A Rare μ-Hydroxo-Bridged Species. Synthesis, Structure, and Properties of μ-Hydroxo(tetraphenylporphyrinatomanganese(III))(phthalocyaninato(azido)chromium(III)), [(TPP)Mn−O(H)−CrPc(N3)]

A novel ditetrapyrrolic, heteroleptic, and heterometallic (Mn−Cr) μ-hydroxo-bridged complex has been prepared, and its structural and general properties have been studied. The species μ-hydroxo(tetraphenylporphyrinatomanganese(III))(phthalocyaninato(azido)chromium(III)), [(TPP)Mn−O(H)−CrPc(N3)], isolated as a chloronaphthalene (ClNP) solvate, has been structurally characterized by single-crystal X-ray work. The two (TPP)Mn and CrPc(N3) fragments are held together by the bridging μ-hydroxo ion with long Mn−O [1.993(5) Å] and Cr−O [1.976(5) Å] bond distances and a Mn−O(H)−Cr angle of 163.7(3)°. The five-coordinate Mn center in the (TPP)Mn fragment is displaced from the TPP rigorously planar central N4 core by 0.128 Å, and the environment is typical of a MnIII high-spin site. The six-coordinate CrIII in the CrPc(N3) moiety lies practically in the plane of the phthalocyanine macrocycle (displacement toward the azido group: 0.054 Å). The average Mn−Npyr and Cr−Npyr bond distances are 2.011(6) and 1.982(6) Å, respectively, and the Mn−Cr bond distance is 3.929(2) Å. The porphyrin and phthalocyanine rings are in an almost eclipsed position [5.16(2)°], and the mean planes of the two macrocycles form a dihedral angle of 5.79(4)°. Crystal data for [(TPP)Mn−O(H)−CrPc(N3)]·2ClNP, C76H45CrMnN15O·2C10H7Cl: a = 16.645(3) Å, b = 17.692(4) Å, c = 25.828(5) Å, α = 90°, β = 98.79(3)°, γ = 90°, space group P21/c (No. 14), V = 7517(3) Å3, Z = 4, R1 = 0.086, and wR2 = 0.267. IR and UV−vis−near-IR spectral and room temperature magnetic susceptibility data of the [Mn−Cr] species are also presented.