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The here reported compounds of the isotypic series Ln 4 O 4 Cl[BO 3 ] with Ln = Eu-Tm represent the first type of oxide chloride oxoborates with trivalent lanthanoid cations. They crystallize monoclinically with the space group P2 1 /n and four formula units per unit cell. The cell dimensions range from a = 878.21(6), b = 818.42(5), c = 1091.50(7) pm, β = 101.49(1)º for Eu 4 O 4 Cl[BO 3 ] to a = 847.08(6), b = 795.23(5), c = 1083.16(7) pm, β = 103.64(1)º for Tm 4 O 4 Cl[BO 3 ] and are in good agreement with the lanthanoid contraction. The basic building blocks of this structure consist of O 2-  -centered (Ln 3+ ) 4  tetrahedra ([OLn 4 ] 10+ ) linked first via common edges to  1   ∞ {[O 12 Ln 10 ] 6+ } double chains running along the [010] direction. Their further fusion again via shared edges leads to highly corrugated  2  ∞ {[O 4 Ln 4 ] 4+ } layers spreading out parallel to the (101) plane. These layers are held together by isolated [BO 3 ] 3-  triangles and Cl -  anions. The four crystallographically different Ln 3+  cations show seven or eight O2 -  and Cl -  anions in their coordination spheres.

Syntheses and crystal structures of the novel oxide chloride oxoborates Ln 4 O 4 Cl[BO 3 ] (Ln = Eu–Tm)