Raw and processed data for a rhodium(I) dicarbonyl Schiff-base complex (Rh-4-Br) studied under high pressure by X-ray diffraction and by Raman and luminescence spectroscopy
Repository DOI: 10.58132/jxy8gl
Publisher: University of Warsaw (danebadawcze.uw.edu.pl)
RELATED PUBLICATION
Vijayakumar-Syamala, V.; Borowski, P.; Bosman, L.; Potempa, K.; Paliwoda, D.; Korona, K. P.; Laski, P.; Kaminski, R.; Kama, D. V.; Roodt, A.; Brink, A.; Jarzembska, K. N. "Metallophilicity-assisted piezochromism in a rhodium(I) dicarbonyl Schiff-base complex: structural, energetic, electronic and spectroscopic investigations under high pressure." J. Mater. Chem. C 2025, 13 (30), 15634. DOI: 10.1039/d5tc00925a
COMPOUND
Rh-4-Br = dicarbonyl[(N,O)-salicylidene-p-bromoaniline]rhodium(I), C15H9BrNO3Rh, monoclinic, space group P2_1/n, Z = 4.
1. WHAT THIS REPOSITORY CONTAINS
This repository holds the complete experimental data behind the publication cited above:
- 29 single-crystal X-ray diffraction (SCXRD) data sets, that is raw detector frames together with the full CrysAlisPro data-reduction and structure-refinement trees, namely 20 high-pressure synchrotron data sets (ESRF, ID15B; "exp1" in the paper) covering 0.00(5)-10.45(5) GPa, 8 high-pressure laboratory data sets (in-house Mo-Kalpha diffractometer; "exp2" in the paper) covering 0.00(5)-5.71(5) GPa, and 1 ambient-condition laboratory data set (in-house Cu-Kalpha diffractometer) measured at 296 K;
- the five published CIF collections (experiment and theory) together with their IUCr checkCIF validation reports;
- high-pressure Raman spectra recorded on compression and decompression;
- high-pressure luminescence data (OriginLab projects).
Only the data sets that were actually used for the published results are included; superseded trial reductions and duplicated copies present in the authors' working directories have been removed (see section 6).
Every data set is deposited as one ZIP archive, and every ZIP archive is accompanied by a TXT file of the same name holding the description of that particular archive. The CIF files are deposited uncompressed so that they can be opened directly from the repository.
2. FILE NAMING CONVENTION
The repository is a flat list of files, so the name of each archive carries all the information needed to place it. Data archives are named <GROUP>__<NN>-<pressure>__<original experiment folder name>.zip, where:
<GROUP> is XRD-HP-ESRF for the high-pressure synchrotron series ("exp1"), XRD-HP-UW for the high-pressure laboratory series ("exp2"), or XRD-ambient-UW for the ambient-condition laboratory measurement.
<NN> is the running number of the measurement point within the published series, identical to the number used in the name of the corresponding CIF data block.
<pressure> is the calibrated pressure as reported in the publication, with the decimal point written as "p" (e.g. 10p45GPa means 10.45(5) GPa).
<original experiment folder name> is the name of the CrysAlisPro experiment directory as it was used by the authors; this is also the name of the single top-level folder found inside the archive.
For example, XRD-HP-ESRF__10-4p55GPa__Rh1_0007-Try1_4p55GPa.zip is the synchrotron series, 10th point, 4.55(5) GPa; it unpacks to the folder _Rh1_0007-Try1_4p55GPa and corresponds to the CIF data block Rh-4-Br-10-HP-ESRF-4p55GPa.
Note that the original ESRF folder names begin with an underscore. The leading underscore is omitted from the ZIP file name but is preserved inside the archive.
Each <name>.zip is accompanied by <name>.txt, which describes the contents of that archive; the same text is used as the per-file description in this repository.
CAUTION: for the laboratory high-pressure series the pressure written in the original experiment folder name is NOT the published one. See section 4.2.
3. LIST OF FILES
Documentation:
- data-summary-10.58132.jxy8gl.pdf - repository-file name to publication-set name table for all data sets (5 pages).
Crystallographic information files (uncompressed):
- Rh-4-Br-RT-UW.cif - ambient-temperature structure (1 data block).
