Habib Nasri

Synthesis, crystal structures and spectroscopic characterization of Co(II) bis(4,4′-bipyridine) with meso-porphyrins α,β,α,β-tetrakis(o-pivalamidophenyl) porphyrin (α,β,α,β-TpivPP) and tetraphenylporphyrin (TPP)

The reaction of the starting materials [CoII(Porph)] (Porph = α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrin (TpivPP) and the meso-tetraphenylporphyrin (TPP)) with an excess of 4,4′-bipyridine in chlorobenzene leads to the creation of two cobalt(II) derivatives: [CoII(α,β,α,β-TpivPP)(4,4′-bpy)2]·C6H5Cl·C6H14(1) and [CoII(TPP)(4,4′-bpy)2]·2bpy(2). These compounds have been characterized by UV-vis, IR, 1H NMR and MALDI-TOF spectroscopy. The proton NMR spectra of (1) and (2) clearly indicated that these derivatives are paramagnetic while the UV-vis data confirmed creation of a new six-coordinated or penta-coordinated Co(II)-meso-porphyrin complexes by displaying red shifted Soret bands. The determined X-ray structures of (1) and (2) show that in the solid state these species are considered as coordination polymers which consist of 1D chains of alternating [CoII(Porph)] and 4,4′-bipyridine molecules located at the axial positions of the cobalt(II) coordination sphere. The coordination geometry of Co(II) in (1) and (2) is octahedral; the porphyrin (TpivPP or TPP) acts as a tetradentate chelating ligand with four nitrogen atoms from the pyrrole moieties occupying the equatorial positions along the porphyrin core. The N-donor atoms of the 4,4′-bipyridine create the axial ligands. It is noteworthy that for complex (1) the starting porphyrin is the α,α,α,α-TpivPP atropisomer but the final coordination polymer contains the α,β,α,β-TpivPP conformer.

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

The asymmetric unit of the title compound, [Co(C44H28N4)]·C12H24O6, contains one half of a CoII(TPP) (TPP is tetraphenylporphyrin) complex and one half of an 18-crown-6 molecule of crystallization, both lying on inversion centers. The CoII(TPP) complex exhibits a nearly planar conformation of the porphyrinate core [maximum deviation = 0.069 (2) Å] with an average Co—N distance of 1.971 (4) Å. The distance between the Co atom and the closest O atom of the 18-crown-6 molecule is 2.533 (2) Å, indicating a short non-bonded contact between the Co atom and the crown ether molecule. An ethylene group of the 18-crown-6 molecule is disordered over two sites with occupancies of 0.565 (7) and 0.435 (7).

(Cryptand-222)potassium(+) (hydrogensulfido)[5,10,15,20-tetra-kis(2-pival-amido-phen-yl)porphyrinato]ferrate(II).

As part of a systematic investigation for a number of FeII porphyrin complexes used as biomimetic models for cytochrome P450, crystals of the title compound, [K(C18H36N2O6)][FeII(C64H64N8O4)(HS)], were prepared. The compound exhibits a non-planar conformation with major ruffling and saddling distortions. The average equatorial iron–pyrrole N atom [Fe—Np = 2.102 (2) Å] bond length and the distance between the FeII atom and the 24-atom core of the porphyrin ring (Fe—PC= 0.558 Å) are typical for high-spin iron(II) pentacoordinate porphyrinates. One of the tert-butyl groups in the structure is disordered over two sets with occupancies of 0.84 and 0.16.

