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Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir 6 In 32 S 21 , a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P 31 m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of −4.95(5) eV, conduction band minimum of −3.47(5) eV, and a photoresponse shift of the Fermi level by ∼0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir 6 In 32 S 21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBM (1.19 m e ) are substantially smaller than the average electron masses near the CBM (2.51 m e ), an unusual feature for most semiconductors. The crystal and electronic structure of Ir 6 In 32 S 21 , along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes. 

Abstract Perovskite photovoltaic ABX₃systems are being studied due to their high energy‐conversion efficiencies with current emphasis placed on pure inorganic systems. In this work, synchrotron single‐crystal diffraction measurements combined with second harmonic generation measurements reveal the absence of inversion symmetry below room temperature in CsPbBr₃. Local structural analysis by pair distribution function and X‐ray absorption fine structure methods are performed to ascertain the local ordering, atomic pair correlations, and phase evolution in a broad range of temperatures. The currently accepted space group assignments for CsPbBr₃are found to be incorrect in a manner that profoundly impacts physical properties. New assignments are obtained for the bulk structure: (above ≈410 K),P2₁/m(between ≈300 K and ≈410 K), and the polar groupPm(below ≈300 K), respectively. The newly observed structural distortions exist in the bulk structure consistent with the expectation of previous photoluminescence and Raman measurements. High‐pressure measurements reveal multiple low‐pressure phases, one of which exists as a metastable phase at ambient pressure. This work should help guide research in the perovskite photovoltaic community to better control the structure under operational conditions and further improve transport and optical properties.