Ag5BiO4 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a linear geometry to one O(2) and one O(3) atom. In the second Ag site, Ag(2) is bonded in a linear geometry to two equivalent O(1) atoms. In the third Ag site, Ag(3) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(4) atom. In the fourth Ag site, Ag(4) is bonded in a linear geometry to one O(1) and one O(4) atom. In the fifth Ag site, Ag(5) is bonded in a linear geometry to two equivalent O(4) atoms. In the sixth Ag site, Ag(6) is bonded in a linear geometry to one O(2) and one O(3) atom. Bi(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form edge-sharing BiO5 square pyramids. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Ag(3), one Ag(4), one Ag(5), and one Bi(1) atom to form OAg3Bi tetrahedra that share  a cornercorner with one O(4)Ag3Bi tetrahedra, corners with two equivalent O(3)Ag2Bi2 tetrahedra, corners with two equivalent O(2)Ag3Bi tetrahedra, and corners with three equivalent O(1)Ag3Bi tetrahedra. In the second O site, O(1) is bonded to one Ag(2), one Ag(3), one Ag(4), and one Bi(1) atom to form OAg3Bi tetrahedra that share  a cornercorner with one O(1)Ag3Bi tetrahedra, corners with two equivalent O(3)Ag2Bi2 tetrahedra, corners with two equivalent O(2)Ag3Bi tetrahedra, and corners with three equivalent O(4)Ag3Bi tetrahedra. In the third O site, O(2) is bonded to one Ag(1), one Ag(3), one Ag(6), and one Bi(1) atom to form OAg3Bi tetrahedra that share corners with two equivalent O(1)Ag3Bi tetrahedra, corners with two equivalent O(4)Ag3Bi tetrahedra, and corners with four equivalent O(3)Ag2Bi2 tetrahedra. In the fourth O site, O(3) is bonded to one Ag(1), one Ag(6), and two equivalent Bi(1) atoms to form OAg2Bi2 tetrahedra that share corners with two equivalent O(1)Ag3Bi tetrahedra, corners with two equivalent O(4)Ag3Bi tetrahedra, corners with four equivalent O(2)Ag3Bi tetrahedra, and  an edgeedge with one O(3)Ag2Bi2 tetrahedra.
Ag5BiO4 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a linear geometry to one O(2) and one O(3) atom. The Ag(1)-O(2) bond length is 2.09 Å. The Ag(1)-O(3) bond length is 2.09 Å. In the second Ag site, Ag(2) is bonded in a linear geometry to two equivalent O(1) atoms. Both Ag(2)-O(1) bond lengths are 2.10 Å. In the third Ag site, Ag(3) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(4) atom. The Ag(3)-O(1) bond length is 2.58 Å. The Ag(3)-O(2) bond length is 2.17 Å. The Ag(3)-O(4) bond length is 2.19 Å. In the fourth Ag site, Ag(4) is bonded in a linear geometry to one O(1) and one O(4) atom. The Ag(4)-O(1) bond length is 2.11 Å. The Ag(4)-O(4) bond length is 2.19 Å. In the fifth Ag site, Ag(5) is bonded in a linear geometry to two equivalent O(4) atoms. Both Ag(5)-O(4) bond lengths are 2.16 Å. In the sixth Ag site, Ag(6) is bonded in a linear geometry to one O(2) and one O(3) atom. The Ag(6)-O(2) bond length is 2.09 Å. The Ag(6)-O(3) bond length is 2.07 Å. Bi(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form edge-sharing BiO5 square pyramids. The Bi(1)-O(1) bond length is 2.20 Å. The Bi(1)-O(2) bond length is 2.32 Å. The Bi(1)-O(4) bond length is 2.17 Å. There is one shorter (2.29 Å) and one longer (2.42 Å) Bi(1)-O(3) bond length. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Ag(3), one Ag(4), one Ag(5), and one Bi(1) atom to form OAg3Bi tetrahedra that share  a cornercorner with one O(4)Ag3Bi tetrahedra, corners with two equivalent O(3)Ag2Bi2 tetrahedra, corners with two equivalent O(2)Ag3Bi tetrahedra, and corners with three equivalent O(1)Ag3Bi tetrahedra. In the second O site, O(1) is bonded to one Ag(2), one Ag(3), one Ag(4), and one Bi(1) atom to form OAg3Bi tetrahedra that share  a cornercorner with one O(1)Ag3Bi tetrahedra, corners with two equivalent O(3)Ag2Bi2 tetrahedra, corners with two equivalent O(2)Ag3Bi tetrahedra, and corners with three equivalent O(4)Ag3Bi tetrahedra. In the third O site, O(2) is bonded to one Ag(1), one Ag(3), one Ag(6), and one Bi(1) atom to form OAg3Bi tetrahedra that share corners with two equivalent O(1)Ag3Bi tetrahedra, corners with two equivalent O(4)Ag3Bi tetrahedra, and corners with four equivalent O(3)Ag2Bi2 tetrahedra. In the fourth O site, O(3) is bonded to one Ag(1), one Ag(6), and two equivalent Bi(1) atoms to form OAg2Bi2 tetrahedra that share corners with two equivalent O(1)Ag3Bi tetrahedra, corners with two equivalent O(4)Ag3Bi tetrahedra, corners with four equivalent O(2)Ag3Bi tetrahedra, and  an edgeedge with one O(3)Ag2Bi2 tetrahedra.