Supramolecular covalency of halogen bonds revealed by NMR contact shifts in paramagnetic cocrystals
Sasikumar, Anagha; Novotný, Jan; Chyba, Jan; Kobera, Libor; Marek, Radek; Chemical Science 16 (2025) 20239–20244; doi:10.1039/D5SC05769H

data_1575919
_publ_section_title
;
 Supramolecular covalency of halogen bonds revealed by NMR contact shifts
 in paramagnetic cocrystals
;
_journal_issue                   43
_journal_name_full               'Chemical Science'
_journal_page_first              20239
_journal_page_last               20244
_journal_paper_doi               10.1039/D5SC05769H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_sum            'C16 H14 Br2 Cu F4 O4'
_chemical_formula_weight         569.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-I 2y'
_space_group_name_H-M_alt        'I 1 2/m 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2019/3
_audit_update_record
;
2025-07-11 deposited with the CCDC.	2025-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.9291(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   4.66104(5)
_cell_length_b                   15.4164(2)
_cell_length_c                   12.48705(16)
_cell_measurement_reflns_used    3408
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      76.9260
_cell_measurement_theta_min      4.5560
_cell_volume                     895.166(19)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0256
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            4004
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.178
_diffrn_reflns_theta_min         4.563
_diffrn_source                   'Rotating-anode X-ray tube'
_exptl_absorpt_coefficient_mu    7.535
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42806
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    2.113
_exptl_crystal_description       Needle
_exptl_crystal_F_000             554
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.354
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.079
_refine_ls_extinction_coef       0.00211(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     86
_refine_ls_number_reflns         975
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0217
_refine_ls_R_factor_gt           0.0215
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0337P)^2^+1.2103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0569
_refine_ls_wR_factor_ref         0.0570
_reflns_Friedel_coverage         0.000
_reflns_number_gt                966
_reflns_number_total             975
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05769h3.cif
_cod_data_source_block           1Br
_cod_depositor_comments
'Adding full bibliography for 1575919--1575921.cif.'
_cod_original_sg_symbol_H-M      'I 2/m'
_cod_database_code               1575919
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_min   0.314
_shelx_estimated_absorpt_t_max   0.864
_oxdiff_exptl_absorpt_empirical_full_min 0.663
_oxdiff_exptl_absorpt_empirical_full_max 1.942
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_res_checksum              70098