Li3NiSiO5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with three equivalent Si(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. Ni(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form NiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. Si(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form SiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(4), two equivalent Ni(1), and one Si(1) atom to form OLi3SiNi2 octahedra that share  a cornercorner with one O(2)Li4Si2 octahedra,  a cornercorner with one O(3)Li4SiNi octahedra, corners with two equivalent O(4)Li3SiNi2 octahedra, corners with two equivalent O(5)Li4SiNi octahedra, edges with two equivalent O(1)Li3SiNi2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with two equivalent O(3)Li4SiNi octahedra, edges with three equivalent O(4)Li3SiNi2 octahedra, and edges with three equivalent O(5)Li4SiNi octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(1)Li3SiNi2 octahedra,  a cornercorner with one O(5)Li4SiNi octahedra, corners with two equivalent O(4)Li3SiNi2 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(2)Li4Si2 octahedra, edges with two equivalent O(1)Li3SiNi2 octahedra, edges with two equivalent O(4)Li3SiNi2 octahedra, edges with three equivalent O(5)Li4SiNi octahedra, and edges with four equivalent O(3)Li4SiNi octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), one Ni(1), and one Si(1) atom to form distorted OLi4SiNi octahedra that share  a cornercorner with one O(1)Li3SiNi2 octahedra,  a cornercorner with one O(4)Li3SiNi2 octahedra, corners with two equivalent O(3)Li4SiNi octahedra, corners with two equivalent O(5)Li4SiNi octahedra,  an edgeedge with one O(3)Li4SiNi octahedra, edges with two equivalent O(1)Li3SiNi2 octahedra, edges with two equivalent O(5)Li4SiNi octahedra, edges with three equivalent O(4)Li3SiNi2 octahedra, and edges with four equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), two equivalent Ni(1), and one Si(1) atom to form OLi3SiNi2 octahedra that share  a cornercorner with one O(4)Li3SiNi2 octahedra,  a cornercorner with one O(3)Li4SiNi octahedra, corners with two equivalent O(1)Li3SiNi2 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(4)Li3SiNi2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with three equivalent O(1)Li3SiNi2 octahedra, edges with three equivalent O(3)Li4SiNi octahedra, and edges with three equivalent O(5)Li4SiNi octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), two equivalent Li(4), one Ni(1), and one Si(1) atom to form OLi4SiNi octahedra that share  a cornercorner with one O(2)Li4Si2 octahedra,  a cornercorner with one O(5)Li4SiNi octahedra, corners with two equivalent O(1)Li3SiNi2 octahedra, corners with two equivalent O(3)Li4SiNi octahedra,  an edgeedge with one O(5)Li4SiNi octahedra, edges with two equivalent O(3)Li4SiNi octahedra, edges with three equivalent O(1)Li3SiNi2 octahedra, edges with three equivalent O(4)Li3SiNi2 octahedra, and edges with three equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.
Li3NiSiO5 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with four equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. Both Li(1)-O(2) bond lengths are 2.15 Å. Both Li(1)-O(3) bond lengths are 1.99 Å. Both Li(1)-O(5) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(2)-O(2) bond lengths are 2.15 Å. Both Li(2)-O(3) bond lengths are 2.33 Å. Both Li(2)-O(4) bond lengths are 2.04 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Si(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The Li(3)-O(1) bond length is 2.20 Å. The Li(3)-O(2) bond length is 2.04 Å. The Li(3)-O(4) bond length is 2.07 Å. The Li(3)-O(5) bond length is 2.08 Å. There is one shorter (2.03 Å) and one longer (2.10 Å) Li(3)-O(3) bond length. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with three equivalent Si(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The Li(4)-O(2) bond length is 2.15 Å. The Li(4)-O(4) bond length is 2.14 Å. There is one shorter (2.08 Å) and one longer (2.11 Å) Li(4)-O(1) bond length. There is one shorter (2.03 Å) and one longer (2.30 Å) Li(4)-O(5) bond length. Ni(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form NiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. The Ni(1)-O(3) bond length is 1.91 Å. The Ni(1)-O(5) bond length is 1.91 Å. There is one shorter (1.95 Å) and one longer (2.07 Å) Ni(1)-O(1) bond length. There is one shorter (1.96 Å) and one longer (2.08 Å) Ni(1)-O(4) bond length. Si(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form SiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Si(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Si(1)-O(1) bond length is 1.81 Å. The Si(1)-O(3) bond length is 1.83 Å. The Si(1)-O(4) bond length is 1.83 Å. The Si(1)-O(5) bond length is 1.83 Å. There is one shorter (1.82 Å) and one longer (1.83 Å) Si(1)-O(2) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(4), two equivalent Ni(1), and one Si(1) atom to form OLi3SiNi2 octahedra that share  a cornercorner with one O(2)Li4Si2 octahedra,  a cornercorner with one O(3)Li4SiNi octahedra, corners with two equivalent O(4)Li3SiNi2 octahedra, corners with two equivalent O(5)Li4SiNi octahedra, edges with two equivalent O(1)Li3SiNi2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with two equivalent O(3)Li4SiNi octahedra, edges with three equivalent O(4)Li3SiNi2 octahedra, and edges with three equivalent O(5)Li4SiNi octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(1)Li3SiNi2 octahedra,  a cornercorner with one O(5)Li4SiNi octahedra, corners with two equivalent O(4)Li3SiNi2 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(2)Li4Si2 octahedra, edges with two equivalent O(1)Li3SiNi2 octahedra, edges with two equivalent O(4)Li3SiNi2 octahedra, edges with three equivalent O(5)Li4SiNi octahedra, and edges with four equivalent O(3)Li4SiNi octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), one Ni(1), and one Si(1) atom to form distorted OLi4SiNi octahedra that share  a cornercorner with one O(1)Li3SiNi2 octahedra,  a cornercorner with one O(4)Li3SiNi2 octahedra, corners with two equivalent O(3)Li4SiNi octahedra, corners with two equivalent O(5)Li4SiNi octahedra,  an edgeedge with one O(3)Li4SiNi octahedra, edges with two equivalent O(1)Li3SiNi2 octahedra, edges with two equivalent O(5)Li4SiNi octahedra, edges with three equivalent O(4)Li3SiNi2 octahedra, and edges with four equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), two equivalent Ni(1), and one Si(1) atom to form OLi3SiNi2 octahedra that share  a cornercorner with one O(4)Li3SiNi2 octahedra,  a cornercorner with one O(3)Li4SiNi octahedra, corners with two equivalent O(1)Li3SiNi2 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(4)Li3SiNi2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with three equivalent O(1)Li3SiNi2 octahedra, edges with three equivalent O(3)Li4SiNi octahedra, and edges with three equivalent O(5)Li4SiNi octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), two equivalent Li(4), one Ni(1), and one Si(1) atom to form OLi4SiNi octahedra that share  a cornercorner with one O(2)Li4Si2 octahedra,  a cornercorner with one O(5)Li4SiNi octahedra, corners with two equivalent O(1)Li3SiNi2 octahedra, corners with two equivalent O(3)Li4SiNi octahedra,  an edgeedge with one O(5)Li4SiNi octahedra, edges with two equivalent O(3)Li4SiNi octahedra, edges with three equivalent O(1)Li3SiNi2 octahedra, edges with three equivalent O(4)Li3SiNi2 octahedra, and edges with three equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.