Bis(2-carboxybenzo­ato-κO 1)bis­[1-cyclo­propyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydro­quinoline-3-carboxyl­ato-κ2 O 3,O 4]manganese(II) dihydrate

Guang-Ju Zhang; Jiang-Hong He; Shi-Wei Yan; Dian-Zhen Sun; Hai-Yan Chen

doi:10.1107/S1600536811011615

. 2011 Apr 7;67(Pt 5):m538–m539. doi: 10.1107/S1600536811011615

Bis(2-carboxybenzoato-κO ¹)bis[1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-4-ium-1-yl)-1,4-dihydroquinoline-3-carboxylato-κ² O ³,O ⁴]manganese(II) dihydrate

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

PMCID: PMC3089319 PMID: 21754278

Abstract

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,
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
Δρ_max = 0.45 e Å⁻³
Δρ_min = −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.

Supplementary Material

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

e-67-0m538-sup1.cif^{(26.7KB, cif)}

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

e-67-0m538-Isup2.hkl^{(274.4KB, hkl)}

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

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)

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.