Li3Mn(CuO3)2 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with five equivalent Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. Mn(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Cu(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form CuO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-12°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), one Mn(1), and two equivalent Cu(1) atoms to form OLi3MnCu2 octahedra that share  a cornercorner with one O(3)Li3Mn2Cu octahedra,  a cornercorner with one O(1)Li3MnCu2 octahedra, corners with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(3)Li3Mn2Cu octahedra, and edges with four equivalent O(1)Li3MnCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Cu(1) atoms to form OLi3Cu3 octahedra that share  a cornercorner with one O(2)Li3Cu3 octahedra,  a cornercorner with one O(3)Li3Mn2Cu octahedra, corners with four equivalent O(1)Li3MnCu2 octahedra, edges with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(3)Li3Mn2Cu octahedra, and edges with four equivalent O(1)Li3MnCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Cu(1) atom to form OLi3Mn2Cu octahedra that share  a cornercorner with one O(2)Li3Cu3 octahedra,  a cornercorner with one O(1)Li3MnCu2 octahedra, corners with four equivalent O(3)Li3Mn2Cu octahedra, edges with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(3)Li3Mn2Cu octahedra, and edges with four equivalent O(1)Li3MnCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
Li3Mn(CuO3)2 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Li(1)-O(2) bond lengths are 2.11 Å. All Li(1)-O(3) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with five equivalent Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. The Li(2)-O(3) bond length is 2.09 Å. Both Li(2)-O(2) bond lengths are 2.09 Å. There are two shorter (2.14 Å) and one longer (2.25 Å) Li(2)-O(1) bond length. Mn(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Mn(1)-O(1) bond lengths are 1.97 Å. All Mn(1)-O(3) bond lengths are 1.94 Å. Cu(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form CuO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-12°. The Cu(1)-O(3) bond length is 2.28 Å. Both Cu(1)-O(1) bond lengths are 2.03 Å. There are two shorter (1.99 Å) and one longer (2.09 Å) Cu(1)-O(2) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), one Mn(1), and two equivalent Cu(1) atoms to form OLi3MnCu2 octahedra that share  a cornercorner with one O(3)Li3Mn2Cu octahedra,  a cornercorner with one O(1)Li3MnCu2 octahedra, corners with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(3)Li3Mn2Cu octahedra, and edges with four equivalent O(1)Li3MnCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Cu(1) atoms to form OLi3Cu3 octahedra that share  a cornercorner with one O(2)Li3Cu3 octahedra,  a cornercorner with one O(3)Li3Mn2Cu octahedra, corners with four equivalent O(1)Li3MnCu2 octahedra, edges with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(3)Li3Mn2Cu octahedra, and edges with four equivalent O(1)Li3MnCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Cu(1) atom to form OLi3Mn2Cu octahedra that share  a cornercorner with one O(2)Li3Cu3 octahedra,  a cornercorner with one O(1)Li3MnCu2 octahedra, corners with four equivalent O(3)Li3Mn2Cu octahedra, edges with four equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(3)Li3Mn2Cu octahedra, and edges with four equivalent O(1)Li3MnCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.