Li2Pd3B crystallizes in the trigonal R32 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent Li(2), three equivalent Pd(1), three equivalent Pd(2), and three equivalent Pd(3) atoms to form distorted LiLi3Pd9 cuboctahedra that share corners with three equivalent Li(1)Li3Pd9 cuboctahedra, corners with twelve equivalent Li(2)Li3Pd9 cuboctahedra, edges with three equivalent B(1)Pd6 octahedra,  a faceface with one Li(1)Li3Pd9 cuboctahedra, faces with nine equivalent Li(2)Li3Pd9 cuboctahedra,  a faceface with one B(2)Pd6 octahedra, and faces with three equivalent B(1)Pd6 octahedra. In the second Li site, Li(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Pd(1), two equivalent Pd(3), and five equivalent Pd(2) atoms to form distorted LiLi3Pd9 cuboctahedra that share corners with four equivalent Li(1)Li3Pd9 cuboctahedra, corners with eleven equivalent Li(2)Li3Pd9 cuboctahedra,  an edgeedge with one B(2)Pd6 octahedra, edges with two equivalent B(1)Pd6 octahedra, faces with three equivalent Li(1)Li3Pd9 cuboctahedra, faces with seven equivalent Li(2)Li3Pd9 cuboctahedra,  a faceface with one B(2)Pd6 octahedra, and faces with three equivalent B(1)Pd6 octahedra. There are three inequivalent Pd sites. In the first Pd site, Pd(1) is bonded in a 8-coordinate geometry to two equivalent Li(1), four equivalent Li(2), and two equivalent B(1) atoms. In the second Pd site, Pd(2) is bonded in a 8-coordinate geometry to one Li(1), five equivalent Li(2), one B(1), and one B(2) atom. In the third Pd site, Pd(3) is bonded in a 8-coordinate geometry to two equivalent Li(1), four equivalent Li(2), and two equivalent B(1) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded to two equivalent Pd(1), two equivalent Pd(2), and two equivalent Pd(3) atoms to form distorted BPd6 octahedra that share corners with two equivalent B(2)Pd6 octahedra, corners with four equivalent B(1)Pd6 octahedra, edges with two equivalent Li(1)Li3Pd9 cuboctahedra, edges with four equivalent Li(2)Li3Pd9 cuboctahedra, faces with two equivalent Li(1)Li3Pd9 cuboctahedra, and faces with six equivalent Li(2)Li3Pd9 cuboctahedra. The corner-sharing octahedral tilt angles are 29°. In the second B site, B(2) is bonded to six equivalent Pd(2) atoms to form distorted BPd6 octahedra that share corners with six equivalent B(1)Pd6 octahedra, edges with six equivalent Li(2)Li3Pd9 cuboctahedra, faces with two equivalent Li(1)Li3Pd9 cuboctahedra, and faces with six equivalent Li(2)Li3Pd9 cuboctahedra. The corner-sharing octahedral tilt angles are 29°.
Li2Pd3B crystallizes in the trigonal R32 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent Li(2), three equivalent Pd(1), three equivalent Pd(2), and three equivalent Pd(3) atoms to form distorted LiLi3Pd9 cuboctahedra that share corners with three equivalent Li(1)Li3Pd9 cuboctahedra, corners with twelve equivalent Li(2)Li3Pd9 cuboctahedra, edges with three equivalent B(1)Pd6 octahedra,  a faceface with one Li(1)Li3Pd9 cuboctahedra, faces with nine equivalent Li(2)Li3Pd9 cuboctahedra,  a faceface with one B(2)Pd6 octahedra, and faces with three equivalent B(1)Pd6 octahedra. All Li(1)-Li(2) bond lengths are 2.57 Å. All Li(1)-Pd(1) bond lengths are 2.85 Å. All Li(1)-Pd(2) bond lengths are 2.83 Å. All Li(1)-Pd(3) bond lengths are 2.74 Å. In the second Li site, Li(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Pd(1), two equivalent Pd(3), and five equivalent Pd(2) atoms to form distorted LiLi3Pd9 cuboctahedra that share corners with four equivalent Li(1)Li3Pd9 cuboctahedra, corners with eleven equivalent Li(2)Li3Pd9 cuboctahedra,  an edgeedge with one B(2)Pd6 octahedra, edges with two equivalent B(1)Pd6 octahedra, faces with three equivalent Li(1)Li3Pd9 cuboctahedra, faces with seven equivalent Li(2)Li3Pd9 cuboctahedra,  a faceface with one B(2)Pd6 octahedra, and faces with three equivalent B(1)Pd6 octahedra. Both Li(2)-Li(2) bond lengths are 2.57 Å. There is one shorter (2.74 Å) and one longer (2.83 Å) Li(2)-Pd(1) bond length. There is one shorter (2.83 Å) and one longer (2.85 Å) Li(2)-Pd(3) bond length. There are a spread of Li(2)-Pd(2) bond distances ranging from 2.74-2.85 Å. There are three inequivalent Pd sites. In the first Pd site, Pd(1) is bonded in a 8-coordinate geometry to two equivalent Li(1), four equivalent Li(2), and two equivalent B(1) atoms. Both Pd(1)-B(1) bond lengths are 2.14 Å. In the second Pd site, Pd(2) is bonded in a 8-coordinate geometry to one Li(1), five equivalent Li(2), one B(1), and one B(2) atom. The Pd(2)-B(1) bond length is 2.14 Å. The Pd(2)-B(2) bond length is 2.14 Å. In the third Pd site, Pd(3) is bonded in a 8-coordinate geometry to two equivalent Li(1), four equivalent Li(2), and two equivalent B(1) atoms. Both Pd(3)-B(1) bond lengths are 2.14 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to two equivalent Pd(1), two equivalent Pd(2), and two equivalent Pd(3) atoms to form distorted BPd6 octahedra that share corners with two equivalent B(2)Pd6 octahedra, corners with four equivalent B(1)Pd6 octahedra, edges with two equivalent Li(1)Li3Pd9 cuboctahedra, edges with four equivalent Li(2)Li3Pd9 cuboctahedra, faces with two equivalent Li(1)Li3Pd9 cuboctahedra, and faces with six equivalent Li(2)Li3Pd9 cuboctahedra. The corner-sharing octahedral tilt angles are 29°. In the second B site, B(2) is bonded to six equivalent Pd(2) atoms to form distorted BPd6 octahedra that share corners with six equivalent B(1)Pd6 octahedra, edges with six equivalent Li(2)Li3Pd9 cuboctahedra, faces with two equivalent Li(1)Li3Pd9 cuboctahedra, and faces with six equivalent Li(2)Li3Pd9 cuboctahedra. The corner-sharing octahedral tilt angles are 29°.