LiNbAs2 crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one As(7), two equivalent As(9), and three equivalent As(8) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one As(8), two equivalent As(10), and two equivalent As(9) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one As(12), two equivalent As(11), and three equivalent As(10) atoms. In the fourth Li site, Li(4) is bonded in a 7-coordinate geometry to one As(10), three equivalent As(11), and three equivalent As(12) atoms. In the fifth Li site, Li(5) is bonded in a distorted square co-planar geometry to two equivalent As(1) and two equivalent As(12) atoms. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. There are six inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 6-coordinate geometry to one As(1), two equivalent As(3), and three equivalent As(2) atoms. In the second Nb site, Nb(2) is bonded to one As(2), two equivalent As(4), and three equivalent As(3) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. In the third Nb site, Nb(3) is bonded to one As(3), two equivalent As(5), and three equivalent As(4) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. In the fourth Nb site, Nb(4) is bonded to one As(4), two equivalent As(6), and three equivalent As(5) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. In the fifth Nb site, Nb(5) is bonded to one As(5), two equivalent As(7), and three equivalent As(6) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. In the sixth Nb site, Nb(6) is bonded in a 6-coordinate geometry to one As(6), two equivalent As(8), and three equivalent As(7) atoms. There are twelve inequivalent As sites. In the first As site, As(1) is bonded in a 6-coordinate geometry to two equivalent Li(5), three equivalent Li(6), and one Nb(1) atom. In the second As site, As(2) is bonded to two equivalent Li(6), one Nb(2), and three equivalent Nb(1) atoms to form distorted AsLi2Nb4 pentagonal pyramids that share corners with two equivalent As(3)Nb6 pentagonal pyramids, corners with two equivalent As(4)Nb6 pentagonal pyramids, corners with four equivalent As(2)Li2Nb4 pentagonal pyramids, edges with two equivalent As(2)Li2Nb4 pentagonal pyramids, edges with two equivalent As(3)Nb6 pentagonal pyramids, and  a faceface with one As(3)Nb6 pentagonal pyramid. In the third As site, As(3) is bonded to one Nb(3), two equivalent Nb(1), and three equivalent Nb(2) atoms to form distorted AsNb6 pentagonal pyramids that share corners with two equivalent As(2)Li2Nb4 pentagonal pyramids, corners with two equivalent As(4)Nb6 pentagonal pyramids, corners with two equivalent As(5)Nb6 pentagonal pyramids, corners with four equivalent As(3)Nb6 pentagonal pyramids, edges with two equivalent As(2)Li2Nb4 pentagonal pyramids, edges with two equivalent As(3)Nb6 pentagonal pyramids, edges with two equivalent As(4)Nb6 pentagonal pyramids,  a faceface with one As(2)Li2Nb4 pentagonal pyramid, and  a faceface with one As(4)Nb6 pentagonal pyramid. In the fourth As site, As(4) is bonded to one Nb(4), two equivalent Nb(2), and three equivalent Nb(3) atoms to form distorted AsNb6 pentagonal pyramids that share corners with two equivalent As(2)Li2Nb4 pentagonal pyramids, corners with two equivalent As(3)Nb6 pentagonal pyramids, corners with two equivalent As(5)Nb6 pentagonal pyramids, corners with two equivalent As(6)Nb6 pentagonal pyramids, corners with four equivalent As(4)Nb6 pentagonal pyramids, edges with two equivalent As(3)Nb6 pentagonal pyramids, edges with two equivalent As(4)Nb6 pentagonal pyramids, edges with two equivalent As(5)Nb6 pentagonal pyramids,  a faceface with one As(3)Nb6 pentagonal pyramid, and  a faceface with one As(5)Nb6 pentagonal pyramid. In the fifth As site, As(5) is bonded to one Nb(5), two equivalent Nb(3), and three equivalent Nb(4) atoms to form a mixture of distorted edge, face, and corner-sharing AsNb6 pentagonal pyramids. In the sixth As site, As(6) is bonded to one Nb(6), two equivalent Nb(4), and three