Ni2Re5As12 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Re sites. In the first Re site, Re(1) is bonded to one As(3), one As(6), two equivalent As(4), and two equivalent As(5) atoms to form distorted ReAs6 octahedra that share corners with two equivalent Re(3)As6 octahedra, corners with five equivalent Ni(1)As6 octahedra,  a cornercorner with one As(1)Re3As tetrahedra, edges with two equivalent Re(1)As6 octahedra, and edges with two equivalent Re(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. In the second Re site, Re(2) is bonded to one As(1), one As(5), two equivalent As(2), and two equivalent As(3) atoms to form distorted ReAs6 octahedra that share corners with two equivalent Re(3)As6 octahedra, corners with four equivalent Ni(1)As6 octahedra,  a cornercorner with one As(6)ReNi2As tetrahedra, edges with two equivalent Re(1)As6 octahedra, edges with two equivalent Re(2)As6 octahedra, and  a faceface with one Ni(1)As6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. In the third Re site, Re(3) is bonded to two equivalent As(4) and four equivalent As(1) atoms to form ReAs6 octahedra that share corners with four equivalent Re(1)As6 octahedra, corners with four equivalent Re(2)As6 octahedra, corners with four equivalent As(6)ReNi2As tetrahedra, and edges with two equivalent Re(3)As6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. Ni(1) is bonded to one As(3), one As(5), two equivalent As(2), and two equivalent As(6) atoms to form NiAs6 octahedra that share corners with four equivalent Re(2)As6 octahedra, corners with five equivalent Re(1)As6 octahedra, corners with two equivalent As(1)Re3As tetrahedra, edges with two equivalent Ni(1)As6 octahedra, and  a faceface with one Re(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. There are six inequivalent As sites. In the first As site, As(6) is bonded to one Re(1), two equivalent Ni(1), and one As(1) atom to form distorted AsReNi2As tetrahedra that share  a cornercorner with one Re(2)As6 octahedra, corners with two equivalent Re(3)As6 octahedra, and corners with two equivalent As(6)ReNi2As tetrahedra. The corner-sharing octahedral tilt angles are 72°. In the second As site, As(1) is bonded to one Re(2), two equivalent Re(3), and one As(6) atom to form distorted AsRe3As tetrahedra that share  a cornercorner with one Re(1)As6 octahedra, corners with two equivalent Ni(1)As6 octahedra, corners with four equivalent As(1)Re3As tetrahedra, and  an edgeedge with one As(1)Re3As tetrahedra. The corner-sharing octahedral tilt angles range from 69-75°. In the third As site, As(2) is bonded in a 5-coordinate geometry to two equivalent Re(2), two equivalent Ni(1), and one As(4) atom. In the fourth As site, As(3) is bonded in a 4-coordinate geometry to one Re(1), two equivalent Re(2), and one Ni(1) atom. In the fifth As site, As(4) is bonded in a 4-coordinate geometry to one Re(3), two equivalent Re(1), and one As(2) atom. In the sixth As site, As(5) is bonded in a 5-coordinate geometry to one Re(2), two equivalent Re(1), one Ni(1), and one As(5) atom.
Ni2Re5As12 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Re sites. In the first Re site, Re(1) is bonded to one As(3), one As(6), two equivalent As(4), and two equivalent As(5) atoms to form distorted ReAs6 octahedra that share corners with two equivalent Re(3)As6 octahedra, corners with five equivalent Ni(1)As6 octahedra,  a cornercorner with one As(1)Re3As tetrahedra, edges with two equivalent Re(1)As6 octahedra, and edges with two equivalent Re(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. The Re(1)-As(3) bond length is 2.50 Å. The Re(1)-As(6) bond length is 2.54 Å. Both Re(1)-As(4) bond lengths are 2.57 Å. Both Re(1)-As(5) bond lengths are 2.52 Å. In the second Re site, Re(2) is bonded to one As(1), one As(5), two equivalent As(2), and two equivalent As(3) atoms to form distorted ReAs6 octahedra that share corners with two equivalent Re(3)As6 octahedra, corners with four equivalent Ni(1)As6 octahedra,  a cornercorner with one As(6)ReNi2As tetrahedra, edges with two equivalent Re(1)As6 octahedra, edges with two equivalent Re(2)As6 octahedra, and  a faceface with one Ni(1)As6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. The Re(2)-As(1) bond length is 2.58 Å. The Re(2)-As(5) bond length is 2.58 Å. Both Re(2)-As(2) bond lengths are 2.51 Å. Both Re(2)-As(3) bond lengths are 2.48 Å. In the third Re site, Re(3) is bonded to two equivalent As(4) and four equivalent As(1) atoms to form ReAs6 octahedra that share corners with four equivalent Re(1)As6 octahedra, corners with four equivalent Re(2)As6 octahedra, corners with four equivalent As(6)ReNi2As tetrahedra, and edges with two equivalent Re(3)As6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. Both Re(3)-As(4) bond lengths are 2.47 Å. All Re(3)-As(1) bond lengths are 2.53 Å. Ni(1) is bonded to one As(3), one As(5), two equivalent As(2), and two equivalent As(6) atoms to form NiAs6 octahedra that share corners with four equivalent Re(2)As6 octahedra, corners with five equivalent Re(1)As6 octahedra, corners with two equivalent As(1)Re3As tetrahedra, edges with two equivalent Ni(1)As6 octahedra, and  a faceface with one Re(2)As6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. The Ni(1)-As(3) bond length is 2.33 Å. The Ni(1)-As(5) bond length is 2.38 Å. Both Ni(1)-As(2) bond lengths are 2.48 Å. Both Ni(1)-As(6) bond lengths are 2.41 Å. There are six inequivalent As sites. In the first As site, As(6) is bonded to one Re(1), two equivalent Ni(1), and one As(1) atom to form distorted AsReNi2As tetrahedra that share  a cornercorner with one Re(2)As6 octahedra, corners with two equivalent Re(3)As6 octahedra, and corners with two equivalent As(6)ReNi2As tetrahedra. The corner-sharing octahedral tilt angles are 72°. The As(6)-As(1) bond length is 2.60 Å. In the second As site, As(1) is bonded to one Re(2), two equivalent Re(3), and one As(6) atom to form distorted AsRe3As tetrahedra that share  a cornercorner with one Re(1)As6 octahedra, corners with two equivalent Ni(1)As6 octahedra, corners with four equivalent As(1)Re3As tetrahedra, and  an edgeedge with one As(1)Re3As tetrahedra. The corner-sharing octahedral tilt angles range from 69-75°. In the third As site, As(2) is bonded in a 5-coordinate geometry to two equivalent Re(2), two equivalent Ni(1), and one As(4) atom. The As(2)-As(4) bond length is 2.57 Å. In the fourth As site, As(3) is bonded in a 4-coordinate geometry to one Re(1), two equivalent Re(2), and one Ni(1) atom. In the fifth As site, As(4) is bonded in a 4-coordinate geometry to one Re(3), two equivalent Re(1), and one As(2) atom. In the sixth As site, As(5) is bonded in a 5-coordinate geometry to one Re(2), two equivalent Re(1), one Ni(1), and one As(5) atom. The As(5)-As(5) bond length is 2.60 Å.