Zr8As5 crystallizes in the monoclinic P2/m space group. There are seventeen inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted square co-planar geometry to two equivalent As(6) and two equivalent As(9) atoms. In the second Zr site, Zr(2) is bonded in a 4-coordinate geometry to two equivalent As(10) and two equivalent As(5) atoms. In the third Zr site, Zr(3) is bonded to one As(3), one As(7), one As(8), and two equivalent As(2) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. In the fourth Zr site, Zr(4) is bonded to one As(4), one As(7), one As(8), and two equivalent As(1) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. In the fifth Zr site, Zr(5) is bonded in a 5-coordinate geometry to one As(1), two equivalent As(3), and two equivalent As(7) atoms. In the sixth Zr site, Zr(6) is bonded to one As(2), two equivalent As(4), and two equivalent As(8) atoms to form a mixture of distorted edge and corner-sharing ZrAs5 trigonal bipyramids. In the seventh Zr site, Zr(7) is bonded in a 5-coordinate geometry to one As(3), two equivalent As(10), and two equivalent As(5) atoms. In the eighth Zr site, Zr(8) is bonded to one As(4), two equivalent As(6), and two equivalent As(9) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. In the ninth Zr site, Zr(9) is bonded to one As(9), two equivalent As(4), and two equivalent As(7) atoms to form a mixture of distorted edge and corner-sharing ZrAs5 trigonal bipyramids. In the tenth Zr site, Zr(10) is bonded in a 5-coordinate geometry to one As(10), two equivalent As(3), and two equivalent As(8) atoms. In the eleventh Zr site, Zr(11) is bonded to one As(7), two equivalent As(2), and two equivalent As(9) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 square pyramids. In the twelfth Zr site, Zr(12) is bonded to one As(8), two equivalent As(1), and two equivalent As(10) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. In the thirteenth Zr site, Zr(13) is bonded to one As(3), two equivalent As(1), and two equivalent As(5) atoms to form a mixture of distorted edge and corner-sharing ZrAs5 trigonal bipyramids. In the fourteenth Zr site, Zr(14) is bonded to one As(4), two equivalent As(2), and two equivalent As(6) atoms to form a mixture of edge, corner, and face-sharing ZrAs5 square pyramids. In the fifteenth Zr site, Zr(15) is bonded in a distorted square co-planar geometry to two equivalent As(10) and two equivalent As(5) atoms. In the sixteenth Zr site, Zr(16) is bonded in a distorted square co-planar geometry to two equivalent As(6) and two equivalent As(9) atoms. In the seventeenth Zr site, Zr(17) is bonded in a distorted T-shaped geometry to one As(1), one As(10), and one As(5) atom. There are ten inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one Zr(17), one Zr(5), two equivalent Zr(12), two equivalent Zr(13), and two equivalent Zr(4) atoms. In the second As site, As(2) is bonded to one Zr(6), two equivalent Zr(11), two equivalent Zr(14), and two equivalent Zr(3) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the third As site, As(3) is bonded to one Zr(13), one Zr(3), one Zr(7), two equivalent Zr(10), and two equivalent Zr(5) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the fourth As site, As(4) is bonded to one Zr(14), one Zr(4), one Zr(8), two equivalent Zr(6), and two equivalent Zr(9) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the fifth As site, As(5) is bonded in a 8-coordinate geometry to one Zr(15), one Zr(17), two equivalent Zr(13), two equivalent Zr(2), and two equivalent Zr(7) atoms. In the sixth As site, As(6) is bonded to one Zr(16), two equivalent Zr(1), two equivalent Zr(14), and