Bis(2-carboxybenzo-ato-κO)bis-[1-cyclo-propyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydro-quinoline-3-carboxyl-ato-κO,O]manganese(II) dihydrate.

The title compound, [Mn(C(17)H(18)FN(3)O(3))(2)(C(8)H(5)O(4))(2)]·2H(2)O or [Mn(cfH)(2)(1,2-Hbdc)(2)]·2H(2)O (cfH = ciprofloxacin = 1-cyclo-propyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazin-yl)-3-quinoline carb-oxy-lic acid, 1,2-bdc = benzene-1,2-dicarboxyl-ate), has been prepared under hydro-thermal conditions. The Mn(2+) atom, located on an inversion centre, exhibits a distorted octa-hedral geometry, coordinated by four O atoms from two symmetry-related zwitterionic ciprofloxacin ligands in the equatorial positions and two O atoms of two 1,2-Hbdc ligands in the axial positions. The complex mol-ecules are linked into a two-dimensional network through N-H⋯O and OW-H⋯O hydrogen bonds. A strong intramolecular hydrogen bond between the carboxyl/carboxylate groups of the 1,2-Hbdc anion is also present. The layers are further extended through off-set aromatic π-π stacking inter-actions of cfH groups [centroid-centroid distance of 3.657 (2) Å] into the final three-dimensional supra-molecular arrays.

Related literature

For background to the anti­biotic drug ciprofloxacin, see: Turel (2002 ▶); Xiao et al. (2005 ▶). The mechanisms of action of the quinolone anti­bacterial agents are either their inhibition of DNA gyrase (Topoisomerase II) or their inter­action with the DNA mol­ecule via a metal complex inter­mediate, see: Chulvi et al. (1991 ▶); Ruiz et al. (1993 ▶); Wallis et al. (1995 ▶). For related structures, see: Fabbiani & Dittrich (2008 ▶); Wang et al. (2009 ▶).

Experimental

Crystal data

[Mn(C17H18FN3O3)2(C8H5O4)2]·2H2O

M = 1083.90

Monoclinic,

a = 9.4510 (19) Å

b = 22.042 (4) Å

c = 11.695 (2) Å

β = 98.44 (3)°

V = 2409.9 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.36 mm−1

T = 293 K

0.58 × 0.47 × 0.32 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.817, T max = 0.893

22913 measured reflections

5494 independent reflections

3555 reflections with I > 2σ(I)

R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.145

S = 1.00

5494 reflections

350 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.36 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011615/vm2075sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011615/vm2075Isup2.hkl

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

[Mn(C17H18FN3O3)2(C8H5O4)2]·2H2O	F(000) = 1126
Mr = 1083.90	Dx = 1.494 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 22913 reflections
a = 9.4510 (19) Å	θ = 3.1–27.5°
b = 22.042 (4) Å	µ = 0.36 mm−1
c = 11.695 (2) Å	T = 293 K
β = 98.44 (3)°	Block, yellow
V = 2409.9 (8) Å3	0.58 × 0.47 × 0.32 mm
Z = 2

