Li4MnP6(H4O11)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(3), one O(4), and two equivalent O(11) atoms to form distorted LiO5 square pyramids that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(1)O5 square pyramid, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 61°. In the second Li site, Li(2) is bonded to one O(10), one O(11), one O(3), one O(8), and one O(9) atom to form LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent Li(1)O5 square pyramids. Mn(1) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the second P site, P(2) is bonded to one O(1), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 30°. In the third P site, P(3) is bonded to one O(11), one O(2), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. There are four inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(6) and one O(8) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) and one O(9) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(10) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(10) atom. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to one Mn(1), one H(1), and one H(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one P(3), and one H(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one P(2), and one H(2) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Li(1), one Li(2), one H(3), and one H(4) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one P(3) atom.
Li4MnP6(H4O11)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(3), one O(4), and two equivalent O(11) atoms to form distorted LiO5 square pyramids that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(1)O5 square pyramid, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 61°. The Li(1)-O(10) bond length is 2.09 Å. The Li(1)-O(3) bond length is 2.39 Å. The Li(1)-O(4) bond length is 2.55 Å. There is one shorter (2.05 Å) and one longer (2.14 Å) Li(1)-O(11) bond length. In the second Li site, Li(2) is bonded to one O(10), one O(11), one O(3), one O(8), and one O(9) atom to form LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent Li(1)O5 square pyramids. The Li(2)-O(10) bond length is 2.26 Å. The Li(2)-O(11) bond length is 2.15 Å. The Li(2)-O(3) bond length is 2.00 Å. The Li(2)-O(8) bond length is 2.44 Å. The Li(2)-O(9) bond length is 2.05 Å. Mn(1) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. Both Mn(1)-O(4) bond lengths are 2.30 Å. Both Mn(1)-O(5) bond lengths are 2.15 Å. Both Mn(1)-O(6) bond lengths are 2.17 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The P(1)-O(1) bond length is 1.64 Å. The P(1)-O(2) bond length is 1.63 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(1), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 30°. The P(2)-O(1) bond length is 1.63 Å. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(7) bond length is 1.63 Å. The P(2)-O(9) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(11), one O(2), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(2) bond length is 1.62 Å. The P(3)-O(7) bond length is 1.63 Å. The P(3)-O(8) bond length is 1.49 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(6) and one O(8) atom. The H(1)-O(6) bond length is 1.01 Å. The H(1)-O(8) bond length is 1.58 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) and one O(9) atom. The H(2)-O(6) bond length is 1.00 Å. The H(2)-O(9) bond length is 1.71 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(10) atom. The H(3)-O(10) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(10) atom. The H(4)-O(10) bond length is 0.98 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to one Mn(1), one H(1), and one H(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one P(3), and one H(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one P(2), and one H(2) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Li(1), one Li(2), one H(3), and one H(4) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one P(3) atom.