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-κ4N)bis(perchlorato-κO)copper(II), [Cu(ClO4)2(C18H40N4)], (I), (meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)bis(nitrato-κO)zinc(II), [Zn(NO3)2(C18H40N4)], (II), and aquachlorido(meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)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 hydrogen-bond 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.

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

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-κO)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-κO)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 Cu(II) 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.

cis-(Acetato-κ(2)O,O')(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κ(4)N,N',N'',N''')nickel(II) perchlorate monohydrate.

The complete cation in the title hydrated mol-ecular salt, [Ni(CH(3)CO(2))(C(16)H(36)N(4))]ClO(4)·H(2)O, is generated by the application of crystallographic twofold symmetry; the perchlorate anion and water mol-ecule are each disordered around a twofold axis. The Ni(II) atom exists within a cis-N(4)O(2) donor set based on a strongly distorted octa-hedron and defined by the four N atoms of the macrocyclic ligand and two O atoms of a symmetrically coordinating acetate ligand. In the crystal, hydrogen bonding (water-acetate/perchlorate O-H⋯O and amine-perchlorate N-H⋯O) leads to layers in the ab plane. The layers stack along the c axis, being connected by C-H⋯O(water) inter-actions. The crystal studied was found to be a non-merohedral twin; the minor component refined to 15.9 (6)%.

Benzyl 3-[(E)-(furan-2-yl)methyl-idene]-2-methyldithio-carbazate.

In the title compound, C(14)H(14)N(2)OS(2), the furan ring exhibits rotational disorder over two orientations, with an occupancy ratio of 0.508 (7):0.492 (7). The furan and phenyl rings form dihedral angles of 8.2 (6) (major occupancy component), 14.8 (6) (minor occupancy component) and 73.65 (9)°, respectively, with the central residue (C(4)N(2)S(2)), indicating a twisted conformation for the mol-ecule. The methyl group and the thione S atom are syn and the conformation about the imine bond is E. In the crystal, C-H⋯π inter-actions involving the phenyl ring are observed.

5,7,7,12,14,14-Hexamethyl-4,11-diaza-1,8-diazo-niacyclo-tetra-decane bis-(perchlorate) monohydrate.

In the title hydrated salt, C(16)H(38)N(4) (2+)·2ClO(4) (-)·H(2)O, the dication is protonated at the diagonally opposite N atoms proximate to the -C(CH(3))(2)- groups. Within the cavity, there are two ammonium-amine N-H⋯N hydrogen bonds. Supra-molecular layers are formed in the crystal packing whereby the water mol-ecule 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 inter-actions.

Benzyl 2-methyl-3-[(E)-(thio-phen-2-yl)methyl-idene]dithio-carbazate.

In the title compound, C(14)H(14)N(2)S(3), the thione S atom and methyl group are syn, as are the two thio-ether S atoms. The mol-ecule is twisted, the dihedral angles between the central (C(2)N(2)S(2)) residue and the pendent 2-thienyl and phenyl rings being 21.57 (6) and 77.54 (3)°, respectively. In the crystal, mol-ecules assemble into a three-dimensional architecture via C-H⋯π inter-actions, involving both the five- and six-membered rings as acceptors, as well as S⋯S inter-actions [3.3406 (5) Å] between centrosymmetrically related 2-thienyl rings.

cis-(Nitrato-κ(2)O,O')(2,5,5,7,9,12,12,14-octa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κ(4)N,N',N'',N''')cadmium nitrate hemihydrate.

The Cd(II) atom in the title complex, [Cd(NO(3))(C(18)H(40)N(4))]NO(3)·0.5H(2)O, is coordinated within a cis-N(4)O(2) donor set provided by the tetra-dentate macrocyclic ligand and two O atoms of a nitrate anion; the coordination geometry is distorted octa-hedral. The lattice water mol-ecule is located on a twofold rotation axis. N-H⋯O hydrogen bonds and weak C-H⋯O inter-actions link the complex cations into a supra-molecular layer in the bc plane. Layers are connected by O-H⋯O hydrogen bonds between the lattice water mol-ecule and the non-coordinating nitrate anion, as well as by weak C-H⋯O contacts.

(Acetato-κO)(2,5,5,7,9,12,12,14-octa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κN,N',N'',N''')zinc perchlorate.

