Eu3(GaP2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 6-coordinate geometry to two equivalent P(2) and four equivalent P(1) atoms. In the second Eu site, Eu(2) is bonded to two equivalent P(1) and four equivalent P(2) atoms to form distorted EuP6 octahedra that share corners with four equivalent Ga(1)P4 tetrahedra, edges with two equivalent Eu(2)P6 octahedra, and edges with four equivalent Ga(1)P4 tetrahedra. Ga(1) is bonded to two equivalent P(1) and two equivalent P(2) atoms to form distorted GaP4 tetrahedra that share corners with two equivalent Eu(2)P6 octahedra, corners with two equivalent Ga(1)P4 tetrahedra, edges with two equivalent Eu(2)P6 octahedra, and  an edgeedge with one Ga(1)P4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-57°. There are two inequivalent P sites. In the first P site, P(1) is bonded in a 7-coordinate geometry to one Eu(2), four equivalent Eu(1), and two equivalent Ga(1) atoms. In the second P site, P(2) is bonded to two equivalent Eu(1), two equivalent Eu(2), and two equivalent Ga(1) atoms to form a mixture of distorted corner and edge-sharing PEu4Ga2 pentagonal pyramids.
Eu3(GaP2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 6-coordinate geometry to two equivalent P(2) and four equivalent P(1) atoms. There is one shorter (2.94 Å) and one longer (2.98 Å) Eu(1)-P(2) bond length. There are a spread of Eu(1)-P(1) bond distances ranging from 3.05-3.38 Å. In the second Eu site, Eu(2) is bonded to two equivalent P(1) and four equivalent P(2) atoms to form distorted EuP6 octahedra that share corners with four equivalent Ga(1)P4 tetrahedra, edges with two equivalent Eu(2)P6 octahedra, and edges with four equivalent Ga(1)P4 tetrahedra. Both Eu(2)-P(1) bond lengths are 3.09 Å. There are two shorter (2.92 Å) and two longer (3.00 Å) Eu(2)-P(2) bond lengths. Ga(1) is bonded to two equivalent P(1) and two equivalent P(2) atoms to form distorted GaP4 tetrahedra that share corners with two equivalent Eu(2)P6 octahedra, corners with two equivalent Ga(1)P4 tetrahedra, edges with two equivalent Eu(2)P6 octahedra, and  an edgeedge with one Ga(1)P4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-57°. There is one shorter (2.45 Å) and one longer (2.47 Å) Ga(1)-P(1) bond length. There is one shorter (2.40 Å) and one longer (2.41 Å) Ga(1)-P(2) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded in a 7-coordinate geometry to one Eu(2), four equivalent Eu(1), and two equivalent Ga(1) atoms. In the second P site, P(2) is bonded to two equivalent Eu(1), two equivalent Eu(2), and two equivalent Ga(1) atoms to form a mixture of distorted corner and edge-sharing PEu4Ga2 pentagonal pyramids.