Cs7Co4F15 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), one F(8), two equivalent F(6), and two equivalent F(7) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one F(3), one F(4), one F(5), one F(6), one F(7), one F(8), two equivalent F(1), and two equivalent F(2) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one F(1), one F(4), one F(5), one F(6), two equivalent F(2), and two equivalent F(3) atoms. In the fourth Cs site, Cs(4) is bonded in a 10-coordinate geometry to two equivalent F(3), two equivalent F(4), two equivalent F(5), two equivalent F(6), and two equivalent F(7) atoms. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form a mixture of corner and face-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Co site, Co(2) is bonded to one F(1), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form a mixture of corner and face-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are eight inequivalent F sites. In the first F site, F(6) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Co(2) atom. In the second F site, F(7) is bonded to one Cs(2), one Cs(4), two equivalent Cs(1), one Co(1), and one Co(2) atom to form a mixture of distorted corner and face-sharing FCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°. In the third F site, F(8) is bonded in a distorted linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Co(2) atoms. In the fourth F site, F(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), one Co(1), and one Co(2) atom. In the fifth F site, F(2) is bonded in a distorted single-bond geometry to one Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Co(1) atom. In the sixth F site, F(3) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one Co(1) atom. In the seventh F site, F(4) is bonded in a distorted linear geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Co(1), and one Co(2) atom. In the eighth F site, F(5) is bonded to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Co(1), and one Co(2) atom to form a mixture of distorted corner and face-sharing FCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°.
Cs7Co4F15 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), one F(8), two equivalent F(6), and two equivalent F(7) atoms. The Cs(1)-F(1) bond length is 3.09 Å. The Cs(1)-F(2) bond length is 2.99 Å. The Cs(1)-F(3) bond length is 3.05 Å. The Cs(1)-F(4) bond length is 3.12 Å. The Cs(1)-F(5) bond length is 3.05 Å. The Cs(1)-F(8) bond length is 3.14 Å. There is one shorter (3.07 Å) and one longer (3.08 Å) Cs(1)-F(6) bond length. There is one shorter (3.03 Å) and one longer (3.11 Å) Cs(1)-F(7) bond length. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one F(3), one F(4), one F(5), one F(6), one F(7), one F(8), two equivalent F(1), and two equivalent F(2) atoms. The Cs(2)-F(3) bond length is 3.41 Å. The Cs(2)-F(4) bond length is 3.04 Å. The Cs(2)-F(5) bond length is 3.14 Å. The Cs(2)-F(6) bond length is 3.16 Å. The Cs(2)-F(7) bond length is 3.11 Å. The Cs(2)-F(8) bond length is 3.15 Å. There is one shorter (3.11 Å) and one longer (3.28 Å) Cs(2)-F(1) bond length. There is one shorter (3.10 Å) and one longer (3.29 Å) Cs(2)-F(2) bond length. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one F(1), one F(4), one F(5), one F(6), two equivalent F(2), and two equivalent F(3) atoms. The Cs(3)-F(1) bond length is 3.02 Å. The Cs(3)-F(4) bond length is 3.09 Å. The Cs(3)-F(5) bond length is 2.97 Å. The Cs(3)-F(6) bond length is 2.93 Å. There is one shorter (2.98 Å) and one longer (2.99 Å) Cs(3)-F(2) bond length. There is one shorter (2.95 Å) and one longer (2.97 Å) Cs(3)-F(3) bond length. In the fourth Cs site, Cs(4) is bonded in a 10-coordinate geometry to two equivalent F(3), two equivalent F(4), two equivalent F(5), two equivalent F(6), and two equivalent F(7) atoms. Both Cs(4)-F(3) bond lengths are 3.04 Å. Both Cs(4)-F(4) bond lengths are 3.29 Å. Both Cs(4)-F(5) bond lengths are 3.16 Å. Both Cs(4)-F(6) bond lengths are 3.16 Å. Both Cs(4)-F(7) bond lengths are 3.18 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form a mixture of corner and face-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles are 5°. The Co(1)-F(1) bond length is 2.12 Å. The Co(1)-F(2) bond length is 1.98 Å. The Co(1)-F(3) bond length is 1.98 Å. The Co(1)-F(4) bond length is 2.09 Å. The Co(1)-F(5) bond length is 2.08 Å. The Co(1)-F(7) bond length is 2.08 Å. In the second Co site, Co(2) is bonded to one F(1), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form a mixture of corner and face-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. The Co(2)-F(1) bond length is 2.07 Å. The Co(2)-F(4) bond length is 2.04 Å. The Co(2)-F(5) bond length is 2.12 Å. The Co(2)-F(6) bond length is 1.97 Å. The Co(2)-F(7) bond length is 2.11 Å. The Co(2)-F(8) bond length is 2.06 Å. There are eight inequivalent F sites. In the first F site, F(6) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Co(2) atom. In the second F site, F(7) is bonded to one Cs(2), one Cs(4), two equivalent Cs(1), one Co(1), and one Co(2) atom to form a mixture of distorted corner and face-sharing FCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°. In the third F site, F(8) is bonded in a distorted linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Co(2) atoms. In the fourth F site, F(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), one Co(1), and one Co(2) atom. In the fifth F site, F(2) is bonded in a distorted single-bond geometry to one Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Co(1) atom. In the sixth F site, F(3) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one Co(1) atom. In the seventh F site, F(4) is bonded in a distorted linear geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Co(1), and one Co(2) atom. In the eighth F site, F(5) is bonded to one Cs(1), one Cs(2), one Cs(3), one Cs(4), one Co(1), and one Co(2) atom to form a mixture of distorted corner and face-sharing FCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°.