Ag2GeSe3 is Enargite-like structured and crystallizes in the orthorhombic Cmc2_1 space group. Ag(1) is bonded to one Se(2) and three equivalent Se(1) atoms to form AgSe4 tetrahedra that share corners with five equivalent Ge(1)Se4 tetrahedra and corners with seven equivalent Ag(1)Se4 tetrahedra. Ge(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form GeSe4 tetrahedra that share corners with two equivalent Ge(1)Se4 tetrahedra and corners with ten equivalent Ag(1)Se4 tetrahedra. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent Ag(1) and one Ge(1) atom to form SeAg3Ge tetrahedra that share corners with five equivalent Se(2)Ag2Ge2 tetrahedra and corners with seven equivalent Se(1)Ag3Ge tetrahedra. In the second Se site, Se(2) is bonded to two equivalent Ag(1) and two equivalent Ge(1) atoms to form SeAg2Ge2 tetrahedra that share corners with two equivalent Se(2)Ag2Ge2 tetrahedra and corners with ten equivalent Se(1)Ag3Ge tetrahedra.
Ag2GeSe3 is Enargite-like structured and crystallizes in the orthorhombic Cmc2_1 space group. Ag(1) is bonded to one Se(2) and three equivalent Se(1) atoms to form AgSe4 tetrahedra that share corners with five equivalent Ge(1)Se4 tetrahedra and corners with seven equivalent Ag(1)Se4 tetrahedra. The Ag(1)-Se(2) bond length is 2.68 Å. There are two shorter (2.63 Å) and one longer (2.67 Å) Ag(1)-Se(1) bond length. Ge(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form GeSe4 tetrahedra that share corners with two equivalent Ge(1)Se4 tetrahedra and corners with ten equivalent Ag(1)Se4 tetrahedra. Both Ge(1)-Se(1) bond lengths are 2.33 Å. There is one shorter (2.44 Å) and one longer (2.50 Å) Ge(1)-Se(2) bond length. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent Ag(1) and one Ge(1) atom to form SeAg3Ge tetrahedra that share corners with five equivalent Se(2)Ag2Ge2 tetrahedra and corners with seven equivalent Se(1)Ag3Ge tetrahedra. In the second Se site, Se(2) is bonded to two equivalent Ag(1) and two equivalent Ge(1) atoms to form SeAg2Ge2 tetrahedra that share corners with two equivalent Se(2)Ag2Ge2 tetrahedra and corners with ten equivalent Se(1)Ag3Ge tetrahedra.