Synthesis, Characterization And Electrolytic Behavior Of Cadmium(II) Complexes Of 5,7,7,12,14,14- Hexamethyl-1,4,8,11-Tetraazacyclotetradeca-4,11- Diene And Isomers Of Its Saturated Analogue

Condensation of ethylendiamine with acetone in the presence of quantitative amount of perchloric acid, yielded the ligand 5,7,7,12,14,14- hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene dihydroperchlorate (denoted by L.2HClO4). The ligand L.2HClO4 on reduction with NaBH4, yielded an isomeric mixture of saturated macrocycles, the Me6[14]anes, which were resolved into two distinct C-chiral isomers (denoted by ‘tet-a’ and ‘tet-b’). Interaction of ligands L.2HClO4, ‘tet-a’ and ‘tet-b’ with salts CdI2, Cd(NO3)2.4H2O, CdCl2.2H2O and Cd(ClO4)2.6H2O produced different five coordinated square pyramidal and six coordinated octahedral cdmium(II) complexes. Among them the complexes, cis-[Cd(teta)( NO3)](NO3) and cis-[Cd(tet-b)(NO3)](NO3) underwent axial ligand substitution reaction with KCNS; whereas complex [Cd(tet-a)I2] underwent axial ligand substitution reaction and complex [CdLI](ClO4) underwent simultaneous ligand substitution and addition reaction with NaNO2. Characterization of all the complexes were carried out on the basis of elemental analysis; FT-IR, UV-Vis. and 1H-NMR spectroscopy; melting point determination as well as by magnetic moment and conductivity measurements. Molar conductivity measurment of the complexes reavealed that they show different electrolytic behavior in different solvents

Two solvatomorphic forms of a copper complex formulated as Cu(L1)(ClO4)2- 1.2H2O and Cu(L1)(ClO4)2, where L1 is 3,10-C-meso-3,5,7,7,10,12,14,14- octamethyl-1,4,8,11-tetraazacyclo- tetradecane

Two copper complex solvatomorphs, namely (3,10-C-meso- 3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane) bis(perchlorato-O)copper(II) 1.2-hydrate, [Cu(ClO4)2 (C18H40N4)]1.2H2O, (I), and (3,10-C-meso-3,5,7,7,10,12,14,14 octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato O)copper(II), [Cu(ClO4)2(C18H40N4)], (II), are described and compared with each other and with a third, already reported, anhydrous diastereomer, denoted (III). Both compounds present very similar centrosymmetic coordination environments, with the CuII cation lying on an inversion centre in a distorted 4+2 octahedral environment, defined by the macrocyclic N4 group in the equatorial sites and two perchlorate groups in trans-axial positions [one of the perchlorate ligands in (I) is partially disordered]. The most significant difference in molecular shape is seen in the orientation of the perchlorate anions, and the influence of this on the intramolecular hydrogen bonding is discussed. The (partially) hydrated state of (I) favours the formation of chains along [011], while the anhydrous character of (II) and (III) promotes loosely bound structures with low packing indices.Fil: Nath, Babul Chandra. University Of Chittagong; BangladeshFil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Roy, Tapashi G.. University of Chittagong; BangladeshFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentin

Three transition-metal complexes with the macrocyclic ligand meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L): [Cu(ClO4)2(L)], [Zn(NO3)2(L)] and [CuCl(L)(H2O)]Cl

The three transition-metal complexes, (meso-5,7,7,12,14,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane-4N)bis(perchlorato- O)copper(II), [Cu(ClO4)2(C18H40N4)], (I), (meso- 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane- 4N)bis(nitrato-O)zinc(II), [Zn(NO3)2(C18H40N4)], (II), and aquachlorido(meso-5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane-4N)copper(II) chloride, [CuCl- (C18H40N4)(H2O)]Cl, (III), are described. The molecules display a very similarly distorted 4+2 octahedral environment for the cation [located at an inversion centre in (I) and (II)], defined by the macrocycle N4 group in the equatorial sites and two further ligands in trans-axial positions [two O? ClO3 ligands in (I), two O?NO2 ligands in (II) and one chloride and one aqua ligand in (III)]. The most significant difference in molecular shape resides in these axial ligands, the effect of which on the intra- and intermolecular hydrogen bonding is discussed. In the case of (I), all strong hydrogenbond donors are saturated in intramolecular interactions, while weak intermolecular C?H O contacts result in a three-dimensional network. In (II) and (III), instead, there are N?H and O?H donors left over for intermolecular interactions, giving rise to the formation of strongly linked but weakly interacting chains.Fil: Yasmin, Sabina. University of Chittagong; BangladeshFil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Roy, Tapashi G.. University of Chittagong; BangladeshFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentin

Zinc(II) complexes of 3,10-C-meso-2,5,5,7,9,12,12,14- octamethyl-1,8-diaza-4,11-diazoniacyclotetradecane as its bis(acetate) trihydrate, [LBH2][CH3COO]2.3H2O: Synthesis, Characterization and antimicrobial studies

