Na4B3Cl is Caswellsilverite-like structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent B(1), two equivalent B(2), and two equivalent Cl(1) atoms to form NaB4Cl2 octahedra that share corners with six equivalent Na(1)B4Cl2 octahedra, edges with four equivalent Na(1)B4Cl2 octahedra, and edges with eight equivalent Na(2)B5Cl octahedra. The corner-sharing octahedra are not tilted. In the second Na site, Na(2) is bonded to one B(2), four equivalent B(1), and one Cl(1) atom to form NaB5Cl octahedra that share corners with six equivalent Na(2)B5Cl octahedra, edges with four equivalent Na(2)B5Cl octahedra, and edges with eight equivalent Na(1)B4Cl2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two inequivalent B sites. In the first B site, B(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form BNa6 octahedra that share corners with six equivalent B(1)Na6 octahedra; edges with four equivalent B(1)Na6 octahedra; edges with four equivalent B(2)Na6 octahedra; and edges with four Cl(1,1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second B site, B(2) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form BNa6 octahedra that share corners with two equivalent Cl(1)Na6 octahedra, corners with four equivalent B(2)Na6 octahedra, edges with four equivalent Cl(1)Na6 octahedra, and edges with eight equivalent B(1)Na6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form ClNa6 octahedra that share corners with two equivalent B(2)Na6 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with four equivalent B(2)Na6 octahedra, and edges with eight equivalent B(1)Na6 octahedra. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form ClNa6 octahedra that share corners with two equivalent B(2)Na6 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with four equivalent B(2)Na6 octahedra, and edges with eight equivalent B(1)Na6 octahedra. The corner-sharing octahedra are not tilted.
Na4B3Cl is Caswellsilverite-like structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent B(1), two equivalent B(2), and two equivalent Cl(1) atoms to form NaB4Cl2 octahedra that share corners with six equivalent Na(1)B4Cl2 octahedra, edges with four equivalent Na(1)B4Cl2 octahedra, and edges with eight equivalent Na(2)B5Cl octahedra. The corner-sharing octahedra are not tilted. Both Na(1)-B(1) bond lengths are 2.75 Å. Both Na(1)-B(2) bond lengths are 2.77 Å. Both Na(1)-Cl(1) bond lengths are 2.77 Å. In the second Na site, Na(2) is bonded to one B(2), four equivalent B(1), and one Cl(1) atom to form NaB5Cl octahedra that share corners with six equivalent Na(2)B5Cl octahedra, edges with four equivalent Na(2)B5Cl octahedra, and edges with eight equivalent Na(1)B4Cl2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Na(2)-B(2) bond length is 2.77 Å. All Na(2)-B(1) bond lengths are 2.77 Å. The Na(2)-Cl(1) bond length is 2.72 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form BNa6 octahedra that share corners with six equivalent B(1)Na6 octahedra; edges with four equivalent B(1)Na6 octahedra; edges with four equivalent B(2)Na6 octahedra; and edges with four Cl(1,1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second B site, B(2) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form BNa6 octahedra that share corners with two equivalent Cl(1)Na6 octahedra, corners with four equivalent B(2)Na6 octahedra, edges with four equivalent Cl(1)Na6 octahedra, and edges with eight equivalent B(1)Na6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form ClNa6 octahedra that share corners with two equivalent B(2)Na6 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with four equivalent B(2)Na6 octahedra, and edges with eight equivalent B(1)Na6 octahedra. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form ClNa6 octahedra that share corners with two equivalent B(2)Na6 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with four equivalent B(2)Na6 octahedra, and edges with eight equivalent B(1)Na6 octahedra. The corner-sharing octahedra are not tilted. Both Cl(1)-Na(2) bond lengths are 2.72 Å. All Cl(1)-Na(1) bond lengths are 2.77 Å.