equivalent Nb(5) atoms to form a mixture of distorted edge, face, and corner-sharing AsNb6 pentagonal pyramids. In the seventh As site, As(7) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Nb(5), and three equivalent Nb(6) atoms. In the eighth As site, As(8) is bonded in a 8-coordinate geometry to one Li(2), three equivalent Li(1), two equivalent Nb(6), and two equivalent As(9) atoms. In the ninth As site, As(9) is bonded in a 4-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent As(8) atoms. In the tenth As site, As(10) is bonded in a 8-coordinate geometry to one Li(4), two equivalent Li(2), three equivalent Li(3), and two equivalent As(11) atoms. In the eleventh As site, As(11) is bonded in a 4-coordinate geometry to two equivalent Li(3), three equivalent Li(4), two equivalent As(10), and two equivalent As(12) atoms. In the twelfth As site, As(12) is bonded in a 8-coordinate geometry to one Li(3), two equivalent Li(5), three equivalent Li(4), and two equivalent As(11) atoms.
LiNbAs2 crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one As(7), two equivalent As(9), and three equivalent As(8) atoms. The Li(1)-As(7) bond length is 2.62 Å. Both Li(1)-As(9) bond lengths are 2.53 Å. There are two shorter (2.53 Å) and one longer (2.93 Å) Li(1)-As(8) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one As(8), two equivalent As(10), and two equivalent As(9) atoms. The Li(2)-As(8) bond length is 2.96 Å. Both Li(2)-As(10) bond lengths are 2.66 Å. Both Li(2)-As(9) bond lengths are 2.72 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one As(12), two equivalent As(11), and three equivalent As(10) atoms. The Li(3)-As(12) bond length is 2.94 Å. Both Li(3)-As(11) bond lengths are 2.70 Å. There are two shorter (2.64 Å) and one longer (2.75 Å) Li(3)-As(10) bond length. In the fourth Li site, Li(4) is bonded in a 7-coordinate geometry to one As(10), three equivalent As(11), and three equivalent As(12) atoms. The Li(4)-As(10) bond length is 2.82 Å. There are two shorter (2.68 Å) and one longer (3.03 Å) Li(4)-As(11) bond length. There are two shorter (2.64 Å) and one longer (2.82 Å) Li(4)-As(12) bond length. In the fifth Li site, Li(5) is bonded in a distorted square co-planar geometry to two equivalent As(1) and two equivalent As(12) atoms. Both Li(5)-As(1) bond lengths are 2.70 Å. Both Li(5)-As(12) bond lengths are 2.70 Å. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to two equivalent As(2) and three equivalent As(1) atoms. Both Li(6)-As(2) bond lengths are 2.64 Å. There are two shorter (2.68 Å) and one longer (2.73 Å) Li(6)-As(1) bond length. There are six inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 6-coordinate geometry to one As(1), two equivalent As(3), and three equivalent As(2) atoms. The Nb(1)-As(1) bond length is 2.67 Å. Both Nb(1)-As(3) bond lengths are 2.69 Å. There are two shorter (2.61 Å) and one longer (2.71 Å) Nb(1)-As(2) bond length. In the second Nb site, Nb(2) is bonded to one As(2), two equivalent As(4), and three equivalent As(3) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. The Nb(2)-As(2) bond length is 2.58 Å. Both Nb(2)-As(4) bond lengths are 2.65 Å. All Nb(2)-As(3) bond lengths are 2.67 Å. In the third Nb site, Nb(3) is bonded to one As(3), two equivalent As(5), and three equivalent As(4) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. The Nb(3)-As(3) bond length is 2.66 Å. Both Nb(3)-As(5) bond lengths are 2.67 Å. There are two shorter (2.66 Å) and one longer (2.68 Å) Nb(3)-As(4) bond length. In the fourth Nb site, Nb(4) is bonded to one As(4), two equivalent As(6), and three equivalent As(5) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. The Nb(4)-As(4) bond length is 2.63 Å. Both Nb(4)-As(6) bond lengths are 2.65 Å. There are two shorter (2.66 Å) and one longer (2.67 Å) Nb(4)-As(5) bond length. In the fifth Nb site, Nb(5) is bonded to one As(5), two equivalent As(7), and three equivalent As(6) atoms to form a mixture of distorted