Li3CoPO5 is Stannite-like structured and crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Co(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(3), one O(5), and two equivalent O(2) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Co(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(3), and two equivalent O(4) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Co(1)O4 tetrahedra. Co(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form CoO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with four equivalent Li(3)O4 tetrahedra. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent Co(1) atoms to form OLi2Co2 tetrahedra that share  a cornercorner with one O(2)Li3P tetrahedra, corners with two equivalent O(1)Li2Co2 tetrahedra, corners with two equivalent O(3)Li3P tetrahedra, corners with three equivalent O(5)Li2CoP tetrahedra, and corners with four equivalent O(4)Li2CoP tetrahedra. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and one P(1) atom to form distorted OLi3P tetrahedra that share  a cornercorner with one O(1)Li2Co2 tetrahedra,  a cornercorner with one O(4)Li2CoP tetrahedra, corners with two equivalent O(2)Li3P tetrahedra, corners with four equivalent O(5)Li2CoP tetrahedra, and corners with four equivalent O(3)Li3P tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(1)Li2Co2 tetrahedra, corners with three equivalent O(4)Li2CoP tetrahedra, corners with three equivalent O(5)Li2CoP tetrahedra, and corners with four equivalent O(2)Li3P tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Co(1), and one P(1) atom to form distorted OLi2CoP tetrahedra that share  a cornercorner with one O(2)Li3P tetrahedra, corners with two equivalent O(4)Li2CoP tetrahedra, corners with two equivalent O(5)Li2CoP tetrahedra, corners with three equivalent O(3)Li3P tetrahedra, and corners with four equivalent O(1)Li2Co2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Co(1), and one P(1) atom to form OLi2CoP tetrahedra that share corners with two equivalent O(4)Li2CoP tetrahedra, corners with three equivalent O(1)Li2Co2 tetrahedra, corners with three equivalent O(3)Li3P tetrahedra, and corners with four equivalent O(2)Li3P tetrahedra.
Li3CoPO5 is Stannite-like structured and crystallizes in the orthorhombic Pna2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Co(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. The Li(1)-O(1) bond length is 1.88 Å. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(5) bond length is 2.02 Å. In the second Li site, Li(2) is bonded to one O(3), one O(5), and two equivalent O(2) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Co(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(5) bond length is 1.99 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(3), and two equivalent O(4) atoms to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Co(1)O4 tetrahedra. The Li(3)-O(1) bond length is 1.93 Å. The Li(3)-O(3) bond length is 2.07 Å. Both Li(3)-O(4) bond lengths are 2.09 Å. Co(1) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form CoO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with four equivalent Li(3)O4 tetrahedra. The Co(1)-O(4) bond length is 2.07 Å. The Co(1)-O(5) bond length is 2.09 Å. There is one shorter (1.90 Å) and one longer (1.91 Å) Co(1)-O(1) bond length. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with four equivalent Li(2)O4 tetrahedra. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.57 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent Co(1) atoms to form OLi2Co2 tetrahedra that share  a cornercorner with one O(2)Li3P tetrahedra, corners with two equivalent O(1)Li2Co2 tetrahedra, corners with two equivalent O(3)Li3P tetrahedra, corners with three equivalent O(5)Li2CoP tetrahedra, and corners with four equivalent O(4)Li2CoP tetrahedra. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and one P(1) atom to form distorted OLi3P tetrahedra that share  a cornercorner with one O(1)Li2Co2 tetrahedra,  a cornercorner with one O(4)Li2CoP tetrahedra, corners with two equivalent O(2)Li3P tetrahedra, corners with four equivalent O(5)Li2CoP tetrahedra, and corners with four equivalent O(3)Li3P tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(1)Li2Co2 tetrahedra, corners with three equivalent O(4)Li2CoP tetrahedra, corners with three equivalent O(5)Li2CoP tetrahedra, and corners with four equivalent O(2)Li3P tetrahedra. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Co(1), and one P(1) atom to form distorted OLi2CoP tetrahedra that share  a cornercorner with one O(2)Li3P tetrahedra, corners with two equivalent O(4)Li2CoP tetrahedra, corners with two equivalent O(5)Li2CoP tetrahedra, corners with three equivalent O(3)Li3P tetrahedra, and corners with four equivalent O(1)Li2Co2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Co(1), and one P(1) atom to form OLi2CoP tetrahedra that share corners with two equivalent O(4)Li2CoP tetrahedra, corners with three equivalent O(1)Li2Co2 tetrahedra, corners with three equivalent O(3)Li3P tetrahedra, and corners with four equivalent O(2)Li3P tetrahedra.