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Eu3W crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Eu is bonded in a 4-coordinate geometry to four equivalent W atoms. There are two shorter (3.44 Å) and two longer (3.73 Å) Eu–W bond lengths. W is bonded to twelve equivalent Eu atoms to form a mixture of corner and face-sharing WEu12 cuboctahedra.
Eu3W(O2Cl)3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Eu3+ is bonded in a 10-coordinate geometry to six equivalent O2- and four equivalent Cl1- atoms. There are a spread of Eu–O bond distances ranging from 2.41–2.66 Å. There are a spread of Eu–Cl bond distances ranging from 2.97–3.05 Å. W6+ is bonded in a distorted pentagonal pyramidal geometry to six equivalent O2- atoms. All W–O bond lengths are 1.95 Å. O2- is bonded to three equivalent Eu3+ and one W6+ atom to form a mixture of distorted edge and corner-sharing OEu3W tetrahedra. Cl1- is bonded in a 4-coordinate geometry to four equivalent Eu3+ atoms.