Rigaku R-AXIS RAPID IP diffractometer	5494 independent reflections
Radiation source: fine-focus sealed tube	3555 reflections with I > 2σ(I)
graphite	Rint = 0.068
Detector resolution: 100x100 microns pixels mm-1	θmax = 27.5°, θmin = 3.1°
Oscillation scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −28→27
Tmin = 0.817, Tmax = 0.893	l = −14→15
22913 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.080P)2] where P = (Fo2 + 2Fc2)/3
5494 reflections	(Δ/σ)max < 0.001
350 parameters	Δρmax = 0.45 e Å−3
10 restraints	Δρmin = −0.36 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
Mn1	0.0000	0.0000	0.5000	0.02941 (16)
F1	0.36711 (17)	−0.03305 (7)	1.05085 (13)	0.0405 (4)
O1	−0.3533 (2)	0.08833 (10)	0.61415 (16)	0.0463 (5)
OW1	−0.1255 (4)	0.13296 (13)	0.2728 (2)	0.0820 (9)
HW1A	−0.094 (5)	0.0991 (10)	0.298 (3)	0.110*
HW1B	−0.138 (5)	0.1555 (15)	0.328 (2)	0.109*
O2	−0.20086 (19)	0.03315 (9)	0.53302 (15)	0.0357 (4)
O3	0.0395 (2)	−0.00587 (8)	0.68591 (15)	0.0343 (4)
O4	0.0782 (2)	0.09397 (9)	0.50461 (18)	0.0439 (5)
O5	−0.0132 (3)	0.18400 (11)	0.5170 (2)	0.0750 (8)
O6	−0.0126 (4)	0.26486 (14)	0.6518 (3)	0.1005 (12)
O7	0.0876 (4)	0.28742 (12)	0.8236 (3)	0.0931 (11)
N1	0.5198 (2)	0.10018 (9)	1.39405 (17)	0.0314 (5)
H1A	0.5482	0.1366	1.3711	0.038*
H1B	0.5652	0.0931	1.4660	0.038*
N2	0.3244 (2)	0.06259 (10)	1.19684 (17)	0.0305 (5)
N3	−0.0836 (2)	0.12018 (9)	0.91028 (17)	0.0298 (5)
C1	−0.2347 (3)	0.06311 (11)	0.6166 (2)	0.0295 (5)
C2	−0.1306 (3)	0.06868 (11)	0.7272 (2)	0.0276 (5)
C3	−0.0053 (3)	0.03176 (11)	0.75371 (19)	0.0259 (5)
C4	0.0734 (2)	0.03979 (11)	0.8693 (2)	0.0259 (5)
C5	0.1887 (3)	0.00113 (11)	0.9079 (2)	0.0286 (5)
H5A	0.2133	−0.0297	0.8601	0.034*
