Pr4MnSb9 crystallizes in the monoclinic C2/m space group. There are four inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to one Sb(3), two equivalent Sb(1), two equivalent Sb(10), two equivalent Sb(2), and two equivalent Sb(7) atoms. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to one Sb(1), one Sb(5), one Sb(9), two equivalent Sb(10), two equivalent Sb(4), and two equivalent Sb(6) atoms. In the third Pr site, Pr(3) is bonded in a 9-coordinate geometry to one Sb(3), one Sb(5), one Sb(9), two equivalent Sb(10), two equivalent Sb(4), and two equivalent Sb(8) atoms. In the fourth Pr site, Pr(4) is bonded in a 9-coordinate geometry to one Sb(1), one Sb(8), two equivalent Sb(3), two equivalent Sb(6), and three equivalent Sb(7) atoms. Mn(1) is bonded to one Sb(6), two equivalent Sb(8), and three equivalent Sb(9) atoms to form edge-sharing MnSb6 octahedra. There are ten inequivalent Sb sites. In the first Sb site, Sb(8) is bonded in a 5-coordinate geometry to one Pr(4), two equivalent Pr(3), two equivalent Mn(1), and two equivalent Sb(3) atoms. In the second Sb site, Sb(9) is bonded in a 3-coordinate geometry to one Pr(2), one Pr(3), three equivalent Mn(1), and two equivalent Sb(4) atoms. In the third Sb site, Sb(10) is bonded to two equivalent Pr(1), two equivalent Pr(2), and two equivalent Pr(3) atoms to form distorted face-sharing SbPr6 pentagonal pyramids. In the fourth Sb site, Sb(1) is bonded in a 8-coordinate geometry to one Pr(2), one Pr(4), two equivalent Pr(1), two equivalent Sb(2), and two equivalent Sb(6) atoms. In the fifth Sb site, Sb(2) is bonded in a distorted body-centered cubic geometry to four equivalent Pr(1) and four equivalent Sb(1) atoms. In the sixth Sb site, Sb(3) is bonded in a 8-coordinate geometry to one Pr(1), one Pr(3), two equivalent Pr(4), two equivalent Sb(7), and two equivalent Sb(8) atoms. In the seventh Sb site, Sb(4) is bonded in a distorted body-centered cubic geometry to two equivalent Pr(2), two equivalent Pr(3), two equivalent Sb(5), and two equivalent Sb(9) atoms. In the eighth Sb site, Sb(5) is bonded in a 8-coordinate geometry to two equivalent Pr(2), two equivalent Pr(3), and four equivalent Sb(4) atoms. In the ninth Sb site, Sb(6) is bonded in a 7-coordinate geometry to two equivalent Pr(2), two equivalent Pr(4), one Mn(1), and two equivalent Sb(1) atoms. In the tenth Sb site, Sb(7) is bonded in a 7-coordinate geometry to two equivalent Pr(1), three equivalent Pr(4), and two equivalent Sb(3) atoms.
