Zn2GeSiN4 is Stannite-like structured and crystallizes in the monoclinic P2_1 space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(1), one N(2), and two equivalent N(4) atoms to form ZnN4 tetrahedra that share corners with two equivalent Zn(1)N4 tetrahedra, corners with two equivalent Zn(2)N4 tetrahedra, corners with four equivalent Ge(1)N4 tetrahedra, and corners with four equivalent Si(1)N4 tetrahedra. In the second Zn site, Zn(2) is bonded to one N(1), one N(2), and two equivalent N(3) atoms to form ZnN4 tetrahedra that share corners with two equivalent Zn(1)N4 tetrahedra, corners with two equivalent Zn(2)N4 tetrahedra, corners with four equivalent Ge(1)N4 tetrahedra, and corners with four equivalent Si(1)N4 tetrahedra. Ge(1) is bonded to one N(3), one N(4), and two equivalent N(1) atoms to form GeN4 tetrahedra that share corners with two equivalent Ge(1)N4 tetrahedra, corners with two equivalent Si(1)N4 tetrahedra, corners with four equivalent Zn(1)N4 tetrahedra, and corners with four equivalent Zn(2)N4 tetrahedra. Si(1) is bonded to one N(3), one N(4), and two equivalent N(2) atoms to form SiN4 tetrahedra that share corners with two equivalent Ge(1)N4 tetrahedra, corners with two equivalent Si(1)N4 tetrahedra, corners with four equivalent Zn(1)N4 tetrahedra, and corners with four equivalent Zn(2)N4 tetrahedra. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Zn(1), one Zn(2), and two equivalent Ge(1) atoms to form NZn2Ge2 tetrahedra that share corners with two equivalent N(1)Zn2Ge2 tetrahedra, corners with two equivalent N(2)Zn2Si2 tetrahedra, corners with four equivalent N(3)Zn2SiGe tetrahedra, and corners with four equivalent N(4)Zn2SiGe tetrahedra. In the second N site, N(2) is bonded to one Zn(1), one Zn(2), and two equivalent Si(1) atoms to form NZn2Si2 tetrahedra that share corners with two equivalent N(1)Zn2Ge2 tetrahedra, corners with two equivalent N(2)Zn2Si2 tetrahedra, corners with four equivalent N(3)Zn2SiGe tetrahedra, and corners with four equivalent N(4)Zn2SiGe tetrahedra. In the third N site, N(3) is bonded to two equivalent Zn(2), one Ge(1), and one Si(1) atom to form NZn2SiGe tetrahedra that share corners with two equivalent N(3)Zn2SiGe tetrahedra, corners with two equivalent N(4)Zn2SiGe tetrahedra, corners with four equivalent N(1)Zn2Ge2 tetrahedra, and corners with four equivalent N(2)Zn2Si2 tetrahedra. In the fourth N site, N(4) is bonded to two equivalent Zn(1), one Ge(1), and one Si(1) atom to form NZn2SiGe tetrahedra that share corners with two equivalent N(3)Zn2SiGe tetrahedra, corners with two equivalent N(4)Zn2SiGe tetrahedra, corners with four equivalent N(1)Zn2Ge2 tetrahedra, and corners with four equivalent N(2)Zn2Si2 tetrahedra.
Zn2GeSiN4 is Stannite-like structured and crystallizes in the monoclinic P2_1 space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(1), one N(2), and two equivalent N(4) atoms to form ZnN4 tetrahedra that share corners with two equivalent Zn(1)N4 tetrahedra, corners with two equivalent Zn(2)N4 tetrahedra, corners with four equivalent Ge(1)N4 tetrahedra, and corners with four equivalent Si(1)N4 tetrahedra. The Zn(1)-N(1) bond length is 2.05 Å. The Zn(1)-N(2) bond length is 2.08 Å. Both Zn(1)-N(4) bond lengths are 2.08 Å. In the second Zn site, Zn(2) is bonded to one N(1), one N(2), and two equivalent N(3) atoms to form ZnN4 tetrahedra that share corners with two equivalent Zn(1)N4 tetrahedra, corners with two equivalent Zn(2)N4 tetrahedra, corners with four equivalent Ge(1)N4 tetrahedra, and corners with four equivalent Si(1)N4 tetrahedra. The Zn(2)-N(1) bond length is 2.02 Å. The Zn(2)-N(2) bond length is 2.08 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) Zn(2)-N(3) bond length. Ge(1) is bonded to one N(3), one N(4), and two equivalent N(1) atoms to form GeN4 tetrahedra that share corners with two equivalent Ge(1)N4 tetrahedra, corners with two equivalent Si(1)N4 tetrahedra, corners with four equivalent Zn(1)N4 tetrahedra, and corners with four equivalent Zn(2)N4 tetrahedra. The Ge(1)-N(3) bond length is 1.88 Å. The Ge(1)-N(4) bond length is 1.88 Å. There is one shorter (1.86 Å) and one longer (1.87 Å) Ge(1)-N(1) bond length. Si(1) is bonded to one N(3), one N(4), and two equivalent N(2) atoms to form SiN4 tetrahedra that share corners with two equivalent Ge(1)N4 tetrahedra, corners with two equivalent Si(1)N4 tetrahedra, corners with four equivalent Zn(1)N4 tetrahedra, and corners with four equivalent Zn(2)N4 tetrahedra. The Si(1)-N(3) bond length is 1.76 Å. The Si(1)-N(4) bond length is 1.77 Å. There is one shorter (1.76 Å) and one longer (1.77 Å) Si(1)-N(2) bond length. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Zn(1), one Zn(2), and two equivalent Ge(1) atoms to form NZn2Ge2 tetrahedra that share corners with two equivalent N(1)Zn2Ge2 tetrahedra, corners with two equivalent N(2)Zn2Si2 tetrahedra, corners with four equivalent N(3)Zn2SiGe tetrahedra, and corners with four equivalent N(4)Zn2SiGe tetrahedra. In the second N site, N(2) is bonded to one Zn(1), one Zn(2), and two equivalent Si(1) atoms to form NZn2Si2 tetrahedra that share corners with two equivalent N(1)Zn2Ge2 tetrahedra, corners with two equivalent N(2)Zn2Si2 tetrahedra, corners with four equivalent N(3)Zn2SiGe tetrahedra, and corners with four equivalent N(4)Zn2SiGe tetrahedra. In the third N site, N(3) is bonded to two equivalent Zn(2), one Ge(1), and one Si(1) atom to form NZn2SiGe tetrahedra that share corners with two equivalent N(3)Zn2SiGe tetrahedra, corners with two equivalent N(4)Zn2SiGe tetrahedra, corners with four equivalent N(1)Zn2Ge2 tetrahedra, and corners with four equivalent N(2)Zn2Si2 tetrahedra. In the fourth N site, N(4) is bonded to two equivalent Zn(1), one Ge(1), and one Si(1) atom to form NZn2SiGe tetrahedra that share corners with two equivalent N(3)Zn2SiGe tetrahedra, corners with two equivalent N(4)Zn2SiGe tetrahedra, corners with four equivalent N(1)Zn2Ge2 tetrahedra, and corners with four equivalent N(2)Zn2Si2 tetrahedra.