Spin transitions in ferric catecholate complexes mediated by outer-sphere counteranions.
Chegerev, Maxim; Demidov, Oleg; Vasilyev, Pavel; Efimov, Nikolay; Kubrin, Stanislav; Starikov, Andrey; Vlasenko, Valery; Piskunov, Alexander; Shapovalova, Svetlana; Guda, Alexander; Rusalev, Yury; Soldatov, Alexander; Dalton transactions (Cambridge, England : 2003) 51 (2022) 10909–10919; doi:10.1039/d2dt01207c

data_7710604
_publ_section_title
;
 Spin transitions in ferric catecholate complexes mediated by outer-sphere
 counteranions.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10909
_journal_page_last               10919
_journal_paper_doi               10.1039/d2dt01207c
_journal_volume                  51
_journal_year                    2022
_chemical_formula_moiety         'C32 H38 Fe N4 O2, 2(F3 P0.5)'
_chemical_formula_sum            'C32 H38 F6 Fe N4 O2 P'
_chemical_formula_weight         711.48
_chemical_name_common
'(3,6-Di-tert-butylcatecholato)-(tris(2-pyridylmethyl)amine)-iron(iii) hexafluorophosphate'
_chemical_name_systematic
'(3,6-Di-tert-butylcatecholato)-(tris(2-pyridylmethyl)amine)-iron(iii) hexafluorophosphate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      60
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-04-03 deposited with the CCDC.	2022-06-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.0039(3)
_cell_length_b                   18.8295(2)
_cell_length_c                   15.30660(10)
_cell_measurement_reflns_used    22603
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.0780
_cell_measurement_theta_min      2.9570
_cell_volume                     6918.30(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2529
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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   -105.00 -19.00   1.00    4.50    --  -41.72 -38.00 -90.00   86
  2  \w    -71.00  34.00   1.00    4.50    --  -41.72  77.00  30.00  105
  3  \w    -60.00  19.00   1.00    4.50    --  -41.72  57.00 150.00   79
  4  \w   -115.00 -17.00   1.00    4.50    --  -41.72 -38.00-180.00   98
  5  \w     46.00  75.00   1.00    4.50    --   41.72  57.00 -60.00   29
  6  \w     39.00  95.00   1.00    4.50    --   41.72-125.00-120.00   56
  7  \w     84.00 148.00   1.00   18.00    --  112.00  61.00 120.00   64
  8  \w     81.00 107.00   1.00   18.00    --  112.00 -21.00  17.88   26
  9  \w     83.00 109.00   1.00   18.00    --  112.00 -87.00  83.69   26
 10  \w     40.00 109.00   1.00   18.00    --  112.00-111.00-120.00   69
 11  \w     73.00  98.00   1.00   18.00    --  112.00 -95.00 -30.00   25
 12  \w     36.00  62.00   1.00   18.00    --  112.00-111.00 -90.00   26
 13  \w     71.00 109.00   1.00   18.00    --  112.00-111.00 -90.00   38
 14  \w     69.00 120.00   1.00   18.00    --  112.00 178.00-180.00   51
 15  \w     60.00  93.00   1.00   18.00    --  112.00 -95.00 -90.00   33
 16  \w     58.00  85.00   1.00   18.00    --  112.00 -24.00  15.13   27
 17  \w     25.00  54.00   1.00   18.00    --  112.00   0.00 -60.00   29
 18  \w     73.00 109.00   1.00   18.00    --  112.00-111.00 -30.00   36
 19  \w     79.00 113.00   1.00   18.00    --  112.00   0.00 -60.00   34
 20  \w    120.00 178.00   1.00   18.00    --  112.00   0.00 -60.00   58
 21  \w     34.00  61.00   1.00   18.00    --  112.00 -15.00 -60.00   27
 22  \w     61.00 109.00   1.00   18.00    --  112.00-111.00  90.00   48
 23  \w     55.00  81.00   1.00   18.00    --  112.00 -95.00 -60.00   26
 24  \w    128.00 177.00   1.00   18.00    --  112.00  61.00   0.00   49
 25  \w     59.00 109.00   1.00   18.00    --  112.00-111.00-180.00   50
 26  \w     70.00 102.00   1.00   18.00    --  112.00-111.00 120.00   32
 27  \w     69.00 109.00   1.00   18.00    --  112.00-111.00 150.00   40
 28  \w     42.00 108.00   1.00   18.00    --  112.00 -45.00 -60.00   66
 29  \w     68.00  96.00   1.00   18.00    --  112.00  18.00  35.32   28
 30  \w     69.00 109.00   1.00   18.00    --  112.00-111.00-150.00   40
 31  \w     97.00 130.00   1.00   18.00    --  112.00 -61.00 -60.00   33
 32  \w     42.00  81.00   1.00   18.00    --  112.00 -61.00 -60.00   39
 33  \w    104.00 132.00   1.00   18.00    --  112.00 111.00  60.00   28
 34  \w     58.00 108.00   1.00   18.00    --  112.00 -45.00 120.00   50
 35  \w     54.00  86.00   1.00   18.00    --  112.00 -61.00-120.00   32
 36  \w     70.00 109.00   1.00   18.00    --  112.00-111.00  30.00   39
 37  \w     41.00 136.00   1.00   18.00    --  112.00 -30.00 -60.00   95
 38  \w     81.00 116.00   1.00   18.00    --  112.00  15.00-150.00   35
 39  \w    125.00 167.00   1.00   18.00    --  112.00  15.00-150.00   42
 40  \w     43.00  69.00   1.00   18.00    --  112.00 -45.00 150.00   26
 41  \w     84.00 133.00   1.00   18.00    --  112.00 -45.00 150.00   49
 42  \w     43.00  72.00   1.00   18.00    --  112.00 -61.00 -90.00   29
 43  \w     73.00 109.00   1.00   18.00    --  112.00-111.00  60.00   36
 44  \w     77.00 126.00   1.00   18.00    --  112.00 -15.00 -60.00   49
 45  \w     70.00 131.00   1.00   18.00    --  112.00 -30.00  60.00   61
 46  \w     43.00  98.00   1.00   18.00    --  112.00 -77.00  60.00   55
 47  \w    130.00 177.00   1.00   18.00    --  112.00  77.00 -90.00   47
 48  \w     66.00  91.00   1.00   18.00    --  112.00 178.00  60.00   25
 49  \w    118.00 144.00   1.00   18.00    --  112.00 178.00  60.00   26
 50  \w     73.00 120.00   1.00   18.00    --  112.00 -61.00  60.00   47
 51  \w    148.00 174.00   1.00   18.00    --  112.00  77.00  30.00   26
 52  \w     74.00 106.00   1.00   18.00    --  112.00-111.00   0.00   32
 53  \w     37.00  88.00   1.00   18.00    --  112.00 -26.00-134.70   51
 54  \w    106.00 133.00   1.00   18.00    --  112.00 111.00-150.00   27
 55  \w    120.00 145.00   1.00   18.00    --  112.00 111.00 -30.00   25
 56  \w     61.00  87.00   1.00   18.00    --  112.00 -95.00-180.00   26
 57  \w     55.00  80.00   1.00   18.00    --  112.00 -95.00  60.00   25
 58  \w    120.00 145.00   1.00   18.00    --  112.00 178.00 -30.00   25
 59  \w     32.00  57.00   1.00   18.00    --  112.00 -87.00  83.69   25
 60  \w     79.00 107.00   1.00   18.00    --  112.00 -83.00  -2.69   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0526730000
_diffrn_orient_matrix_UB_12      0.0040453000
_diffrn_orient_matrix_UB_13      -0.0572582000
_diffrn_orient_matrix_UB_21      0.0026495000
_diffrn_orient_matrix_UB_22      -0.0808867000
_diffrn_orient_matrix_UB_23      -0.0146325000
_diffrn_orient_matrix_UB_31      -0.0365785000
_diffrn_orient_matrix_UB_32      -0.0117003000
_diffrn_orient_matrix_UB_33      0.0814438000
_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  0.1058
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            104873
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.500
_diffrn_reflns_theta_min         2.983
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.518
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.547
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       block
_exptl_crystal_F_000             2952
_exptl_crystal_size_max          0.388
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.518
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     442
_refine_ls_number_reflns         7262
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0784P)^2^+1.0696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1256
_refine_ls_wR_factor_ref         0.1332
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6188
_reflns_number_total             7262
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01207c2.cif
_cod_data_source_block           tpa36fepf6
_cod_depositor_comments
'Adding full bibliography for 7710599--7710604.cif.'
_cod_database_code               7710604
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C32 H38 F6 Fe N4 O2 P'
_shelx_estimated_absorpt_t_max   0.773
_shelx_estimated_absorpt_t_min   0.273
_reflns_odcompleteness_completeness 98.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_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. Others
 Sof(F7A)=Sof(F6A)=1-FVAR(1)
 Sof(F6)=Sof(F7)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C26(H26A,H26B), C20(H20A,H20B)
3.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C15(H15), C5(H5), C4(H4), C30(H30), C27(H27), C16(H16), C18(H18),
 C29(H29), C24(H24), C28(H28), C22(H22), C17(H17), C23(H23)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C9(H9A,H9B,
 H9C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              92457
_shelx_hkl_checksum              31876
_shelx_fab_checksum              49793
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.577
_oxdiff_exptl_absorpt_empirical_full_min 0.535