One isomeric ligand, LB among three isomers (LA, LB and LC) of 2,9- C-meso-2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecanes, differing in the orientation of methyl groups on the chiral carbon atoms) on interaction with vinyl acetate produces 2,9-C-meso-2,5,5,7,9,12,12,14- octamethyl-1,8-diaza-4,11-diazoniacyclotetradecane as its bis(acetate) trihydrate, [LBH2][OOCCH3]2.3H2O. This ligand salt trihydrate reacts with Zn(CH3COO)2.2H2O to produce square pyramidal monoacetatozinc(II) acetate complex [ZnLB(CH3COO)](CH3COO), which undergoes anion exchange reaction with NaClO4.6H2O to produce monoacetatozinc(II) perchlorate complex, [ZnLB(CH3COO)](ClO4). The complex, [ZnLB(CH3COO)](ClO4) undergoes axial substitution reactions with KSCN, NaNO2 and KNO3 to form the substitution products, [ZnLB(NCS)](NCS), [ZnLB(NO2)](ClO4) and [ZnLB(NO3)](ClO4) respectively where CH3COOis replaced by NCS- , NO3 - and NO2 - . All these complexes have been characterized on the basis of analytical, spectroscopic, conductometric and magnetochemical data. The antifungal and antibacterial activities of these compounds have been studied against some phytopathogenic fungi and bacteria

(Acetato-κO)(2,5,5,7,9,12,12,14-octa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4 N,N′,N′′,N′′′)zinc perchlorate

The ZnII atom in the cation of the title salt, [Zn(C2H3O2)(C18H40N4)]ClO4, is five-coordinated by the four N atoms of the macrocycle and the O atom of the monodentate acetate ligand. The N4O donor set is based on a trigonal bipyramid with two N atoms occupying axial positions [N—Zn—N = 170.89 (16)°]. The perchlorate anions are associated with the cations via N—H⋯O hydrogen bonds; intra­molecular N—H⋯O(acetate) inter­actions are also observed. The neutral aggregates are connected into an helical chain along the b axis via N—H⋯O(acetate) hydrogen bonds. The perchlorate anion was found to be disordered about a pseudo-threefold axis: the major component of the disorder had a site occupancy factor of 0.692 (11)

Synthesis, Characterisation and Antifungal Activities of Some New Copper(II) Complexes of Isomeric 3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11-Tetraazacyclotetradecanes

Three isomeric Me8[14]anes, LA, LB and LC, undergo complexation with copper(II) salts to form a series of [CuLXn(H2O)x]Xy.(H2O)z complexes where L = LA, LB and LC; X = Cl, Br, NO3; n, x, y and z may have values of 0, 1 or 2. The complexes have been characterised on the basis of analytical, spectroscopic, magnetic and conductance data. Further, the X-ray crystal structure of one complex, [CuLB(OH2)2](NO3)2, has been determined. The antifungal activity of all three isomeric ligands and their complexes has been investigated against a range of phytopathogenic fungi

Dichlorido[(4E,11E)-5,7,12,14-tetra­benzyl-7,14-dimethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene]cobalt(III) perchlorate

The CoIII atom in the title complex, [CoCl2(C40H48N4)]ClO4, is octa­hedrally coordinated within a trans-Cl2N4 donor set provided by the tetra­dentate macrocylic ligand and two chloride ions. The N—H atoms, which are orientated to one side of the N4 plane, form hydrogen bonds with chloride ions and perchlorate-O atoms. These along with C—H⋯O inter­actions consolidate the three-dimensional crystal structure. One of the benzene rings was disordered. This was resolved over two positions with the major component of the disorder having a site-occupancy factor of 0.672 (4)

3,10-C-meso-3,5,7,7,10,12,14,14-Octa­methyl-4,11-diaza-1,8-diazo­niacyclo­tetra­decane bis­(perchlorate)

The structure determination of the title salt, C18H42N4 2+·2ClO4 −, reveals that protonation has occurred at diagonally opposite amine N atoms. Intra­molecular N—H⋯N hydrogen bonds stabilize the conformation of the dication. In the crystal, the dications are bridged by perchlorate ions via N—H⋯O hydrogen bonds into supra­molecular chains propagating along the c axis and weak C—H⋯O inter­actions cross-link the chains

5,7,7,12,14,14-Hexamethyl-4,11-diaza-1,8-diazo­niacyclo­tetra­decane bis­(perchlorate) monohydrate

In the title hydrated salt, C16H38N4 2+·2ClO4 −·H2O, the dication is protonated at the diagonally opposite N atoms proximate to the –C(CH3)2– groups. Within the cavity, there are two ammonium–amine N—H⋯N hydrogen bonds. Supra­molecular layers are formed in the crystal packing whereby the water mol­ecule links two perchlorate anions, and the resultant aggregates are connected to the dications via N—H⋯O hydrogen bonds. Layers, with an undulating topology, stack along the a axis being connected by C—H⋯O inter­actions

trans-(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene-κ4 N,N′,N′′,N′′′)bis­(nitrito-κN)cobalt(III) perchlorate hemihydrate

The asymmetric unit of the title CoIII complex, [Co(NO2)2(C16H32N4)]ClO4·0.5H2O, comprises two complex cations, two perchlorate anions and a water mol­ecule of crystallization. The CoIII atoms exist within distorted octa­hedral N6 geometries defined by four N atoms of the macrocycle ligand and trans-N atoms derived from the nitrite anions. Systematic variations in the Co—N bond lengths are correlated with the presence of intra­molecular N—H⋯O(nitrite) hydrogen bonds. In the crystal, water-O—H⋯O(perchlorate) hydrogen bonds, involving one of the independent perchlorate anions only, lead to supra­molecular chains along the b-axis direction. The three-dimensional architecture is consolidated by numerous C—H⋯O inter­actions. The crystal studied was a non-merohedral, racemic twin