Fluoride-induced redox-switchable behaviour of a palladium(ii)/(iv) couple
Martínez-Vivas, Sebastián; Poyatos, Macarena; Peris, Eduardo; Chemical Science 16 (2025) 6257–6264; doi:10.1039/D4SC08203F

data_1574091
_publ_section_title
;
 Fluoride-induced redox-switchable behaviour of a palladium(ii)/(iv)
 couple
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              6257
_journal_page_last               6264
_journal_paper_doi               10.1039/D4SC08203F
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C38 H39 Cl N7 O4 Pd, C32 H12 B F24, C6 H4 F2'
_chemical_formula_sum            'C76 H55 B Cl F26 N7 O4 Pd'
_chemical_formula_weight         1776.93
_chemical_name_systematic        str2238
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-09-30
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-30 deposited with the CCDC.	2025-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                72.438(4)
_cell_angle_beta                 78.222(4)
_cell_angle_gamma                81.747(3)
_cell_formula_units_Z            2
_cell_length_a                   13.7465(5)
_cell_length_b                   13.7475(5)
_cell_length_c                   21.0944(9)
_cell_measurement_reflns_used    9717
_cell_measurement_temperature    200.00(14)
_cell_measurement_theta_max      71.2540
_cell_measurement_theta_min      4.1680
_cell_volume                     3706.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4051
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00 -30.00  140
  2  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00 -90.00  140
  3  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00-180.00  140
  4  \w    -87.00  -6.00   0.30    7.50    --  -42.75 125.00  30.00  270
  5  \w    -20.00  31.00   0.30    7.50    --  -42.75  37.00-120.00  170
  6  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00  30.00  140
  7  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00 120.00  140
  8  \w     27.00  99.00   0.30    7.50    --   42.75-125.00 -90.00  240
  9  \w     10.00  40.90   0.30    7.50    --   42.75  79.00  17.54  103
 10  \w     26.00  56.00   0.30   20.00    --  102.61 -30.00-120.00  100
 11  \w     29.00 113.00   0.30   20.00    --  102.61-125.00 150.00  280
 12  \w     23.00 107.00   0.30   20.00    --  102.61-103.00  47.00  280
 13  \w     30.00  72.00   0.30   20.00    --  102.61 -45.00 -60.00  140
 14  \w     30.00  93.00   0.30   20.00    --  102.61 -61.00  90.00  210
 15  \w     20.00 105.20   0.30   20.00    --  102.61 -94.00-180.00  284
 16  \w     30.00  72.00   0.30   20.00    --  102.61 -45.00 -90.00  140
 17  \w    103.00 178.00   0.30   20.00    --  102.61  77.00 -90.00  250
 18  \w     20.00 105.20   0.30   20.00    --  102.61 -94.00 -30.00  284
 19  \w     26.00  56.00   0.30   20.00    --  102.61 -30.00   0.00  100
 20  \w     30.00  72.00   0.30   20.00    --  102.61 -45.00 150.00  140
 21  \w     30.00  93.00   0.30   20.00    --  102.61 -61.00   0.00  210
 22  \w     14.00 177.20   0.30   20.00    --  102.61   0.00 -90.00  544
 23  \w     30.00  72.00   0.30   20.00    --  102.61 -45.00-180.00  140
 24  \w     30.00  72.00   0.30   20.00    --  102.61 -45.00  30.00  140
 25  \w     24.00 108.00   0.30   20.00    --  102.61-106.00 -73.10  280
 26  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00-150.00  140
 27  \w     -5.00  37.00   0.30    7.50    --  -42.75  19.00 -60.00  140
 28  \w      9.00  42.00   0.30    7.50    --   42.75  81.00-174.96  110
 29  \w     10.00  40.90   0.30    7.50    --   42.75  80.00  62.30  103
 30  \w      9.00  42.00   0.30    7.50    --   42.75  82.00 -59.47  110
 31  \w      9.00  42.00   0.30    7.50    --   42.75  81.00 118.89  110
 32  \w     10.00  40.90   0.30    7.50    --   42.75  79.00-114.54  103
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0318074000
_diffrn_orient_matrix_UB_12      -0.0135402000
_diffrn_orient_matrix_UB_13      0.0763296000
_diffrn_orient_matrix_UB_21      -0.0030245000
_diffrn_orient_matrix_UB_22      0.1166506000
_diffrn_orient_matrix_UB_23      -0.0124791000
_diffrn_orient_matrix_UB_31      -0.1103907000
_diffrn_orient_matrix_UB_32      0.0114920000
_diffrn_orient_matrix_UB_33      -0.0078561000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0875
_diffrn_reflns_av_unetI/netI     0.0866
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            39557
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.804
_diffrn_reflns_theta_min         3.491
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.439
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54860
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_description       needle
_exptl_crystal_F_000             1788
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.046
_refine_diff_density_max         1.603
_refine_diff_density_min         -1.443
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1049
_refine_ls_number_reflns         14153
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1109
_refine_ls_R_factor_gt           0.0799
_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^)+(0.1294P)^2^+3.7194P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2072
_refine_ls_wR_factor_ref         0.2348
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10198
_reflns_number_total             14153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08203f2.cif
_cod_data_source_block           str2238_auto
_cod_depositor_comments
'Adding full bibliography for 1574089--1574091.cif.'
_cod_original_cell_volume        3706.3(3)
_cod_database_code               1574091
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Pd Cl B F'
_shelx_estimated_absorpt_t_max   0.858
_shelx_estimated_absorpt_t_min   0.486
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C34(H34)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C35(H35A,H35B), C37(H37A,H37B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C24(H24),
 C26(H26), C27(H27), C29(H29), C40(H40), C43(H43), C46(H46), C48(H48), C51(H51),
  C54(H54), C56(H56), C59(H59), C62(H62), C64(H64), C67(H67), C70(H70),
 C72(H72), C73(H73), C74(H74), C75(H75)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.754
_oxdiff_exptl_absorpt_empirical_full_min 0.226