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2004
Structure
D 2000
51- 004
Nonclassical Bonding in the Novel Structure of Ba2Bi 3 and Unexpected Site
Preference in the Coloring Variant Ba2BiSb2. — Single crystals of the new phase
Ba2Bi 3 are prepared by reaction of the elements (850 °C, sealed Nb tubes, 2 h). The
compound crystallizes in the W2CoB2 structure type (space group Immm, Z = 2). The
structure contains rigorously planar anionic layers of (4.6.4.6)(4.62)2 nets with threeand four-bonded Bi, that are separated by Ba atoms. An unexpected site preference is
observed in the coloring variant Ba2BiSb2 with Sb occupying only the three-bonded
sites. The nonclassical bonding in the anionic network can be rationalized from a reformulation of the Zintl concept as (Ba2+)2[Bi3]3-(e-). Bonding distances suggest that the
extra electrons fill Bi-Bi antibonding states. The densities of states obtained from
TB-LMTO-ASA calculations show metallic character for both compounds. —
(PONOU, S.; FAESSLER*, T. F.; Inorg. Chem. 43 (2004) 20, 6124-6126; Lehrstuhl
Org. Chem., TU Muenchen, D-85747 Garching, Germany; Eng.) — Schramke
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