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_7710600
_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                97.511(2)
_cell_angle_beta                 92.574(2)
_cell_angle_gamma                106.888(2)
_cell_formula_units_Z            2
_cell_length_a                   8.3709(2)
_cell_length_b                   10.3122(2)
_cell_length_c                   19.7722(3)
_cell_measurement_reflns_used    15672
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      75.8030
_cell_measurement_theta_min      4.5070
_cell_volume                     1612.97(6)
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(11)
_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 0.996
_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   -113.00 -13.00   1.00    1.00    --  -41.35 -57.00-180.00  100
  2  \w   -114.00 -62.00   1.00    1.00    --  -41.35-148.00-106.00   52
  3  \w   -116.00 -17.00   1.00    1.00    --  -41.35 -38.00 -90.00   99
  4  \w     27.00  97.00   1.00    1.00    --   41.35-125.00  60.00   70
  5  \w     17.00 116.00   1.00    1.00    --   41.35  38.00 120.00   99
  6  \w    -21.00  74.00   1.00    1.00    --   41.35 -77.00-120.00   95
  7  \w      8.00  42.00   1.00    1.00    --   41.35  80.00 153.97   34
  8  \w     61.00 146.00   1.00    2.57    --  112.00 178.00  90.00   85
  9  \w     30.00 106.00   1.00    2.57    --  112.00 -95.00-120.00   76
 10  \w     37.00 136.00   1.00    2.57    --  112.00 -36.00-159.88   99
 11  \w     84.00 178.00   1.00    2.57    --  112.00  30.00 -90.00   94
 12  \w     36.00 109.00   1.00    2.57    --  112.00-111.00 -30.00   73
 13  \w     36.00 145.00   1.00    2.57    --  112.00 -77.00  90.00  109
 14  \w    103.00 178.00   1.00    2.57    --  112.00  77.00 120.00   75
 15  \w    104.00 178.00   1.00    2.57    --  112.00 111.00 -60.00   74
 16  \w     61.00 146.00   1.00    2.57    --  112.00 178.00  30.00   85
 17  \w     30.00 106.00   1.00    2.57    --  112.00 -95.00 -90.00   76
 18  \w    104.00 178.00   1.00    2.57    --  112.00 111.00  90.00   74
 19  \w     36.00 145.00   1.00    2.57    --  112.00 -77.00 -30.00  109
 20  \w    104.00 178.00   1.00    2.57    --  112.00 111.00 -30.00   74
 21  \w     36.00 109.00   1.00    2.57    --  112.00-111.00  30.00   73
 22  \w     30.00 106.00   1.00    2.57    --  112.00 -95.00  90.00   76
 23  \w     61.00 146.00   1.00    2.57    --  112.00 178.00 -30.00   85
 24  \w     40.00 141.00   1.00    2.57    --  112.00 -61.00   0.00  101
 25  \w     30.00 165.00   1.00    2.57    --  112.00 -15.00 -90.00  135
 26  \w     39.00 138.00   1.00    2.57    --  112.00 -45.00-120.00   99
 27  \w     30.00 106.00   1.00    2.57    --  112.00 -95.00-180.00   76
 28  \w     40.00 141.00   1.00    2.57    --  112.00 -61.00  30.00  101
 29  \w     36.00 145.00   1.00    2.57    --  112.00 -77.00-180.00  109
 30  \w     30.00 165.00   1.00    2.57    --  112.00 -15.00  60.00  135
 31  \w     61.00 146.00   1.00    2.57    --  112.00 178.00 150.00   85
 32  \w     36.00 109.00   1.00    2.57    --  112.00-111.00-120.00   73
 33  \w     36.00 109.00   1.00    2.57    --  112.00-111.00 -60.00   73
 34  \w     39.00 111.00   1.00    2.57    --  112.00-124.00  58.00   72
 35  \w     30.00 106.00   1.00    2.57    --  112.00 -95.00 -30.00   76
 36  \w     73.00 106.00   1.00    2.57    --  112.00 -95.00 120.00   33
 37  \w     95.00 175.00   1.00    2.57    --  112.00  45.00  60.00   80
 38  \w     90.00 147.00   1.00    2.57    --  112.00 -86.00  30.95   57
 39  \w     84.00 116.00   1.00    2.57    --  112.00  61.00  30.00   32
 40  \w    135.00 162.00   1.00    2.57    --  112.00  61.00  30.00   27
 41  \w     40.00  68.00   1.00    2.57    --  112.00 -61.00  90.00   28
 42  \w     77.00 132.00   1.00    2.57    --  112.00 -30.00 -30.00   55
 43  \w     40.00  67.00   1.00    2.57    --  112.00 -86.00  30.95   27
;
_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      -0.1880655000
_diffrn_orient_matrix_UB_12      -0.0361513000
_diffrn_orient_matrix_UB_13      0.0108268000
_diffrn_orient_matrix_UB_21      -0.0435410000
_diffrn_orient_matrix_UB_22      -0.0419626000
_diffrn_orient_matrix_UB_23      -0.0778507000
_diffrn_orient_matrix_UB_31      -0.0033656000
_diffrn_orient_matrix_UB_32      -0.1478900000
_diffrn_orient_matrix_UB_33      0.0067740000
_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  0.0289
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            33846
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.446
_diffrn_reflns_theta_min         2.263
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.936
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.664
_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    1.390
_exptl_crystal_description       block
_exptl_crystal_F_000             708
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.232
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.662
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         6759
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0535P)^2^+0.8414P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0941
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6557
_reflns_number_total             6759
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01207c2.cif
_cod_data_source_block           tpafe36clo4_100
_cod_depositor_comments
'Adding full bibliography for 7710599--7710604.cif.'
_cod_original_formula_sum        'C32 H39 Cl Fe N4 O6.50'
_cod_database_code               7710600
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C32 H38 Fe N4 O2, Cl O4'
_shelx_estimated_absorpt_t_max   0.424
_shelx_estimated_absorpt_t_min   0.277
_reflns_odcompleteness_completeness 98.69
_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
 O3A-O6A \\sim O6-O3
 with sigma of 0.04
 Cl1-O5 \\sim Cl1A-O5
 with sigma of 0.02
 Cl1-O3A \\sim Cl1A-O6
 with sigma of 0.02
 Cl1-O6A \\sim Cl1A-O3
 with sigma of 0.02
 Cl1-O4A \\sim Cl1A-O4
 with sigma of 0.02
 O5-O6A \\sim O5-O3
 with sigma of 0.04
 O6A-O4A \\sim O3-O4
 with sigma of 0.04
 O5-O3A \\sim O5-O6
 with sigma of 0.04
 O5-O4A \\sim O5-O4
 with sigma of 0.04
 O3A-O4A \\sim O6-O4
 with sigma of 0.04
3. Others
 Sof(O6)=Sof(O3)=Sof(Cl1A)=Sof(O4)=1-FVAR(1)
 Sof(Cl1)=Sof(O3A)=Sof(O6A)=Sof(O4A)=FVAR(1)
 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:
 C26(H26A,H26B), C20(H20A,H20B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C30(H30), C29(H29), C15(H15), C21(H21), C5(H5), C23(H23), C4(H4),
 C22(H22), C24(H24), C18(H18), C16(H16), C28(H28), C17(H17)
4.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C8(H8A,H8B,H8C),
 C10(H10A,H10B,H10C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              60966
_shelx_hkl_checksum              73512
_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 1.466
_oxdiff_exptl_absorpt_empirical_full_min 0.779