Li4H(PO3)5 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(9) atom to form LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Li(3)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(11), one O(12), one O(14), one O(3), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(5)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. In the fourth Li site, Li(4) is bonded to one O(11), one O(12), one O(15), one O(2), and two equivalent O(10) atoms to form LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. There are five inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-60°. In the third P site, P(3) is bonded to one O(10), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-62°. In the fourth P site, P(4) is bonded to one O(12), one O(15), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the fifth P site, P(5) is bonded to one O(13), one O(14), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 41°. H(1) is bonded in a linear geometry to one O(1) and one O(2) atom. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one P(2), and one H(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(4), one P(3), and one H(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(2) and one P(5) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(5) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(3) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one P(5) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(5) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one P(4) atom.
Li4H(PO3)5 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(9) atom to form LiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Li(3)O4 tetrahedra. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(10) bond length is 2.24 Å. The Li(1)-O(11) bond length is 2.31 Å. The Li(1)-O(13) bond length is 2.14 Å. The Li(1)-O(15) bond length is 2.04 Å. The Li(1)-O(9) bond length is 2.15 Å. In the second Li site, Li(2) is bonded to one O(11), one O(12), one O(14), one O(3), and one O(9) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Li(2)-O(11) bond length is 2.00 Å. The Li(2)-O(12) bond length is 2.01 Å. The Li(2)-O(14) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.11 Å. The Li(2)-O(9) bond length is 2.39 Å. In the third Li site, Li(3) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(5)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The Li(3)-O(13) bond length is 1.99 Å. The Li(3)-O(14) bond length is 1.92 Å. The Li(3)-O(3) bond length is 2.02 Å. The Li(3)-O(9) bond length is 1.96 Å. In the fourth Li site, Li(4) is bonded to one O(11), one O(12), one O(15), one O(2), and two equivalent O(10) atoms to form LiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The Li(4)-O(11) bond length is 2.40 Å. The Li(4)-O(12) bond length is 2.08 Å. The Li(4)-O(15) bond length is 2.11 Å. The Li(4)-O(2) bond length is 2.24 Å. There is one shorter (2.17 Å) and one longer (2.38 Å) Li(4)-O(10) bond length. There are five inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(5) bond length is 1.63 Å. The P(1)-O(6) bond length is 1.61 Å. The P(1)-O(9) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-60°. The P(2)-O(1) bond length is 1.51 Å. The P(2)-O(11) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.63 Å. In the third P site, P(3) is bonded to one O(10), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-62°. The P(3)-O(10) bond length is 1.50 Å. The P(3)-O(2) bond length is 1.56 Å. The P(3)-O(5) bond length is 1.58 Å. The P(3)-O(7) bond length is 1.59 Å. In the fourth P site, P(4) is bonded to one O(12), one O(15), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-56°. The P(4)-O(12) bond length is 1.49 Å. The P(4)-O(15) bond length is 1.50 Å. The P(4)-O(7) bond length is 1.64 Å. The P(4)-O(8) bond length is 1.62 Å. In the fifth P site, P(5) is bonded to one O(13), one O(14), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 41°. The P(5)-O(13) bond length is 1.50 Å. The P(5)-O(14) bond length is 1.50 Å. The P(5)-O(4) bond length is 1.62 Å. The P(5)-O(6) bond length is 1.62 Å. H(1) is bonded in a linear geometry to one O(1) and one O(2) atom. The H(1)-O(1) bond length is 1.46 Å. The H(1)-O(2) bond length is 1.06 Å. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one P(2), and one H(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(4), one P(3), and one H(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(2) and one P(5) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(5) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(3) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one P(5) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(5) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one P(4) atom.