Bis(2-carboxybenzo­ato-κO1)bis­[1-cyclo­propyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydro­quinoline-3-carboxyl­ato-κ2O3,O4]manganese(II) dihydrate

Zhang, G.-J.; He, J.-H.; Yan, S.-W.; Sun, D.-Z.; Chen, H.-Y.

doi:10.1107/S1600536811011615

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages m538-m539

doi:10.1107/S1600536811011615

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Bis(2-carboxybenzoato-κO¹)bis[1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydroquinoline-3-carboxylato-κ²O³,O⁴]manganese(II) dihydrate

Guang-Ju Zhang,^a ^* Jiang-Hong He,^a Shi-Wei Yan,^a Dian-Zhen Sun ^a and Hai-Yan Chen ^a

^aCollege of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, People's Republic of China
^*Correspondence e-mail: guaiguaijuzi@yahoo.com.cn

(Received 20 January 2011; accepted 29 March 2011; online 7 April 2011)

The title compound, [Mn(C₁₇H₁₈FN₃O₃)₂(C₈H₅O₄)₂]·2H₂O or [Mn(cfH)₂(1,2-Hbdc)₂]·2H₂O (cfH = ciprofloxacin = 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid, 1,2-bdc = benzene-1,2-dicarboxylate), has been prepared under hydrothermal conditions. The Mn²⁺ atom, located on an inversion centre, exhibits a distorted octahedral 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 molecules 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 interactions of cfH groups [centroid–centroid distance of 3.657 (2) Å] into the final three-dimensional supramolecular 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_r = 1083.90
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.051
wR(F²) = 0.145
S = 1.00
5494 reflections
350 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z+1; (iii) -x, -y, -z+1.

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.

Supporting information

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

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

checkCIF report

Comment top

Ciprofloxacin [cfH = 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid] belongs to the quinolone family of synthetic antibiotics (Turel, 2002; Xiao et al., 2005) and is a third generation quinolone antibacterial drug with broad-spectrum antibacterial activity (especially aerobic gram-negative bacilli high antibacterial activity). The mechanisms of action of the quinolone antibacterial agents are either their inhibition of DNA gyrase (Topoisomerase II), an essential bacterial enzyme that maintains superhelical twists in DNA, or their interaction with the DNA molecule via a metal complex intermediate (Chulvi et al., 1991; Ruiz et al., 1993; Wallis et al., 1995).

The Ciprofloxacin and its deprotonated anions can show a number of different coordinating or bridging modes. The title complex consists of a Mn²⁺ atom lying on an inversion center, two Ciprofloxacin ligands, two 1,2-benzenedicarboxylate ligands (1,2-bdc) and a water molecule (Fig. 1). The Ciprofloxacin ligand acts as chelating bidentate and the Mn(II) atom is coordinated by four oxygen atoms from two different Ciprofloxacin ligands and two oxygen atoms from two 1,2-bdc ligands. The N—H···O and OW—H···O hydrogen bonds link the discrete molecules into two-dimensional arrays (Table 1). These two-dimensional layers are further extended through off-set aromatic π—π stacking interplanar of cfH groups (centroid distance of 3.657 Å) into the final three-dimensional supramolecular arrays (Fig. 2).

Related literature top

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); Dukhande et al. (2006); Ruiz et al. (1993); Wallis et al. (1995). For related structures, see: Fabbiani & Dittrich (2008); Wang et al. (2009).

Experimental top

A mixture of Mn(OAc)₂.4H₂O (0.5 mmol), ciprofloxacin hydrochloride (0.25 mmol), 1,2-KHbdc (0.5 mmol), and water (7 ml) was stirred for 30 min in air (solution pH = 4.0), then transferred and sealed in an 18 ml Teflon-lined autoclave, which was heated at 110 °C for 96 h. After slow cooling to room temperature, yellow block crystals were filtered off, washed with distilled water, and dried at ambient temperature.

Computing details top

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

Figures top

	Fig. 1. ORTEP drawing of 1 with thermal ellipsoids at 30% probability. Symmetry code (i): -x, -y, -z+1.
	Fig. 2. Perspective view of the three-dimensional supramolecular network in 1. The hydrogen bonds are indicated by pink dotted lines while the aromatic π—π stacking interaction is indicated by a green dotted line.

Bis(2-carboxybenzoato-κO¹)bis[1-cyclopropyl-6-fluoro-4-oxo- 7-(piperazin-4-ium-1-yl)-1,4-dihydroquinoline-3-carboxylato- κ²O³,O⁴]manganese(II) dihydrate top

Crystal data top

[Mn(C₁₇H₁₈FN₃O₃)₂(C₈H₅O₄)₂]·2H₂O	F(000) = 1126
M_r = 1083.90	D_x = 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

Data collection top

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

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	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(F_o²) + (0.080P)²] where P = (F_o² + 2F_c²)/3
5494 reflections	(Δ/σ)_max < 0.001
350 parameters	Δρ_max = 0.45 e Å⁻³
10 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Mn(C₁₇H₁₈FN₃O₃)₂(C₈H₅O₄)₂]·2H₂O	V = 2409.9 (8) Å³
M_r = 1083.90	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.4510 (19) Å	µ = 0.36 mm⁻¹
b = 22.042 (4) Å	T = 293 K
c = 11.695 (2) Å	0.58 × 0.47 × 0.32 mm
β = 98.44 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	5494 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3555 reflections with I > 2σ(I)
T_min = 0.817, T_max = 0.893	R_int = 0.068
22913 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	10 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.45 e Å⁻³
5494 reflections	Δρ_min = −0.36 e Å⁻³
350 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

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)

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

Experimental details

Crystal data
Chemical formula	[Mn(C₁₇H₁₈FN₃O₃)₂(C₈H₅O₄)₂]·2H₂O
M_r	1083.90
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.4510 (19), 22.042 (4), 11.695 (2)
β (°)	98.44 (3)
V (Å³)	2409.9 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.58 × 0.47 × 0.32

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.817, 0.893
No. of measured, independent and observed [I > 2σ(I)] reflections	22913, 5494, 3555
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.145, 1.00
No. of reflections	5494
No. of parameters	350
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.36

Computer programs: RAPID-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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)	174.4
N1—H1B···O1ⁱⁱ	0.90	1.79	2.688 (3)	172.6
N1—H1B···O2ⁱⁱ	0.90	2.60	3.246 (3)	129.7
OW1—HW1A···O3ⁱⁱⁱ	0.84 (3)	2.122 (14)	2.937 (3)	164 (4)
O6—H6···O5	0.85 (4)	1.53 (4)	2.379 (4)	175 (8)

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

Acknowledgements

This work was supported by the Science and Technology Foundation of Southwest University (SWUB2007035).

References

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