CaAgF5 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one F(10), one F(2), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form CaF7 pentagonal bipyramids that share corners with two equivalent Ag(1)F6 octahedra, corners with two equivalent Ag(2)F6 octahedra,  an edgeedge with one Ag(1)F6 octahedra,  an edgeedge with one Ag(2)F6 octahedra, and edges with two equivalent Ca(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-44°. In the second Ca site, Ca(2) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form CaF7 pentagonal bipyramids that share corners with two equivalent Ag(1)F6 octahedra, corners with two equivalent Ag(2)F6 octahedra,  an edgeedge with one Ag(1)F6 octahedra,  an edgeedge with one Ag(2)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-45°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form AgF6 octahedra that share corners with two equivalent Ag(2)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 36-37°. In the second Ag site, Ag(2) is bonded to one F(1), one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form AgF6 octahedra that share corners with two equivalent Ag(1)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 36-37°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Ca(2), one Ag(1), and one Ag(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ag(1), and one Ag(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Ca(2) and one Ag(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(2) and one Ag(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(1) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(2) atom. In the ninth F site, F(9) is bonded in a linear geometry to one Ca(1) and one Ag(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Ca(1) and one Ag(2) atom.
CaAgF5 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one F(10), one F(2), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form CaF7 pentagonal bipyramids that share corners with two equivalent Ag(1)F6 octahedra, corners with two equivalent Ag(2)F6 octahedra,  an edgeedge with one Ag(1)F6 octahedra,  an edgeedge with one Ag(2)F6 octahedra, and edges with two equivalent Ca(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-44°. The Ca(1)-F(10) bond length is 2.20 Å. The Ca(1)-F(2) bond length is 2.41 Å. The Ca(1)-F(5) bond length is 2.52 Å. The Ca(1)-F(6) bond length is 2.48 Å. The Ca(1)-F(7) bond length is 2.36 Å. The Ca(1)-F(8) bond length is 2.36 Å. The Ca(1)-F(9) bond length is 2.25 Å. In the second Ca site, Ca(2) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form CaF7 pentagonal bipyramids that share corners with two equivalent Ag(1)F6 octahedra, corners with two equivalent Ag(2)F6 octahedra,  an edgeedge with one Ag(1)F6 octahedra,  an edgeedge with one Ag(2)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-45°. The Ca(2)-F(1) bond length is 2.40 Å. The Ca(2)-F(3) bond length is 2.21 Å. The Ca(2)-F(4) bond length is 2.25 Å. The Ca(2)-F(5) bond length is 2.35 Å. The Ca(2)-F(6) bond length is 2.36 Å. The Ca(2)-F(7) bond length is 2.54 Å. The Ca(2)-F(8) bond length is 2.47 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form AgF6 octahedra that share corners with two equivalent Ag(2)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 36-37°. The Ag(1)-F(1) bond length is 2.23 Å. The Ag(1)-F(2) bond length is 2.23 Å. The Ag(1)-F(4) bond length is 2.00 Å. The Ag(1)-F(5) bond length is 2.12 Å. The Ag(1)-F(7) bond length is 2.11 Å. The Ag(1)-F(9) bond length is 2.00 Å. In the second Ag site, Ag(2) is bonded to one F(1), one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form AgF6 octahedra that share corners with two equivalent Ag(1)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 36-37°. The Ag(2)-F(1) bond length is 2.08 Å. The Ag(2)-F(10) bond length is 2.05 Å. The Ag(2)-F(2) bond length is 2.07 Å. The Ag(2)-F(3) bond length is 2.04 Å. The Ag(2)-F(6) bond length is 2.14 Å. The Ag(2)-F(8) bond length is 2.14 Å. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Ca(2), one Ag(1), and one Ag(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ag(1), and one Ag(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Ca(2) and one Ag(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(2) and one Ag(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(1) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Ag(2) atom. In the ninth F site, F(9) is bonded in a linear geometry to one Ca(1) and one Ag(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Ca(1) and one Ag(2) atom.