Mg14TiB crystallizes in the orthorhombic Amm2 space group. There are seven inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Mg(2), two equivalent Mg(6), four equivalent Mg(4), and four equivalent Mg(5) atoms to form MgMg12 cuboctahedra that share corners with six equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Mg(2)Mg12 cuboctahedra, edges with four equivalent Mg(6)Mg11Ti cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, faces with two equivalent Ti(1)Mg10B2 cuboctahedra, and faces with four equivalent Mg(4)Mg12 cuboctahedra. In the second Mg site, Mg(2) is bonded to two equivalent Mg(1), two equivalent Mg(7), four equivalent Mg(4), and four equivalent Mg(5) atoms to form MgMg12 cuboctahedra that share corners with four equivalent Ti(1)Mg10B2 cuboctahedra, corners with six equivalent Mg(2)Mg12 cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with four equivalent Mg(4)Mg12 cuboctahedra, and faces with six equivalent Mg(6)Mg11Ti cuboctahedra. In the third Mg site, Mg(3) is bonded in a distorted single-bond geometry to two equivalent Mg(5), two equivalent Mg(6), two equivalent Mg(7), two equivalent Ti(1), and one B(1) atom. In the fourth Mg site, Mg(4) is bonded to two equivalent Mg(1), two equivalent Mg(2), two equivalent Mg(4), two equivalent Mg(5), two equivalent Mg(6), and two equivalent Mg(7) atoms to form MgMg12 cuboctahedra that share corners with four equivalent Ti(1)Mg10B2 cuboctahedra, corners with six equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Mg(2)Mg12 cuboctahedra, edges with two equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, and faces with two equivalent Mg(4)Mg12 cuboctahedra. In the fifth Mg site, Mg(5) is bonded in a 12-coordinate geometry to one Mg(1), one Mg(2), one Mg(3), one Mg(4), two equivalent Mg(5), two equivalent Mg(6), two equivalent Mg(7), one Ti(1), and one B(1) atom. In the sixth Mg site, Mg(6) is bonded to one Mg(1), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(7), four equivalent Mg(5), and one Ti(1) atom to form distorted MgMg11Ti cuboctahedra that share corners with six equivalent Mg(6)Mg11Ti cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Ti(1)Mg10B2 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra,  a faceface with one Mg(1)Mg12 cuboctahedra,  a faceface with one Ti(1)Mg10B2 cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, and faces with three equivalent Mg(2)Mg12 cuboctahedra. In the seventh Mg site, Mg(7) is bonded in a 12-coordinate geometry to one Mg(2), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(6), four equivalent Mg(5), and one B(1) atom. Ti(1) is bonded to two equivalent Mg(6), four equivalent Mg(3), four equivalent Mg(5), and two equivalent B(1) atoms to form TiMg10B2 cuboctahedra that share corners with four equivalent Mg(2)Mg12 cuboctahedra, corners with six equivalent Ti(1)Mg10B2 cuboctahedra, corners with eight equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, and faces with two equivalent Mg(1)Mg12 cuboctahedra. B(1) is bonded in a 10-coordinate geometry to two equivalent Mg(3), two equivalent Mg(7), four equivalent Mg(5), and two equivalent Ti(1) atoms.
