A one-dimensional polymeric cobalt(III)–potassium complex with 18-crown-6, cyanide and porphyrinate ligands

The reaction of Co^II(TpivPP) {TpivPP is the dianion of 5,10,15,20-tetra­kis­[2-(2,2-di­methyl­propanamido)­phen­yl]por­ph­yrin} with an excess of KCN salts and an excess of the 18-crown-6 in chloro­benzene leads to the polymeric title compound catena-poly[[dicyanido-2κ²C-(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-1κ⁶O){μ₃-(2α,2β)-5,10,15,20-tetra­kis­[2-(2,2-di­methyl­propanamido)­phen­yl]porphyrinato-1κO⁵:2κ⁴N,N′,N′′,N′′′:1′κO¹⁵}cobalt(III)potassium] dihydrate], {[CoK(CN)₂(C₁₂H₂₄O₆)(C₆₄H₆₄N₈O₄]·2H₂O}_n. The Co^III ion lies on an inversion center, and the asymmetric unit contains one half of a [Co^III(2α,2β-TpivPP)(CN)₂]⁻ ion complex and one half of a [K(18-C-6]⁺ counter-ion (18-C-6 is 1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne), where the K^I ion lies on an inversion center. The Co^III ion is hexa­coordinated by two C-bonded axial cyanide ligands and the four pyrrole N atoms of the porphyrin ligand. The K^I ion is chelated by the six O atoms of the 18-crown-6 mol­ecule and is further coordinated by two O atoms of pivalamido groups of the porphyrin ligands, leading to the formation of polymeric chains running along [011]. In the crystal, the polymeric chains and the lattice water mol­ecules are linked by N—H...O and O—H...N hydrogen bonds, as well as weak C—H...O, O—H...π and C—H...π inter­actions into a three-dimensional supra­molecular architecture.

Di­chlorido­(5,10,15,20-tetra­phenyl­porphyrinato-κ⁴N)anti­mony(V) hexa­chlorido­anti­monate(V)

The asymmetric unit of the title compound, [Sb(C₄₄H₂₈N₄)Cl₂][SbCl₆], consists of one half of an anti­mony(V) tetra­phenyl­porphyrin complex cation and one half of an hexa­chlorido­anti­monate(V) anion. In the complex cation, the Sb^V atom lies on an inversion center and is octa­hedrally coordinated by four N atoms from a macrocyclic tetra­phenyl­porphyrinate ligand and two chloride ions. The complex cation has approximately a planar core with a maximum deviation of 0.018 (5) Å from the porphyrin mean plane. The average Sb—N distance is 2.062 (11) Å, while the Sb—Cl distance is 2.355 (1) Å. The Sb^V atom of the anion is also located on an inversion center. The [SbCl₆]⁻ octa­hedron exhibits rhombic distortion characterized by the Sb—Cl bond lengths [2.311 (3), 2.374 (2) and 2.393 (4) Å]. In the crystal, the cations and anions are linked C—H... Cl hydrogen bonds, forming a layer parallel to (211).

Di­aqua­[5,10,15,20-tetra­kis­(4-chloro­phen­yl)porphyrinato-κ⁴N]iron(III) tri­fluoro­methane­sulfonate–4-hy­droxy-3-meth­oxy­benzaldehyde–water (1/1/2)

In the title compound, [Fe(C₄₄H₂₄Cl₄N₄)(H₂O)₂](SO₃CF₃)·C₈H₈O₃·2H₂O, the Fe^III cation is chelated by the four N atoms of the deprotonated tetra­kis­(4-chloro­tetra­phen­yl)porphyrin (TClPP) and further coordinated by two water mol­ecules in a distorted octa­hedral geometry. In the crystal, the cations, anions, 4-hy­droxy-3-meth­oxy­benzaldehyde and water mol­ecules of crystallization are linked by classical O—H...O hydrogen bonds and weak C—H...O and C—H...Cl hydrogen bonds into a three-dimensional supra­molecular architecture. The crystal packing is further stabilized by weak C—H...π inter­actions involving pyrrole and benzene rings. π–π stacking between parallel benzene rings of adjacent 4-hy­droxy-3-meth­oxy­benzaldehyde mol­ecules is also observed, the centroid–centroid distance being 3.8003 (13) Å. The three F atoms of the anion are disordered over two sets of sites, with a refined occupancy ratio 0.527 (12):0.473 (12). The O atom of one water mol­ecule of crystallization is also disordered over two positions in an occupancy ratio of 0.68 (5):0.32 (5).