Pr4MnSb9 crystallizes in the monoclinic C2/m space group. There are four inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to one Sb(3), two equivalent Sb(1), two equivalent Sb(10), two equivalent Sb(2), and two equivalent Sb(7) atoms. The Pr(1)-Sb(3) bond length is 3.32 Å. There is one shorter (3.36 Å) and one longer (3.48 Å) Pr(1)-Sb(1) bond length. Both Pr(1)-Sb(10) bond lengths are 3.24 Å. Both Pr(1)-Sb(2) bond lengths are 3.27 Å. Both Pr(1)-Sb(7) bond lengths are 3.28 Å. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to one Sb(1), one Sb(5), one Sb(9), two equivalent Sb(10), two equivalent Sb(4), and two equivalent Sb(6) atoms. The Pr(2)-Sb(1) bond length is 3.30 Å. The Pr(2)-Sb(5) bond length is 3.37 Å. The Pr(2)-Sb(9) bond length is 3.78 Å. Both Pr(2)-Sb(10) bond lengths are 3.24 Å. Both Pr(2)-Sb(4) bond lengths are 3.32 Å. Both Pr(2)-Sb(6) bond lengths are 3.37 Å. In the third Pr site, Pr(3) is bonded in a 9-coordinate geometry to one Sb(3), one Sb(5), one Sb(9), two equivalent Sb(10), two equivalent Sb(4), and two equivalent Sb(8) atoms. The Pr(3)-Sb(3) bond length is 3.35 Å. The Pr(3)-Sb(5) bond length is 3.31 Å. The Pr(3)-Sb(9) bond length is 3.55 Å. Both Pr(3)-Sb(10) bond lengths are 3.27 Å. Both Pr(3)-Sb(4) bond lengths are 3.31 Å. Both Pr(3)-Sb(8) bond lengths are 3.33 Å. In the fourth Pr site, Pr(4) is bonded in a 9-coordinate geometry to one Sb(1), one Sb(8), two equivalent Sb(3), two equivalent Sb(6), and three equivalent Sb(7) atoms. The Pr(4)-Sb(1) bond length is 3.26 Å. The Pr(4)-Sb(8) bond length is 3.35 Å. Both Pr(4)-Sb(3) bond lengths are 3.29 Å. Both Pr(4)-Sb(6) bond lengths are 3.33 Å. There are two shorter (3.28 Å) and one longer (3.46 Å) Pr(4)-Sb(7) bond length. Mn(1) is bonded to one Sb(6), two equivalent Sb(8), and three equivalent Sb(9) atoms to form edge-sharing MnSb6 octahedra. The Mn(1)-Sb(6) bond length is 2.93 Å. Both Mn(1)-Sb(8) bond lengths are 2.78 Å. There are two shorter (2.82 Å) and one longer (2.85 Å) Mn(1)-Sb(9) bond length. There are ten inequivalent Sb sites. In the first Sb site, Sb(8) is bonded in a 5-coordinate geometry to one Pr(4), two equivalent Pr(3), two equivalent Mn(1), and two equivalent Sb(3) atoms. Both Sb(8)-Sb(3) bond lengths are 3.18 Å. In the second Sb site, Sb(9) is bonded in a 3-coordinate geometry to one Pr(2), one Pr(3), three equivalent Mn(1), and two equivalent Sb(4) atoms. Both Sb(9)-Sb(4) bond lengths are 3.28 Å. In the third Sb site, Sb(10) is bonded to two equivalent Pr(1), two equivalent Pr(2), and two equivalent Pr(3) atoms to form distorted face-sharing SbPr6 pentagonal pyramids. In the fourth Sb site, Sb(1) is bonded in a 8-coordinate geometry to one Pr(2), one Pr(4), two equivalent Pr(1), two equivalent Sb(2), and two equivalent Sb(6) atoms. Both Sb(1)-Sb(2) bond lengths are 3.16 Å. Both Sb(1)-Sb(6) bond lengths are 3.13 Å. In the fifth Sb site, Sb(2) is bonded in a distorted body-centered cubic geometry to four equivalent Pr(1) and four equivalent Sb(1) atoms. In the sixth Sb site, Sb(3) is bonded in a 8-coordinate geometry to one Pr(1), one Pr(3), two equivalent Pr(4), two equivalent Sb(7), and two equivalent Sb(8) atoms. Both Sb(3)-Sb(7) bond lengths are 3.01 Å. In the seventh Sb site, Sb(4) is bonded in a distorted body-centered cubic geometry to two equivalent Pr(2), two equivalent Pr(3), two equivalent Sb(5), and two equivalent Sb(9) atoms. Both Sb(4)-Sb(5) bond lengths are 3.12 Å. In the eighth Sb site, Sb(5) is bonded in a 8-coordinate geometry to two equivalent Pr(2), two equivalent Pr(3), and four equivalent Sb(4) atoms. In the ninth Sb site, Sb(6) is bonded in a 7-coordinate geometry to two equivalent Pr(2), two equivalent Pr(4), one Mn(1), and two equivalent Sb(1) atoms. In the tenth Sb site, Sb(7) is bonded in a 7-coordinate geometry to two equivalent Pr(1), three equivalent Pr(4), and two equivalent Sb(3) atoms.