edge, face, and corner-sharing NbAs6 pentagonal pyramids. The Nb(5)-As(5) bond length is 2.65 Å. Both Nb(5)-As(7) bond lengths are 2.65 Å. All Nb(5)-As(6) bond lengths are 2.67 Å. In the sixth Nb site, Nb(6) is bonded in a 6-coordinate geometry to one As(6), two equivalent As(8), and three equivalent As(7) atoms. The Nb(6)-As(6) bond length is 2.62 Å. Both Nb(6)-As(8) bond lengths are 2.69 Å. There is one shorter (2.65 Å) and two longer (2.67 Å) Nb(6)-As(7) bond lengths. There are twelve inequivalent As sites. In the first As site, As(1) is bonded in a 6-coordinate geometry to two equivalent Li(5), three equivalent Li(6), and one Nb(1) atom. In the second As site, As(2) is bonded to two equivalent Li(6), one Nb(2), and three equivalent Nb(1) atoms to form distorted AsLi2Nb4 pentagonal pyramids that share corners with two equivalent As(3)Nb6 pentagonal pyramids, corners with two equivalent As(4)Nb6 pentagonal pyramids, corners with four equivalent As(2)Li2Nb4 pentagonal pyramids, edges with two equivalent As(2)Li2Nb4 pentagonal pyramids, edges with two equivalent As(3)Nb6 pentagonal pyramids, and  a faceface with one As(3)Nb6 pentagonal pyramid. In the third As site, As(3) is bonded to one Nb(3), two equivalent Nb(1), and three equivalent Nb(2) atoms to form distorted AsNb6 pentagonal pyramids that share corners with two equivalent As(2)Li2Nb4 pentagonal pyramids, corners with two equivalent As(4)Nb6 pentagonal pyramids, corners with two equivalent As(5)Nb6 pentagonal pyramids, corners with four equivalent As(3)Nb6 pentagonal pyramids, edges with two equivalent As(2)Li2Nb4 pentagonal pyramids, edges with two equivalent As(3)Nb6 pentagonal pyramids, edges with two equivalent As(4)Nb6 pentagonal pyramids,  a faceface with one As(2)Li2Nb4 pentagonal pyramid, and  a faceface with one As(4)Nb6 pentagonal pyramid. In the fourth As site, As(4) is bonded to one Nb(4), two equivalent Nb(2), and three equivalent Nb(3) atoms to form distorted AsNb6 pentagonal pyramids that share corners with two equivalent As(2)Li2Nb4 pentagonal pyramids, corners with two equivalent As(3)Nb6 pentagonal pyramids, corners with two equivalent As(5)Nb6 pentagonal pyramids, corners with two equivalent As(6)Nb6 pentagonal pyramids, corners with four equivalent As(4)Nb6 pentagonal pyramids, edges with two equivalent As(3)Nb6 pentagonal pyramids, edges with two equivalent As(4)Nb6 pentagonal pyramids, edges with two equivalent As(5)Nb6 pentagonal pyramids,  a faceface with one As(3)Nb6 pentagonal pyramid, and  a faceface with one As(5)Nb6 pentagonal pyramid. In the fifth As site, As(5) is bonded to one Nb(5), two equivalent Nb(3), and three equivalent Nb(4) atoms to form a mixture of distorted edge, face, and corner-sharing AsNb6 pentagonal pyramids. In the sixth As site, As(6) is bonded to one Nb(6), two equivalent Nb(4), and three equivalent Nb(5) atoms to form a mixture of distorted edge, face, and corner-sharing AsNb6 pentagonal pyramids. In the seventh As site, As(7) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Nb(5), and three equivalent Nb(6) atoms. In the eighth As site, As(8) is bonded in a 8-coordinate geometry to one Li(2), three equivalent Li(1), two equivalent Nb(6), and two equivalent As(9) atoms. Both As(8)-As(9) bond lengths are 2.57 Å. In the ninth As site, As(9) is bonded in a 4-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent As(8) atoms. In the tenth As site, As(10) is bonded in a 8-coordinate geometry to one Li(4), two equivalent Li(2), three equivalent Li(3), and two equivalent As(11) atoms. Both As(10)-As(11) bond lengths are 2.68 Å. In the eleventh As site, As(11) is bonded in a 4-coordinate geometry to two equivalent Li(3), three equivalent Li(4), two equivalent As(10), and two equivalent As(12) atoms. Both As(11)-As(12) bond lengths are 2.61 Å. In the twelfth As site, As(12) is bonded in a 8-coordinate geometry to one Li(3), two equivalent Li(5), three equivalent Li(4), and two equivalent As(11) atoms.