two equivalent Zr(8) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the seventh As site, As(7) is bonded to one Zr(11), one Zr(3), one Zr(4), two equivalent Zr(5), and two equivalent Zr(9) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the eighth As site, As(8) is bonded to one Zr(12), one Zr(3), one Zr(4), two equivalent Zr(10), and two equivalent Zr(6) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the ninth As site, As(9) is bonded in a 8-coordinate geometry to one Zr(16), one Zr(9), two equivalent Zr(1), two equivalent Zr(11), and two equivalent Zr(8) atoms. In the tenth As site, As(10) is bonded in a 9-coordinate geometry to one Zr(10), one Zr(15), one Zr(17), two equivalent Zr(12), two equivalent Zr(2), and two equivalent Zr(7) atoms.
Zr8As5 crystallizes in the monoclinic P2/m space group. There are seventeen inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted square co-planar geometry to two equivalent As(6) and two equivalent As(9) atoms. Both Zr(1)-As(6) bond lengths are 2.77 Å. Both Zr(1)-As(9) bond lengths are 2.81 Å. In the second Zr site, Zr(2) is bonded in a 4-coordinate geometry to two equivalent As(10) and two equivalent As(5) atoms. Both Zr(2)-As(10) bond lengths are 2.88 Å. Both Zr(2)-As(5) bond lengths are 2.79 Å. In the third Zr site, Zr(3) is bonded to one As(3), one As(7), one As(8), and two equivalent As(2) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. The Zr(3)-As(3) bond length is 2.88 Å. The Zr(3)-As(7) bond length is 2.72 Å. The Zr(3)-As(8) bond length is 2.84 Å. Both Zr(3)-As(2) bond lengths are 2.82 Å. In the fourth Zr site, Zr(4) is bonded to one As(4), one As(7), one As(8), and two equivalent As(1) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. The Zr(4)-As(4) bond length is 2.90 Å. The Zr(4)-As(7) bond length is 2.88 Å. The Zr(4)-As(8) bond length is 2.73 Å. Both Zr(4)-As(1) bond lengths are 2.83 Å. In the fifth Zr site, Zr(5) is bonded in a 5-coordinate geometry to one As(1), two equivalent As(3), and two equivalent As(7) atoms. The Zr(5)-As(1) bond length is 2.85 Å. Both Zr(5)-As(3) bond lengths are 2.74 Å. Both Zr(5)-As(7) bond lengths are 2.75 Å. In the sixth Zr site, Zr(6) is bonded to one As(2), two equivalent As(4), and two equivalent As(8) atoms to form a mixture of distorted edge and corner-sharing ZrAs5 trigonal bipyramids. The Zr(6)-As(2) bond length is 2.79 Å. Both Zr(6)-As(4) bond lengths are 2.73 Å. Both Zr(6)-As(8) bond lengths are 2.73 Å. In the seventh Zr site, Zr(7) is bonded in a 5-coordinate geometry to one As(3), two equivalent As(10), and two equivalent As(5) atoms. The Zr(7)-As(3) bond length is 2.77 Å. Both Zr(7)-As(10) bond lengths are 2.82 Å. Both Zr(7)-As(5) bond lengths are 2.91 Å. In the eighth Zr site, Zr(8) is bonded to one As(4), two equivalent As(6), and two equivalent As(9) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. The Zr(8)-As(4) bond length is 2.72 Å. Both Zr(8)-As(6) bond lengths are 2.88 Å. Both Zr(8)-As(9) bond lengths are 2.77 Å. In the ninth Zr site, Zr(9) is bonded to one As(9), two equivalent As(4), and two equivalent As(7) atoms to form a mixture of distorted edge and corner-sharing ZrAs5 trigonal bipyramids. The Zr(9)-As(9) bond length is 2.85 Å. Both Zr(9)-As(4) bond lengths are 2.72 Å. Both Zr(9)-As(7) bond lengths are 2.72 Å. In the tenth Zr site, Zr(10) is bonded in a 5-coordinate geometry to one As(10), two equivalent As(3), and two equivalent As(8) atoms. The Zr(10)-As(10) bond length is 2.96 Å. Both Zr(10)-As(3) bond lengths are 2.72 Å. Both Zr(10)-As(8) bond lengths are 2.73 Å. In the eleventh Zr site, Zr(11) is bonded to one As(7), two equivalent As(2), and