Preparation and spectroscopic properties of the (cyanato-N) and (oxalato) iron(III) “picket fence” porphyrins: Structure of the (cyanato-N)(α,α,α,α-tetrakis(o-pivalamidophenyl)porphinato)iron(III) complex

The reaction of the iron(III) aqua triflato picket fence porphyrin starting material with NaOCN and K2C2O4 salts, solubilized by the crown ether 18-C-6 in organic solvents, yields respectively the iron(III) porphyrin species [FeIII(TpivPP)(NCO)] and [FeIII(TpivPP)(ox)]−. These compounds have been characterized by UV-vis, IR, and 1H NMR spectroscopies. Proton NMR data for the isolated products are in accordance with high-spin (S = 5/2) ferric porphyrin derivatives. The X-ray molecular structure of the (cyanato-N)(α,α,α,α-tertakis(o-pivalamidophenyl)porphinato)iron(III), has been determined. This structure, which is the first one reported of an iron-cyanato species, confirms the spin-state of the cyanato derivative. The iron atom is pentacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atom of the NCO− group. It lies at 0.540(1) A out of the porphinato plane and 0.486(1) A out of the four nitrogen plane of the porphyrin ring. The Fe–N(NCO) bond length is 1.970(2) A and the Fe-N-C(NCO) bond angle is 169.9(3)°.

Crystal structure of di-aqua-[5,10,15,20-tetra-kis-(4-bromo-phen-yl)porphyrinato-κ(4) N]magnesium.

The title compound, [Mg(C44H24Br4N4)(H2O)2] or [Mg(TBrPP)(H2O)2], where TBrPP is the 5,10,15,20-tetrakis(4-bromophenyl)porphyrinato ligand, was obtained unintentionally as a by-product of the reaction of the [Mg(TBrPP)] complex with an excess of dimethylglyoxime in dichloromethane. The entire molecule exhibits point group symmetry 4/m. In the asymmetric unit, except for two C atoms of the phenyl ring, all other atoms lie on special positions. The MgII atom is situated at a site with symmetry 4/m, while the N and the C atoms of the porphyrin macrocycle, as well as two C atoms of the phenyl ring and the Br atom lie in the mirror plane containing the porphyrin core. The H atoms of the axially bonded water molecule are incompatible with the fourfold rotation axis and are disordered over two sites. In the crystal, molecules are packed in rows along [001]. Weak intermolecular C—H⋯π and C—H⋯Br interactions, as well as O—H⋯Br hydrogen bonds, stabilize the crystal packing.

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.

Di-μ-azido-bis-(μ-1,4,7,10,13,16-hexa-oxacyclo-octa-deca-ne)bis-(5,10,15,20-tetra-phenyl-porphyrinato)dicadmium-disodium.

The asymmetric unit of the title compound, [Cd2Na2(N3)2(C44H28N4)2(C12H24O6)2], consists of one half of the dimeric complex; the tetranuclear molecule lies about an inversion centre. The CdII atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetraphenylporphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the NaI atom, which is surrounded by one 18-crown-6 molecule and additionally bonded to a second 18-crown-6 molecule trans to the azide group. The porphyrin core exhibits a major doming distortion (∼40%) and the crystal structure is stabilized by weak C—H⋯π interactions. The molecular structure features weak intramolecular hydrogen bonds: two O—H⋯O interactions within the 18-crown-6 molecule and one C—H(18-crown-6)⋯N(azido) contact.

Chlorido(pyridine-κN)(5,10,15,20-tetra­phenyl­porphyrinato-κ4N)cobalt(III) chloro­form hemisolvate

In the title complex, [CoCl(C44H28N4)(C5H5N)]·0.5CHCl3 or [CoIII(TPP)Cl(py)]·0.5CHCl3 (where TPP is the dianion of tetraphenylporphyrin and py is pyridine), the average equatorial cobalt–pyrrole N atom bond length (Co—Np) is 1.958 (7) Å and the axial Co—Cl and Co—Npy distances are 2.2339 (6) and 1.9898 (17) Å, respectively. The tetraphenylporphyrinate dianion exhibits an important nonplanar conformation with major ruffling and saddling distortions. In the crystal, molecules are linked via weak C—H⋯π interactions. In the difference Fourier map, a region of highly disordered electron density was estimated using the SQUEEZE routine [PLATON; Spek (2009 ▶), Acta Cryst. D65, 148–155] to be equivalent to one half-molecule of CHCl3 per molecule of the complex.