An octameric fluoridopalladate(IV) [Pd8F36]4− anion in KPd2F9 revealed by 3D electron diffraction

3D Electron diffraction 3D ED data were collected on a Tecnai G2 transmission electron microscope (TEM). Data sets were collected at a temperature of 100 K using a continuous rotation electron diffraction (cRED) method. The electron beam was generated using a LaB6 source at 200 kV (λ = 0.02508 Å), and a Medipix 3 hybrid pixel detector ASI CheeTah (512 × 512 pixels, 24-bit dynamic range) was used to collect the diffraction patterns. The data reduction and processing were done in PETS2 (1), and the structure solution and refinements were done in JANA2020 (2) software. For the 3D ED data analysis, measurements from two different crystals were merged. The processed merged PETS2 file is named "Merged". 3D_ED-data folder: The submitted 3D ED data contains raw diffraction images in .tiff format for each crystal. It also contains the relevant data reduction and processing files (PETS2 files), the final refined file (JANA2020 files), final CIF, and structure factor (.fcf) files. Measurement conditions for a crystal and PETS parameters can be found in .pts file (file names ending with "*-crot-030"). A standardized table containing parameters related to the 3D ED measurements (KPd2F9_3DED_parameter_table) is provided in both .txt and .docx formats. Raman Spectroscopy Low-temperature Raman spectra were measured at 100 K on a Bruker Senterra II confocal Raman microscope coupled with a Linkam LTS420 low-temperature stage, using a 785-nm emission line. The spectra were measured in the 50–1410 cm−1 range with a resolution of 1.5 cm−1. Prior to analysis, the samples were homogenized in an agate mortar within a glovebox and loaded into F2-passivated quartz capillaries (500 µm diameter), which were subsequently flame-sealed in a hydrogen–oxygen flame. Background subtraction using 3 iterations of concave rubber band correction with 64 baseline points was performed in Bruker Opus 8.7 software suite. Complete set of measurement parameters for each spectrum is given below: KPd2F9 – 15 × 1000 µm aperture, 25 mW laser power. Rb2PdF6 + AsF5 product (labelled as RbPdF) – 50 × 1000 µm aperture, 10 mW laser power. Cs2PdF6 + AsF5 product (labelled as CsPdF) – 50 × 1000 µm aperture, 10 mW laser power. Raman-data folder: The subfolders labeled "processed" and "raw" contain, respectively, the final background subtracted Raman spectra and the spectra prior to background subtraction. All spectra are provided in the comma-delimited .dpt file format. Powder X-ray Diffraction Powder X-ray diffraction patterns were obtained on a Rigaku OD XtaLAB Synergy-S diffractometer equipped with a Dectris EIGER2 R CdTe 1M detector using microfocused Ag Kα radiation (λ = 0.56087 Å). In each measurement, 6 frames were recorded with an exposure time of 300 s per frame with the detector positioned 90 mm away from the sample. The measurements were conducted at ambient temperature. PXRD profiles were extracted and processed using CrysAlisPro software. Prior to analysis, the samples were pulverized in an agate mortar within a glovebox and loaded into F2-passivated quartz capillaries (500 µm diameter), which were subsequently flame-sealed in a hydrogen–oxygen flame. PXRD-data folder: The supplied dataset consists of extracted powder diffractograms for K2PdF6, KPd2F9, and the anhydrous HF-soluble byproducts from the synthesis of the latter, provided in .dat format together with the raw diffraction images in .odeiger format. References: (1) Palatinus, L.; Brázda, P.; Jelínek, M.; Hrdá, J.; Steciuk, G.; Klementová, M. Specifics of the Data Processing of Precession Electron Diffraction Tomography Data and Their Implementation in the Program PETS2.0. Acta Crystallogr. B 2019, 75 (4), 512–522. https://doi.org/10.1107/S2052520619007534. (2) Petříček, V.; Palatinus, L.; Plášil J.; Dušek, M, JANA2020 – a new version of the crystallographic computing system JANA. Z. Kristallogr. Cryst. Mater. 2023, 238 (7–8), 271–282. https://doi.org/10.1515/zkri-2023-0005.