A Series of Octahedral First-Row Transition-Metal Ion Complexes Templated by Wells-Dawson Polyoxometalates: Synthesis, Crystal Structure, Spectroscopic, and Thermal Characterizations, and Electrochemical Properties.

Three Wells-Dawson polyoxotungstates-based hybrid compounds of general formula [M(CHNO)][{M(CHNO)}(μ-PWO)]· nCHNO· n'HO [with M = Mn (1), Fe (2), Co (3) ; n = 2, 2, 3 and n' = 0, 0, 1, respectively] were synthesized at room temperature by a facile method and characterized by IR and H and P NMR spectroscopy studies, thermogravimetric analysis-differential scanning calorimetry thermal analyses, UV-vis, X-ray diffraction (XRD) powder and single-crystal XRD analyses, and cyclic voltammetry studies. From the X-ray study, it was established that the metal (M = Mn, Fe, Co) is located on an inversion center, being octahedrally coordinated to six dimethylformamide (DMF) molecules to form the complex cation [M(dmf)]. Also, in the dinuclear complex anion [{M(dmf)}(μ-PWO)], the M atoms are coordinated to five DMF molecules through the oxygen atoms, while the sixth coordination site is occupied by a terminal oxygen atom of the Wells-Dawson anion [PWO] that plays the role of a bridging ligand.

Crystal structure of octa-kis-(N,N-di-methyl-formamide-κO)europium(III) tetra-cosa-μ2-oxido-dodeca-oxido-μ12-phosphato-dodeca-molybdate(VI).

In the title salt, [Eu(C3H7NO)8][PMo12O40], the asymmetric unit comprises one α-Keggin-type [PMo12O40](3-) polyoxidometalate anion and one distorted dodeca-hedral [Eu(C3H7NO)8](3+) complex cation. In the crystal, the isolated polyoxidometalate anions are packed into hexa-gonally arranged rows extending parallel to [001]. The complex cations are situated between the rows and are linked to the neighbouring anions through weak C-H⋯O hydrogen-bonding inter-actions, leading to the formation of a three-dimensional network structure.

Crystal structure of hexa-kis-(di-methyl-formamide-κO)manganese(II) deca-kis-(di-methyl-formamide)-1κ(5) O,2κ(5) O-[μ-octa-deca-tungstodiphosphato(V)-κO:κO']dimanganate(II) di-methyl-formamide disolvate.

The crystal structure of the title compound, [Mn(C3H7NO)6][{Mn(C3H7NO)5}2(μ-P2W18O62)]·2C3H7NO, reveals that the Wells-Dawson-type polyanion [P2W18O62](6-), through terminal O atoms from the belts, bridges two Mn(II) octa-hedral complexes. In the complex anion [{Mn(dmf)5}2(μ-P2W18O62)](2-), located around a twofold rotation axis, the Mn(II) ions are coordinated by five O atoms from di-methyl-formamide (dmf) ligands and to a terminal O atom from the [P2W18O62](6-) polyanion. Another Mn(II) ion, located on an inversion centre, is coordinated by six O atoms from the dmf ligands and forms the [Mn(dmf)6](2+) cation.

Di-chlorido-(5,10,15,20-tetra-phenyl-porphyrinato-κ(4) N)anti-mony(V) hexa-chlorido-anti-monate(V).

The asymmetric unit of the title compound, [Sb(C44H28N4)Cl2][SbCl6], consists of one half of an anti-mony(V) tetra-phenyl-porphyrin complex cation and one half of an hexa-chlorido-anti-monate(V) anion. In the complex cation, the Sb(V) atom lies on an inversion center and is octa-hedrally coordinated by four N atoms from a macrocyclic tetra-phenyl-porphyrinate ligand and two chloride ions. The complex cation has approximately a planar core with a maximum deviation of 0.

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-mol-ecule, 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 mol-ecular mean plane ranging from 0.0037 (19) to 0.

(5,10,15,20-Tetra-phenyl-porphyrinato-κ(4) N)zinc-18-crown-6 (1/1).

In the title compound, [Zn(C44H28N4)]·C12H24O6, the Zn(II) ion lies on an inversion center and the asymmetric unit contains one half of a Zn(TPP) complex (TPP = 5,10,15,20-tetra-phenyl-porphyrin dianion) and one half of a centrosymmetric 18-crown-6 mol-ecule. 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.

Aqua-(4-cyano-pyridine-κN (4))(5,10,15,20-tetra-phenyl-porphyrinato-κ(4) N)magnesium.

In the title complex, [Mg(C44H28N4)(C6H4N2)(H2O)], the Mg(2+) cation is octa-hedrally coordinated and lies on an inversion center with the axially located 4-cyano-pyridine and aqua ligands exhibiting 50% substitutional disorder. The cyano-bound 4-cyano-pyridine mol-ecule also is disordered across the inversion centre. The four N atoms of the pyrrole rings of the dianionic 5,10,15,20-tetra-phenyl-porphyrin ligand occupy the equatorial sites of the octa-hedron [Mg-N = 2.