C6	0.2637 (3)	0.00873 (11)	1.0142 (2)	0.0285 (5)
C7	0.2384 (3)	0.05589 (11)	1.0898 (2)	0.0277 (5)
C8	0.1208 (3)	0.09297 (11)	1.0534 (2)	0.0298 (5)
H8A	0.0973	0.1239	1.1015	0.036*
C9	0.0374 (3)	0.08415 (11)	0.9447 (2)	0.0259 (5)
C10	−0.1624 (3)	0.10961 (12)	0.8066 (2)	0.0315 (5)
H10A	−0.2456	0.1322	0.7878	0.038*
C11	−0.1357 (3)	0.16131 (13)	0.9927 (2)	0.0404 (6)
H11A	−0.1788	0.1415	1.0542	0.048*
C12	−0.0615 (4)	0.21907 (14)	1.0259 (3)	0.0578 (9)
H12A	0.0223	0.2289	0.9906	0.069*
H12B	−0.0577	0.2326	1.1052	0.069*
C13	−0.2032 (4)	0.21968 (15)	0.9507 (3)	0.0606 (10)
H13A	−0.2854	0.2334	0.9844	0.073*
H13B	−0.2054	0.2297	0.8697	0.073*
C14	0.4800 (3)	0.06480 (13)	1.1950 (2)	0.0358 (6)
H14A	0.5066	0.1044	1.1691	0.043*
H14B	0.5065	0.0346	1.1416	0.043*
C15	0.5581 (3)	0.05253 (13)	1.3150 (2)	0.0384 (6)
H15A	0.5314	0.0130	1.3412	0.046*
H15B	0.6606	0.0527	1.3140	0.046*
C16	0.3629 (3)	0.10097 (13)	1.3950 (2)	0.0346 (6)
H16A	0.3392	0.1339	1.4439	0.041*
H16B	0.3341	0.0632	1.4276	0.041*
C17	0.2812 (3)	0.10894 (13)	1.2747 (2)	0.0349 (6)
H17A	0.1793	0.1057	1.2772	0.042*
H17B	0.2999	0.1489	1.2457	0.042*
C18	0.0744 (3)	0.14291 (12)	0.5553 (2)	0.0376 (6)
C19	0.1798 (3)	0.15346 (11)	0.6640 (2)	0.0321 (6)
C20	0.2873 (3)	0.10976 (13)	0.6846 (3)	0.0399 (6)
H20A	0.2873	0.0778	0.6327	0.048*
C21	0.3928 (4)	0.11212 (16)	0.7781 (3)	0.0531 (8)
H21A	0.4638	0.0826	0.7883	0.064*
C22	0.3934 (4)	0.15842 (18)	0.8571 (3)	0.0626 (10)
H22A	0.4640	0.1601	0.9214	0.075*
C23	0.2886 (4)	0.20213 (16)	0.8400 (3)	0.0573 (9)
H23A	0.2890	0.2330	0.8943	0.069*
C24	0.1812 (3)	0.20172 (12)	0.7437 (2)	0.0394 (6)
C25	0.0795 (4)	0.25462 (14)	0.7399 (3)	0.0562 (9)
H6	−0.017 (6)	0.2366 (18)	0.602 (4)	0.13 (2)*

