Crystal structures of the complexes containing macrocyclic cations [M(cyclam)]2+ (M = Ni, Zn) and tetra-iodido-cadmate(2-) anion.

The asymmetric units of the isostructural compounds (1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N)nickel(II) tetra-iodido-cadmate(II), [Ni(C10H24N4)][CdI4] (I), and tri-iodido-1κ3 I-µ-iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-2κ4 N)cad-mium(II)zinc(II), [CdZnI4(C10H24N4)] (II) (C10H24N4 = 1,4,8,11-tetra-aza-cyclo-tetra-decane, cyclam, L), consist of the centrosymmetric macrocyclic cation [M(L)]2+ [M = NiII or ZnII] with the metal ion lying on a twofold screw axis, and the tetra-iodo-cadmate anion [CdI4]2- located on the mirror plane. In I, the anion acts as an uncoordinated counter-ion while in II it is bound to the ZnII atom via one of the iodide atoms, thus forming an electroneutral heterobimetallic complex [Zn(L)(CdI4)]. The NiII and ZnII ions are coordinated in a square-planar manner by the four secondary N atoms of the macrocyclic ligand L, which adopts the most energetically stable trans-III conformation. The [CdI4]2- anions in I and II are structurally very similar and represent slightly deformed tetra-hedrons with average Cd-I bond lengths and I-Cd-I angles of ca 2.79 Šand 109.6°, respectively. The supra-molecular organization of the complexes under consideration in the crystals is very similar and is determined by the hydrogen-bonding inter-actions between the secondary amino groups of the ligand L in the [M(L)]2+ cations and iodide atoms of the [CdI4]2- anion. In particular, the alternating cations and anions form chains running along the b-axis direction that are arranged into di-periodic sheets oriented parallel to the (101) and (01) planes. Because both kinds of sheets are built from the same cations and anions, this feature provides the three-dimensional coherence of the crystals of I and II.

Synthesis and crystal structure of di-aqua-(1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)zinc(II) bis-(hydrogen 4-phospho-natobiphenyl-4'-carboxyl-ato)(1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)zinc(II).

In the asymmetric unit of the title compound, trans-di-aqua-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N 1,N 4,N 8,N 11)zinc(II) trans-bis-(hydrogen 4-phospho-natobiphenyl-4'-carboxyl-ato-κO)(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N 1,N 4,N 8,N 11)zinc(II), [Zn(C10H24N4)(H2O)2][Zn(C13H9O5P)2(C10H24N4)], both Zn atoms lie on crystallographic inversion centres and the atoms of the macrocycle in the cation are disordered over two sets of sites. In both macrocyclic units, the metal ions possess a tetra-gonally elongated ZnN4O2 octa-hedral environment formed by the four secondary N atoms of the macrocyclic ligand in the equatorial plane and the two trans O atoms of the water mol-ecules or anions in the axial positions, with the macrocyclic ligands adopting the most energetically favourable trans-III conformation. The average Zn-N bond lengths in both macrocyclic units do not differ significantly [2.112 (12) Šfor the anion and 2.101 (3) Šfor the cation] and are shorter than the average axial Zn-O bond lengths [2.189 (4) Šfor phospho-nate and 2.295 (4) Šfor aqua ligands]. In the crystal, the complex cations and anions are connected via hydrogen-bonding inter-actions between the N-H groups of the macrocycles, the O-H groups of coordinated water mol-ecules and the P-O-H groups of the acids as proton donors, and the O atoms of the phospho-nate and carboxyl-ate groups as acceptors, resulting in the formation of layers lying parallel to the (110) plane.

Crystal structure of [{[Ni(C10H24N4)][Ni(CN)4]}·2H2O] n , a one-dimensional coordination polymer formed from the [Ni(cyclam)]2+ cation and the [Ni(CN)4]2- anion.

The asymmetric unit of the title compound, catena-poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-µ-cyanido-κ2 N:C-[bis-(cyanido-κC)nickel(II)]-µ-cyanido-κ2 C:N] dihydrate], {[Ni2(CN)4(C10H24N4)]·2H2O] n or [{[Ni(C10H24N4)][Ni(CN)4]}·2H2O] n , consists of a pair of crystallographically non-equivalent macrocyclic cations and anions. The nickel(II) ions (all with site symmetry ) are coordinated by the four secondary N atoms of the macrocyclic ligands, which adopt the most energetically stable trans-III conformation, and the mutually trans N atoms of the tetra-cyano-nickelate anion in a slightly tetra-gonally distorted NiN6 octa-hedral coordination geometry. The [Ni(CN)4)]2- anion exhibits a bridging function, resulting in the formation of parallel polymeric chains running along the [10] direction. The water mol-ecules of crystallization play a pivotal role in the three-dimensional supra-molecular organization of the crystal. Acting as acceptors, they form N-H⋯Ow (w = water) hydrogen bonds with the secondary amino groups of the macrocycles, forming layers oriented parallel to the (001) plane. At the same time, as donors, they inter-act with the non-coordinated cyano groups of the anion via Ow-H⋯Nc (c = cyanide) hydrogen bonds, giving two-dimensional layers oriented parallel to the (100) plane and thus generating a three-dimensional network.

