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Ba3Pt4Al4 was prepared from the elements in niobium ampules and crystallizes in an orthorhombic structure, space group Cmcm (oP44, a = 1073.07(3), b = 812.30(3), c = 1182.69(3) pm) isopointal to the Zintl phase A2Zn5As4 (A = K, Rb). The structure features strands of distorted [Pt4Al4] heterocubane-like units connected by condensation over Pt/Al edges. These are arranged in a hexagonal rod packing by further condensation over Pt and Al atoms with the barium atoms located inside cavities of the [Pt4Al4]δ− framework. Structural relaxation confirmed the electronic stability of the new phase, while band structure calculations indicate metallic behavior. Crystal orbital Hamilton bonding analysis coupled with Bader effective charge analysis suggest a polar intermetallic phase in which strong Al-Pt covalent bonds are present, while a significant electron transfer from Ba to the [Pt4Al4]δ− network is found. By X-ray photoelectron spectroscopy measurements the Pt 4f5/2 and 4f7/2 energies for Ba3Pt4Al4 were found in the range of those of elemental Pt due to the electron transfer of Ba, while PtAl and PtAl2 show a pronounced shift toward a more cationic platinum state. 27Al magic-angle spinning NMR investigations verified the two independent crystallographic Al sites with differently distorted tetrahedrally coordinated [AlPt4] units. Peak assignments could be made based on both geometrical considerations and in relation to electric field gradient calculations. [ABSTRACT FROM AUTHOR]