Cs4Re6Se13 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to one Cs(2), one Se(4), two equivalent Se(1), two equivalent Se(2), two equivalent Se(5), two equivalent Se(6), and two equivalent Se(7) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Cs(1), one Se(2), one Se(3), one Se(4), one Se(5), one Se(6), and two equivalent Se(7) atoms. There are three inequivalent Re sites. In the first Re site, Re(1) is bonded to one Se(1), one Se(2), one Se(3), one Se(5), and one Se(6) atom to form distorted edge-sharing ReSe5 square pyramids. In the second Re site, Re(2) is bonded to one Se(1), one Se(2), one Se(3), one Se(5), and one Se(7) atom to form distorted edge-sharing ReSe5 square pyramids. In the third Re site, Re(3) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Se(5) atom to form a mixture of distorted corner and edge-sharing ReSe5 square pyramids. There are seven inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom to form distorted edge-sharing SeCs2Re3 square pyramids. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to one Cs(2), one Re(1), one Re(2), and one Re(3) atom. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Re(3) atoms. In the fifth Se site, Se(5) is bonded in a 3-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), and one Se(6) atom. In the seventh Se site, Se(7) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Re(2), and one Se(7) atom.
Cs4Re6Se13 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to one Cs(2), one Se(4), two equivalent Se(1), two equivalent Se(2), two equivalent Se(5), two equivalent Se(6), and two equivalent Se(7) atoms. The Cs(1)-Cs(2) bond length is 3.99 Å. The Cs(1)-Se(4) bond length is 4.17 Å. There is one shorter (3.48 Å) and one longer (3.55 Å) Cs(1)-Se(1) bond length. Both Cs(1)-Se(2) bond lengths are 3.80 Å. There is one shorter (4.23 Å) and one longer (4.27 Å) Cs(1)-Se(5) bond length. There is one shorter (3.62 Å) and one longer (3.79 Å) Cs(1)-Se(6) bond length. There is one shorter (4.08 Å) and one longer (4.10 Å) Cs(1)-Se(7) bond length. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Cs(1), one Se(2), one Se(3), one Se(4), one Se(5), one Se(6), and two equivalent Se(7) atoms. The Cs(2)-Se(2) bond length is 3.60 Å. The Cs(2)-Se(3) bond length is 3.45 Å. The Cs(2)-Se(4) bond length is 3.53 Å. The Cs(2)-Se(5) bond length is 3.86 Å. The Cs(2)-Se(6) bond length is 3.58 Å. There is one shorter (3.51 Å) and one longer (4.03 Å) Cs(2)-Se(7) bond length. There are three inequivalent Re sites. In the first Re site, Re(1) is bonded to one Se(1), one Se(2), one Se(3), one Se(5), and one Se(6) atom to form distorted edge-sharing ReSe5 square pyramids. The Re(1)-Se(1) bond length is 2.53 Å. The Re(1)-Se(2) bond length is 2.53 Å. The Re(1)-Se(3) bond length is 2.54 Å. The Re(1)-Se(5) bond length is 2.55 Å. The Re(1)-Se(6) bond length is 2.67 Å. In the second Re site, Re(2) is bonded to one Se(1), one Se(2), one Se(3), one Se(5), and one Se(7) atom to form distorted edge-sharing ReSe5 square pyramids. The Re(2)-Se(1) bond length is 2.55 Å. The Re(2)-Se(2) bond length is 2.53 Å. The Re(2)-Se(3) bond length is 2.54 Å. The Re(2)-Se(5) bond length is 2.56 Å. The Re(2)-Se(7) bond length is 2.58 Å. In the third Re site, Re(3) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Se(5) atom to form a mixture of distorted corner and edge-sharing ReSe5 square pyramids. The Re(3)-Se(1) bond length is 2.52 Å. The Re(3)-Se(2) bond length is 2.55 Å. The Re(3)-Se(3) bond length is 2.51 Å. The Re(3)-Se(4) bond length is 2.61 Å. The Re(3)-Se(5) bond length is 2.56 Å. There are seven inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom to form distorted edge-sharing SeCs2Re3 square pyramids. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to one Cs(2), one Re(1), one Re(2), and one Re(3) atom. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Re(3) atoms. In the fifth Se site, Se(5) is bonded in a 3-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), one Re(2), and one Re(3) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), one Re(1), and one Se(6) atom. The Se(6)-Se(6) bond length is 2.46 Å. In the seventh Se site, Se(7) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Re(2), and one Se(7) atom. The Se(7)-Se(7) bond length is 2.41 Å.