K2Zn3SiAs4 crystallizes in the orthorhombic C222 space group. K(1) is bonded in a body-centered cubic geometry to eight equivalent As(1) atoms. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to four equivalent As(1) atoms to form ZnAs4 tetrahedra that share corners with four equivalent Si(1)Zn4As4 tetrahedra, edges with two equivalent Zn(2)Si2As4 tetrahedra, and edges with two equivalent Zn(3)Si2As4 tetrahedra. In the second Zn site, Zn(2) is bonded to two equivalent Si(1) and four equivalent As(1) atoms to form distorted ZnSi2As4 tetrahedra that share corners with two equivalent Zn(2)Si2As4 tetrahedra, edges with two equivalent Zn(1)As4 tetrahedra, edges with two equivalent Si(1)Zn4As4 tetrahedra, and edges with four equivalent Zn(3)Si2As4 tetrahedra. In the third Zn site, Zn(3) is bonded to two equivalent Si(1) and four equivalent As(1) atoms to form distorted ZnSi2As4 tetrahedra that share corners with two equivalent Zn(3)Si2As4 tetrahedra, edges with two equivalent Zn(1)As4 tetrahedra, edges with two equivalent Si(1)Zn4As4 tetrahedra, and edges with four equivalent Zn(2)Si2As4 tetrahedra. Si(1) is bonded to two equivalent Zn(2), two equivalent Zn(3), and four equivalent As(1) atoms to form distorted SiZn4As4 tetrahedra that share corners with four equivalent Zn(1)As4 tetrahedra, corners with four equivalent Si(1)Zn4As4 tetrahedra, edges with two equivalent Zn(2)Si2As4 tetrahedra, and edges with two equivalent Zn(3)Si2As4 tetrahedra. As(1) is bonded in a 8-coordinate geometry to four equivalent K(1), one Zn(1), one Zn(2), one Zn(3), and one Si(1) atom.
K2Zn3SiAs4 crystallizes in the orthorhombic C222 space group. K(1) is bonded in a body-centered cubic geometry to eight equivalent As(1) atoms. There are a spread of K(1)-As(1) bond distances ranging from 3.48-3.66 Å. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to four equivalent As(1) atoms to form ZnAs4 tetrahedra that share corners with four equivalent Si(1)Zn4As4 tetrahedra, edges with two equivalent Zn(2)Si2As4 tetrahedra, and edges with two equivalent Zn(3)Si2As4 tetrahedra. All Zn(1)-As(1) bond lengths are 2.67 Å. In the second Zn site, Zn(2) is bonded to two equivalent Si(1) and four equivalent As(1) atoms to form distorted ZnSi2As4 tetrahedra that share corners with two equivalent Zn(2)Si2As4 tetrahedra, edges with two equivalent Zn(1)As4 tetrahedra, edges with two equivalent Si(1)Zn4As4 tetrahedra, and edges with four equivalent Zn(3)Si2As4 tetrahedra. Both Zn(2)-Si(1) bond lengths are 2.89 Å. All Zn(2)-As(1) bond lengths are 2.56 Å. In the third Zn site, Zn(3) is bonded to two equivalent Si(1) and four equivalent As(1) atoms to form distorted ZnSi2As4 tetrahedra that share corners with two equivalent Zn(3)Si2As4 tetrahedra, edges with two equivalent Zn(1)As4 tetrahedra, edges with two equivalent Si(1)Zn4As4 tetrahedra, and edges with four equivalent Zn(2)Si2As4 tetrahedra. Both Zn(3)-Si(1) bond lengths are 2.89 Å. All Zn(3)-As(1) bond lengths are 2.56 Å. Si(1) is bonded to two equivalent Zn(2), two equivalent Zn(3), and four equivalent As(1) atoms to form distorted SiZn4As4 tetrahedra that share corners with four equivalent Zn(1)As4 tetrahedra, corners with four equivalent Si(1)Zn4As4 tetrahedra, edges with two equivalent Zn(2)Si2As4 tetrahedra, and edges with two equivalent Zn(3)Si2As4 tetrahedra. All Si(1)-As(1) bond lengths are 2.44 Å. As(1) is bonded in a 8-coordinate geometry to four equivalent K(1), one Zn(1), one Zn(2), one Zn(3), and one Si(1) atom.