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_7710602
_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, B F4, 0.333(H2 O)'
_chemical_formula_sum            'C32 H38.67 B F4 Fe N4 O2.33'
_chemical_formula_weight         659.27
_chemical_name_common
'3 - (3,6-Di-tert-butylcatecholato)-(tris(2-pyridylmethyl)amine)-iron(iii) tetrafluoroborate'
_chemical_name_systematic
'3 - (3,6-Di-tert-butylcatecholato)-(tris(2-pyridylmethyl)amine)-iron(iii) tetrafluoroborate'
_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                94.460(3)
_cell_angle_beta                 94.614(4)
_cell_angle_gamma                106.445(4)
_cell_formula_units_Z            2
_cell_length_a                   8.5955(5)
_cell_length_b                   10.2994(4)
_cell_length_c                   20.1677(8)
_cell_measurement_reflns_used    5129
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.6600
_cell_measurement_theta_min      4.4210
_cell_volume                     1697.36(14)
_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 1.000
_diffrn_measured_fraction_theta_max 0.994
_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    -65.00  33.00   1.00    4.00    --  -40.97  38.00-180.00   98
  2  \w   -113.00 -13.00   1.00    4.00    --  -40.97 -57.00-120.00  100
  3  \w   -115.00 -16.00   1.00    4.00    --  -40.97 -38.00   0.00   99
  4  \w    -87.00  -6.00   1.00    4.00    --  -40.97 125.00 -60.00   81
  5  \w      6.00  32.00   1.00    4.00    --   40.97  85.00 134.59   26
  6  \w      6.00  82.00   1.00    4.00    --   40.97 -99.00-150.00   76
  7  \w     36.00 109.00   1.00   16.00    --  112.00-111.00 120.00   73
  8  \w     36.00 109.00   1.00   16.00    --  112.00-111.00 -60.00   73
  9  \w     83.00 178.00   1.00   16.00    --  112.00  61.00  60.00   95
 10  \w     36.00 109.00   1.00   16.00    --  112.00-111.00-180.00   73
 11  \w     30.00 106.00   1.00   16.00    --  112.00 -95.00  30.00   76
 12  \w     36.00 109.00   1.00   16.00    --  112.00-111.00 150.00   73
 13  \w     39.00 138.00   1.00   16.00    --  112.00 -45.00 -90.00   99
 14  \w     86.00 178.00   1.00   16.00    --  112.00  45.00-120.00   92
 15  \w     83.00 178.00   1.00   16.00    --  112.00  61.00  90.00   95
 16  \w     36.00 109.00   1.00   16.00    --  112.00-111.00 -90.00   73
 17  \w    104.00 178.00   1.00   16.00    --  112.00 111.00-180.00   74
 18  \w    104.00 178.00   1.00   16.00    --  112.00 111.00 -30.00   74
 19  \w     86.00 178.00   1.00   16.00    --  112.00  45.00 120.00   92
 20  \w    104.00 178.00   1.00   16.00    --  112.00 111.00  90.00   74
 21  \w    103.00 178.00   1.00   16.00    --  112.00  77.00 -30.00   75
 22  \w     36.00 109.00   1.00   16.00    --  112.00-111.00 -30.00   73
 23  \w     84.00 178.00   1.00   16.00    --  112.00  30.00 -60.00   94
 24  \w     40.00 141.00   1.00   16.00    --  112.00 -61.00  90.00  101
 25  \w     83.00 178.00   1.00   16.00    --  112.00  61.00 120.00   95
 26  \w     83.00 178.00   1.00   16.00    --  112.00  61.00 150.00   95
 27  \w     36.00 109.00   1.00   16.00    --  112.00-111.00  30.00   73
 28  \w     40.00 141.00   1.00   16.00    --  112.00 -61.00 -30.00  101
 29  \w     46.00  73.00   1.00   16.00    --  112.00 -77.00 -90.00   27
 30  \w     94.00 126.00   1.00   16.00    --  112.00 -77.00 -90.00   32
 31  \w     79.00 104.00   1.00   16.00    --  112.00-111.00-150.00   25
 32  \w     72.00 109.00   1.00   16.00    --  112.00-111.00-120.00   37
 33  \w    105.00 161.00   1.00   16.00    --  112.00 111.00 -60.00   56
 34  \w    107.00 140.00   1.00   16.00    --  112.00 111.00 150.00   33
 35  \w     65.00 131.00   1.00   16.00    --  112.00 178.00 -30.00   66
 36  \w     33.00  65.00   1.00   16.00    --  112.00 -95.00   0.00   32
 37  \w     69.00  97.00   1.00   16.00    --  112.00 178.00 120.00   28
