Li3Mn3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(12), one O(13), one O(5), and one O(8) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(13) and two equivalent O(16) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(11), one O(14), and one O(15) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(9) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Mn(3)O5 trigonal bipyramids. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(14), one O(15), one O(2), one O(3), one O(6), and one O(8) atom. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(2), one O(4), and one O(7) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Mn(1)O5 trigonal bipyramids. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O5 trigonal bipyramids and corners with two equivalent Mn(3)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(1), one O(12), one O(15), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O5 trigonal bipyramid and  a cornercorner with one Mn(3)O5 trigonal bipyramid. In the third P site, P(3) is bonded to one O(10), one O(16), one O(2), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O5 trigonal bipyramids. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O5 trigonal bipyramids. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to one Mn(1), one Mn(2), and one P(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Mn(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Mn(3) and one P(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one Mn(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Li(3) and one P(1) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(3), one Mn(2), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(2), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one P(3) atom.
Li3Mn3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(12), one O(13), one O(5), and one O(8) atom. The Li(1)-O(12) bond length is 1.97 Å. The Li(1)-O(13) bond length is 2.04 Å. The Li(1)-O(5) bond length is 2.06 Å. The Li(1)-O(8) bond length is 2.15 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(13) and two equivalent O(16) atoms. The Li(2)-O(13) bond length is 2.09 Å. There is one shorter (1.94 Å) and one longer (2.07 Å) Li(2)-O(16) bond length. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(11), one O(14), and one O(15) atom. The Li(3)-O(11) bond length is 1.95 Å. The Li(3)-O(14) bond length is 1.99 Å. The Li(3)-O(15) bond length is 2.26 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(9) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Mn(3)O5 trigonal bipyramids. The Mn(1)-O(1) bond length is 2.04 Å. The Mn(1)-O(3) bond length is 1.97 Å. The Mn(1)-O(4) bond length is 2.29 Å. The Mn(1)-O(5) bond length is 1.95 Å. The Mn(1)-O(9) bond length is 1.87 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(14), one O(15), one O(2), one O(3), one O(6), and one O(8) atom. The Mn(2)-O(14) bond length is 2.39 Å. The Mn(2)-O(15) bond length is 1.96 Å. The Mn(2)-O(2) bond length is 2.12 Å. The Mn(2)-O(3) bond length is 2.50 Å. The Mn(2)-O(6) bond length is 1.92 Å. The Mn(2)-O(8) bond length is 1.97 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(2), one O(4), and one O(7) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Mn(1)O5 trigonal bipyramids. The Mn(3)-O(1) bond length is 2.24 Å. The Mn(3)-O(10) bond length is 1.93 Å. The Mn(3)-O(2) bond length is 1.98 Å. The Mn(3)-O(4) bond length is 1.96 Å. The Mn(3)-O(7) bond length is 1.93 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O5 trigonal bipyramids and corners with two equivalent Mn(3)O5 trigonal bipyramids. The P(1)-O(11) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(12), one O(15), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O5 trigonal bipyramid and  a cornercorner with one Mn(3)O5 trigonal bipyramid. The P(2)-O(1) bond length is 1.59 Å. The P(2)-O(12) bond length is 1.50 Å. The P(2)-O(15) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(10), one O(16), one O(2), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O5 trigonal bipyramids. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(16) bond length is 1.49 Å. The P(3)-O(2) bond length is 1.60 Å. The P(3)-O(8) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O5 trigonal bipyramids. The P(4)-O(13) bond length is 1.53 Å. The P(4)-O(14) bond length is 1.54 Å. The P(4)-O(3) bond length is 1.60 Å. The P(4)-O(9) bond length is 1.55 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to one Mn(1), one Mn(2), and one P(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Mn(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Mn(3) and one P(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one Mn(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Mn(3) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Li(3) and one P(1) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(3), one Mn(2), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(2), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one P(3) atom.