0.0402 (9)	0.0377 (10)	0.0325 (9)	−0.0152 (7)	−0.0031 (7)	−0.0047 (8)
C2	0.0416 (9)	0.0395 (10)	0.0310 (9)	−0.0138 (8)	−0.0066 (7)	0.0024 (8)
C3	0.0439 (9)	0.0336 (10)	0.0362 (10)	−0.0135 (7)	−0.0027 (7)	−0.0010 (8)
C4	0.0556 (11)	0.0425 (11)	0.0330 (10)	−0.0240 (9)	−0.0026 (8)	−0.0049 (8)
C5	0.0565 (11)	0.0398 (11)	0.0333 (10)	−0.0226 (9)	−0.0138 (8)	0.0050 (8)
C6	0.0438 (10)	0.0316 (10)	0.0443 (11)	−0.0131 (8)	−0.0118 (8)	0.0006 (8)
F1	0.0842 (8)	0.0348 (6)	0.0393 (6)	−0.0115 (5)	−0.0012 (5)	−0.0083 (5)
O8	0.0905 (12)	0.0572 (11)	0.0693 (11)	−0.0164 (9)	−0.0349 (9)	0.0226 (8)
O9	0.0922 (12)	0.0720 (12)	0.0470 (9)	−0.0327 (10)	−0.0345 (8)	0.0176 (8)
O10	0.0940 (11)	0.0621 (10)	0.0345 (8)	−0.0367 (8)	−0.0223 (7)	0.0031 (7)
N4	0.0437 (8)	0.0334 (8)	0.0361 (8)	−0.0114 (6)	−0.0087 (6)	0.0029 (6)
N5	0.0403 (7)	0.0311 (8)	0.0285 (7)	−0.0093 (6)	−0.0023 (6)	0.0002 (6)
N6	0.0377 (7)	0.0351 (8)	0.0320 (8)	−0.0092 (6)	−0.0041 (6)	0.0057 (7)
C7	0.0468 (10)	0.0387 (11)	0.0453 (11)	−0.0154 (9)	−0.0107 (8)	0.0066 (9)
C8	0.0454 (10)	0.0489 (12)	0.0415 (11)	−0.0233 (9)	−0.0161 (8)	0.0133 (9)
C9	0.0529 (11)	0.0516 (12)	0.0352 (10)	−0.0310 (9)	−0.0149 (8)	0.0066 (9)
C10	0.0455 (9)	0.0406 (10)	0.0299 (9)	−0.0230 (8)	−0.0085 (7)	0.0038 (7)
C11	0.0595 (11)	0.0435 (11)	0.0293 (9)	−0.0265 (9)	−0.0054 (8)	−0.0045 (8)
C12	0.0490 (10)	0.0306 (10)	0.0352 (10)	−0.0154 (8)	−0.0019 (8)	−0.0033 (7)
C13	0.0350 (8)	0.0342 (9)	0.0281 (9)	−0.0141 (7)	−0.0029 (7)	0.0002 (7)
C14	0.0387 (9)	0.0334 (10)	0.0287 (9)	−0.0129 (7)	−0.0033 (7)	−0.0030 (7)
C15	0.0360 (8)	0.0324 (9)	0.0332 (9)	−0.0144 (7)	−0.0063 (7)	0.0025 (7)
C16	0.0508 (10)	0.0286 (10)	0.0322 (10)	−0.0089 (8)	−0.0008 (8)	0.0012 (8)
C17	0.0506 (10)	0.0344 (10)	0.0328 (10)	−0.0154 (8)	−0.0088 (8)	0.0035 (8)
C18	0.0506 (10)	0.0355 (10)	0.0314 (10)	−0.0132 (8)	0.0014 (8)	−0.0033 (8)
C19	0.0456 (10)	0.0404 (11)	0.0277 (9)	−0.0156 (8)	−0.0083 (7)	0.0013 (8)
C20	0.0404 (10)	0.0558 (14)	0.0611 (15)	−0.0133 (10)	0.0024 (10)	0.0048 (12)
C21	0.0618 (13)	0.0315 (11)	0.0475 (12)	−0.0074 (9)	−0.0142 (10)	−0.0037 (9)
C22	0.0521 (13)	0.080 (2)	0.0512 (14)	−0.0029 (12)	−0.0062 (11)	−0.0177 (14)
C23	0.0603 (12)	0.0582 (14)	0.0483 (13)	−0.0283 (11)	−0.0245 (10)	0.0201 (11)

O1—C2	1.2375 (19)	N6—H1N6	0.905 (19)
O2—N1	1.212 (8)	C7—C8	1.365 (3)
O3—N1	1.228 (13)	C7—H7	0.94 (2)
O2B—N1	1.196 (13)	C8—C9	1.426 (3)
O3B—N1	1.177 (17)	C8—C23	1.488 (3)
