NaMg14W crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded to two equivalent Mg(6), four equivalent Mg(3), four equivalent Mg(5), and two equivalent W(1) atoms to form NaMg10W2 cuboctahedra that share corners with four equivalent Mg(2)Mg12 cuboctahedra, corners with six equivalent Na(1)Mg10W2 cuboctahedra, corners with eight equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent W(1)Na2Mg10 cuboctahedra, edges with four equivalent Mg(6)NaMg11 cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(6)NaMg11 cuboctahedra, and faces with two equivalent W(1)Na2Mg10 cuboctahedra. 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 four equivalent W(1)Na2Mg10 cuboctahedra, corners with six equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Mg(2)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(6)NaMg11 cuboctahedra, faces with two equivalent Na(1)Mg10W2 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, faces with two equivalent Mg(6)NaMg11 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 Na(1)Mg10W2 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 two equivalent W(1)Na2Mg10 cuboctahedra, faces with four equivalent Mg(4)Mg12 cuboctahedra, and faces with six equivalent Mg(6)NaMg11 cuboctahedra. In the third Mg site, Mg(3) is bonded in a 12-coordinate geometry to two equivalent Na(1), two equivalent Mg(3), two equivalent Mg(5), two equivalent Mg(6), two equivalent Mg(7), and two equivalent W(1) atoms. 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 Na(1)Mg10W2 cuboctahedra, corners with four equivalent W(1)Na2Mg10 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)NaMg11 cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, and faces with two equivalent Mg(6)NaMg11 cuboctahedra. In the fifth Mg site, Mg(5) is bonded in a 2-coordinate geometry to one Na(1), one Mg(1), one Mg(2), one Mg(3), one Mg(4), two equivalent Mg(6), and one W(1) atom. In the sixth Mg site, Mg(6) is bonded to one Na(1), one Mg(1), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(7), and four equivalent Mg(5) atoms to form distorted MgNaMg11 cuboctahedra that share corners with six equivalent Mg(6)NaMg11 cuboctahedra, edges with two equivalent Na(1)Mg10W2 cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra,  a faceface with one Na(1)Mg10W2 cuboctahedra,  a faceface with one Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(6)NaMg11 cuboctahedra, faces with three equivalent Mg(2)Mg12 cuboctahedra, and faces with three equivalent W(1)Na2Mg10 cuboctahedra. In the seventh Mg site, Mg(7) is bonded in a distorted single-bond geometry to one Mg(2), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(6), and one W(1) atom. W(1) is bonded to two equivalent Na(1), two equivalent Mg(7), four equivalent Mg(3), and four equivalent Mg(5) atoms to form WNa2Mg10 cuboctahedra that share corners with four equivalent Mg(1)Mg12 cuboctahedra, corners with six equivalent W(1)Na2Mg10 cuboctahedra, corners with eight equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent Na(1)Mg10W2 cuboctahedra, faces with two equivalent Na(1)Mg10W2 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, and faces with six equivalent Mg(6)NaMg11 cuboctahedra.
NaMg14W crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded to two equivalent Mg(6), four equivalent Mg(3), four equivalent Mg(5), and two equivalent W(1) atoms to form NaMg10W2 cuboctahedra that share corners with four equivalent Mg(2)Mg12 cuboctahedra, corners with six equivalent Na(1)Mg10W2 cuboctahedra, corners with eight equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent W(1)Na2Mg10 cuboctahedra, edges with four equivalent Mg(6)NaMg11 cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(6)NaMg11 cuboctahedra, and faces with two equivalent W(1)Na2Mg10 cuboctahedra. Both Na(1)-Mg(6) bond lengths are 3.15 Å. There are two shorter (3.15 Å) and two longer (3.16 Å) Na(1)-Mg(3) bond lengths. All Na(1)-Mg(5) bond lengths are 3.09 Å. Both Na(1)-W(1) bond lengths are 3.24 Å. 