	U11	U22	U33	U12	U13	U23
Mn1	0.0300 (3)	0.0375 (3)	0.0188 (3)	0.0027 (2)	−0.0029 (2)	−0.0051 (2)
F1	0.0374 (8)	0.0479 (9)	0.0314 (8)	0.0147 (7)	−0.0111 (7)	−0.0025 (7)
O1	0.0317 (10)	0.0791 (15)	0.0242 (10)	0.0190 (10)	−0.0087 (8)	−0.0106 (9)
OW1	0.122 (3)	0.0689 (17)	0.0486 (16)	0.0195 (17)	−0.0109 (16)	0.0000 (13)
O2	0.0290 (9)	0.0515 (11)	0.0236 (9)	0.0050 (8)	−0.0064 (7)	−0.0084 (8)
O3	0.0407 (10)	0.0397 (10)	0.0193 (9)	0.0100 (8)	−0.0059 (7)	−0.0051 (7)
O4	0.0489 (12)	0.0417 (11)	0.0405 (12)	−0.0045 (9)	0.0045 (9)	−0.0119 (8)
O5	0.0855 (19)	0.0603 (15)	0.0650 (17)	0.0255 (14)	−0.0361 (14)	−0.0108 (12)
O6	0.115 (3)	0.0683 (19)	0.106 (3)	0.0507 (19)	−0.027 (2)	−0.0308 (18)
O7	0.152 (3)	0.0554 (15)	0.073 (2)	0.0280 (18)	0.021 (2)	−0.0228 (14)
N1	0.0332 (11)	0.0370 (11)	0.0207 (10)	−0.0053 (9)	−0.0077 (8)	0.0009 (8)
N2	0.0263 (10)	0.0451 (12)	0.0178 (10)	0.0021 (9)	−0.0045 (8)	−0.0056 (8)
N3	0.0305 (11)	0.0366 (11)	0.0204 (10)	0.0057 (9)	−0.0021 (8)	−0.0045 (8)
C1	0.0260 (12)	0.0396 (13)	0.0200 (12)	0.0012 (10)	−0.0056 (10)	−0.0004 (9)
C2	0.0255 (12)	0.0378 (13)	0.0177 (11)	0.0011 (10)	−0.0032 (9)	−0.0009 (9)
C3	0.0263 (12)	0.0325 (12)	0.0171 (11)	−0.0031 (10)	−0.0023 (9)	0.0015 (9)
C4	0.0241 (11)	0.0351 (12)	0.0171 (11)	−0.0007 (10)	−0.0019 (9)	0.0005 (9)
C5	0.0282 (12)	0.0336 (12)	0.0226 (12)	0.0043 (11)	−0.0015 (9)	−0.0034 (10)
C6	0.0242 (11)	0.0358 (13)	0.0242 (12)	0.0051 (10)	−0.0011 (9)	0.0029 (9)
C7	0.0247 (12)	0.0385 (13)	0.0176 (11)	−0.0020 (10)	−0.0041 (9)	0.0016 (9)
C8	0.0295 (12)	0.0390 (13)	0.0192 (12)	0.0026 (11)	−0.0019 (10)	−0.0051 (9)
C9	0.0254 (11)	0.0316 (12)	0.0193 (11)	0.0011 (10)	−0.0018 (9)	0.0000 (9)
C10	0.0268 (12)	0.0401 (13)	0.0253 (13)	0.0049 (11)	−0.0040 (10)	0.0004 (10)
C11	0.0410 (15)	0.0462 (16)	0.0326 (15)	0.0093 (13)	0.0010 (12)	−0.0077 (12)
C12	0.068 (2)	0.0489 (18)	0.052 (2)	0.0073 (17)	−0.0037 (17)	−0.0163 (15)
C13	0.073 (2)	0.0552 (19)	0.050 (2)	0.0284 (18)	−0.0030 (18)	−0.0135 (15)
C14	0.0240 (12)	0.0563 (17)	0.0253 (13)	−0.0002 (11)	−0.0023 (10)	−0.0054 (11)
C15	0.0285 (13)	0.0539 (17)	0.0298 (14)	0.0020 (12)	−0.0053 (11)	−0.0067 (12)
C16	0.0343 (14)	0.0467 (15)	0.0211 (13)	−0.0018 (12)	−0.0011 (11)	−0.0045 (10)
C17	0.0279 (12)	0.0505 (15)	0.0235 (13)	0.0024 (11)	−0.0050 (10)	−0.0080 (11)
C18	0.0369 (14)	0.0368 (14)	0.0389 (16)	−0.0007 (12)	0.0046 (12)	−0.0013 (11)
C19	0.0358 (14)	0.0326 (13)	0.0288 (13)	−0.0023 (11)	0.0075 (11)	−0.0012 (10)
C20	0.0406 (15)	0.0419 (15)	0.0373 (16)	0.0048 (12)	0.0062 (12)	0.0008 (12)
C21	0.0460 (18)	0.063 (2)	0.0484 (19)	0.0104 (16)	0.0003 (15)	0.0069 (15)
C22	0.056 (2)	0.083 (3)	0.0423 (19)	−0.0044 (19)	−0.0149 (16)	−0.0008 (17)
C23	0.066 (2)	0.058 (2)	0.046 (2)	−0.0099 (17)	0.0002 (17)	−0.0156 (15)
C24	0.0456 (16)	0.0369 (14)	0.0355 (15)	−0.0026 (13)	0.0052 (13)	−0.0046 (11)
C25	0.078 (3)	0.0341 (16)	0.058 (2)	0.0072 (16)	0.0164 (19)	−0.0045 (14)

