ZrAl3N4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pmmm space group. Zr(1) is bonded to two equivalent N(3) and four equivalent N(2) atoms to form ZrN6 octahedra that share corners with two equivalent Zr(1)N6 octahedra, corners with four equivalent Al(2)N6 octahedra, edges with two equivalent Zr(1)N6 octahedra, edges with two equivalent Al(2)N6 octahedra, and edges with eight equivalent Al(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form AlN6 octahedra that share corners with six equivalent Al(1)N6 octahedra, edges with four equivalent Zr(1)N6 octahedra, edges with four equivalent Al(1)N6 octahedra, and edges with four equivalent Al(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second Al site, Al(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form AlN6 octahedra that share corners with two equivalent Al(2)N6 octahedra, corners with four equivalent Zr(1)N6 octahedra, edges with two equivalent Zr(1)N6 octahedra, edges with two equivalent Al(2)N6 octahedra, and edges with eight equivalent Al(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are three inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Al(2) and four equivalent Al(1) atoms to form NAl6 octahedra that share corners with two equivalent N(1)Al6 octahedra, corners with four equivalent N(3)Zr2Al4 octahedra, edges with two equivalent N(1)Al6 octahedra, edges with two equivalent N(3)Zr2Al4 octahedra, and edges with eight equivalent N(2)Zr2Al4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second N site, N(2) is bonded to two equivalent Zr(1), two equivalent Al(1), and two equivalent Al(2) atoms to form NZr2Al4 octahedra that share corners with six equivalent N(2)Zr2Al4 octahedra, edges with four equivalent N(1)Al6 octahedra, edges with four equivalent N(2)Zr2Al4 octahedra, and edges with four equivalent N(3)Zr2Al4 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third N site, N(3) is bonded to two equivalent Zr(1) and four equivalent Al(1) atoms to form NZr2Al4 octahedra that share corners with two equivalent N(3)Zr2Al4 octahedra, corners with four equivalent N(1)Al6 octahedra, edges with two equivalent N(1)Al6 octahedra, edges with two equivalent N(3)Zr2Al4 octahedra, and edges with eight equivalent N(2)Zr2Al4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
ZrAl3N4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pmmm space group. Zr(1) is bonded to two equivalent N(3) and four equivalent N(2) atoms to form ZrN6 octahedra that share corners with two equivalent Zr(1)N6 octahedra, corners with four equivalent Al(2)N6 octahedra, edges with two equivalent Zr(1)N6 octahedra, edges with two equivalent Al(2)N6 octahedra, and edges with eight equivalent Al(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Zr(1)-N(3) bond lengths are 2.16 Å. All Zr(1)-N(2) bond lengths are 2.26 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form AlN6 octahedra that share corners with six equivalent Al(1)N6 octahedra, edges with four equivalent Zr(1)N6 octahedra, edges with four equivalent Al(1)N6 octahedra, and edges with four equivalent Al(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. Both Al(1)-N(1) bond lengths are 2.06 Å. Both Al(1)-N(2) bond lengths are 2.16 Å. Both Al(1)-N(3) bond lengths are 2.19 Å. In the second Al site, Al(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form AlN6 octahedra that share corners with two equivalent Al(2)N6 octahedra, corners with four equivalent Zr(1)N6 octahedra, edges with two equivalent Zr(1)N6 octahedra, edges with two equivalent Al(2)N6 octahedra, and edges with eight equivalent Al(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Al(2)-N(1) bond lengths are 2.16 Å. All Al(2)-N(2) bond lengths are 1.99 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Al(2) and four equivalent Al(1) atoms to form NAl6 octahedra that share corners with two equivalent N(1)Al6 octahedra, corners with four equivalent N(3)Zr2Al4 octahedra, edges with two equivalent N(1)Al6 octahedra, edges with two equivalent N(3)Zr2Al4 octahedra, and edges with eight equivalent N(2)Zr2Al4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second N site, N(2) is bonded to two equivalent Zr(1), two equivalent Al(1), and two equivalent Al(2) atoms to form NZr2Al4 octahedra that share corners with six equivalent N(2)Zr2Al4 octahedra, edges with four equivalent N(1)Al6 octahedra, edges with four equivalent N(2)Zr2Al4 octahedra, and edges with four equivalent N(3)Zr2Al4 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third N site, N(3) is bonded to two equivalent Zr(1) and four equivalent Al(1) atoms to form NZr2Al4 octahedra that share corners with two equivalent N(3)Zr2Al4 octahedra, corners with four equivalent N(1)Al6 octahedra, edges with two equivalent N(1)Al6 octahedra, edges with two equivalent N(3)Zr2Al4 octahedra, and edges with eight equivalent N(2)Zr2Al4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.