Ba3As14 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a body-centered cubic geometry to two equivalent As(3), two equivalent As(4), two equivalent As(5), and two equivalent As(6) atoms. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one As(1), one As(4), one As(5), one As(7), two equivalent As(2), two equivalent As(3), and two equivalent As(6) atoms. There are seven inequivalent As sites. In the first As site, As(1) is bonded in a 4-coordinate geometry to one Ba(2), one As(2), one As(3), and one As(5) atom. In the second As site, As(2) is bonded in a 5-coordinate geometry to two equivalent Ba(2), one As(1), one As(5), and one As(6) atom. In the third As site, As(3) is bonded to one Ba(1), two equivalent Ba(2), one As(1), and one As(7) atom to form AsBa3As2 square pyramids that share  a cornercorner with one As(3)Ba3As2 square pyramid, corners with two equivalent As(7)BaAs3 tetrahedra, corners with three equivalent As(6)Ba3As2 trigonal bipyramids,  an edgeedge with one As(3)Ba3As2 square pyramid, and edges with two equivalent As(6)Ba3As2 trigonal bipyramids. In the fourth As site, As(4) is bonded in a see-saw-like geometry to one Ba(1), one Ba(2), one As(5), and one As(7) atom. In the fifth As site, As(5) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one As(1), one As(2), and one As(4) atom. In the sixth As site, As(6) is bonded to one Ba(1), two equivalent Ba(2), one As(2), and one As(7) atom to form distorted AsBa3As2 trigonal bipyramids that share corners with three equivalent As(3)Ba3As2 square pyramids, corners with two equivalent As(7)BaAs3 tetrahedra, corners with three equivalent As(6)Ba3As2 trigonal bipyramids, and edges with two equivalent As(3)Ba3As2 square pyramids. In the seventh As site, As(7) is bonded to one Ba(2), one As(3), one As(4), and one As(6) atom to form distorted corner-sharing AsBaAs3 tetrahedra.
Ba3As14 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a body-centered cubic geometry to two equivalent As(3), two equivalent As(4), two equivalent As(5), and two equivalent As(6) atoms. Both Ba(1)-As(3) bond lengths are 3.47 Å. Both Ba(1)-As(4) bond lengths are 3.42 Å. Both Ba(1)-As(5) bond lengths are 3.52 Å. Both Ba(1)-As(6) bond lengths are 3.48 Å. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one As(1), one As(4), one As(5), one As(7), two equivalent As(2), two equivalent As(3), and two equivalent As(6) atoms. The Ba(2)-As(1) bond length is 3.66 Å. The Ba(2)-As(4) bond length is 3.45 Å. The Ba(2)-As(5) bond length is 3.74 Å. The Ba(2)-As(7) bond length is 3.66 Å. There is one shorter (3.73 Å) and one longer (3.92 Å) Ba(2)-As(2) bond length. There is one shorter (3.46 Å) and one longer (3.55 Å) Ba(2)-As(3) bond length. There is one shorter (3.38 Å) and one longer (3.46 Å) Ba(2)-As(6) bond length. There are seven inequivalent As sites. In the first As site, As(1) is bonded in a 4-coordinate geometry to one Ba(2), one As(2), one As(3), and one As(5) atom. The As(1)-As(2) bond length is 2.50 Å. The As(1)-As(3) bond length is 2.40 Å. The As(1)-As(5) bond length is 2.47 Å. In the second As site, As(2) is bonded in a 5-coordinate geometry to two equivalent Ba(2), one As(1), one As(5), and one As(6) atom. The As(2)-As(5) bond length is 2.54 Å. The As(2)-As(6) bond length is 2.41 Å. In the third As site, As(3) is bonded to one Ba(1), two equivalent Ba(2), one As(1), and one As(7) atom to form AsBa3As2 square pyramids that share  a cornercorner with one As(3)Ba3As2 square pyramid, corners with two equivalent As(7)BaAs3 tetrahedra, corners with three equivalent As(6)Ba3As2 trigonal bipyramids,  an edgeedge with one As(3)Ba3As2 square pyramid, and edges with two equivalent As(6)Ba3As2 trigonal bipyramids. The As(3)-As(7) bond length is 2.44 Å. In the fourth As site, As(4) is bonded in a see-saw-like geometry to one Ba(1), one Ba(2), one As(5), and one As(7) atom. The As(4)-As(5) bond length is 2.39 Å. The As(4)-As(7) bond length is 2.44 Å. In the fifth As site, As(5) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one As(1), one As(2), and one As(4) atom. In the sixth As site, As(6) is bonded to one Ba(1), two equivalent Ba(2), one As(2), and one As(7) atom to form distorted AsBa3As2 trigonal bipyramids that share corners with three equivalent As(3)Ba3As2 square pyramids, corners with two equivalent As(7)BaAs3 tetrahedra, corners with three equivalent As(6)Ba3As2 trigonal bipyramids, and edges with two equivalent As(3)Ba3As2 square pyramids. The As(6)-As(7) bond length is 2.43 Å. In the seventh As site, As(7) is bonded to one Ba(2), one As(3), one As(4), and one As(6) atom to form distorted corner-sharing AsBaAs3 tetrahedra.