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 four equivalent W(1)Na2Mg10 cuboctahedra, corners with six equivalent Mg(1)Mg12 cuboctahedra, edges with two equivalent Mg(2)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra, edges with four equivalent Mg(6)NaMg11 cuboctahedra, faces with two equivalent Na(1)Mg10W2 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, faces with two equivalent Mg(6)NaMg11 cuboctahedra, and faces with four equivalent Mg(4)Mg12 cuboctahedra. Both Mg(1)-Mg(2) bond lengths are 3.24 Å. Both Mg(1)-Mg(6) bond lengths are 3.10 Å. There are two shorter (3.13 Å) and two longer (3.18 Å) Mg(1)-Mg(4) bond lengths. All Mg(1)-Mg(5) bond lengths are 3.22 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 Na(1)Mg10W2 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 two equivalent W(1)Na2Mg10 cuboctahedra, faces with four equivalent Mg(4)Mg12 cuboctahedra, and faces with six equivalent Mg(6)NaMg11 cuboctahedra. Both Mg(2)-Mg(7) bond lengths are 3.15 Å. There are two shorter (3.15 Å) and two longer (3.16 Å) Mg(2)-Mg(4) bond lengths. All Mg(2)-Mg(5) bond lengths are 3.14 Å. In the third Mg site, Mg(3) is bonded in a 12-coordinate geometry to two equivalent Na(1), two equivalent Mg(3), two equivalent Mg(5), two equivalent Mg(6), two equivalent Mg(7), and two equivalent W(1) atoms. There is one shorter (3.24 Å) and one longer (3.25 Å) Mg(3)-Mg(3) bond length. Both Mg(3)-Mg(5) bond lengths are 3.06 Å. Both Mg(3)-Mg(6) bond lengths are 3.15 Å. Both Mg(3)-Mg(7) bond lengths are 3.06 Å. There is one shorter (3.10 Å) and one longer (3.21 Å) Mg(3)-W(1) bond length. 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 Na(1)Mg10W2 cuboctahedra, corners with four equivalent W(1)Na2Mg10 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)NaMg11 cuboctahedra, faces with two equivalent Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, and faces with two equivalent Mg(6)NaMg11 cuboctahedra. There is one shorter (3.21 Å) and one longer (3.27 Å) Mg(4)-Mg(4) bond length. Both Mg(4)-Mg(5) bond lengths are 3.19 Å. Both Mg(4)-Mg(6) bond lengths are 3.10 Å. Both Mg(4)-Mg(7) bond lengths are 3.22 Å. In the fifth Mg site, Mg(5) is bonded in a 2-coordinate geometry to one Na(1), one Mg(1), one Mg(2), one Mg(3), one Mg(4), two equivalent Mg(6), and one W(1) atom. There is one shorter (3.13 Å) and one longer (3.19 Å) Mg(5)-Mg(6) bond length. The Mg(5)-W(1) bond length is 2.98 Å. In the sixth Mg site, Mg(6) is bonded to one Na(1), one Mg(1), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(7), and four equivalent Mg(5) atoms to form distorted MgNaMg11 cuboctahedra that share corners with six equivalent Mg(6)NaMg11 cuboctahedra, edges with two equivalent Na(1)Mg10W2 cuboctahedra, edges with two equivalent Mg(1)Mg12 cuboctahedra, edges with four equivalent Mg(4)Mg12 cuboctahedra,  a faceface with one Na(1)Mg10W2 cuboctahedra,  a faceface with one Mg(1)Mg12 cuboctahedra, faces with two equivalent Mg(4)Mg12 cuboctahedra, faces with two equivalent Mg(6)NaMg11 cuboctahedra, faces with three equivalent Mg(2)Mg12 cuboctahedra, and faces with three equivalent W(1)Na2Mg10 cuboctahedra. Both Mg(6)-Mg(7) bond lengths are 3.25 Å. In the seventh Mg site, Mg(7) is bonded in a distorted single-bond geometry to one Mg(2), two equivalent Mg(3), two equivalent Mg(4), two equivalent Mg(6), and one W(1) atom. The Mg(7)-W(1) bond length is 3.01 Å. W(1) is bonded to two equivalent Na(1), two equivalent Mg(7), four equivalent Mg(3), and four equivalent Mg(5) atoms to form WNa2Mg10 cuboctahedra that share corners with four equivalent Mg(1)Mg12 cuboctahedra, corners with six equivalent W(1)Na2Mg10 cuboctahedra, corners with eight equivalent Mg(4)Mg12 cuboctahedra, edges with two equivalent Na(1)Mg10W2 cuboctahedra, faces with two equivalent Na(1)Mg10W2 cuboctahedra, faces with two equivalent Mg(2)Mg12 cuboctahedra, and faces with six equivalent Mg(6)NaMg11 cuboctahedra.