O4—N2	1.221 (2)	C9—C10	1.451 (2)
O5—N2	1.229 (2)	C10—C15	1.404 (2)
O6—N3	1.222 (2)	C10—C11	1.407 (3)
O7—N3	1.214 (2)	C11—C12	1.351 (2)
N1—C1	1.460 (2)	C11—H11	0.932 (19)
N2—C5	1.448 (2)	C12—C13	1.415 (2)
N3—C3	1.457 (2)	C13—C14	1.388 (2)
C1—C6	1.368 (2)	C14—C15	1.401 (2)
C1—C2	1.446 (2)	C14—H14	0.936 (17)
C2—C3	1.452 (2)	C16—C17	1.508 (3)
C3—C4	1.369 (2)	C16—H16A	0.97 (2)
C4—C5	1.377 (3)	C16—H16B	0.98 (2)
C4—H4	0.90 (2)	C17—H17A	0.929 (19)
C5—C6	1.380 (3)	C17—H17B	1.02 (2)
C6—H6	0.882 (19)	C18—C19	1.514 (3)
F1—C12	1.3609 (19)	C18—H18A	0.942 (19)
O8—C23	1.206 (3)	C18—H18B	0.956 (19)
O9—C23	1.329 (3)	C19—H19A	0.959 (18)
O9—H1O9	0.96 (3)	C19—H19B	0.994 (18)
O10—C9	1.264 (2)	C20—H20A	0.97 (2)
N4—C7	1.343 (2)	C20—H20B	0.96 (3)
N4—C15	1.396 (2)	C20—H20C	1.01 (3)
N4—C21	1.480 (2)	C21—C22	1.502 (3)
N5—C13	1.396 (2)	C21—H21A	0.964 (19)
N5—C19	1.462 (2)	C21—H21B	0.90 (2)
N5—C16	1.477 (2)	C22—H22A	0.91 (3)
N6—C20	1.491 (2)	C22—H22B	0.97 (3)
N6—C17	1.496 (2)	C22—H22C	0.98 (3)
N6—C18	1.498 (2)
O3B—N1—O2B	120.7 (12)	C12—C11—H11	119.8 (12)
O3B—N1—O2	119.9 (11)	C10—C11—H11	119.8 (12)
O2B—N1—O2	25.4 (19)	C11—C12—F1	118.09 (16)
O3B—N1—O3	17.2 (18)	C11—C12—C13	123.53 (16)
O2B—N1—O3	114.2 (11)	F1—C12—C13	118.36 (14)
O2—N1—O3	121.9 (8)	C14—C13—N5	123.69 (15)
O3B—N1—C1	116.8 (10)	C14—C13—C12	115.50 (15)
O2B—N1—C1	122.4 (7)	N5—C13—C12	120.75 (15)
O2—N1—C1	118.6 (5)	C13—C14—C15	122.18 (16)
O3—N1—C1	119.3 (7)	C13—C14—H14	120.3 (11)
O4—N2—O5	122.98 (17)	C15—C14—H14	117.5 (11)
O4—N2—C5	118.14 (18)	N4—C15—C14	120.91 (15)
O5—N2—C5	118.87 (17)	N4—C15—C10	118.98 (14)
O7—N3—O6	122.52 (18)	C14—C15—C10	120.08 (16)
O7—N3—C3	119.07 (17)	N5—C16—C17	111.86 (15)
O6—N3—C3	118.41 (17)	N5—C16—H16A	111.3 (12)
C6—C1—C2	124.48 (16)	C17—C16—H16A	109.6 (12)
C6—C1—N1	116.28 (16)	N5—C16—H16B	106.4 (11)
C2—C1—N1	119.24 (15)	C17—C16—H16B	111.3 (11)
O1—C2—C1	123.51 (16)	H16A—C16—H16B	106.2 (16)
O1—C2—C3	124.90 (16)	N6—C17—C16	111.76 (15)
C1—C2—C3	111.58 (14)	N6—C17—H17A	105.8 (11)
C4—C3—C2	124.16 (16)	C16—C17—H17A	110.2 (11)
C4—C3—N3	116.38 (16)	N6—C17—H17B	105.1 (11)
C2—C3—N3	119.44 (15)	C16—C17—H17B	112.0 (11)
C3—C4—C5	119.36 (18)	H17A—C17—H17B	111.7 (16)
C3—C4—H4	119.3 (13)	N6—C18—C19	110.49 (15)
C5—C4—H4	121.4 (13)	N6—C18—H18A	107.9 (11)
C4—C5—C6	121.23 (16)	C19—C18—H18A	110.3 (11)
C4—C5—N2	119.28 (18)	N6—C18—H18B	105.3 (11)
C6—C5—N2	119.49 (17)	C19—C18—H18B	111.5 (11)
C1—C6—C5	119.18 (17)	H18A—C18—H18B	111.3 (16)
