Pr5(C2Br)3 crystallizes in the triclinic P-1 space group. There are five inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one C(2), four equivalent C(5), one Br(2), and two equivalent Br(3) atoms. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one C(6), four equivalent C(1), one Br(1), and two equivalent Br(3) atoms. In the third Pr site, Pr(3) is bonded in a 8-coordinate geometry to one C(1), two equivalent C(3), two equivalent C(6), one Br(2), and two equivalent Br(1) atoms. In the fourth Pr site, Pr(4) is bonded in a 10-coordinate geometry to two equivalent C(2), two equivalent C(3), two equivalent C(6), three equivalent C(4), and one Br(3) atom. In the fifth Pr site, Pr(5) is bonded in a 8-coordinate geometry to one C(3), one C(5), two equivalent C(2), two equivalent C(4), and two equivalent Br(2) atoms. There are six inequivalent C sites. In the first C site, C(1) is bonded in a 6-coordinate geometry to one Pr(3), four equivalent Pr(2), and one C(1) atom. In the second C site, C(2) is bonded in a 6-coordinate geometry to one Pr(1), two equivalent Pr(4), two equivalent Pr(5), and one C(4) atom. In the third C site, C(3) is bonded in a 6-coordinate geometry to one Pr(5), two equivalent Pr(3), two equivalent Pr(4), and one C(6) atom. In the fourth C site, C(4) is bonded in a 6-coordinate geometry to two equivalent Pr(5), three equivalent Pr(4), and one C(2) atom. In the fifth C site, C(5) is bonded in a 6-coordinate geometry to one Pr(5), four equivalent Pr(1), and one C(5) atom. In the sixth C site, C(6) is bonded in a 6-coordinate geometry to one Pr(2), two equivalent Pr(3), two equivalent Pr(4), and one C(3) atom. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted T-shaped geometry to one Pr(2) and two equivalent Pr(3) atoms. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to one Pr(1), one Pr(3), and two equivalent Pr(5) atoms. In the third Br site, Br(3) is bonded to one Pr(4), two equivalent Pr(1), and two equivalent Pr(2) atoms to form distorted edge-sharing BrPr5 square pyramids.
Pr5(C2Br)3 crystallizes in the triclinic P-1 space group. There are five inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 8-coordinate geometry to one C(2), four equivalent C(5), one Br(2), and two equivalent Br(3) atoms. The Pr(1)-C(2) bond length is 2.50 Å. There are a spread of Pr(1)-C(5) bond distances ranging from 2.65-2.77 Å. The Pr(1)-Br(2) bond length is 3.23 Å. Both Pr(1)-Br(3) bond lengths are 3.12 Å. In the second Pr site, Pr(2) is bonded in a 8-coordinate geometry to one C(6), four equivalent C(1), one Br(1), and two equivalent Br(3) atoms. The Pr(2)-C(6) bond length is 2.53 Å. There are two shorter (2.63 Å) and two longer (2.77 Å) Pr(2)-C(1) bond lengths. The Pr(2)-Br(1) bond length is 3.15 Å. There is one shorter (3.12 Å) and one longer (3.13 Å) Pr(2)-Br(3) bond length. In the third Pr site, Pr(3) is bonded in a 8-coordinate geometry to one C(1), two equivalent C(3), two equivalent C(6), one Br(2), and two equivalent Br(1) atoms. The Pr(3)-C(1) bond length is 2.40 Å. Both Pr(3)-C(3) bond lengths are 2.75 Å. Both Pr(3)-C(6) bond lengths are 2.75 Å. The Pr(3)-Br(2) bond length is 3.24 Å. Both Pr(3)-Br(1) bond lengths are 3.03 Å. In the fourth Pr site, Pr(4) is bonded in a 10-coordinate geometry to two equivalent C(2), two equivalent C(3), two equivalent C(6), three equivalent C(4), and one Br(3) atom. There is one shorter (2.89 Å) and one longer (2.90 Å) Pr(4)-C(2) bond length. Both Pr(4)-C(3) bond lengths are 2.83 Å. Both Pr(4)-C(6) bond lengths are 2.89 Å. There is one shorter (2.46 Å) and two longer (2.75 Å) Pr(4)-C(4) bond lengths. The Pr(4)-Br(3) bond length is 3.58 Å. In the fifth Pr site, Pr(5) is bonded in a 8-coordinate geometry to one C(3), one C(5), two equivalent C(2), two equivalent C(4), and two equivalent Br(2) atoms. The Pr(5)-C(3) bond length is 2.62 Å. The Pr(5)-C(5) bond length is 2.49 Å. Both Pr(5)-C(2) bond lengths are 2.73 Å. There is one shorter (2.76 Å) and one longer (2.77 Å) Pr(5)-C(4) bond length. Both Pr(5)-Br(2) bond lengths are 3.11 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a 6-coordinate geometry to one Pr(3), four equivalent Pr(2), and one C(1) atom. The C(1)-C(1) bond length is 1.35 Å. In the second C site, C(2) is bonded in a 6-coordinate geometry to one Pr(1), two equivalent Pr(4), two equivalent Pr(5), and one C(4) atom. The C(2)-C(4) bond length is 1.31 Å. In the third C site, C(3) is bonded in a 6-coordinate geometry to one Pr(5), two equivalent Pr(3), two equivalent Pr(4), and one C(6) atom. The C(3)-C(6) bond length is 1.30 Å. In the fourth C site, C(4) is bonded in a 6-coordinate geometry to two equivalent Pr(5), three equivalent Pr(4), and one C(2) atom. In the fifth C site, C(5) is bonded in a 6-coordinate geometry to one Pr(5), four equivalent Pr(1), and one C(5) atom. The C(5)-C(5) bond length is 1.34 Å. In the sixth C site, C(6) is bonded in a 6-coordinate geometry to one Pr(2), two equivalent Pr(3), two equivalent Pr(4), and one C(3) atom. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted T-shaped geometry to one Pr(2) and two equivalent Pr(3) atoms. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to one Pr(1), one Pr(3), and two equivalent Pr(5) atoms. In the third Br site, Br(3) is bonded to one Pr(4), two equivalent Pr(1), and two equivalent Pr(2) atoms to form distorted edge-sharing BrPr5 square pyramids.