Mn1—O2	2.1219 (18)	C6—C7	1.408 (3)
Mn1—O2i	2.1219 (18)	C7—C8	1.394 (3)
Mn1—O3	2.1552 (17)	C8—C9	1.408 (3)
Mn1—O3i	2.1552 (17)	C8—H8A	0.9300
Mn1—O4	2.1971 (19)	C10—H10A	0.9300
Mn1—O4i	2.1971 (19)	C11—C12	1.478 (4)
F1—C6	1.365 (3)	C11—C13	1.488 (4)
O1—C1	1.247 (3)	C11—H11A	0.9800
OW1—HW1A	0.84 (3)	C12—C13	1.491 (5)
OW1—HW1B	0.84 (3)	C12—H12A	0.9700
O2—C1	1.259 (3)	C12—H12B	0.9700
O3—C3	1.263 (3)	C13—H13A	0.9700
O4—C18	1.234 (3)	C13—H13B	0.9700
O5—C18	1.264 (4)	C14—C15	1.510 (4)
O6—C25	1.268 (5)	C14—H14A	0.9700
O6—H6	0.85 (4)	C14—H14B	0.9700
O7—C25	1.210 (4)	C15—H15A	0.9700
N1—C15	1.480 (3)	C15—H15B	0.9700
N1—C16	1.485 (3)	C16—C17	1.513 (3)
N1—H1A	0.9000	C16—H16A	0.9700
N1—H1B	0.9000	C16—H16B	0.9700
N2—C7	1.396 (3)	C17—H17A	0.9700
N2—C17	1.466 (3)	C17—H17B	0.9700
N2—C14	1.475 (3)	C18—C19	1.514 (4)
N3—C10	1.346 (3)	C19—C20	1.395 (4)
N3—C9	1.402 (3)	C19—C24	1.413 (4)
N3—C11	1.460 (3)	C20—C21	1.369 (4)
C1—C2	1.511 (3)	C20—H20A	0.9300
C2—C10	1.360 (3)	C21—C22	1.376 (5)
C2—C3	1.433 (3)	C21—H21A	0.9300
C3—C4	1.455 (3)	C22—C23	1.375 (5)
C4—C9	1.392 (3)	C22—H22A	0.9300
C4—C5	1.405 (3)	C23—C24	1.402 (4)
C5—C6	1.349 (3)	C23—H23A	0.9300
C5—H5A	0.9300	C24—C25	1.508 (4)
O2—Mn1—O2i	180.00 (9)	C12—C11—C13	60.4 (2)
O2—Mn1—O3	82.19 (7)	N3—C11—H11A	115.1
O2i—Mn1—O3	97.81 (7)	C12—C11—H11A	115.1
O2—Mn1—O3i	97.81 (7)	C13—C11—H11A	115.1
O2i—Mn1—O3i	82.19 (7)	C11—C12—C13	60.2 (2)
O3—Mn1—O3i	180.0	C11—C12—H12A	117.8
O2—Mn1—O4	88.72 (8)	C13—C12—H12A	117.8
O2i—Mn1—O4	91.28 (8)	C11—C12—H12B	117.8
O3—Mn1—O4	91.37 (7)	C13—C12—H12B	117.8
O3i—Mn1—O4	88.63 (7)	H12A—C12—H12B	114.9
O2—Mn1—O4i	91.28 (8)	C11—C13—C12	59.5 (2)
O2i—Mn1—O4i	88.72 (8)	C11—C13—H13A	117.8
O3—Mn1—O4i	88.63 (7)	C12—C13—H13A	117.8
O3i—Mn1—O4i	91.37 (7)	C11—C13—H13B	117.8
O4—Mn1—O4i	180.0	C12—C13—H13B	117.8
HW1A—OW1—HW1B	109.7 (18)	H13A—C13—H13B	115.0
C1—O2—Mn1	131.15 (16)	N2—C14—C15	109.5 (2)
C3—O3—Mn1	124.73 (15)	N2—C14—H14A	109.8
C18—O4—Mn1	143.4 (2)	C15—C14—H14A	109.8
C25—O6—H6	113 (4)	N2—C14—H14B	109.8
C15—N1—C16	110.5 (2)	C15—C14—H14B	109.8
C15—N1—H1A	109.6	H14A—C14—H14B	108.2
C16—N1—H1A	109.6	N1—C15—C14	108.8 (2)
C15—N1—H1B	109.6	N1—C15—H15A	109.9
C16—N1—H1B	109.6	C14—C15—H15A	109.9
H1A—N1—H1B	108.1	N1—C15—H15B	109.9
