Complexes of DOTAM with d10 Divalent Metal Ions: X-ray Diffraction and NMR Studies in Solution and the Solid State (MDOTAM)

Complexes of DOTAM with d10 Divalent Metal Ions: X-ray Diffraction and NMR Studies in Solution and the Solid State (MDOTAM) ReadMe version: 1.0 (2026-06-22) Dataset version: 1.0 (2026-06-22) Dataset DOI: 10.5281/zenodo.20797964 CONTACT [Jakub Obuch][[e-mail]]ORCID: [0000-0001-8960-6639]Department of Structure Analysis, Institute of Macromolecular Chemistry, Czech Academy of SciencesHeyrovskeho square 2, 162 00, Prague 6, Czech Republic Creators Jakub Obuch (ORCiD 0000-0001-8960-6639), Institute of Macromolecular Chemistry, Czech Academy of Sciences(IMC CAS); Faculty of Science, Charles University (FoS CUNI) Jiri Brus (ORCiD 0000-0003-2692-612X), IMC CAS Contributors Jiri Czernek (ORCiD 0000-0003-1474-1822), IMC CAS Ivana Cisarova (ORCiD 0000-0002-9612-9831), FoS CUNI Petr Hermann (ORCiD 0000-0001-6250-5125), FoS CUNI DATA AVAILABILITY AND ACCESS INSTRUCTIONS The dataset is openly accessible under the DOI listed above. The license and terms of reuse are shown in the following chapter below. LICENSE ReadMe file license ReadMe by Jakub Obuch is licensed under CC BY 4.0License information: https://creativecommons.org/licenses/by/4.0/ Dataset license MDOTAM by Jakub Obuch and Jiri Brus is licensed under CC BY 4.0License information: https://creativecommons.org/licenses/by/4.0/ DESCRIPTION AND METHODOLOGY About the dataset This dataset supports findings on macrocyclic complexes of the tetrakis(acetamide) cyclen derivative DOTAM with diamagnetic d10 metal ions: Zinc(II), Cadmium(II), and Mercury(II). The dataset contains single-crystal X-ray diffraction (SC-XRD) structural files (.cif) alongside raw solid-state NMR (ss-NMR) spectroscopic files (1H, 13C, and 15N). These methods reveal the structural evolution and local coordination asymmetry spanning from hexacoordinated Zn(II) complex configurations up to octacoordinated Cd(II) and Hg(II) square-antiprismatic geometries, which were further validated using GIPAW-DFT calculations. Sample preparation The metal complexes of DOTAM (1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane) were synthesized by reacting the free macrocyclic DOTAM ligand with the corresponding divalent metal salts (Zn(II), Cd(II), or Hg(II)) in an aqueous medium or appropriate solvent mixtures under controlled pH conditions. Crystals suitable for single-crystal X-ray diffraction were grown via slow cooling of hot saturated aqueous solutions of the complexes. For solid-state NMR measurements, the bulk crystalline phases were packed firmly into Magic-Angle Spinning (MAS) zirconia rotors. Methods of data collection Single-Crystal X-Ray Diffraction (SC-XRD) · Hardware: Bruker D8 Venture diffractometer system. · Radiation & Monochromator: Microfocus sealed tube radiation source with multilayer optics. · Radiation Type: Mo Kα radiation (λ = 0.71073 Å). · Acquisition Parameters: Data collections were performed under a cold nitrogen stream (at 120(2) K using ω and φ scans to maximize completeness and redundancy. Solid-State NMR (ss-NMR) Spectra · Nuclei Probed: 1H, 13C, and 15N. · Magic Angle Spinning: Samples were spun at the Magic Angle (54.74°) using zirconia rotors. · For 13C and 15N CP-ssNMR: Bruker Avance III HD 500 NMR spectrometer (11.7 T magnetic field strength, operational resonance frequencies of 126 MHz for 13C and 51 MHz for 15N). Acquired using a 4 mm broad-band MAS probe with a spinning speed of 10 kHz. Cross-Polarization Magic-Angle Spinning (CP-MAS) sequences were utilized to optimize sensitivity. High-power 1H decoupling (e.g., SPINAL-64 or TPPM) was continuously applied during