Rb3Pr3(PS4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one S(13), one S(14), one S(3), one S(4), one S(7), one S(8), and one S(9) atom. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one S(1), one S(10), one S(11), one S(12), one S(15), one S(4), one S(6), one S(9), and two equivalent S(5) atoms. In the third Rb site, Rb(3) is bonded in a 7-coordinate geometry to one S(11), one S(12), one S(15), one S(3), one S(7), and two equivalent S(16) atoms. There are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one S(10), one S(12), one S(4), one S(9), two equivalent S(13), and two equivalent S(14) atoms. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one S(11), one S(15), one S(6), one S(7), two equivalent S(2), and two equivalent S(8) atoms. In the third Pr site, Pr(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(14), one S(16), one S(2), one S(3), one S(5), and one S(6) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one S(14), one S(4), one S(5), and one S(9) atom. In the second P site, P(2) is bonded in a tetrahedral geometry to one S(10), one S(12), one S(13), and one S(3) atom. In the third P site, P(3) is bonded in a tetrahedral geometry to one S(1), one S(11), one S(2), and one S(7) atom. In the fourth P site, P(4) is bonded in a tetrahedral geometry to one S(15), one S(16), one S(6), and one S(8) atom. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Rb(2), one Pr(3), and one P(3) atom. In the second S site, S(2) is bonded to one Pr(3), two equivalent Pr(2), and one P(3) atom to form distorted SPr3P trigonal pyramids that share  a cornercorner with one S(14)RbPr3P trigonal bipyramid, corners with four equivalent S(8)RbPr2P trigonal pyramids, and  an edgeedge with one S(2)Pr3P trigonal pyramid. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(3), one Pr(3), and one P(2) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Rb(2), one Pr(1), and one P(1) atom. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to two equivalent Rb(2), one Pr(3), and one P(1) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Rb(2), one Pr(2), one Pr(3), and one P(4) atom. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(3), one Pr(2), and one P(3) atom. In the eighth S site, S(8) is bonded to one Rb(1), two equivalent Pr(2), and one P(4) atom to form distorted SRbPr2P trigonal pyramids that share  a cornercorner with one S(14)RbPr3P trigonal bipyramid, corners with four equivalent S(2)Pr3P trigonal pyramids, and  an edgeedge with one S(8)RbPr2P trigonal pyramid. In the ninth S site, S(9) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Pr(1), and one P(1) atom. In the tenth S site, S(10) is bonded in a distorted rectangular see-saw-like geometry to one Rb(2), one Pr(1), one Pr(3), and one P(2) atom. In the eleventh S site, S(11) is bonded in a 4-coordinate geometry to one Rb(2), one Rb(3), one Pr(2), and one P(3) atom. In the twelfth S site, S(12) is bonded to one Rb(2), one Rb(3), one Pr(1), and one P(2) atom to form distorted corner-sharing SRb2PrP trigonal pyramids. In the thirteenth S site, S(13) is bonded in a 4-coordinate geometry to one Rb(1), two equivalent Pr(1), and one P(2) atom. In the fourteenth S site, S(14) is bonded to one Rb(1), one Pr(3), two equivalent Pr(1), and one P(1) atom to form distorted SRbPr3P trigonal bipyramids that share  a cornercorner with one S(2)Pr3P trigonal pyramid,  a cornercorner with one S(8)RbPr2P trigonal pyramid, corners with two equivalent S(12)Rb2PrP trigonal pyramids, and  an edgeedge with one S(14)RbPr3P trigonal bipyramid. In the fifteenth S site, S(15) is bonded in a 4-coordinate geometry to one Rb(2), one Rb(3), one Pr(2), and one P(4) atom. In the sixteenth S site, S(16) is bonded in a 4-coordinate geometry to two equivalent Rb(3), one Pr(3), and one P(4) atom.
Rb3Pr3(PS4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one S(13), one S(14), one S(3), one S(4), one S(7), one S(8), and one S(9) atom. The Rb(1)-S(13) bond length is 3.71 Å. The Rb(1)-S(14) bond length is 3.72 Å. The Rb(1)-S(3) bond length is 3.60 Å. The Rb(1)-S(4) bond length is 3.49 Å. The Rb(1)-S(7) bond length is 3.36 Å. The Rb(1)-S(8) bond length is 3.55 Å. The Rb(1)-S(9) bond length is 3.31 Å. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one S(1), one S(10), one S(11), one S(12), one S(15), one S(4), one S(6), one S(9), and two equivalent S(5) atoms. The Rb(2)-S(1) bond length is 3.66 Å. The Rb(2)-S(10) bond length is 3.58 Å. The Rb(2)-S(11) bond length is 3.73 Å. The Rb(2)-S(12) bond length is 3.66 Å. The Rb(2)-S(15) bond length is 3.80 Å. The Rb(2)-S(4) bond length is 3.54 Å. The Rb(2)-S(6) bond length is 3.94 Å. The Rb(2)-S(9) bond length is 3.52 Å. There is one shorter (3.62 Å) and one longer (3.84 Å) Rb(2)-S(5) bond length. In the third Rb site, Rb(3) is bonded in a 7-coordinate geometry to one S(11), one S(12), one S(15), one S(3), one S(7), and two equivalent S(16) atoms. The Rb(3)-S(11) bond length is 3.51 Å. The Rb(3)-S(12) bond length is 3.51 Å. The Rb(3)-S(15) bond length is 3.62 Å. The Rb(3)-S(3) bond length is 3.84 Å. The Rb(3)-S(7) bond length is 3.57 Å. There is one shorter (3.76 Å) and one longer (3.77 Å) Rb(3)-S(16) bond length. There are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one S(10), one S(12), one S(4), one S(9), two equivalent S(13), and two equivalent S(14) atoms. The Pr(1)-S(10) bond length is 3.11 Å. The Pr(1)-S(12) bond length is 2.90 Å. The Pr(1)-S(4) bond length is 2.86 Å. The Pr(1)-S(9) bond length is 2.91 Å. There is one shorter (2.95 Å) and one longer (3.01 Å) Pr(1)-S(13) bond length. There is one shorter (3.00 Å) and one longer (3.28 Å) Pr(1)-S(14) bond length. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one S(11), one S(15), one S(6), one S(7), two equivalent S(2), and two equivalent S(8) atoms. The Pr(2)-S(11) bond length is 2.91 Å. The Pr(2)-S(15) bond length is 2.91 Å. The Pr(2)-S(6) bond length is 3.11 Å. The Pr(2)-S(7) bond length is 2.87 Å. There is one shorter (2.99 Å) and one longer (3.17 Å) Pr(2)-S(2) bond length. There is one shorter (2.96 Å) and one longer (3.05 Å) Pr(2)-S(8) bond length. In the third Pr site, Pr(3) is bonded in a 8-coordinate geometry to one S(1), one S(10), one S(14), one S(16), one S(2), one S(3), one S(5), and one S(6) atom. The Pr(3)-S(1) bond length is 2.91 Å. The Pr(3)-S(10) bond length is 3.00 Å. The Pr(3)-S(14) bond length is 3.28 Å. The Pr(3)-S(16) bond length is 2.98 Å. The Pr(3)-S(2) bond length is 3.24 Å. The Pr(3)-S(3) bond length is 2.94 Å. The Pr(3)-S(5) bond length is 2.89 Å. The Pr(3)-S(6) bond length is 3.00 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one S(14), one S(4), one S(5), and one S(9) atom. The P(1)-S(14) bond length is 2.10 Å. The P(1)-S(4) bond length is 2.05 Å. The P(1)-S(5) bond length is 2.03 Å. The P(1)-S(9) bond length is 2.04 Å. In the second P site, P(2) is bonded in a tetrahedral geometry to one S(10), one S(12), one S(13), and one S(3) atom. The P(2)-S(10) bond length is 2.07 Å. The P(2)-S(12) bond length is 2.03 Å. The P(2)-S(13) bond length is 2.07 Å. The P(2)-S(3) bond length is 2.05 Å. In the third P site, P(3) is bonded in a tetrahedral geometry to one S(1), one S(11), one S(2), and one S(7) atom. The P(3)-S(1) bond length is 2.02 Å. The P(3)-S(11) bond length is 2.05 Å. The P(3)-S(2) bond length is 2.10 Å. The P(3)-S(7) bond length is 2.06 Å. In the fourth P site, P(4) is bonded in a tetrahedral geometry to one S(15), one S(16), one S(6), and one S(8) atom. The P(4)-S(15) bond length is 2.03 Å. The P(4)-S(16) bond length is 2.05 Å. The P(4)-S(6) bond length is 2.07 Å. The P(4)-S(8) bond length is 2.08 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Rb(2), one Pr(3), and one P(3) atom. In the second S site, S(2) is bonded to one Pr(3), two equivalent Pr(2), and one P(3) atom to form distorted SPr3P trigonal pyramids that share  a cornercorner with one S(14)RbPr3P trigonal bipyramid, corners with four equivalent S(8)RbPr2P trigonal pyramids, and  an edgeedge with one S(2)Pr3P trigonal pyramid. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(3), one Pr(3), and one P(2) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Rb(2), one Pr(1), and one P(1) atom. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to two equivalent Rb(2), one Pr(3), and one P(1) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Rb(2), one Pr(2), one Pr(3), and one P(4) atom. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(3), one Pr(2), and one P(3) atom. In the eighth S site, S(8) is bonded to one Rb(1), two equivalent Pr(2), and one P(4) atom to form distorted SRbPr2P trigonal pyramids that share  a cornercorner with one S(14)RbPr3P trigonal bipyramid, corners with four equivalent S(2)Pr3P trigonal pyramids, and  an edgeedge with one S(8)RbPr2P trigonal pyramid. In the ninth S site, S(9) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Pr(1), and one P(1) atom. In the tenth S site, S(10) is bonded in a distorted rectangular see-saw-like geometry to one Rb(2), one Pr(1), one Pr(3), and one P(2) atom. In the eleventh S site, S(11) is bonded in a 4-coordinate geometry to one Rb(2), one Rb(3), one Pr(2), and one P(3) atom. In the twelfth S site, S(12) is bonded to one Rb(2), one Rb(3), one Pr(1), and one P(2) atom to form distorted corner-sharing SRb2PrP trigonal pyramids. In the thirteenth S site, S(13) is bonded in a 4-coordinate geometry to one Rb(1), two equivalent Pr(1), and one P(2) atom. In the fourteenth S site, S(14) is bonded to one Rb(1), one Pr(3), two equivalent Pr(1), and one P(1) atom to form distorted SRbPr3P trigonal bipyramids that share  a cornercorner with one S(2)Pr3P trigonal pyramid,  a cornercorner with one S(8)RbPr2P trigonal pyramid, corners with two equivalent S(12)Rb2PrP trigonal pyramids, and  an edgeedge with one S(14)RbPr3P trigonal bipyramid. In the fifteenth S site, S(15) is bonded in a 4-coordinate geometry to one Rb(2), one Rb(3), one Pr(2), and one P(4) atom. In the sixteenth S site, S(16) is bonded in a 4-coordinate geometry to two equivalent Rb(3), one Pr(3), and one P(4) atom.