C7—N2—C17	116.8 (2)	C14—C15—H15B	109.9
C7—N2—C14	116.2 (2)	H15A—C15—H15B	108.3
C17—N2—C14	110.8 (2)	N1—C16—C17	111.6 (2)
C10—N3—C9	118.7 (2)	N1—C16—H16A	109.3
C10—N3—C11	120.4 (2)	C17—C16—H16A	109.3
C9—N3—C11	120.1 (2)	N1—C16—H16B	109.3
O1—C1—O2	123.1 (2)	C17—C16—H16B	109.3
O1—C1—C2	116.9 (2)	H16A—C16—H16B	108.0
O2—C1—C2	120.0 (2)	N2—C17—C16	110.2 (2)
C10—C2—C3	119.2 (2)	N2—C17—H17A	109.6
C10—C2—C1	117.3 (2)	C16—C17—H17A	109.6
C3—C2—C1	123.5 (2)	N2—C17—H17B	109.6
O3—C3—C2	125.5 (2)	C16—C17—H17B	109.6
O3—C3—C4	119.4 (2)	H17A—C17—H17B	108.1
C2—C3—C4	115.2 (2)	O4—C18—O5	121.3 (3)
C9—C4—C5	118.2 (2)	O4—C18—C19	118.4 (2)
C9—C4—C3	122.3 (2)	O5—C18—C19	120.3 (2)
C5—C4—C3	119.4 (2)	C20—C19—C24	118.1 (3)
C6—C5—C4	119.9 (2)	C20—C19—C18	114.3 (2)
C6—C5—H5A	120.0	C24—C19—C18	127.6 (2)
C4—C5—H5A	120.0	C21—C20—C19	122.5 (3)
C5—C6—F1	117.4 (2)	C21—C20—H20A	118.7
C5—C6—C7	123.8 (2)	C19—C20—H20A	118.7
F1—C6—C7	118.8 (2)	C20—C21—C22	119.7 (3)
C8—C7—N2	123.0 (2)	C20—C21—H21A	120.2
C8—C7—C6	116.3 (2)	C22—C21—H21A	120.2
N2—C7—C6	120.7 (2)	C23—C22—C21	119.4 (3)
C7—C8—C9	120.7 (2)	C23—C22—H22A	120.3
C7—C8—H8A	119.7	C21—C22—H22A	120.3
C9—C8—H8A	119.7	C22—C23—C24	122.2 (3)
C4—C9—N3	118.7 (2)	C22—C23—H23A	118.9
C4—C9—C8	120.8 (2)	C24—C23—H23A	118.9
N3—C9—C8	120.4 (2)	C23—C24—C19	118.0 (3)
N3—C10—C2	125.6 (2)	C23—C24—C25	113.7 (3)
N3—C10—H10A	117.2	C19—C24—C25	128.3 (3)
C2—C10—H10A	117.2	O7—C25—O6	120.4 (4)
N3—C11—C12	121.0 (3)	O7—C25—C24	118.3 (4)
N3—C11—C13	119.2 (3)	O6—C25—C24	121.3 (3)
O2i—Mn1—O2—C1	−97 (100)	C5—C4—C9—C8	4.6 (4)
O3—Mn1—O2—C1	31.5 (2)	C3—C4—C9—C8	−176.3 (2)
O3i—Mn1—O2—C1	−148.5 (2)	C10—N3—C9—C4	1.5 (3)
O4—Mn1—O2—C1	−60.0 (2)	C11—N3—C9—C4	171.6 (2)
O4i—Mn1—O2—C1	120.0 (2)	C10—N3—C9—C8	−178.7 (2)
O2—Mn1—O3—C3	−36.48 (19)	C11—N3—C9—C8	−8.6 (4)
O2i—Mn1—O3—C3	143.52 (19)	C7—C8—C9—C4	−2.5 (4)
O3i—Mn1—O3—C3	−147 (100)	C7—C8—C9—N3	177.7 (2)
O4—Mn1—O3—C3	52.0 (2)	C9—N3—C10—C2	−4.1 (4)
O4i—Mn1—O3—C3	−128.0 (2)	C11—N3—C10—C2	−174.2 (3)
O2—Mn1—O4—C18	39.5 (3)	C3—C2—C10—N3	1.5 (4)
O2i—Mn1—O4—C18	−140.5 (3)	C1—C2—C10—N3	179.1 (2)
O3—Mn1—O4—C18	−42.7 (3)	C10—N3—C11—C12	−114.2 (3)
O3i—Mn1—O4—C18	137.3 (3)	C9—N3—C11—C12	75.8 (3)
