Zr3As2 is Stibnite structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. In the second Zr site, Zr(2) is bonded to two equivalent As(1) and three equivalent As(2) atoms to form edge-sharing ZrAs5 square pyramids. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to two equivalent Zr(2), three equivalent Zr(1), and three equivalent Zr(3) atoms. In the second As site, As(2) is bonded to two equivalent Zr(1), two equivalent Zr(3), and three equivalent Zr(2) atoms to form a mixture of distorted corner and edge-sharing AsZr7 pentagonal bipyramids.
Zr3As2 is Stibnite structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. There is one shorter (2.73 Å) and one longer (2.84 Å) Zr(1)-As(2) bond length. There are two shorter (2.81 Å) and one longer (3.15 Å) Zr(1)-As(1) bond length. In the second Zr site, Zr(2) is bonded to two equivalent As(1) and three equivalent As(2) atoms to form edge-sharing ZrAs5 square pyramids. Both Zr(2)-As(1) bond lengths are 2.77 Å. There is one shorter (2.70 Å) and two longer (2.72 Å) Zr(2)-As(2) bond lengths. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. Both Zr(3)-As(2) bond lengths are 2.74 Å. There are two shorter (2.77 Å) and one longer (2.83 Å) Zr(3)-As(1) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to two equivalent Zr(2), three equivalent Zr(1), and three equivalent Zr(3) atoms. In the second As site, As(2) is bonded to two equivalent Zr(1), two equivalent Zr(3), and three equivalent Zr(2) atoms to form a mixture of distorted corner and edge-sharing AsZr7 pentagonal bipyramids.