Mohamed Salah Belkhiria

Diaqua­(5,10,15,20-tetra­phenyl­porphyrinato-κ4N)magnesium–18-crown-6 (1/1)

In the title compound, [Mg(C44H28N4)(H2O)2]·C12H24O6, the MgII cation lies on an inversion center and is octahedrally coordinated by the four N atoms of the deprotonated tetraphenylporphyrin (TPP) ligand and by two water molecules. The asymmetric unit contains one half of the [Mg(TPP)(H2O)2] complex and one half of an 18-crown-6 molecule. The average equatorial magnesium–pyrrole N atom distance (Mg—Np) is 2.071 (1) Å and the axial Mg—O(H2O) bond length is 2.213 (1) Å. The crystal packing is stabilized by two O—H⋯O hydrogen bonds between coordinating water molecules and adjacent 18-crown-6 molecules, and exhibits a one-dimensional supramolecular structure along the a axis. The supramolecular architecture is futher stabilized by weak C—H⋯π interactions. The 18-crown-6 molecule is disordered over two sets of sites with an occupancy ratio of 0.8:0.2.

(2.2.2-Cryptand)potassium bis­(cyanato-κN)(5,10,15,20-tetra­phenyl­por­phy­rin­ato-κ4N)cobaltate(III) chloro­benzene hemisolvate

In the title compound, [K(C18H36N2O6)][Co(NCO)2(C44H28N4)]·0.5C6H5Cl or [K(2,2,2-crypt)+][CoIII(NCO)2(TPP)−]·0.5C6H5Cl, the CoIII ion is octahedrally coordinated by two axial N-bonded NCO− anions and four pyrrole N atoms of the porphyrin. There is a major ruffling distortion of the porphyrin: the dihedral angles between trans pyrrole rings are 34.32 (14) and 34.72 (14)°. The potassium ion is coordinated by the six O atoms and two N atoms of the cryptand-222 molecule and a weak K—O [3.407 (3) Å] bond to one of the cyanate O atoms also occurs. The packing also features weak C—H⋯O and C—H⋯π interactions. The contribution to the scattering of the disordered chlorobenzene solvent molecules was removed with the SQUEEZE function in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155].

(5,10,15,20-Tetra­phenyl­porphyrinato-κ4N)zinc–18-crown-6 (1/1)

In the title compound, [Zn(C44H28N4)]·C12H24O6, the ZnII ion lies on an inversion center and the asymmetric unit contains one half of a Zn(TPP) complex (TPP = 5,10,15,20-tetraphenylporphyrin dianion) and one half of a centrosymmetric 18-crown-6 molecule. The Zn(TPP) complex exhibits a nearly planar conformation of the porphyrin core [maximum deviation = 0.106 (2) Å] with an average Zn—N distance of 2.047 (2) Å. The title compound is considered as a one-dimensional polymer along [010], in which the Zn(TPP) moiety is linked to the closest O atoms of two symmetry-related 18-crown-6 molecules with a Zn—O distance of 2.582 (1) Å, completing a distorted octahedral coordination environment of the metal ion. The chains are mainly sustained by weak C—H⋯π interactions. An ethylene group of the 18-crown-6 molecule is disordered over three sites with occupancies of 0.50, 0.25 and 0.25.

Substitutional disorder in bis-[(cyanato-κO)/hydroxido(0.5/0.5)](5,10,15,20-tetra-phenyl-porphyrinato-κN)tin(IV).

The title complex, [SnIV(C44H28N4)(CNO)(OH)], exhibits substitutional disorder of the OH− and OCN− axial ligands. Thus, the cyanato-O ligand and the hydroxyl group bonded to the central SnIV atom share statistically the axial position. The SnIV ion is hexacoordinated by the four N atoms of the pyrrole rings of the tetraphenylporphyrin (TPP) and the O atoms of the two disordered OCN− and OH− axial ligands. The equatorial tin–pyrrole N atom distance (Sn—Np) is 2.100 (2) Å and the axial Sn—O(OCN) or Sn—O(OH) bond length is 2.074 (2) Å.