- Rh-4-Br-MT-UW.cif - multi-temperature series, 100-300 K (8 data blocks).
- Rh-4-Br-HP-UW.cif - high-pressure laboratory series "exp2" (8 data blocks).
- Rh-4-Br-HP-ESRF.cif - high-pressure synchrotron series "exp1" (20 data blocks).
- Rh-4-Br-CASTEP.cif - CASTEP-optimised structures, 0-11 GPa (23 data blocks).
- checkcifs.7z - IUCr checkCIF reports for all of the above.
High-pressure synchrotron diffraction data, 20 archives plus 20 TXT descriptions:
- XRD-HP-ESRF__01-0p00GPa__Rhodium1and3_0002-Try2.zip
- XRD-HP-ESRF__02-0p28GPa__Rhodium1and3_0005-Try1_0p28GPa.zip
- XRD-HP-ESRF__03-0p50GPa__Rhodium1and3_0008-Try1_0p50GPa.zip
- XRD-HP-ESRF__04-0p97GPa__Rh1_0001-Try1_0p97GPa.zip
- XRD-HP-ESRF__05-1p50GPa__Rh1_0002-Try1_1p50GPa.zip
- XRD-HP-ESRF__06-2p03GPa__Rh1_0003-Try1_2p03GPa.zip
- XRD-HP-ESRF__07-2p74GPa__Rh1_0004-Try1_2p74GPa.zip
- XRD-HP-ESRF__08-3p18GPa__Rh1_0005-Try1_3p18Gpa.zip
- XRD-HP-ESRF__09-3p75GPa__Rh1_0006-Try1_3p75GPa.zip
- XRD-HP-ESRF__10-4p55GPa__Rh1_0007-Try1_4p55GPa.zip
- XRD-HP-ESRF__11-5p01GPa__Rh1_0010-Try1_5p01GPa.zip
- XRD-HP-ESRF__12-5p60GPa__Rh1_0011-Try1_5p60GPa.zip
- XRD-HP-ESRF__13-6p14GPa__Rh1_0012-Try1_6p14GPa.zip
- XRD-HP-ESRF__14-6p82GPa__Rh1_0013-Try1_6p82GPa.zip
- XRD-HP-ESRF__15-7p34GPa__Rh1_0014-Try1_7p34GPa.zip
- XRD-HP-ESRF__16-8p05GPa__Rh1_0015-Try1_8p05GPa.zip
- XRD-HP-ESRF__17-8p72GPa__Rh1_0016-Try1_8p72GPa.zip
- XRD-HP-ESRF__18-9p04GPa__Rh1_0017-Try1_9p04GPa.zip
- XRD-HP-ESRF__19-9p87GPa__Rh1_0018-Try1_9p87GPa.zip
- XRD-HP-ESRF__20-10p45GPa__Rh1_0019-Try1_10p45GPa.zip
High-pressure laboratory diffraction data, 8 archives plus 8 TXT descriptions:
- XRD-HP-UW__01-0p00GPa__2023_08_28_VS_Rh4Br-2-0p4GPa_HP-Try1.zip
- XRD-HP-UW__02-0p28GPa__2023_08_30_VS_Rh4Br-2-1p19GPa_HP-Try1.zip
- XRD-HP-UW__03-1p54GPa__2023_08_31_VS_Rh4Br-2-2p03GPa_HP-Try1.zip
- XRD-HP-UW__04-2p06GPa__2023_09_01_VS_Rh4Br-2-2p70GPa_HP-Try1.zip
- XRD-HP-UW__05-2p68GPa__2023_09_03_VS_Rh4Br-3-3p11GPa_HP-Try1.zip
- XRD-HP-UW__06-3p36GPa__2023_09_04_VS_Rh4Br-3-3p94GPa_HP-Try1.zip
- XRD-HP-UW__07-3p92GPa__2023_09_05_VS_Rh4Br-3-4p3GPa_HP-Try1.zip
- XRD-HP-UW__08-5p71GPa__2023_09_07_VS_Rh4Br-3-5p38GPa_HP-Try1.zip
Ambient-condition laboratory diffraction data, 1 archive plus 1 TXT description:
- XRD-ambient-UW__RT-296K__2023_07_03_vvs_Rh4Br_RT_01_Test1-BEST.zip
Spectroscopic data, 2 archives plus 2 TXT descriptions:
- Raman-HP.zip
- Luminescence-HP.zip
4. EXPERIMENTAL DATA - DETAILS
4.1 High-pressure synchrotron SCXRD ("exp1", XRD-HP-ESRF__* archives)
Beamline: ID15B, European Synchrotron Radiation Facility (ESRF), Grenoble.
