NiAg4(PO4)6 crystallizes in the triclinic P-1 space group. Ni(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(12) atoms to form distorted NiO6 octahedra that share corners with two equivalent Ag(2)O5 square pyramids. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(2), one O(5), one O(6), and one O(9) atom to form distorted AgO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Ag(2)O5 square pyramid. In the second Ag site, Ag(2) is bonded to one O(1), one O(10), one O(9), and two equivalent O(8) atoms to form distorted AgO5 square pyramids that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Ag(2)O5 square pyramid, and  an edgeedge with one Ag(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 41°. 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 Ag(2)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Ag(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Ag(1)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(4), one O(7), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with three equivalent Ag(2)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one Ag(1)O5 trigonal bipyramid. There are twelve inequivalent O sites. In the first O site, O(12) is bonded in a single-bond geometry to one Ni(1) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(1) atom. In the third O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Ag(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Ag(1) and one P(2) atom. In the seventh O site, O(6) is bonded in a bent 120 degrees geometry to one Ag(1) and one P(2) atom. In the eighth O site, O(7) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Ag(2) and one P(3) atom. In the tenth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(2), and one P(3) atom. In the eleventh O site, O(10) is bonded in a bent 150 degrees geometry to one Ni(1) and one Ag(2) atom. In the twelfth O site, O(11) is bonded in a single-bond geometry to one Ni(1) atom.
NiAg4(PO4)6 crystallizes in the triclinic P-1 space group. Ni(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(12) atoms to form distorted NiO6 octahedra that share corners with two equivalent Ag(2)O5 square pyramids. Both Ni(1)-O(10) bond lengths are 1.85 Å. Both Ni(1)-O(11) bond lengths are 1.80 Å. Both Ni(1)-O(12) bond lengths are 1.82 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(2), one O(5), one O(6), and one O(9) atom to form distorted AgO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Ag(2)O5 square pyramid. The Ag(1)-O(1) bond length is 2.24 Å. The Ag(1)-O(2) bond length is 2.19 Å. The Ag(1)-O(5) bond length is 2.54 Å. The Ag(1)-O(6) bond length is 2.24 Å. The Ag(1)-O(9) bond length is 2.32 Å. In the second Ag site, Ag(2) is bonded to one O(1), one O(10), one O(9), and two equivalent O(8) atoms to form distorted AgO5 square pyramids that share  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Ag(2)O5 square pyramid, and  an edgeedge with one Ag(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 41°. The Ag(2)-O(1) bond length is 2.49 Å. The Ag(2)-O(10) bond length is 2.17 Å. The Ag(2)-O(9) bond length is 2.39 Å. There is one shorter (2.32 Å) and one longer (2.48 Å) Ag(2)-O(8) bond length. 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 Ag(2)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Ag(1)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.49 Å. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(4) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Ag(1)O5 trigonal bipyramids. The P(2)-O(3) bond length is 1.65 Å. The P(2)-O(5) bond length is 1.48 Å. The P(2)-O(6) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.65 Å. In the third P site, P(3) is bonded to one O(4), one O(7), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with three equivalent Ag(2)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one Ag(1)O5 trigonal bipyramid. The P(3)-O(4) bond length is 1.62 Å. The P(3)-O(7) bond length is 1.61 Å. The P(3)-O(8) bond length is 1.51 Å. The P(3)-O(9) bond length is 1.52 Å. There are twelve inequivalent O sites. In the first O site, O(12) is bonded in a single-bond geometry to one Ni(1) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(1) atom. In the third O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Ag(1) and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Ag(1) and one P(2) atom. In the seventh O site, O(6) is bonded in a bent 120 degrees geometry to one Ag(1) and one P(2) atom. In the eighth O site, O(7) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(8) is bonded in a distorted trigonal planar geometry to two equivalent Ag(2) and one P(3) atom. In the tenth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(2), and one P(3) atom. In the eleventh O site, O(10) is bonded in a bent 150 degrees geometry to one Ni(1) and one Ag(2) atom. In the twelfth O site, O(11) is bonded in a single-bond geometry to one Ni(1) atom.