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_1574090
_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         'C39 H39 Br3 N6 O4 Pd, C H3 Cl2'
_chemical_formula_sum            'C40 H42 Br3 Cl2 N6 O4 Pd'
_chemical_formula_weight         1087.82
_chemical_name_systematic        'complex 7'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-09-04
_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                90
_cell_angle_beta                 110.129(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0685(6)
_cell_length_b                   27.3218(10)
_cell_length_c                   14.8974(6)
_cell_measurement_reflns_used    4719
_cell_measurement_temperature    270(5)
_cell_measurement_theta_max      70.0020
_cell_measurement_theta_min      4.1780
_cell_volume                     4230.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_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      270(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4051
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  38.20   0.30   10.00    --  -41.25  19.00 -90.00  144
  2  \w     -5.00  38.20   0.30   10.00    --  -41.25  19.00  30.00  144
  3  \w     -5.00  38.20   0.30   10.00    --  -41.25  19.00 -30.00  144
  4  \w     -5.00  38.20   0.30   10.00    --  -41.25  19.00-120.00  144
  5  \w     -5.00  38.20   0.30   10.00    --  -41.25  19.00 -60.00  144
  6  \w     -5.00  38.20   0.30   10.00    --  -41.25  19.00-180.00  144
  7  \w    103.00 178.00   0.30   26.00    --  102.61  77.00 -30.00  250
  8  \w     30.00  72.00   0.30   26.00    --  102.61 -45.00-150.00  140
  9  \w     26.00  56.00   0.30   26.00    --  102.61 -30.00 -90.00  100
 10  \w     31.00 112.00   0.30   26.00    --  102.61-125.00 150.00  270
 11  \w     26.00  56.00   0.30   26.00    --  102.61 -30.00-120.00  100
 12  \w     30.00  93.00   0.30   26.00    --  102.61 -61.00 -60.00  210
 13  \w     77.00 176.00   0.30   26.00    --  102.61  45.00  60.00  330
 14  \w     30.00  72.00   0.30   26.00    --  102.61 -45.00 -60.00  140
 15  \w     26.00  56.00   0.30   26.00    --  102.61 -30.00 -30.00  100
 16  \w     26.00 126.20   0.30   26.00    --  102.61 -77.00 150.00  334
 17  \w     -5.00  26.20   0.30   10.00    --  -41.25  19.00 120.00  104
;
_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      -0.0979742000
_diffrn_orient_matrix_UB_12      -0.0414880000
_diffrn_orient_matrix_UB_13      -0.0097897000
_diffrn_orient_matrix_UB_21      0.0235206000
_diffrn_orient_matrix_UB_22      0.0030369000
_diffrn_orient_matrix_UB_23      0.1079071000
_diffrn_orient_matrix_UB_31      -0.1087967000
_diffrn_orient_matrix_UB_32      0.0380710000
_diffrn_orient_matrix_UB_33      -0.0194362000
_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  0.0631
_diffrn_reflns_av_unetI/netI     0.0609
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            22366
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.595
_diffrn_reflns_theta_max         66.595
_diffrn_reflns_theta_min         3.550
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.412
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.708
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.117a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.708
_exptl_crystal_description       needle
_exptl_crystal_F_000             2164
_exptl_crystal_size_max          0.328
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.024
_refine_diff_density_max         1.274
_refine_diff_density_min         -0.935
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         7471
_refine_ls_number_restraints     475
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1157
_refine_ls_R_factor_gt           0.0791
_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^)+(0.1333P)^2^+4.6854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2130
_refine_ls_wR_factor_ref         0.2549
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4589
_reflns_number_total             7471
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08203f2.cif
_cod_data_source_block           str2296_auto
_cod_depositor_comments
'Adding full bibliography for 1574089--1574091.cif.'
_cod_original_cell_volume        4230.0(3)
_cod_database_code               1574090
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Pd Br Cl'
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.169
_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, All Cl(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C8) = Uanis(C9) = Uanis(C10) = Uanis(C11)
Uanis(C13) = Uanis(C14) = Uanis(C15)
Uanis(C37) = Uanis(C36) = Uanis(C35) = Uanis(C38) = Uanis(C39)
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C35(H35)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C36(H36A,H36B), C38(H38A,H38B), C40(H40A,H40B)
4.c Me refined with riding coordinates:
 C11(H11A,H11B,H11C), C15(H15A,H15B,H15C)
4.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C18(H18), C19(H19), C25(H25), C27(H27),
 C28(H28), C30(H30)
4.e Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C39(H39A,H39B,H39C)
4.f Idealised tetrahedral OH refined as rotating group:
 Cl2(H2)
;
_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 1.903
_oxdiff_exptl_absorpt_empirical_full_min 0.585