K2LiGaAs2 crystallizes in the orthorhombic Cmce space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent Ga(1), two equivalent As(2), and three equivalent As(1) atoms. In the second K site, K(2) is bonded in a 5-coordinate geometry to two equivalent As(1) and three equivalent As(2) atoms. Li(1) is bonded to two equivalent As(1) and two equivalent As(2) atoms to form distorted LiAs4 tetrahedra that share corners with two equivalent Li(1)As4 tetrahedra, corners with two equivalent Ga(1)K2As4 tetrahedra,  an edgeedge with one Li(1)As4 tetrahedra, and edges with three equivalent Ga(1)K2As4 tetrahedra. Ga(1) is bonded to two equivalent K(1), two equivalent As(1), and two equivalent As(2) atoms to form distorted GaK2As4 tetrahedra that share corners with two equivalent Li(1)As4 tetrahedra, edges with three equivalent Li(1)As4 tetrahedra, and edges with three equivalent Ga(1)K2As4 tetrahedra. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 9-coordinate geometry to two equivalent K(2), three equivalent K(1), two equivalent Li(1), and two equivalent Ga(1) atoms. In the second As site, As(2) is bonded in a 9-coordinate geometry to two equivalent K(1), three equivalent K(2), two equivalent Li(1), and two equivalent Ga(1) atoms.
K2LiGaAs2 crystallizes in the orthorhombic Cmce space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent Ga(1), two equivalent As(2), and three equivalent As(1) atoms. Both K(1)-Ga(1) bond lengths are 3.45 Å. Both K(1)-As(2) bond lengths are 3.39 Å. There are two shorter (3.38 Å) and one longer (3.65 Å) K(1)-As(1) bond length. In the second K site, K(2) is bonded in a 5-coordinate geometry to two equivalent As(1) and three equivalent As(2) atoms. Both K(2)-As(1) bond lengths are 3.38 Å. There are a spread of K(2)-As(2) bond distances ranging from 3.33-3.68 Å. Li(1) is bonded to two equivalent As(1) and two equivalent As(2) atoms to form distorted LiAs4 tetrahedra that share corners with two equivalent Li(1)As4 tetrahedra, corners with two equivalent Ga(1)K2As4 tetrahedra,  an edgeedge with one Li(1)As4 tetrahedra, and edges with three equivalent Ga(1)K2As4 tetrahedra. Both Li(1)-As(1) bond lengths are 2.69 Å. Both Li(1)-As(2) bond lengths are 2.76 Å. Ga(1) is bonded to two equivalent K(1), two equivalent As(1), and two equivalent As(2) atoms to form distorted GaK2As4 tetrahedra that share corners with two equivalent Li(1)As4 tetrahedra, edges with three equivalent Li(1)As4 tetrahedra, and edges with three equivalent Ga(1)K2As4 tetrahedra. Both Ga(1)-As(1) bond lengths are 2.61 Å. Both Ga(1)-As(2) bond lengths are 2.57 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 9-coordinate geometry to two equivalent K(2), three equivalent K(1), two equivalent Li(1), and two equivalent Ga(1) atoms. In the second As site, As(2) is bonded in a 9-coordinate geometry to two equivalent K(1), three equivalent K(2), two equivalent Li(1), and two equivalent Ga(1) atoms.