The Zn(II) atom in the cation of the title salt, [Zn(C(2)H(3)O(2))(C(18)H(40)N(4))]ClO(4), is five-coordinated by the four N atoms of the macrocycle and the O atom of the monodentate acetate ligand. The N(4)O 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; intra-molecular N-H⋯O(acetate) inter-actions 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).

trans-(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene-κN,N',N'',N''')bis-(nitrito-κN)cobalt(III) perchlorate hemihydrate.

The asymmetric unit of the title Co(III) complex, [Co(NO(2))(2)(C(16)H(32)N(4))]ClO(4)·0.5H(2)O, comprises two complex cations, two perchlorate anions and a water mol-ecule of crystallization. The Co(III) atoms exist within distorted octa-hedral N(6) 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 intra-molecular 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 supra-molecular chains along the b-axis direction. The three-dimensional architecture is consolidated by numerous C-H⋯O inter-actions. The crystal studied was a non-merohedral, racemic twin.

Dichlorido[(4E,11E)-5,7,12,14-tetra-benzyl-7,14-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene]cobalt(III) perchlorate.

The Co(III) atom in the title complex, [CoCl(2)(C(40)H(48)N(4))]ClO(4), is octa-hedrally coordinated within a trans-Cl(2)N(4) donor set provided by the tetra-dentate macrocylic ligand and two chloride ions. The N-H atoms, which are orientated to one side of the N(4) plane, form hydrogen bonds with chloride ions and perchlorate-O atoms. These along with C-H⋯O inter-actions 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).

[(4E,11E)-5,7,12,14-Tetra-benzyl-7,14-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene]copper(II) bis(per-chlorate).

The complete cation in the title compound, [Cu(C(40)H(48)N(4))](ClO(4))(2), is generated by the operation of a crystallographic centre of inversion. The Cu(II) ion exists in a tetra-gonally distorted trans-N(4)O(2) coordination geometry defined by the four N atoms of the macrocyclic ligand and two weakly bound perchlorate-O atoms from two anions. The N-H atoms form intra-molecular N-H⋯O(perchlorate) hydrogen bonds. Disorder was resolved in the -CH(2)-NH- portion of the macrocycle with the major component having a site-occupancy factor of 0.570 (6).

3,10-C-meso-3,5,7,7,10,12,14,14-Octa-methyl-4,11-diaza-1,8-diazo-niacyclo-tetra-decane bis-(perchlorate).

The structure determination of the title salt, C(18)H(42)N(4) (2+)·2ClO(4) (-), reveals that protonation has occurred at diagonally opposite amine N atoms. Intra-molecular 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 supra-molecular chains propagating along the c axis and weak C-H⋯O inter-actions cross-link the chains.

Synthesis and antimicrobial activities of isomers of N(4),N(11)-dimethyl-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane and their nickel(II) complexes.

The reactions of two isomers of 3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (differing in the orientation of the methyl groups on the chiral carbon atoms), designated as L(B) and L(C), with CH(3)I in the ratio of 1:4 resulted in the substitution of the N(4) and N(11) protons by CH(3) groups, forming the dimethyl derivatives L(BZ) and L(CZ), respectively. These ligands, on interaction with nickel(II) acetate tetrahydrate and subsequent addition of lithium perchlorate, produce square-planar yellow [NiL(BZ)][ClO(4)](2) and orange [NiL(C'Z)][ClO(4)](2). These nickel complexes undergo axial ligand addition reactions with NCS(-), Cl(-), Br(-), and I(-) as X(-) to form six-coordinate trans-diisothiocyanato, -dichloro, -dibromo, and -diiodo complexes of formula [NiLX(2)], where L = L(BZ) or L(C'Z), and X = SCN, Cl, Br, or I. All these compounds have been characterized on the basis of analytical, spectroscopic, conductometric, and magnetochemical data. The structures of L(BZ) and two variants of [Ni"L(BZ)"][ClO(4)](2) (crystallizing in the space group P2(1)/n and Pn, respectively; "L(BZ)" symbolizes partially methylated ligand) have been determined by single-crystal X-ray analyses. The antifungal and antibacterial activities of these compounds have been studied against some phytopathogenic fungi and bacteria.