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Synthesis, characterization, and bonding of indium clusters: A[sub 3]Na[sub 26]In[sub 48] (A = K, Rb, Cs) with a novel cubic network of arachno- and closo-In[sub 12] clusters

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00061a016· OSTI ID:6299062

The title compounds are obtained in high yield by slow cooling of the appropriate fused mixture of elements in welded Ta. They occur in the cubic space group Pm[bar 3]n, Z = 2, with a = 16.0640(4), 16.101(1), 16.130(1) [Angstrom] for A = K, Rb, Cs, respectively. The structure was refined by single-crystal means for A = K, Rb to R, R[sub w] = 2.5, 3.3 and 2.0, 2.5%. The structure contains closo-In[sub 12] icosahedra (T[sub h] symmetry) plus arachno-In[sub 12] (D[sub 2d]) as approximate (D[sub 6d]) hexagonal antiprisms (drums) with 12 exo In-In bonds about each cluster. Nonintersecting chains of [open quotes]drums[close quotes] lie in the faces of the cubic cell and parallel to the cell edges. Adjacent arachno clusters are interconnected only indirectly at chain crossings via the closo polyhedra that define a body-centered cube. The structure is A15 (Cr[sub 3]-Si)-like with arachno- and closo-In[sub 12] clusters, respectively, replacing the metal and non-metal atoms of the parent. The larger A cations order in, and appear required for, the larger cavities lying between drums in each chain. The compounds are electron-rich by 5.5% according to theory, and the potassium example is metallic ([rho][sub 295] [approximately] 23 [mu][Omega] cm) and Pauli paramagnetic (2.2 [times] 10[sup [minus]3] emu mol[sup [minus]1]) by measurement. 23 refs., 2 figs., 3 tabs.

DOE Contract Number:
W-7405-ENG-82
OSTI ID:
6299062
Journal Information:
Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:9; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English