O4i—Mn1—O4—C18	−161 (100)	C10—N3—C11—C13	−43.1 (4)
Mn1—O2—C1—O1	167.0 (2)	C9—N3—C11—C13	146.9 (3)
Mn1—O2—C1—C2	−14.3 (4)	N3—C11—C12—C13	108.3 (3)
O1—C1—C2—C10	−12.1 (4)	N3—C11—C13—C12	−111.2 (3)
O2—C1—C2—C10	169.1 (2)	C7—N2—C14—C15	−162.5 (2)
O1—C1—C2—C3	165.3 (2)	C17—N2—C14—C15	61.0 (3)
O2—C1—C2—C3	−13.4 (4)	C16—N1—C15—C14	58.7 (3)
Mn1—O3—C3—C2	26.7 (3)	N2—C14—C15—N1	−61.2 (3)
Mn1—O3—C3—C4	−153.29 (17)	C15—N1—C16—C17	−55.8 (3)
C10—C2—C3—O3	−176.6 (2)	C7—N2—C17—C16	167.0 (2)
C1—C2—C3—O3	5.9 (4)	C14—N2—C17—C16	−56.8 (3)
C10—C2—C3—C4	3.4 (3)	N1—C16—C17—N2	54.2 (3)
C1—C2—C3—C4	−174.0 (2)	Mn1—O4—C18—O5	−95.6 (4)
O3—C3—C4—C9	174.2 (2)	Mn1—O4—C18—C19	85.7 (4)
C2—C3—C4—C9	−5.8 (3)	O4—C18—C19—C20	10.4 (4)
O3—C3—C4—C5	−6.8 (3)	O5—C18—C19—C20	−168.3 (3)
C2—C3—C4—C5	173.2 (2)	O4—C18—C19—C24	−170.2 (3)
C9—C4—C5—C6	−1.9 (4)	O5—C18—C19—C24	11.1 (5)
C3—C4—C5—C6	179.0 (2)	C24—C19—C20—C21	−0.1 (4)
C4—C5—C6—F1	174.8 (2)	C18—C19—C20—C21	179.4 (3)
C4—C5—C6—C7	−3.2 (4)	C19—C20—C21—C22	1.2 (5)
C17—N2—C7—C8	3.5 (4)	C20—C21—C22—C23	−0.8 (5)
C14—N2—C7—C8	−130.4 (3)	C21—C22—C23—C24	−0.8 (6)
C17—N2—C7—C6	−173.9 (2)	C22—C23—C24—C19	1.9 (5)
C14—N2—C7—C6	52.3 (3)	C22—C23—C24—C25	−178.4 (3)
C5—C6—C7—C8	5.3 (4)	C20—C19—C24—C23	−1.4 (4)
F1—C6—C7—C8	−172.7 (2)	C18—C19—C24—C23	179.2 (3)
C5—C6—C7—N2	−177.2 (2)	C20—C19—C24—C25	178.9 (3)
F1—C6—C7—N2	4.8 (4)	C18—C19—C24—C25	−0.5 (5)
N2—C7—C8—C9	−179.8 (2)	C23—C24—C25—O7	−8.7 (5)
C6—C7—C8—C9	−2.4 (4)	C19—C24—C25—O7	171.0 (3)
C5—C4—C9—N3	−175.6 (2)	C23—C24—C25—O6	171.3 (4)
C3—C4—C9—N3	3.5 (4)	C19—C24—C25—O6	−9.0 (6)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1B···O5	0.84 (3)	2.43 (3)	3.108 (4)	139 (4)
N1—H1A···O7ii	0.90	1.82	2.717 (3)	174.
N1—H1B···O1iii	0.90	1.79	2.688 (3)	173.
N1—H1B···O2iii	0.90	2.60	3.246 (3)	130.
OW1—HW1A···O3i	0.84 (3)	2.12 (1)	2.937 (3)	164 (4)
O6—H6···O5	0.85 (4)	1.53 (4)	2.379 (4)	175 (8)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—HW1B⋯O5	0.84 (3)	2.43 (3)	3.108 (4)	139 (4)
N1—H1A⋯O7i	0.90	1.82	2.717 (3)	174
N1—H1B⋯O1ii	0.90	1.79	2.688 (3)	173
N1—H1B⋯O2ii	0.90	2.60	3.246 (3)	130
OW1—HW1A⋯O3iii	0.84 (3)	2.12 (1)	2.937 (3)	164 (4)
O6—H6⋯O5	0.85 (4)	1.53 (4)	2.379 (4)	175 (8)

Symmetry codes: (i) ; (ii) ; (iii) .