A novel dinuclear Mo^VI complex with tris­(3,5-dimethyl-1H-pyrazol-1-yl)methane

Recrystallization of [MoO₂Cl{HC(3,5-Me₂pz)₃}]Cl [where HC(3,5-Me₂pz)₃ is tris­(3,5-dimethyl-1H-pyrazol-1-yl)methane] led to the isolation of large quanti­ties of the dinuclear complex dichlorido-2[kappa]²Cl-[mu]-oxido-[kappa]²O:O-tetra­ox­ido-1[kappa]²O,2[kappa]²O-[tris(3,5-dimethyl-1H-pyrazol-1-yl-1[kappa]N²)methane]­dimolybdenum(IV) acetonitrile monosolvate, [Mo₂Cl₂O₄(C₁₆H₂₂N₆)]·CH₃CN or [{MoO₂Cl₂}([mu]₂-O){MoO₂[HC(3,5-Me₂pz)₃]}]·CH₃CN. At 150 K, this complex cocrystallizes in the ortho­rhom­bic space group Pbcm with an acetonitrile mol­ecule. The complex has mirror symmetry: only half of the complex constitutes the asymmetric unit and all the heavy elements (namely Mo and Cl) are located on the mirror plane. The acetonitrile molecule also lies on a mirror plane. The two crystallographically independent Mo⁶⁺ centres have drastically different coordination environments: while one Mo atom is hexa­coordinated and chelated to HC(3,5-Me₂pz)₃ (which occupies one face of the octa­hedron), the other Mo atom is instead penta­coordinated, having two chloride anions in the apical positions of the distorted trigonal bipyramid. This latter coordination mode of Mo^VI was found to be unprecedented. Individual complexes and solvent mol­ecules are close-packed in the solid state, mediated by various supra­molecular contacts.

5-[4-(Dieth­oxy­phosphor­yl)-2,3,5,6-tetra­fluoro­phen­yl]-10,15,20-tris(penta­fluoro­phen­yl)porphyrin

The title compound, C₄₈H₂₀F₁₉N₄O₃P, prepared by the nucleo­philic attack of triethyl phosphite on one of the 4-fluoro atoms of 5,10,15,20-tetra­kis­(penta­fluoro­phenyl)por­phy­rin, contains a single mol­ecule in the asymmetric unit. The porphyrin unit is almost planar [largest non-H atom deviation = 0.174 (6) Å], and has the planes of the neighbouring benzene rings oriented at angles ranging from 64.3 (2) to 89.6 (3)° relative to the porphyrin core. The P=O group is almost coplanar with the attached benzene ring, subtending an angle of 4.0 (3)°. Several weak supra­molecular inter­actions, namely C—H...π, C—F...π, P=O...π, C—H...(O,F) and F...F contacts, contribute to the crystal packing.