Fluorinated metal-organic frameworks of 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetrafluorobenzene: synergistic interactions of ligand isomerism and counteranions.

A fluorinated bis(triazole) ligand, 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetrafluorobenzene (Fbtz), was applied to coordinate with a series of Mn(II), Co(II), Fe(II), and Cu(II) ions, respectively. In comparison with its nonfluorinated analogue 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (btx), Fbtz is able to build six novel metal-organic frameworks by acting as a versatile bridge combining with the terminal chlorides (1-5) or acetates (6) ligands. The solid-state crystal structures of 1-6 are studied by single-crystal X-ray crystallography to form the following structures: 3D polymers [M(Fbtz)2Cl2]n (1: M = Mn, 2: M = Co), 1D double chain polymers {[M(Fbtz)2Cl2]·CH2Cl2·xH2O}n (3: M = Co, x = 1; 4: M = Fe, x = 2), {[Cu(Fbtz)2Cl2]·4H2O}n (5), and a 1D double-stranded helical polymer {[Cu2(Fbtz)(OAc)2]·2H2O}n (6). Conformations of Fbtz in 1-6 can be tuned as a result of varying the anions or solvent system, which ultimately form a series of novel coordination frameworks with different supramolecular architectures. The antibacterial activities of all complexes are investigated. Complexes 4 and 5 show a wide range of bactericidal activities to Gram positive (B. subtilis and S. aureus) and negative (E. coli and P. fluorescence) bacterial strains. The synergistic interactions of ligand isomerism and counteranions have profound effects on the supramolecular networks and properties.

An ice-like water hexamer with 3 symmetry in the hydrogen-bonded structure of 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-ylmethyl)benzene dihydrate.

An ice-like hexameric water cluster, stabilized by the flexible bis-imidazolyl compound 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-ylmethyl)benzene (Fbix), is found in the trigonal R3 crystal structure of the title compound, C(14)H(10)F(4)N(4).2H(2)O or Fbix.2H(2)O. The Fbix molecule lies about an inversion centre with one water molecule in the asymmetric unit in a general position. A cyclic chair-like hexameric water cluster with 3 symmetry is generated with a hydrogen-bonded O...O distance within the hexamer of 2.786 (3) A. The Fbix molecule adopts a trans conformation, where the imidazole ring makes a dihedral angle of 70.24 (11) degrees with the central tetrafluorinated aromatic ring. Each water hexamer is connected by six Fbix molecules through intermolecular O-H...N hydrogen bonds [N...O = 2.868 (3) A] to yield a three-dimensional supramolecular network with primitive cubic (pcu) topology. Large voids in each single pcu network lead to fourfold interpenetrated aggregates of Fbix.2H(2)O.

1-{4-[(1H-1,2,4-Triazol-1-yl)meth-yl]benz-yl}-1H-1,2,4-triazol-4-ium perchlorate.

In the crystal structure of the title compound, C(12)H(13)N(6) (+)·ClO(4) (-), the cation, located about an inversion center, is monoprotonated, and one H atom is disordered over two sites on N atoms of the two triazole rings, each with an occupancy factor of 0.5. The perchlorate anion has C(2) symmetry, the Cl atom and one O atom lying on the twofold rotation axis; the anion is thus disordered over two sites of equal occupancy. In the cation, the triazole ring makes a dihedral angle of 84.75 (7)° with the plane of the benzene ring. In the crystal, inter-molecular N-H⋯N hydrogen bonding between the triazole and triazolium rings links the cations into a wave-like supra-molecular chain. Weak inter-molecular C-H⋯N and C-H⋯O hydrogen bonding is also present.

1,4-Bis(3-pyridylmethyl-eneamino-meth-yl)benzene.

The title compound, C(20)H(18)N(4), is a flexible 3,3'-bipyridyl-type ligand with a long spacer group between the two pyridyl functions. The mol-ecule crystallizes around an inversion center, with one half-mol-ecule in the asymmetric unit and a dihedral angle of 71.85 (8)° between the pyridine ring and the central benzene ring.