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 tetra-nuclear mol-ecule lies about an inversion centre. The Cd(II) atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetra-phenyl-porphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the Na(I) 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.

Diaqua-(5,10,15,20-tetra-phenyl-porphyrinato-κ(4)N)magnesium-18-crown-6 (1/1).

In the title compound, [Mg(C(44)H(28)N(4))(H(2)O)(2)]·C(12)H(24)O(6), the Mg(II) cation lies on an inversion center and is octa-hedrally coordinated by the four N atoms of the deprotonated tetra-phenyl-porphyrin (TPP) ligand and by two water mol-ecules. The asymmetric unit contains one half of the [Mg(TPP)(H(2)O)(2)] complex and one half of an 18-crown-6 mol-ecule. The average equatorial magnesium-pyrrole N atom distance (Mg-N(p)) is 2.

(2.2.2-Cryptand)potassium bis-(cyanato-κN)(5,10,15,20-tetra-phenyl-por-phy-rin-ato-κ(4)N)cobaltate(III) chloro-benzene hemisolvate.

In the title compound, [K(C(18)H(36)N(2)O(6))][Co(NCO)(2)(C(44)H(28)N(4))]·0.5C(6)H(5)Cl or [K(2,2,2-crypt)(+)][Co(III)(NCO)(2)(TPP)(-)]·0.5C(6)H(5)Cl, the Co(III) ion is octa-hedrally coordin-ated by two axial N-bonded NCO(-) anions and four pyrrole N atoms of the porphyrin.

1-Benz-yloxy-2,5-bis-(chloro-meth-yl)-4-meth-oxy-benzene.

In the title compound, C(16)H(16)Cl(2)O(2), the dihedral angle between the two rings is 52.65 (10)°. The two Cl atoms are trans to one another being displaced by 1.

Octa-kis(dimethyl sulfoxide-κO)cerium(III) μ(6)-oxido-dodeca-μ(2)-oxido-hexa-oxidohexa-molybdate(VI) dimethyl sulfoxide tetrasolvate.

The title complex, [Ce(C(2)H(6)OS)(8)](2)[Mo(6)O(19)](3)·4C(2)H(6)OS, was obtained as a byproduct of the reaction of [(C(4)H(9))(4)N](2)[Mo(6)O(19)] with Ce(NO(3))(3)·6H(2)O and phthalic acid in dimethyl-sulfoxide solution. The asymmetric unit consists of a complex [Ce(C(2)H(6)OS)(8)](3+) cation, one and a half of the Lindqvist-type [Mo(6)O(19)](2-) polyanions and two dimethyl-sulfoxide solvent mol-ecules; the half polyanion lies on an inversion center. The Ce(3+) ion is coordinated by eight dimethyl-sulfoxide ligands through the O atoms in the form of a distorted square antiprism.

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

The title complex, [Sn(IV)(C(44)H(28)N(4))(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 Sn(IV) atom share statistically the axial position. The Sn(IV) ion is hexa-coordinated by the four N atoms of the pyrrole rings of the tetra-phenyl-porphyrin (TPP) and the O atoms of the two disordered OCN(-) and OH(-) axial ligands.

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

In the title dinuclear Nb(V) compound, [Nb(2)(C(44)H(28)N(4))(2)O(3)], each Nb atom is seven-coordinated with three bridging O atoms and four N atoms from a chelating tetra-phenyl-porphyrinate anion. The Nb-O bond lengths range from 1.757 (6) to 2.

Chlorido{5,10,15,20-tetra-kis-[2-(2,2-dimethyl-propanamido)-phen-yl]porphyrinato-κN,N',N'',N'''}iron(III) chloro-benzene hemisolvate monohydrate.

In the title complex, [Fe(C(64)H(64)N(8)O(4))Cl]·0.5C(6)H(5)Cl·H(2)O, the equatorial iron-pyrrole N atom distance (Fe-N(p)) is 2.065 (2) Å and the axial Fe-Cl distance is 2.

(5,10,15,20-Tetra-phenyl-porphyrinato-κN)cobalt(II)-18-crown-6 (1/1).

The asymmetric unit of the title compound, [Co(C(44)H(28)N(4))]·C(12)H(24)O(6), contains one half of a Co(II)(TPP) (TPP is tetra-phenyl-porphyrin) complex and one half of an 18-crown-6 mol-ecule of crystallization, both lying on inversion centers. The Co(II)(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.

(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 Fe(II) porphyrin complexes used as biomimetic models for cytochrome P450, crystals of the title compound, [K(C(18)H(36)N(2)O(6))][Fe(II)(C(64)H(64)N(8)O(4))(HS)], were prepared. The compound exhibits a non-planar conformation with major ruffling and saddling distortions. The average equatorial iron-pyrrole N atom [Fe-N(p) = 2.