the acquisition window. · For 1H ssNMR: Bruker Avance NEO 700 MHz spectrometer (16.4 T magnetic field strength, operational proton resonance frequency of 700 MHz). Acquired using a 3.2 mm broad-band probe under a MAS frequency of 10 kHz. Specialized homonuclear decoupling sequences (DUMBO ssNMR) were applied. Methods of data processing The raw crystallographic parameters (indexed diffraction intensities) are contained within the structural files. The structures were solved using direct methods (SHELXT2018/2) and refined with full-matrix least-squares techniques (SHELXL2019/2). All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were found in the difference electron density map. However, hydrogen atoms bound to carbon atoms were fixed in theoretical positions using Ueq(H) = 1.2 Ueq(C) to keep the number of fitted parameters low, and only hydrogen atoms bound to oxygen atoms were tried to fully refine. However, some heteroatom-bound hydrogen atoms were fixed in the original positions, as the geometry during the refinement was unstable and heteroatom–hydrogen bond distances became unrealistically long or short. The refined structural data (cell parameters, atomic positions, occupancies, and displacement parameters) are contained within the structural FILES. The solid-state NMR data are supplied as original raw instrument data folders containing free induction decays (fids) and parameter files. Only basic processing (referencing, phase correction and baseline correction, apodization) was applied and the processed are contained within the data folders. DATASET STRUCTURE - 000_ReadMe_MDOTAM.pdf - 001_Data_proc: MDOTAM_Data-ssNMR-500-CdDOTAM_proc MDOTAM_Data-ssNMR-500-ZnDOTAM_proc MDOTAM_Data-ssNMR-700-CdDOTAM_proc MDOTAM_Data-ssNMR-700-ZnDOTAM_proc - 002_Data_anlsd: MDOTAM_Data-XRD_anlsd FILENAME STRUCTURE + ABBREVIATIONS [project]_[WPN]_[IIIII]_[date]_[description]_[version].[extension] WP = work package (WP + number = 3 characters) WP0 – Documentation WP1 – Spectroscopic data WP2 – Diagnoses WP3 – Code WP4 – Publications IIIII = institution abbreviation (max. 5 char.) IMC – Institute of Macromolecular Chemistry, Prague CUNI – Charles University, Prague date = YYYYMMDD (8 characters) description – free form internally separated by “-“ version for: data – “raw”, “proc” (processed), “anlsd” (analysed) code and other – N-N-N (=n.n.n, e.g. 1.0.0) Single-crystal XRD data are described as follows: XRD-[complex]-[temperature] Example: MDOTAM_WP1_CUNI_20260618_XRD-ZnDOTAM-120K_anlsd.cif Solid-state NMR data are organized in folders as follows: MDOTAM_Data-ssNMR-[1H resonance frequency]-[complex]_proc The specific experimental data are in subfolders: 13C CP/MAS: MDOTAM_Data-ssNMR-500-[complex]_proc\1 15N CP/MAS: MDOTAM_Data-ssNMR-500-[complex]_proc\3 1H-13C HETCOR: MDOTAM_Data-ssNMR-500-[complex]_proc\20 1H NMR with variable d1: MDOTAM_Data-ssNMR-500-[complex]_proc\[500-509] 1H DUMBO/MAS: MDOTAM_Data-ssNMR-700-[complex]_proc\[10] 1H-1H 2D DUMBO/MAS: MDOTAM_Data-ssNMR-700-[complex]_proc\200 1H MAS: MDOTAM_Data-ssNMR-700-[complex]_proc\[500] Each individual subfolder contains the raw data and in sub-subfolder named “pdata” also the processed data. FILE TYPES & FORMATS, SW TO OPEN Single-Crystal X-ray Diffraction · Original Format: .cif (Crystallographic Information File) · SW to open: Mercury (CCDC), Olex2, or ShelXLE Solid-State NMR Spectra · Original Format: Raw acquisition directories containing parameter files (.ased, .temp, .info, .par and binary files like acqu, acqus) and data tracks (binary, e.g. fid or ser). These folders can be directly opened by the SW described below. · SW to open: TopSpin (Bruker), Delta (JEOL), or MestReNova.