two equivalent As(9) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 square pyramids. The Zr(11)-As(7) bond length is 2.73 Å. Both Zr(11)-As(2) bond lengths are 2.83 Å. Both Zr(11)-As(9) bond lengths are 2.79 Å. In the twelfth Zr site, Zr(12) is bonded to one As(8), two equivalent As(1), and two equivalent As(10) atoms to form a mixture of distorted edge, corner, and face-sharing ZrAs5 trigonal bipyramids. The Zr(12)-As(8) bond length is 2.72 Å. Both Zr(12)-As(1) bond lengths are 2.84 Å. Both Zr(12)-As(10) bond lengths are 2.79 Å. In the thirteenth Zr site, Zr(13) is bonded to one As(3), two equivalent As(1), and two equivalent As(5) atoms to form a mixture of distorted edge and corner-sharing ZrAs5 trigonal bipyramids. The Zr(13)-As(3) bond length is 2.70 Å. Both Zr(13)-As(1) bond lengths are 2.74 Å. Both Zr(13)-As(5) bond lengths are 2.77 Å. In the fourteenth Zr site, Zr(14) is bonded to one As(4), two equivalent As(2), and two equivalent As(6) atoms to form a mixture of edge, corner, and face-sharing ZrAs5 square pyramids. The Zr(14)-As(4) bond length is 2.70 Å. Both Zr(14)-As(2) bond lengths are 2.77 Å. Both Zr(14)-As(6) bond lengths are 2.78 Å. In the fifteenth Zr site, Zr(15) is bonded in a distorted square co-planar geometry to two equivalent As(10) and two equivalent As(5) atoms. Both Zr(15)-As(10) bond lengths are 3.00 Å. Both Zr(15)-As(5) bond lengths are 2.78 Å. In the sixteenth Zr site, Zr(16) is bonded in a distorted square co-planar geometry to two equivalent As(6) and two equivalent As(9) atoms. Both Zr(16)-As(6) bond lengths are 2.84 Å. Both Zr(16)-As(9) bond lengths are 2.94 Å. In the seventeenth Zr site, Zr(17) is bonded in a distorted T-shaped geometry to one As(1), one As(10), and one As(5) atom. The Zr(17)-As(1) bond length is 3.03 Å. The Zr(17)-As(10) bond length is 3.10 Å. The Zr(17)-As(5) bond length is 2.93 Å. There are ten inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to one Zr(17), one Zr(5), two equivalent Zr(12), two equivalent Zr(13), and two equivalent Zr(4) atoms. In the second As site, As(2) is bonded to one Zr(6), two equivalent Zr(11), two equivalent Zr(14), and two equivalent Zr(3) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the third As site, As(3) is bonded to one Zr(13), one Zr(3), one Zr(7), two equivalent Zr(10), and two equivalent Zr(5) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the fourth As site, As(4) is bonded to one Zr(14), one Zr(4), one Zr(8), two equivalent Zr(6), and two equivalent Zr(9) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the fifth As site, As(5) is bonded in a 8-coordinate geometry to one Zr(15), one Zr(17), two equivalent Zr(13), two equivalent Zr(2), and two equivalent Zr(7) atoms. In the sixth As site, As(6) is bonded to one Zr(16), two equivalent Zr(1), two equivalent Zr(14), and two equivalent Zr(8) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the seventh As site, As(7) is bonded to one Zr(11), one Zr(3), one Zr(4), two equivalent Zr(5), and two equivalent Zr(9) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the eighth As site, As(8) is bonded to one Zr(12), one Zr(3), one Zr(4), two equivalent Zr(10), and two equivalent Zr(6) atoms to form a mixture of distorted edge, corner, and face-sharing AsZr7 pentagonal bipyramids. In the ninth As site, As(9) is bonded in a 8-coordinate geometry to one Zr(16), one Zr(9), two equivalent Zr(1), two equivalent Zr(11), and two equivalent Zr(8) atoms. In the tenth As site, As(10) is bonded in a 9-coordinate geometry to one Zr(10), one Zr(15), one Zr(17), two equivalent Zr(12), two equivalent Zr(2), and two equivalent Zr(7) atoms.