C1—C6—H6	117.8 (12)	N5—C19—C18	112.19 (14)
C5—C6—H6	123.0 (12)	N5—C19—H19A	105.6 (10)
C23—O9—H1O9	108.0 (18)	C18—C19—H19A	108.9 (10)
C7—N4—C15	119.85 (16)	N5—C19—H19B	110.7 (10)
C7—N4—C21	118.47 (16)	C18—C19—H19B	109.8 (10)
C15—N4—C21	121.66 (14)	H19A—C19—H19B	109.6 (14)
C13—N5—C19	117.44 (14)	N6—C20—H20A	108.9 (14)
C13—N5—C16	118.83 (14)	N6—C20—H20B	109.9 (14)
C19—N5—C16	108.08 (14)	H20A—C20—H20B	110 (2)
C20—N6—C17	110.80 (17)	N6—C20—H20C	109.0 (14)
C20—N6—C18	110.72 (16)	H20A—C20—H20C	110 (2)
C17—N6—C18	111.68 (14)	H20B—C20—H20C	109.3 (19)
C20—N6—H1N6	108.7 (11)	N4—C21—C22	112.15 (19)
C17—N6—H1N6	107.7 (11)	N4—C21—H21A	108.2 (11)
C18—N6—H1N6	107.1 (12)	C22—C21—H21A	111.4 (11)
N4—C7—C8	123.61 (19)	N4—C21—H21B	105.7 (13)
N4—C7—H7	113.1 (12)	C22—C21—H21B	108.4 (13)
C8—C7—H7	123.3 (12)	H21A—C21—H21B	110.9 (17)
C7—C8—C9	120.63 (16)	C21—C22—H22A	108.4 (17)
C7—C8—C23	118.05 (19)	C21—C22—H22B	110.9 (15)
C9—C8—C23	121.28 (19)	H22A—C22—H22B	110 (2)
O10—C9—C8	123.29 (16)	C21—C22—H22C	109.2 (17)
O10—C9—C10	121.36 (18)	H22A—C22—H22C	112 (2)
C8—C9—C10	115.36 (17)	H22B—C22—H22C	107 (2)
C15—C10—C11	117.85 (15)	O8—C23—O9	121.43 (19)
C15—C10—C9	121.42 (17)	O8—C23—C8	123.9 (2)
C11—C10—C9	120.73 (16)	O9—C23—C8	114.6 (2)
C12—C11—C10	120.33 (17)
O3B—N1—C1—C6	−2.1 (18)	O10—C9—C10—C11	−0.1 (3)
O2B—N1—C1—C6	−177 (2)	C8—C9—C10—C11	−179.94 (16)
O2—N1—C1—C6	153.5 (6)	C15—C10—C11—C12	3.5 (3)
O3—N1—C1—C6	−21.4 (8)	C9—C10—C11—C12	−177.41 (16)
O3B—N1—C1—C2	178.6 (18)	C10—C11—C12—F1	−175.41 (15)
O2B—N1—C1—C2	3(2)	C10—C11—C12—C13	3.1 (3)
O2—N1—C1—C2	−25.9 (6)	C19—N5—C13—C14	1.4 (2)
O3—N1—C1—C2	159.2 (7)	C16—N5—C13—C14	134.68 (17)
C6—C1—C2—O1	178.26 (18)	C19—N5—C13—C12	178.36 (15)
N1—C1—C2—O1	−2.5 (3)	C16—N5—C13—C12	−48.4 (2)
C6—C1—C2—C3	−0.2 (2)	C11—C12—C13—C14	−7.6 (2)
N1—C1—C2—C3	179.05 (15)	F1—C12—C13—C14	170.87 (14)
O1—C2—C3—C4	−177.76 (18)	C11—C12—C13—N5	175.20 (16)
C1—C2—C3—C4	0.7 (2)	F1—C12—C13—N5	−6.3 (2)
O1—C2—C3—N3	0.3 (3)	N5—C13—C14—C15	−177.14 (15)
C1—C2—C3—N3	178.69 (15)	C12—C13—C14—C15	5.8 (2)
O7—N3—C3—C4	−157.8 (2)	C7—N4—C15—C14	−174.14 (15)
O6—N3—C3—C4	21.9 (2)	C21—N4—C15—C14	4.4 (2)
O7—N3—C3—C2	24.0 (3)	C7—N4—C15—C10	4.2 (2)
O6—N3—C3—C2	−156.28 (17)	C21—N4—C15—C10	−177.34 (16)
C2—C3—C4—C5	−1.4 (3)	C13—C14—C15—N4	178.65 (15)
N3—C3—C4—C5	−179.47 (16)	C13—C14—C15—C10	0.4 (2)
C3—C4—C5—C6	1.6 (3)	C11—C10—C15—N4	176.55 (15)
C3—C4—C5—N2	−178.45 (16)	C9—C10—C15—N4	−2.6 (2)
