Rb4Zr3Se14 crystallizes in the monoclinic C2/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to one Se(1), one Se(3), one Se(4), two equivalent Se(5), two equivalent Se(7), and three equivalent Se(6) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one Se(4), one Se(5), one Se(6), one Se(7), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Se(2), one Se(3), one Se(4), one Se(6), one Se(7), and two equivalent Se(5) atoms to form distorted ZrSe7 pentagonal bipyramids that share  an edgeedge with one Zr(1)Se7 pentagonal bipyramid and  a faceface with one Zr(2)Se8 hexagonal bipyramid. In the second Zr site, Zr(2) is bonded to two equivalent Se(1), two equivalent Se(2), two equivalent Se(3), and two equivalent Se(4) atoms to form distorted face-sharing ZrSe8 hexagonal bipyramids. There are seven inequivalent Se sites. In the first Se site, Se(2) is bonded in a 4-coordinate geometry to two equivalent Rb(2), one Zr(1), one Zr(2), and one Se(7) atom. In the second Se site, Se(3) is bonded in a 2-coordinate geometry to one Rb(1), two equivalent Rb(2), one Zr(1), one Zr(2), and one Se(6) atom. In the third Se site, Se(4) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(2), one Zr(1), one Zr(2), one Se(1), and one Se(7) atom. In the fourth Se site, Se(5) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(1), and two equivalent Zr(1) atoms. In the fifth Se site, Se(6) is bonded in a 6-coordinate geometry to one Rb(2), three equivalent Rb(1), one Zr(1), and one Se(3) atom. In the sixth Se site, Se(7) is bonded in a 6-coordinate geometry to one Rb(2), two equivalent Rb(1), one Zr(1), one Se(2), and one Se(4) atom. In the seventh Se site, Se(1) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Zr(2), and one Se(4) atom.
Rb4Zr3Se14 crystallizes in the monoclinic C2/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to one Se(1), one Se(3), one Se(4), two equivalent Se(5), two equivalent Se(7), and three equivalent Se(6) atoms. The Rb(1)-Se(1) bond length is 3.62 Å. The Rb(1)-Se(3) bond length is 3.84 Å. The Rb(1)-Se(4) bond length is 3.50 Å. There is one shorter (3.43 Å) and one longer (3.97 Å) Rb(1)-Se(5) bond length. There is one shorter (3.66 Å) and one longer (3.67 Å) Rb(1)-Se(7) bond length. There are a spread of Rb(1)-Se(6) bond distances ranging from 3.72-4.01 Å. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one Se(4), one Se(5), one Se(6), one Se(7), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms. The Rb(2)-Se(4) bond length is 3.56 Å. The Rb(2)-Se(5) bond length is 3.74 Å. The Rb(2)-Se(6) bond length is 3.46 Å. The Rb(2)-Se(7) bond length is 3.69 Å. There is one shorter (3.57 Å) and one longer (3.65 Å) Rb(2)-Se(1) bond length. There is one shorter (3.50 Å) and one longer (4.09 Å) Rb(2)-Se(2) bond length. There is one shorter (3.76 Å) and one longer (4.03 Å) Rb(2)-Se(3) bond length. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Se(2), one Se(3), one Se(4), one Se(6), one Se(7), and two equivalent Se(5) atoms to form distorted ZrSe7 pentagonal bipyramids that share  an edgeedge with one Zr(1)Se7 pentagonal bipyramid and  a faceface with one Zr(2)Se8 hexagonal bipyramid. The Zr(1)-Se(2) bond length is 2.78 Å. The Zr(1)-Se(3) bond length is 2.75 Å. The Zr(1)-Se(4) bond length is 2.89 Å. The Zr(1)-Se(6) bond length is 2.66 Å. The Zr(1)-Se(7) bond length is 2.73 Å. There is one shorter (2.57 Å) and one longer (2.72 Å) Zr(1)-Se(5) bond length. In the second Zr site, Zr(2) is bonded to two equivalent Se(1), two equivalent Se(2), two equivalent Se(3), and two equivalent Se(4) atoms to form distorted face-sharing ZrSe8 hexagonal bipyramids. Both Zr(2)-Se(1) bond lengths are 2.72 Å. Both Zr(2)-Se(2) bond lengths are 2.80 Å. Both Zr(2)-Se(3) bond lengths are 2.85 Å. Both Zr(2)-Se(4) bond lengths are 2.71 Å. There are seven inequivalent Se sites. In the first Se site, Se(2) is bonded in a 4-coordinate geometry to two equivalent Rb(2), one Zr(1), one Zr(2), and one Se(7) atom. The Se(2)-Se(7) bond length is 2.40 Å. In the second Se site, Se(3) is bonded in a 2-coordinate geometry to one Rb(1), two equivalent Rb(2), one Zr(1), one Zr(2), and one Se(6) atom. The Se(3)-Se(6) bond length is 2.38 Å. In the third Se site, Se(4) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(2), one Zr(1), one Zr(2), one Se(1), and one Se(7) atom. The Se(4)-Se(1) bond length is 2.42 Å. The Se(4)-Se(7) bond length is 2.98 Å. In the fourth Se site, Se(5) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(1), and two equivalent Zr(1) atoms. In the fifth Se site, Se(6) is bonded in a 6-coordinate geometry to one Rb(2), three equivalent Rb(1), one Zr(1), and one Se(3) atom. In the sixth Se site, Se(7) is bonded in a 6-coordinate geometry to one Rb(2), two equivalent Rb(1), one Zr(1), one Se(2), and one Se(4) atom. In the seventh Se site, Se(1) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Zr(2), and one Se(4) atom.