Cs4Ni3F10 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 11-coordinate geometry to one F(2), two equivalent F(4), four equivalent F(1), and four equivalent F(3) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one F(3), two equivalent F(4), three equivalent F(2), and four equivalent F(1) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form a mixture of face and corner-sharing NiF6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Ni site, Ni(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form face-sharing NiF6 octahedra. There are four inequivalent F sites. In the first F site, F(2) is bonded to one Cs(1), three equivalent Cs(2), one Ni(1), and one Ni(2) atom to form a mixture of distorted corner and edge-sharing FCs4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second F site, F(3) is bonded in a 1-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Ni(1) atom. In the third F site, F(4) is bonded in a linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Ni(1) atoms. In the fourth F site, F(1) is bonded in a 2-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Ni(1), and one Ni(2) atom.
Cs4Ni3F10 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 11-coordinate geometry to one F(2), two equivalent F(4), four equivalent F(1), and four equivalent F(3) atoms. The Cs(1)-F(2) bond length is 3.18 Å. Both Cs(1)-F(4) bond lengths are 3.18 Å. There are two shorter (3.02 Å) and two longer (3.24 Å) Cs(1)-F(1) bond lengths. There are a spread of Cs(1)-F(3) bond distances ranging from 3.11-3.61 Å. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one F(3), two equivalent F(4), three equivalent F(2), and four equivalent F(1) atoms. The Cs(2)-F(3) bond length is 2.92 Å. Both Cs(2)-F(4) bond lengths are 3.13 Å. There is one shorter (2.99 Å) and two longer (3.08 Å) Cs(2)-F(2) bond lengths. There are two shorter (3.06 Å) and two longer (3.10 Å) Cs(2)-F(1) bond lengths. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form a mixture of face and corner-sharing NiF6 octahedra. The corner-sharing octahedral tilt angles are 5°. The Ni(1)-F(2) bond length is 2.07 Å. The Ni(1)-F(3) bond length is 1.94 Å. Both Ni(1)-F(1) bond lengths are 2.06 Å. Both Ni(1)-F(4) bond lengths are 2.02 Å. In the second Ni site, Ni(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form face-sharing NiF6 octahedra. Both Ni(2)-F(2) bond lengths are 2.00 Å. All Ni(2)-F(1) bond lengths are 2.01 Å. There are four inequivalent F sites. In the first F site, F(2) is bonded to one Cs(1), three equivalent Cs(2), one Ni(1), and one Ni(2) atom to form a mixture of distorted corner and edge-sharing FCs4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second F site, F(3) is bonded in a 1-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Ni(1) atom. In the third F site, F(4) is bonded in a linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Ni(1) atoms. In the fourth F site, F(1) is bonded in a 2-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Ni(1), and one Ni(2) atom.