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Cu 4 O 12 -Groups of Square Planar CuO 4 Polygones in the Barium Vanadyl Oxocuprate(II) Phosphate Ba(VO)Cu 4 (PO 4 ) 4 .-Green single crystals of Ba(VO)Cu 4 (PO 4 ) 4 are obtained by solid-state reaction of BaP 2 O 6 , Cu 3 (PO 4 ) 2 , CuO, V 2 O 5 and V 2 O 3 in 4:4:4:1:1 molar ratio for 3 d at 1030 • C. As revealed from the single-crystal XRD analysis, this compound (tetragonal, P42 1 2 1 , Z = 2) represents a new structure type which is characterized by isolated Cu 4 O 12 and (VO)(PO 4 ) 4 units. The Cu 4 O 12 groups consist of square planar CuO 4 polyhedra which are connected in a hitherto unknown mode. Comparisons with compounds containing planar MO 4 polyhedra are discussed in terms of the crosslinking of these polygones. -(MEYER, S.; MUELLER-BUSCHBAUM, HK.

Single crystals of the hitherto unknown title compounds are grown from a B2O3 flux after reaction of V2O5 (MnO2 or Mn2O3) with NiO in a large excess of B2O3 at 1200‐1300 °C. Both compounds crystallize orthorhombic in the Ni5TiB2O10 structural type (Pbam, Z=2).

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Durch Kristallisation aus KF‐Schmelzen unter N2‐Schutzgas werden je nach Präparationsbedingungen dunkelgrüne (NiSO4, MgO, Ni‐Tiegel, 900°C), gelbe (NiSO4, CaO + CaCl2, Pt‐Tiegel, 900°C, 20 h) oder braune (NiSO4, MgO, 900°C, 20 h, Pt‐Tiegel) "NiO"‐Einkristalle erhalten, deren Lichtabsorption beschrieben und diskutiert wird.