 38  \w     96.00 123.00   1.00   16.00    --  112.00 -87.00 -67.78   27
 39  \w     75.00 102.00   1.00   16.00    --  112.00 -77.00 150.00   27
 40  \w     68.00 101.00   1.00   16.00    --  112.00  17.00 -74.92   33
 41  \w    128.00 155.00   1.00   16.00    --  112.00  17.00 -74.92   27
 42  \w     41.00  70.00   1.00   16.00    --  112.00 -87.00 -67.78   29
;
_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      -0.1820835000
_diffrn_orient_matrix_UB_12      -0.0752333000
_diffrn_orient_matrix_UB_13      0.0012486000
_diffrn_orient_matrix_UB_21      -0.0033603000
_diffrn_orient_matrix_UB_22      -0.0748642000
_diffrn_orient_matrix_UB_23      -0.0695095000
_diffrn_orient_matrix_UB_31      0.0464896000
_diffrn_orient_matrix_UB_32      -0.1154562000
_diffrn_orient_matrix_UB_33      0.0332504000
_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  0.0548
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            27902
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.352
_diffrn_reflns_theta_min         2.210
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.046
_exptl_absorpt_correction_T_max  0.797
_exptl_absorpt_correction_T_min  0.548
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       plate
_exptl_crystal_F_000             689
_exptl_crystal_size_max          0.438
_exptl_crystal_size_mid          0.343
_exptl_crystal_size_min          0.158
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         7070
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0799
_refine_ls_R_factor_gt           0.0589
_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^)+(0.1061P)^2^+0.0488P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1612
_refine_ls_wR_factor_ref         0.1818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5109
_reflns_number_total             7070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01207c2.cif
_cod_data_source_block           tpafe36bf4
_cod_depositor_comments
'Adding full bibliography for 7710599--7710604.cif.'
_cod_database_code               7710602
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C32 H38 B F4 Fe N4 O2'
_shelx_estimated_absorpt_t_max   0.567
_shelx_estimated_absorpt_t_min   0.270
_reflns_odcompleteness_completeness 98.37
_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. Restrained distances
 F1''-F1 \\sim F1''-F3 \\sim F1''-F2 \\sim F1-F2 \\sim F3-F2
 with sigma of 0.04
 B1-F1'' \\sim B1-F1 \\sim B1-F3 \\sim B1-F2
 with sigma of 0.02
 F3'-F2' \\sim F3'-F1' \\sim F2'-F1'
 with sigma of 0.04
 B1-F1'' \\sim B1-F3' \\sim B1-F2' \\sim B1-F1'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O1S) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28) = Uanis(C28')
Uanis(C32') = Uanis(C32)
Uanis(N4) = Uanis(N4')
Uanis(C29') = Uanis(C29)
Uanis(C32) = Uanis(C32')
4. Others
 Sof(C32)=Sof(H32C)=Sof(H32D)=Sof(C31')=Sof(N4')=Sof(C27')=Sof(H27')=Sof(C28')=
 Sof(H28')=Sof(C29')=Sof(H29')=Sof(C30')=Sof(H30')=1-FVAR(1)
 Sof(N4)=Sof(C31)=Sof(C32')=Sof(H32A)=Sof(H32B)=Sof(C27)=Sof(H27)=Sof(C29)=
 Sof(H29)=Sof(C30)=Sof(H30)=Sof(C28)=Sof(H28)=FVAR(1)
 Sof(O1S)=Sof(H1SA)=Sof(H1SB)=FVAR(2)
 Fixed Sof: F1(0.55) F3'(0.45) F3(0.55) F2(0.55) F2'(0.45) F1'(0.45)
5.a Free rotating group:
 O1S(H1SA,H1SB)
5.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C20(H20A,H20B), C32'(H32A,H32B), C32(H32C,H32D)
5.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C5(H5), C15(H15), C4(H4), C24(H24), C22(H22), C27(H27), C29(H29),
 C23(H23), C30(H30), C16(H16), C18(H18), C28(H28), C17(H17), C27'(H27'),
 C28'(H28'), C29'(H29'), C30'(H30')
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C13(H13A,H13B,H13C),
 C10(H10A,H10B,H10C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              88679
_shelx_hkl_checksum              88977
_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 1.547
_oxdiff_exptl_absorpt_empirical_full_min 0.575