Wavelength: 0.40965 A.
Detector: Eiger CdTe.
Sample environment: diamond anvil cell, room temperature (296 K).
Pressure range: 0.00(5)-10.45(5) GPa, 20 points.
Software: CrysAlisPro (data reduction), SHELXT / SHELXL, Olex2.
Each archive holds a complete CrysAlisPro experiment directory. The detector images are stored as *.esperanto frames under <set>/[<run>/]scan0001/esp/ together with the run files (*.run, *.par, *.ccd) and the reduction files (*.hkl, *_red.sum). Structure solution and refinement live under the same path in struct/.
For every pressure point several data-reduction variants were tested; they are named Vishnu_Solve1, Vishnu_Solve2 and Vishnu_Solve3 (equivalently Vishnu_Test1/2/3 for the reduction step alone). Following the authors' note in XRD-HP-ESRF__AAA_description.txt these correspond to the reflection-search and frame-rejection settings Re, Fr = 50 for Solve1, Re, Fr = 40 for Solve2 and Re, Fr = 30 for Solve3, in all cases with Rint > 0.1 and an intensity filter applied, with a wrongly indexed reflection removed from the data reduction, and with starting coordinates taken from the 0.00 GPa laboratory (UW) structure. That seed model is deposited separately as XRD-HP-ESRF__Solve_Newattempt_9.ins.
The variant that was carried through to the published refinement is marked in each experiment directory by a folder named Solve<N>-BEST under esp/struct/tmp/, and is additionally listed in the summary sheet and in the per-archive TXT description. Folders with the suffix "-OMIT REJ" contain the same refinement with the OMIT-based reflection rejection applied.
4.2 High-pressure laboratory SCXRD ("exp2", XRD-HP-UW__* archives)
Diffractometer: Rigaku/Oxford Diffraction SuperNova, Eos detector.
Radiation: Mo-Kalpha, 0.71073 A, micro-focus sealed tube.
Sample environment: diamond anvil cell, room temperature (296 K).
Pressure range: 0.00(5)-5.71(5) GPa, 8 points.
Crystals: Rh4Br-2 for the first five points and Rh4Br-3 for the last three points.
IMPORTANT: the pressure values in the original folder names are not the published ones. The pressure written into each original experiment folder name is the preliminary value read on line during the experiment. The calibrated values that appear in the paper, in Rh-4-Br-HP-UW.cif and in the ZIP file names are lower; the correspondence is:
- folder 0p4GPa is 0.00(5) GPa
- folder 1p19GPa is 0.28(5) GPa
- folder 2p03GPa is 1.54(5) GPa
- folder 2p70GPa is 2.06(5) GPa
- folder 3p11GPa is 2.68(5) GPa
- folder 3p94GPa is 3.36(5) GPa
- folder 4p3GPa is 3.92(5) GPa
- folder 5p38GPa is 5.71(5) GPa
The first five entries reproduce the authors' note (deposited as XRD-HP-UW__Note.txt); the remaining three were established by matching the refined unit cells against the deposited CIF. The full mapping is tabulated in the summary sheet.
Each archive holds a complete CrysAlisPro experiment directory: the raw detector images are the *.img files in frames/, the experiment definition and reduction results sit at the top level (*.run, *.par, *.hkl, *_red.sum), and structure solution and refinement live under struct/. Within struct/tmp/ the alternative absorption-correction and filtering treatments are kept in subfolders named "Analy(tical)", "Em.corr" (empirical), "Num.absorb" and "Num.beam" (numerical, Gaussian), and variants with "I-filter" in the name (with an additional intensity filter).
4.3 Ambient-condition laboratory SCXRD (XRD-ambient-UW__* archive)
Diffractometer: Rigaku/Oxford Diffraction SuperNova, Atlas detector.
Radiation: Cu-Kalpha, 1.54184 A, micro-focus sealed tube.
