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Rb3Pr3(PS4)4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Rb–S bond distances ranging from 3.31–3.99 Å. In the second Rb1+ site, Rb1+ is bonded in a 10-coordinate geometry to ten S2- atoms. There are a spread of Rb–S bond distances ranging from 3.52–3.94 Å. In the third Rb1+ site, Rb1+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Rb–S bond distances ranging from 3.51–3.84 Å. There are three inequivalent Pr3+ sites. In the first Pr3+ site, Pr3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Pr–S bond distances ranging from 2.86–3.28 Å. In the second Pr3+ site, Pr3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Pr–S bond distances ranging from 2.87–3.17 Å. In the third Pr3+ site, Pr3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Pr–S bond distances ranging from 2.89–3.28 Å. There are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded in a tetrahedral geometry to four S2- atoms. There are a spread of P–S bond distances ranging from 2.03–2.10 Å. In the second P5+ site, P5+ is bonded in a tetrahedral geometry to four S2- atoms. There are a spread of P–S bond distances ranging from 2.03–2.07 Å. In the third P5+ site, P5+ is bonded in a tetrahedral geometry to four S2- atoms. There are a spread of P–S bond distances ranging from 2.02–2.10 Å. In the fourth P5+ site, P5+ is bonded in a tetrahedral geometry to four S2- atoms. There are a spread of P–S bond distances ranging from 2.03–2.08 Å. There are sixteen inequivalent S2- sites. In the first S2- site, S2- is bonded in a 2-coordinate geometry to one Rb1+, one Pr3+, and one P5+ atom. In the second S2- site, S2- is bonded to three Pr3+ and one P5+ atom to form distorted edge-sharing SPr3P trigonal pyramids. In the third S2- site, S2- is bonded in a 2-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the fourth S2- site, S2- is bonded in a 4-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the fifth S2- site, S2- is bonded in a 2-coordinate geometry to two equivalent Rb1+, one Pr3+, and one P5+ atom. In the sixth S2- site, S2- is bonded in a 1-coordinate geometry to two Rb1+, two Pr3+, and one P5+ atom. In the seventh S2- site, S2- is bonded in a 4-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the eighth S2- site, S2- is bonded in a 4-coordinate geometry to one Rb1+, two equivalent Pr3+, and one P5+ atom. In the ninth S2- site, S2- is bonded in a 4-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the tenth S2- site, S2- is bonded in a 4-coordinate geometry to one Rb1+, two Pr3+, and one P5+ atom. In the eleventh S2- site, S2- is bonded in a 2-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the twelfth S2- site, S2- is bonded in a 4-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the thirteenth S2- site, S2- is bonded in a 1-coordinate geometry to one Rb1+, two equivalent Pr3+, and one P5+ atom. In the fourteenth S2- site, S2- is bonded in a 5-coordinate geometry to one Rb1+, three Pr3+, and one P5+ atom. In the fifteenth S2- site, S2- is bonded in a 2-coordinate geometry to two Rb1+, one Pr3+, and one P5+ atom. In the sixteenth S2- site, S2- is bonded in a 2-coordinate geometry to two equivalent Rb1+, one Pr3+, and one P5+ atom.

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