Chlorido{5,10,15,20-tetra­kis­[2-(2,2-dimethyl­propanamido)­phen­yl]porphyrinato-κ4N,N′,N′′,N′′′}iron(III) chloro­benzene hemisolvate monohydrate

In the title complex, [Fe(C64H64N8O4)Cl]·0.5C6H5Cl·H2O, the equatorial iron–pyrrole N atom distance (Fe—Np) is 2.065 (2) Å and the axial Fe—Cl distance is 2.207 (2) Å. The iron cation is displaced by 0.420 (4) Å from the 24-atom mean plane of the porphyrin core. The asymmetric unit contains a quarter of an [FeIII(C64H64N8O4)Cl] complex molecule, with a fourfold rotation axis passing through the central metal cation and the Cl ligand, along with disordered molecules of chlorobenzene and water of solvation; the solvent molecules were excluded from the refinement.

Aqua­(4-cyano­pyridine-κN4)(5,10,15,20-tetra­phenyl­porphyrinato-κ4N)magnesium

In the title complex, [Mg(C44H28N4)(C6H4N2)(H2O)], the Mg2+ cation is octahedrally coordinated and lies on an inversion center with the axially located 4-cyanopyridine and aqua ligands exhibiting 50% substitutional disorder. The cyano-bound 4-cyanopyridine molecule also is disordered across the inversion centre. The four N atoms of the pyrrole rings of the dianionic 5,10,15,20-tetraphenylporphyrin ligand occupy the equatorial sites of the octahedron [Mg—N = 2.0552 (10) and 2.0678 (11) Å] and the axial Mg—(N,O) bond length is 2.3798 (12) Å. The crystal packing is stabilized by weak intermolecular C—H⋯π interactions.

1-Benz­yloxy-2,5-bis­(chloro­meth­yl)-4-meth­oxy­benzene

In the title compound, C16H16Cl2O2, the dihedral angle between the two rings is 52.65 (10)°. The two Cl atoms are trans to one another being displaced by 1.644 (5) and −1.664 (4) Å from the plane of the benzene ring. Except for the two Cl atoms and the C atoms of the ring of the benzyloxy group, all the other atoms of the compound lie in the same plane [maximum deviation = 0.056 (3) Å]. In the crystal, no significant intermolecular interactions are observed.

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 SbV 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 SbV 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).

3,3'-Bis(chloro-meth-yl)-4,4'-dieth-oxy-1,1'-biphen-yl.

The asymmetric unit of the title compound, C18H20Cl2O2, consists of a half-molecule, the other half being generated by an inversion center, located at the mid-point of the benzene–benzene bond. Except for the two Cl atoms, all other atoms of the compound are nearly coplanar, with the atomic displacements from the molecular mean plane ranging from 0.0037 (19) to 0.071 (2) Å. The two Cl atoms are in trans positions and are displaced with respect to the mean plane by 1.687 (2) and −1.693 (3) Å. The crystal packing is governed by van der Waals interactions.

Tri-μ-oxido-bis-[(5,10,15,20-tetra-phenyl-porphyrinato-κN)niobium(V)].

In the title dinuclear NbV compound, [Nb2(C44H28N4)2O3], each Nb atom is seven-coordinated with three bridging O atoms and four N atoms from a chelating tetraphenylporphyrinate anion. The Nb—O bond lengths range from 1.757 (6) to 2.331 (6) Å, and the average (niobium–pyrrole N atom) distance is 2.239 Å. In the dinuclear molecule, the Nb⋯Nb separation is 2.8200 (8) Å, and the dihedral angle between the two porphyrinate mean planes is 5.4 (1)°. Weak intermolecular C—H⋯π interactions are present in the crystal structure.