A novel ditetrapyrrolic, heteroleptic, and heterometallic (Mn-Cr) mu-hydroxo-bridged complex has been prepared, and its structural and general properties have been studied. The species mu-hydroxo(tetraphenylporphyrin-atomanganese( III))(phthalocyaninato(azido) chromium(III)), [(TPP)Mn-O(H)-CrPc(N-3)], isolated as a chloronaphthalene (CINP) solvate, has been structurally characterized by single-crystal X-ray work. The two (TPP) Mn and CrPc(N-3) fragments are held together by the bridging mu-hydroxo ion with long Mn-O [1.993(5) angstrom] and Cr-O [1.976(5) angstrom] 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 N-4 core by 0.128 angstrom, and the environment is typical of a Mn-III high-spin site. The six-coordinate CrIII in the CrPc(N-3) moiety lies practically in the plane of the phthalocyanine macrocycle (displacement toward the azido group: 0.054 angstrom). The average Mn-N-pyr and Cr-N-pyr bond distances are 2.011(6) and 1.982(6) angstrom, respectively, and the Mn-Cr bond distance is 3.929(2) angstrom. 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(N-3)](.)2CINP, C(76)H(45)CrMnN(15)O(.)2C(10)H(7)Cl: a = 16.645(3) angstrom, b = 17.692(4) angstrom, c = 25.828(5) angstrom, alpha = 90 degrees, beta = 98.79(3)degrees, gamma = 90 degrees, space group P2(1)/c (No. 14), V = 7517(3) angstrom(3), 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.