Na2LiGaAs2 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent Ga(1), two equivalent As(1), and three equivalent As(2) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to two equivalent Ga(1), two equivalent As(2), and three equivalent As(1) atoms. Li(1) is bonded in a 4-coordinate geometry to three equivalent Ga(1), two equivalent As(1), and two equivalent As(2) atoms. Ga(1) is bonded in a 11-coordinate geometry to two equivalent Na(1), two equivalent Na(2), three equivalent Li(1), two equivalent As(1), and two equivalent As(2) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 9-coordinate geometry to two equivalent Na(1), three equivalent Na(2), 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 Na(2), three equivalent Na(1), two equivalent Li(1), and two equivalent Ga(1) atoms.
Na2LiGaAs2 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent Ga(1), two equivalent As(1), and three equivalent As(2) atoms. Both Na(1)-Ga(1) bond lengths are 3.26 Å. Both Na(1)-As(1) bond lengths are 3.21 Å. There is one shorter (3.04 Å) and two longer (3.13 Å) Na(1)-As(2) bond lengths. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to two equivalent Ga(1), two equivalent As(2), and three equivalent As(1) atoms. Both Na(2)-Ga(1) bond lengths are 3.39 Å. Both Na(2)-As(2) bond lengths are 3.20 Å. There are a spread of Na(2)-As(1) bond distances ranging from 3.08-3.13 Å. Li(1) is bonded in a 4-coordinate geometry to three equivalent Ga(1), two equivalent As(1), and two equivalent As(2) atoms. There are two shorter (2.96 Å) and one longer (3.03 Å) Li(1)-Ga(1) bond length. Both Li(1)-As(1) bond lengths are 2.68 Å. Both Li(1)-As(2) bond lengths are 2.65 Å. Ga(1) is bonded in a 11-coordinate geometry to two equivalent Na(1), two equivalent Na(2), three equivalent Li(1), two equivalent As(1), and two equivalent As(2) atoms. Both Ga(1)-As(1) bond lengths are 2.55 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 Na(1), three equivalent Na(2), 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 Na(2), three equivalent Na(1), two equivalent Li(1), and two equivalent Ga(1) atoms.