Mg14TiB crystallizes in the orthorhombic Amm2 space group. There are seven inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent Mg(2), two equivalent Mg(6), four equivalent Mg(4), and four equivalent Mg(5) atoms to form MgMg12 cuboctahedra that share corners with six equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Mg(2)Mg12 cuboctahedra, edges with four equivalent Mg(6)Mg11Ti cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, faces with two equivalent Ti(1)Mg10B2 cuboctahedra, and faces with four equivalent Mg(4)Mg12 cuboctahedra. Both Mg(1)-Mg(2) bond lengths are 3.02 Å. Both Mg(1)-Mg(6) bond lengths are 3.09 Å. There are two shorter (3.11 Å) and two longer (3.20 Å) Mg(1)-Mg(4) bond lengths. All Mg(1)-Mg(5) bond lengths are 3.19 Å. In the second Mg site, Mg(2) is bonded to two equivalent Mg(1), two equivalent Mg(7), four equivalent Mg(4), and four equivalent Mg(5) atoms to form MgMg12 cuboctahedra that share corners with four equivalent Ti(1)Mg10B2 cuboctahedra, corners with six equivalent Mg(2)Mg12 cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with four equivalent Mg(4)Mg12 cuboctahedra, and faces with six equivalent Mg(6)Mg11Ti cuboctahedra. Both Mg(2)-Mg(7) bond lengths are 3.27 Å. There are two shorter (3.14 Å) and two longer (3.17 Å) Mg(2)-Mg(4) bond lengths. All Mg(2)-Mg(5) bond lengths are 3.19 Å. In the third Mg site, Mg(3) is bonded in a distorted single-bond geometry to two equivalent Mg(5), two equivalent Mg(6), two equivalent Mg(7), two equivalent Ti(1), and one B(1) atom. Both Mg(3)-Mg(5) bond lengths are 2.88 Å. Both Mg(3)-Mg(6) bond lengths are 3.10 Å. Both Mg(3)-Mg(7) bond lengths are 2.98 Å. There is one shorter (3.14 Å) and one longer (3.17 Å) Mg(3)-Ti(1) bond length. The Mg(3)-B(1) bond length is 2.67 Å. In the fourth Mg site, Mg(4) is bonded to two equivalent Mg(1), two equivalent Mg(2), two equivalent Mg(4), two equivalent Mg(5), two equivalent Mg(6), and two equivalent Mg(7) atoms to form MgMg12 cuboctahedra that share corners with four equivalent Ti(1)Mg10B2 cuboctahedra, corners with six equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Mg(2)Mg12 cuboctahedra, edges with two equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, and faces with two equivalent Mg(4)Mg12 cuboctahedra. There is one shorter (2.97 Å) and one longer (3.07 Å) Mg(4)-Mg(4) bond length. Both Mg(4)-Mg(5) bond lengths are 3.23 Å. Both Mg(4)-Mg(6) bond lengths are 3.10 Å. Both Mg(4)-Mg(7) bond lengths are 3.38 Å. In the fifth Mg site, Mg(5) is bonded in a 12-coordinate geometry to one Mg(1), one Mg(2), one Mg(3), one Mg(4), two equivalent Mg(5), two equivalent Mg(6), two equivalent Mg(7), one Ti(1), and one B(1) atom. There is one shorter (3.01 Å) and one longer (3.03 Å) Mg(5)-Mg(5) bond length. There is one shorter (3.12 Å) and one longer (3.20 Å) Mg(5)-Mg(6) bond length. There is one shorter (2.99 Å) and one longer (3.32 Å) Mg(5)-Mg(7) bond length. The Mg(5)-Ti(1) bond length is 2.99 Å. The Mg(5)-B(1) bond length is 2.85 Å. In the sixth Mg site, Mg(6) is bonded to one Mg(1), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(7), four equivalent Mg(5), and one Ti(1) atom to form distorted MgMg11Ti cuboctahedra that share corners with six equivalent Mg(6)Mg11Ti cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Ti(1)Mg10B2 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra,  a faceface with one Mg(1)Mg12 cuboctahedra,  a faceface with one Ti(1)Mg10B2 cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, and faces with three equivalent Mg(2)Mg12 cuboctahedra. Both Mg(6)-Mg(7) bond lengths are 3.04 Å. The Mg(6)-Ti(1) bond length is 2.99 Å. In the seventh Mg site, Mg(7) is bonded in a 12-coordinate geometry to one Mg(2), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(6), four equivalent Mg(5), and one B(1) atom. The Mg(7)-B(1) bond length is 2.95 Å. Ti(1) is bonded to two equivalent Mg(6), four equivalent Mg(3), four equivalent Mg(5), and two equivalent B(1) atoms to form TiMg10B2 cuboctahedra that share corners with four equivalent Mg(2)Mg12 cuboctahedra, corners with six equivalent Ti(1)Mg10B2 cuboctahedra, corners with eight equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(6)Mg11Ti cuboctahedra, faces with two equivalent Mg(6)Mg11Ti cuboctahedra, and faces with two equivalent Mg(1)Mg12 cuboctahedra. Both Ti(1)-B(1) bond lengths are 3.06 Å. B(1) is bonded in a 10-coordinate geometry to two equivalent Mg(3), two equivalent Mg(7), four equivalent Mg(5), and two equivalent Ti(1) atoms.