O4—N2—C5—C4	−178.56 (18)	C11—C10—C15—C14	−5.1 (2)
O5—N2—C5—C4	0.5 (3)	C9—C10—C15—C14	175.75 (15)
O4—N2—C5—C6	1.4 (3)	C13—N5—C16—C17	−77.71 (19)
O5—N2—C5—C6	−179.54 (17)	C19—N5—C16—C17	59.43 (18)
C2—C1—C6—C5	0.5 (3)	C20—N6—C17—C16	174.57 (16)
N1—C1—C6—C5	−178.80 (15)	C18—N6—C17—C16	50.64 (19)
C4—C5—C6—C1	−1.2 (3)	N5—C16—C17—N6	−55.40 (19)
N2—C5—C6—C1	178.90 (16)	C20—N6—C18—C19	−175.03 (17)
C15—N4—C7—C8	−2.3 (3)	C17—N6—C18—C19	−51.05 (19)
C21—N4—C7—C8	179.16 (17)	C13—N5—C19—C18	77.00 (19)
N4—C7—C8—C9	−1.3 (3)	C16—N5—C19—C18	−60.83 (18)
N4—C7—C8—C23	−179.19 (17)	N6—C18—C19—N5	57.51 (19)
C7—C8—C9—O10	−177.07 (17)	C7—N4—C21—C22	94.7 (2)
C23—C8—C9—O10	0.7 (3)	C15—N4—C21—C22	−83.8 (2)
C7—C8—C9—C10	2.8 (2)	C7—C8—C23—O8	−2.2 (3)
C23—C8—C9—C10	−179.41 (16)	C9—C8—C23—O8	179.97 (19)
O10—C9—C10—C15	179.02 (15)	C7—C8—C23—O9	177.75 (17)
C8—C9—C10—C15	−0.8 (2)	C9—C8—C23—O9	−0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H1O9···O10	0.96 (3)	1.62 (3)	2.519 (2)	155 (3)
N6—H1N6···O1i	0.91 (2)	1.84 (2)	2.701 (2)	159 (2)
N6—H1N6···O7i	0.91 (2)	2.422 (19)	2.987 (2)	120.6 (15)
C6—H6···O3	0.878 (19)	2.38 (2)	2.706 (16)	102.3 (14)
C11—H11···F1ii	0.933 (19)	2.46 (2)	3.209 (2)	137.3 (18)
C16—H16A···F1	0.97 (2)	2.18 (2)	2.846 (2)	124.6 (15)
C17—H17A···O8iii	0.928 (19)	2.582 (19)	3.430 (3)	152.2 (14)
C17—H17B···O4iv	1.02 (2)	2.55 (2)	3.407 (3)	141.2 (16)
C18—H18A···O3v	0.940 (19)	2.47 (2)	3.241 (16)	139.2 (18)
C19—H19B···O5vi	0.990 (17)	2.566 (17)	3.300 (2)	131.0 (13)
C20—H20A···O7i	0.97 (2)	2.51 (2)	3.079 (3)	118.0 (18)
C20—H20C···O4iv	1.01 (3)	2.39 (3)	3.245 (3)	141.8 (19)
C21—H21B···O8vii	0.90 (3)	2.53 (3)	3.415 (3)	169 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H1O9⋯O10	0.96 (3)	1.62 (3)	2.519 (2)	155 (3)
N6—H1N6⋯O1i	0.91 (2)	1.84 (2)	2.701 (2)	159 (2)
N6—H1N6⋯O7i	0.91 (2)	2.422 (19)	2.987 (2)	120.6 (15)
C6—H6⋯O3	0.878 (19)	2.38 (2)	2.706 (16)	102.3 (14)
C11—H11⋯F1ii	0.933 (19)	2.46 (2)	3.209 (2)	137.3 (18)
C16—H16A⋯F1	0.97 (2)	2.18 (2)	2.846 (2)	124.6 (15)
C17—H17A⋯O8iii	0.928 (19)	2.582 (19)	3.430 (3)	152.2 (14)
C17—H17B⋯O4iv	1.02 (2)	2.55 (2)	3.407 (3)	141.2 (16)
C18—H18A⋯O3v	0.940 (19)	2.47 (2)	3.241 (16)	139.2 (18)
C19—H19B⋯O5vi	0.990 (17)	2.566 (17)	3.300 (2)	131.0 (13)
C20—H20A⋯O7i	0.97 (2)	2.51 (2)	3.079 (3)	118.0 (18)
C20—H20C⋯O4iv	1.01 (3)	2.39 (3)	3.245 (3)	141.8 (19)
C21—H21B⋯O8vii	0.90 (3)	2.53 (3)	3.415 (3)	169 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .