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_7710599
_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_compound_source        'Rostov-on-Don, Russia'
_chemical_formula_moiety         'C32 H38 Fe N4 O2, Cl O4, 0.5(H2 O)'
_chemical_formula_sum            'C32 H39 Cl Fe N4 O6.5'
_chemical_formula_weight         674.97
_chemical_name_common
'3 - (3,6-Di-tert-butylcatecholato)-(tris(2-pyridylmethyl)amine)-iron(iii) percholrate'
_chemical_name_systematic
'3 - (3,6-Di-tert-butylcatecholato)-(tris(2-pyridylmethyl)amine)-iron(iii) percholrate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-08
_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                94.917(2)
_cell_angle_beta                 93.923(3)
_cell_angle_gamma                106.867(3)
_cell_formula_units_Z            2
_cell_length_a                   8.5899(3)
_cell_length_b                   10.3201(3)
_cell_length_c                   20.3051(6)
_cell_measurement_reflns_used    10926
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.1590
_cell_measurement_theta_min      4.5290
_cell_volume                     1708.01(10)
_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 2014/5 (Sheldrick, 2014)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.995
_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    -69.00  32.00   1.00    7.00    --  -41.35  57.00-120.00  101
  2  \w   -116.00 -17.00   1.00    7.00    --  -41.35 -38.00 -30.00   99
  3  \w   -113.00 -13.00   1.00    7.00    --  -41.35 -57.00  90.00  100
  4  \w      7.00  33.00   1.00    7.00    --   41.35  84.00  90.64   26
  5  \w      6.00  82.00   1.00    7.00    --   41.35 -99.00 -60.00   76
  6  \w     17.00 116.00   1.00    7.00    --   41.35  38.00-150.00   99
  7  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00-180.00   76
  8  \w     36.00 109.00   1.00   28.00    --  112.00-111.00  90.00   73
  9  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00 -90.00   76
 10  \w     36.00 109.00   1.00   28.00    --  112.00-111.00 -90.00   73
 11  \w     36.00 109.00   1.00   28.00    --  112.00-111.00  30.00   73
 12  \w     86.00 178.00   1.00   28.00    --  112.00  45.00-150.00   92
 13  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00 -60.00   76
 14  \w     36.00 140.00   1.00   28.00    --  112.00 -30.00 150.00  104
 15  \w    104.00 178.00   1.00   28.00    --  112.00 111.00  30.00   74
 16  \w     36.00 109.00   1.00   28.00    --  112.00-111.00-180.00   73
 17  \w     59.00 178.00   1.00   28.00    --  112.00  15.00  90.00  119
 18  \w     61.00 146.00   1.00   28.00    --  112.00 178.00-150.00   85
 19  \w     61.00 146.00   1.00   28.00    --  112.00 178.00  90.00   85
 20  \w     83.00 178.00   1.00   28.00    --  112.00  61.00  90.00   95
 21  \w     40.00 141.00   1.00   28.00    --  112.00 -61.00 120.00  101
 22  \w     36.00 109.00   1.00   28.00    --  112.00-111.00   0.00   73
 23  \w     36.00 109.00   1.00   28.00    --  112.00-111.00 120.00   73
 24  \w     36.00 109.00   1.00   28.00    --  112.00-111.00 -30.00   73
 25  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00 -30.00   76
 26  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00  60.00   76
 27  \w     86.00 178.00   1.00   28.00    --  112.00  45.00  90.00   92
 28  \w     30.00 165.00   1.00   28.00    --  112.00 -15.00 120.00  135
 29  \w     33.00 146.00   1.00   28.00    --  112.00 -83.00 108.79  113
 30  \w     36.00 145.00   1.00   28.00    --  112.00 -77.00 -30.00  109
 31  \w    103.00 178.00   1.00   28.00    --  112.00  77.00 -60.00   75
 32  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00 150.00   76
 33  \w     36.00 109.00   1.00   28.00    --  112.00-111.00-120.00   73
 34  \w     36.00 109.00   1.00   28.00    --  112.00-111.00  60.00   73
 35  \w     36.00 109.00   1.00   28.00    --  112.00-111.00 150.00   73
 36  \w    138.00 177.00   1.00   28.00    --  112.00 111.00 -30.00   39
 37  \w    117.00 172.00   1.00   28.00    --  112.00 111.00   0.00   55
 38  \w     86.00 156.00   1.00   28.00    --  112.00  61.00 -30.00   70
 39  \w     39.00  84.00   1.00   28.00    --  112.00 -47.00 -45.00   45
 40  \w    104.00 129.00   1.00   28.00    --  112.00 -47.00 -45.00   25
 41  \w     90.00 141.00   1.00   28.00    --  112.00 -61.00-150.00   51
 42  \w    101.00 130.00   1.00   28.00    --  112.00 -77.00  60.00   29
 43  \w    111.00 159.00   1.00   28.00    --  112.00  61.00 120.00   48
;
_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      -0.0779348000
_diffrn_orient_matrix_UB_12      -0.1416689000
_diffrn_orient_matrix_UB_13      -0.0389792000
_diffrn_orient_matrix_UB_21      0.1684361000
_diffrn_orient_matrix_UB_22      -0.0005098000
_diffrn_orient_matrix_UB_23      -0.0214486000
_diffrn_orient_matrix_UB_31      0.0318783000
_diffrn_orient_matrix_UB_32      -0.0675505000
_diffrn_orient_matrix_UB_33      0.0622543000
_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  0.0333
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            35491
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.530
_diffrn_reflns_theta_min         4.392
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.662
_exptl_absorpt_correction_T_max  0.754
_exptl_absorpt_correction_T_min  0.228
_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
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       block
_exptl_crystal_F_000             708
_exptl_crystal_size_max          0.516
_exptl_crystal_size_mid          0.348
_exptl_crystal_size_min          0.286
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.270
_refine_diff_density_rms         0.034
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         7137
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0418
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0682P)^2^+0.1762P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1220
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6365
_reflns_number_total             7137
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01207c2.cif
_cod_data_source_block           tpafe36clo4_cu_300_9
_cod_depositor_comments
'Adding full bibliography for 7710599--7710604.cif.'
_cod_original_formula_sum        'C32 H39 Cl Fe N4 O6.50'
_cod_database_code               7710599
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C32 H38 Cl1 Fe1 N4 O6'
_shelx_estimated_absorpt_t_max   0.349
_shelx_estimated_absorpt_t_min   0.197
_reflns_odcompleteness_completeness 98.56
_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, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(N3A) = Uanis(N3)
3. Others
 Sof(Cl1)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=1-FVAR(1)
 Sof(Cl2)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=FVAR(1)
 Sof(N3A)=Sof(C21')=Sof(H21')=Sof(C22')=Sof(H22')=Sof(C23')=Sof(H23')=
 Sof(C24')=Sof(H24')=Sof(C25')=Sof(C26')=Sof(H26C)=Sof(H26D)=1-FVAR(2)
 Sof(N3)=Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C21)=Sof(H21)=Sof(C23)=
 Sof(H23)=Sof(C24)=Sof(H24)=Sof(C22)=Sof(H22)=FVAR(2)
 Sof(H15A)=Sof(C19')=Sof(C20')=Sof(H20C)=Sof(H20D)=Sof(C18')=Sof(H18')=
 Sof(C17')=Sof(H17')=Sof(C16')=Sof(H16')=1-FVAR(3)
 Sof(C19)=Sof(H15)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C16)=Sof(H16)=Sof(C18)=
 Sof(H18)=Sof(C17)=Sof(H17)=FVAR(3)
 Fixed Sof: O7(0.5) H7A(0.5) H7B(0.5)
4.a Free rotating group:
 O7(H7A,H7B)
4.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C32(H32A,H32B), C26(H26A,H26B), C26'(H26C,H26D), C20'(H20C,
 H20D)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C4(H4), C5(H5), C15(H15), C15(H15A), C28(H28), C29(H29), C21(H21),
 C30(H30), C16(H16), C23(H23), C24(H24), C22(H22), C18(H18), C17(H17),
 C21'(H21'), C22'(H22'), C23'(H23'), C24'(H24'), C18'(H18'), C17'(H17'),
 C16'(H16')
4.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C12(H12A,H12B,
 H12C), C9(H9A,H9B,H9C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              53340
_shelx_hkl_checksum              64615
_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 1.168
_oxdiff_exptl_absorpt_empirical_full_min 0.865