La3Co3O8 crystallizes in the monoclinic P2_1 space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to two equivalent O(4), two equivalent O(5), and three equivalent O(3) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), one O(8), and two equivalent O(6) atoms. In the third La site, La(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with five equivalent Co(2)O6 octahedra and  a cornercorner with one Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-25°. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form CoO6 octahedra that share corners with five equivalent Co(1)O6 octahedra and  a cornercorner with one Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-25°. In the third Co site, Co(3) is bonded to one O(6), one O(8), and two equivalent O(7) atoms to form CoO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and corners with two equivalent Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-37°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one La(2), one La(3), one Co(1), and one Co(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one La(2), one La(3), one Co(1), and one Co(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to three equivalent La(1), one Co(1), and one Co(2) atom. In the fourth O site, O(4) is bonded to one La(2), one La(3), two equivalent La(1), one Co(1), and one Co(2) atom to form distorted OLa4Co2 octahedra that share corners with two equivalent O(4)La4Co2 octahedra, corners with two equivalent O(7)La2Co2 tetrahedra,  an edgeedge with one O(5)La4Co2 octahedra, and faces with two equivalent O(5)La4Co2 octahedra. The corner-sharing octahedral tilt angles are 66°. In the fifth O site, O(5) is bonded to one La(2), one La(3), two equivalent La(1), one Co(1), and one Co(2) atom to form distorted OLa4Co2 octahedra that share corners with two equivalent O(5)La4Co2 octahedra, corners with two equivalent O(7)La2Co2 tetrahedra,  an edgeedge with one O(4)La4Co2 octahedra, and faces with two equivalent O(4)La4Co2 octahedra. The corner-sharing octahedral tilt angles are 66°. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one La(3), two equivalent La(2), one Co(1), and one Co(3) atom. In the seventh O site, O(7) is bonded to one La(2), one La(3), and two equivalent Co(3) atoms to form distorted OLa2Co2 tetrahedra that share corners with two equivalent O(4)La4Co2 octahedra, corners with two equivalent O(5)La4Co2 octahedra, and corners with two equivalent O(7)La2Co2 tetrahedra. The corner-sharing octahedral tilt angles range from 24-45°. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one La(2), two equivalent La(3), one Co(2), and one Co(3) atom.
La3Co3O8 crystallizes in the monoclinic P2_1 space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to two equivalent O(4), two equivalent O(5), and three equivalent O(3) atoms. There is one shorter (2.58 Å) and one longer (2.60 Å) La(1)-O(4) bond length. There is one shorter (2.57 Å) and one longer (2.61 Å) La(1)-O(5) bond length. There is one shorter (2.38 Å) and two longer (2.76 Å) La(1)-O(3) bond lengths. In the second La site, La(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), one O(8), and two equivalent O(6) atoms. The La(2)-O(1) bond length is 2.45 Å. The La(2)-O(2) bond length is 2.44 Å. The La(2)-O(4) bond length is 2.75 Å. The La(2)-O(5) bond length is 2.75 Å. The La(2)-O(7) bond length is 2.39 Å. The La(2)-O(8) bond length is 2.40 Å. There is one shorter (2.65 Å) and one longer (2.91 Å) La(2)-O(6) bond length. In the third La site, La(3) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. The La(3)-O(1) bond length is 2.46 Å. The La(3)-O(2) bond length is 2.46 Å. The La(3)-O(4) bond length is 2.68 Å. The La(3)-O(5) bond length is 2.67 Å. The La(3)-O(6) bond length is 2.38 Å. The La(3)-O(7) bond length is 2.41 Å. There is one shorter (2.69 Å) and one longer (2.82 Å) La(3)-O(8) bond length. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with five equivalent Co(2)O6 octahedra and  a cornercorner with one Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-25°. The Co(1)-O(1) bond length is 2.01 Å. The Co(1)-O(2) bond length is 2.02 Å. The Co(1)-O(3) bond length is 2.08 Å. The Co(1)-O(4) bond length is 2.04 Å. The Co(1)-O(5) bond length is 2.04 Å. The Co(1)-O(6) bond length is 2.26 Å. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form CoO6 octahedra that share corners with five equivalent Co(1)O6 octahedra and  a cornercorner with one Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-25°. The Co(2)-O(1) bond length is 1.93 Å. The Co(2)-O(2) bond length is 1.92 Å. The Co(2)-O(3) bond length is 1.92 Å. The Co(2)-O(4) bond length is 1.95 Å. The Co(2)-O(5) bond length is 1.94 Å. The Co(2)-O(8) bond length is 2.09 Å. In the third Co site, Co(3) is bonded to one O(6), one O(8), and two equivalent O(7) atoms to form CoO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, and corners with two equivalent Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-37°. The Co(3)-O(6) bond length is 1.95 Å. The Co(3)-O(8) bond length is 1.99 Å. There is one shorter (1.99 Å) and one longer (2.03 Å) Co(3)-O(7) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one La(2), one La(3), one Co(1), and one Co(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one La(2), one La(3), one Co(1), and one Co(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to three equivalent La(1), one Co(1), and one Co(2) atom. In the fourth O site, O(4) is bonded to one La(2), one La(3), two equivalent La(1), one Co(1), and one Co(2) atom to form distorted OLa4Co2 octahedra that share corners with two equivalent O(4)La4Co2 octahedra, corners with two equivalent O(7)La2Co2 tetrahedra,  an edgeedge with one O(5)La4Co2 octahedra, and faces with two equivalent O(5)La4Co2 octahedra. The corner-sharing octahedral tilt angles are 66°. In the fifth O site, O(5) is bonded to one La(2), one La(3), two equivalent La(1), one Co(1), and one Co(2) atom to form distorted OLa4Co2 octahedra that share corners with two equivalent O(5)La4Co2 octahedra, corners with two equivalent O(7)La2Co2 tetrahedra,  an edgeedge with one O(4)La4Co2 octahedra, and faces with two equivalent O(4)La4Co2 octahedra. The corner-sharing octahedral tilt angles are 66°. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one La(3), two equivalent La(2), one Co(1), and one Co(3) atom. In the seventh O site, O(7) is bonded to one La(2), one La(3), and two equivalent Co(3) atoms to form distorted OLa2Co2 tetrahedra that share corners with two equivalent O(4)La4Co2 octahedra, corners with two equivalent O(5)La4Co2 octahedra, and corners with two equivalent O(7)La2Co2 tetrahedra. The corner-sharing octahedral tilt angles range from 24-45°. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one La(2), two equivalent La(3), one Co(2), and one Co(3) atom.