Temperature: 296 K, ambient pressure.
Crystal size: 0.12 x 0.08 x 0.04 mm.
Layout: as in section 4.2, with raw *.img frames in frames/ and refinement in struct/.
This is the reference structure Rh-4-Br-RT-UW used throughout the paper and the source of the starting coordinates for the high-pressure refinements.
4.4 High-pressure Raman spectroscopy (Raman-HP.zip)
Spectra were recorded on a Rh-4-Br single crystal inside a diamond anvil cell. Compression branch: 0.00(5), 0.41(5), 0.78(5), 1.24(5), 1.74(5), 2.18(5), 2.49(5), 2.91(5), 3.28(5), 3.83(5), 4.5(5) and 5.34(5) GPa. Decompression branch: 4.08(5), 2.82(5), 1.41(5), 0.91(5), 0.25(5) and 0.00(5) GPa.
Files are supplied both in the native instrument format (*.SPA) and as ASCII exports (subfolder "CSV files"). The pressure is encoded in the file name; the suffix "rev" marks the decompression branch. These spectra were analysed in the paper for the blue shift of the nu(Rh...Rh) band by about 19 cm-1 up to 5.34 GPa.
4.5 High-pressure luminescence (Luminescence-HP.zip)
Emission spectra were measured on a single crystal in a Merrill-Bassett diamond anvil cell between 0.63(5) and 6.93(5) GPa on compression and back on decompression, showing the reversible yellow-to-orange-to-red piezochromism and a bathochromic shift of the emission maximum of about 75 nm. The data are supplied as OriginLab project files (*.opj), which contain both the raw spectra and the worksheets used to produce the figures of the paper.
4.6 Periodic DFT computations
CASTEP optimisations under isotropic external pressures of 0-11 GPa in 0.5 GPa steps ("theor" in the paper) are provided as optimised structures only, in Rh-4-Br-CASTEP.cif (23 data blocks). No computational input or output files are part of this repository.
5. HOW TO LINK A DATA ARCHIVE TO A PUBLISHED STRUCTURE
The archive name already contains the number and the pressure of the measurement point, so the corresponding CIF data block can be read off directly:
XRD-HP-ESRF__10-4p55GPa__Rh1_0007-Try1_4p55GPa.zip corresponds to data_Rh-4-Br-10-HP-ESRF-4p55GPa in Rh-4-Br-HP-ESRF.cif
XRD-HP-UW__05-2p68GPa__2023_09_03_VS_Rh4Br-3-3p11GPa_HP-Try1.zip corresponds to data_Rh-4-Br-05-HP-UW-2p68GPa in Rh-4-Br-HP-UW.cif
XRD-ambient-UW__RT-296K__2023_07_03_vvs_Rh4Br_RT_01_Test1-BEST.zip corresponds to data_Rh-4-Br-RT-UW in Rh-4-Br-RT-UW.cif
The complete table is given in data-summary-10.58132.jxy8gl.pdf, whose fourth column also names the data-reduction and refinement variant inside the archive that was carried through to the published block. The unit-cell parameters given in the CIF data block are the fastest way to verify an assignment independently.
6. SOFTWARE NEEDED TO READ THE DATA
- Any ZIP tool (7-Zip, WinRAR, Windows Explorer, unzip) to unpack the archives. Each archive expands into a single top-level folder.
- CrysAlisPro (Rigaku Oxford Diffraction) to open the *.run and *.par experiment directories and to re-run the data reduction from the raw frames (*.img, *.esperanto).
- SHELXT / SHELXL and Olex2 to reproduce structure solution and refinement from the supplied *.ins and *.hkl pairs.
- Any CIF viewer (Mercury, Olex2, publCIF, or a text editor) for the *.cif files.
- 7-Zip or a compatible tool for checkcifs.7z.
- OriginLab Origin (2018 or newer) for the *.opj luminescence projects.
- Thermo Scientific OMNIC for the Raman *.SPA files, or any software able to read the plain-text *.CSV exports.
7. TERMS OF USE
These data are made openly available so that the results reported in the publication cited above can be scrutinised and re-used. If you make use of them, please cite both the publication (DOI: 10.1039/d5tc00925a) and this repository entry (DOI: 10.58132/jxy8gl).
(2025-07-09)