Crystal structure of trans-di-aqua-(1,4,8,11-tetra-aza-undeca-ne)nickel(II) bis-(pyridine-2,6-di-carboxyl-ato)nickel(II).

The asymmetric unit of the title compound, trans-di-aqua-(1,4,8,11-tetra-aza-undecane-κ4 N 1,N 4,N 8,N 11)nickel(II) bis-(pyridine-2,6-di-carboxyl-ato-κ3 O 2,N,O 6)nickel(II) {[Ni(L)(H2O)2][Ni(pdc)2] where L = 1,4,8,11-tetra-aza-undecane (C7H20N4) and pdc = the dianion of pyridine-2,6-di-carb-oxy-lic acid (C7H3NO4 2-)} consists of an [Ni(L)(H2O)2]2+ complex cation and a [Ni(pdc)2]2- anion. The metal ion in the cation is coordinated by the four N atoms of the tetra-amine ligand and the mutually trans O atoms of the water mol-ecules in a tetra-gonally elongated octa-hedral geometry with the average equatorial Ni-N bond length slightly shorter than the average axial Ni-O bond [2.087 (4) versus 2.128 (4) Å]. The ligand L adopts its energetically favored conformation with five-membered and six-membered chelate rings in gauche and chair conformations, respectively. In the complex anion, the NiII ion is coordinated by the two tridentate pdc2- ligands via their carboxyl-ate and nitro-gen atom donors in a distorted octa-hedral trans-NiO4N2 geometry with nearly orthogonal orientation of the planes defining the carboxyl-ate rings and the average Ni-N bond length [1.965 (4) Å] shorter than the average Ni-O bond distance [2.113 (7) Å]. In the crystal, the NH donor groups of the tetra-amine, the carb-oxy-lic groups of the pdc2- anion and the coordinated water mol-ecules are involved in numerous N-H⋯O and O-H⋯O hydrogen bonds, leading to electroneutral sheets oriented parallel to the (001) plane.

Crystal structures of trans-di-aqua-(3-R-1,3,5,8,12-penta-aza-cyclo-tetra-deca-ne)copper(II) isophthalate hydrates (R = benzyl or pyridin-3-ylmethyl).

The asymmetric units of the title compounds, trans-di-aqua-(3-benzyl-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ4 N 1,N 5,N 8,N 12)copper(II) isophthalate monohydrate, [Cu(C16H29N5)(H2O)2](C8H4O4)·H2O, (I), and trans-di-aqua-[3-(pyridin-3-ylmeth-yl)-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ4 N 1,N 5,N 8,N 12]copper(II) iso-phthalate 0.9-hydrate, [Cu(C15H28N6)(H2O)2](C8H4O4)·0.9H2O, (II) consist of one di-aqua macrocyclic cation, one di-carboxyl-ate anion and uncoordinated water mol-ecule(s). In each compound, the metal ion is coordinated by the four secondary N atoms of the macrocyclic ligand and the mutually trans O atoms of the water mol-ecules in a tetra-gonally distorted octa-hedral geometry. The average equatorial Cu-N bond lengths are significantly shorter than the average axial Cu-O bond lengths [2.020 (9) versus 2.495 (12) Šand 2.015 (4) versus 2.507 (7) Šfor (I) and (II), respectively]. The coordinated macrocyclic ligand in the cations of both compounds adopts the most energetically favorable trans-III conformation. In the crystals, the complex cations and counter-anions are connected via hydrogen-bonding inter-actions between the N-H groups of the macrocycles and the O-H groups of coordinated water mol-ecules as the proton donors and the O atoms of the carboxyl-ate as the proton acceptors. Additionally, as a result of O-H⋯O hydrogen bonding with the coordinated and water mol-ecules of crystallization, the isophthalate dianions form layers lying parallel to the (01) and (100) planes in (I) and (II), respectively.

Crystal structure of trans-di-aqua-(3,10-dimethyl-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne)copper(II) pamoate.

The asymmetric unit of the title compound, trans-di-aqua-(3,10-dimethyl-1,3,5,8,10,12-hexa-aza-cyclo-tetra-decane-κ4 N 1,N 5,N 8,N 12)copper(II) 4,4'-methyl-ene-bis(3-hy-droxy-naphthalene-2-carboxyl-ate), [Cu(C10H26N6)(H2O)2](C23H14O6) {[Cu(L)(H2O)2](pam), where L = 3,10-dimethyl-1,3,5,8,10,12-hexa-aza-cyclo-tetra-decane and pam = dianion of pamoic acid} consists of two independent halves of the [Cu(L)(H2O)2]2+ cation and one di-carboxyl-ate anion. The CuII atoms, lying on inversion centres, are coordinated by the four secondary N atoms of the macrocyclic ligands and the mutually trans O atoms of the water mol-ecules in a tetra-gonally elongated octa-hedral geometry. The average equatorial Cu-N bond length is significantly shorter than the average axial Cu-O bond length [2.007 (10) and 2.486 (18) Å, respectively]. The macrocyclic ligand in the complex cations adopts the most energetically stable trans-III conformation. The complex cations and anions are connected via hydrogen-bonding inter-actions between the N-H groups of the macrocycles and the O-H groups of coordinated water mol-ecules as the proton donors and the O atoms of the carboxyl-ate as the proton acceptors into layers lying parallel to the (11) plane.