Correlations between ligand field ΔO, spin crossover T1/2 and redox potential Epa in a family of five dinuclear helicates
Singh, Sandhya; Brooker, Sally; Chemical Science  (2021) –; doi:10.1039/D1SC01458G

data_1563759
_publ_section_title
;
 Correlations between ligand field \DO, spin crossover T1/2 and redox
 potential Epa in a family of five dinuclear helicates
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01458G
_journal_year                    2021
_chemical_formula_moiety         'C72 H84 Fe2 N30, 4(B F4)'
_chemical_formula_sum            'C72 H84 B4 F16 Fe2 N30'
_chemical_formula_weight         1828.63
_chemical_name_common
'diiron(II) helicate of ditopic 4-imidazole-triazole ligand'
_chemical_name_systematic
'Iron(II) helicate of 1,3-Bis(5-(1H-imidazol-4-yl)-4-isobutyl-4H-1,2,4-triazol-3-yl)benzene'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-03-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2021-02-05 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.0164(7)
_cell_length_b                   30.0399(5)
_cell_length_c                   36.9150(16)
_cell_measurement_reflns_used    11247
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.6140
_cell_measurement_theta_min      4.3550
_cell_volume                     22196.6(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3449
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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      6.00  32.00   1.00    5.00    --  -42.04  38.00-120.00   26
  2  \w    -67.00  30.00   1.00    5.00    --  -42.04  38.00 150.00   97
  3  \w    -67.00 -34.00   1.00    5.00    --  -42.04  38.00-120.00   33
  4  \w     47.00  76.00   1.00    5.00    --   42.04 -99.00 120.00   29
  5  \w     53.00  86.00   1.00   10.00    --  112.00-125.00 120.00   33
  6  \w     93.00 118.00   1.00   10.00    --  112.00-125.00 120.00   25
  7  \w    117.00 173.00   1.00   10.00    --  112.00 125.00 120.00   56
  8  \w     83.00 108.00   1.00   10.00    --  112.00-123.00  15.00   25
  9  \w     38.00  82.00   1.00   10.00    --  112.00-123.00  15.00   44
 10  \w     40.00  80.00   1.00   10.00    --  112.00-125.00-180.00   40
 11  \w    123.00 178.00   1.00   10.00    --  112.00  30.00-150.00   55
 12  \w     92.00 118.00   1.00   10.00    --  112.00-125.00-120.00   26
 13  \w    102.00 133.00   1.00   10.00    --  112.00 -45.00 -90.00   31
 14  \w     79.00 110.00   1.00   10.00    --  112.00 -95.00-180.00   31
 15  \w     84.00 170.00   1.00   10.00    --  112.00  30.00 -60.00   86
 16  \w     42.00  84.00   1.00   10.00    --  112.00-144.00 118.00   42
 17  \w     90.00 124.00   1.00   10.00    --  112.00-144.00 118.00   34
;
_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      0.0432744000
_diffrn_orient_matrix_UB_12      -0.0056562000
_diffrn_orient_matrix_UB_13      -0.0342384000
_diffrn_orient_matrix_UB_21      0.0632137000
_diffrn_orient_matrix_UB_22      -0.0023118000
_diffrn_orient_matrix_UB_23      0.0237218000
_diffrn_orient_matrix_UB_31      -0.0077012000
_diffrn_orient_matrix_UB_32      -0.0508873000
_diffrn_orient_matrix_UB_33      0.0027290000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0915
_diffrn_reflns_av_unetI/netI     0.0738
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            93118
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.636
_diffrn_reflns_theta_min         3.574
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.734
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49487
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.094
_exptl_crystal_description       irregular
_exptl_crystal_F_000             7536
_exptl_crystal_preparation
'Magnetic properties,redox, ligand field strength, UV-Visible spectra, Evans method NMR, DOSY NMR'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: NO2Me by diethylether ether vapour diffusion'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.902
_refine_diff_density_min         -0.482
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1184
_refine_ls_number_reflns         23026
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.1224
_refine_ls_R_factor_gt           0.0795
_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^)+(0.1255P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2127
_refine_ls_wR_factor_ref         0.2399
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12652
_reflns_number_total             23026
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss458
_cod_database_code               1563759
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         FeCHNOBF
_chemical_oxdiff_usercomment     L1038
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.772
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Rigid body (RIGU) restrains
 C53, C54, C56, C55
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
3. Same fragment restrains
{C41, C42, C43, C44} sigma for 1-2: 0.02, 1-3: 0.04
as
{C53, C54, C55, C56}
4. Others
 Fixed Sof: H65A(0.6) H65B(0.6) H65C(0.4) H65D(0.4) C66(0.6) H66(0.6)
 H68A(0.6) H68B(0.6) H68C(0.6) H68D(0.4) H68E(0.4) H68F(0.4) C67(0.6) H67A(0.6)
 H67B(0.6) H67C(0.6) C69(0.4) H69A(0.4) H69B(0.4) H69C(0.4) C70(0.4) H70(0.4)
 F41(0.8) F42(0.8) F43(0.8) F44(0.8) F45(0.2) F47(0.2) F46(0.2) F48(0.2)
5.a Ternary CH refined with riding coordinates:
 C6(H6), C18(H18), C30(H30A), C42(H42), C54(H54), C66(H66), C70(H70)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C17(H17A,H17B), C29(H29A,H29B), C41(H41A,H41B), C53(H53A,H53B),
 C65(H65A,H65B), C65(H65C,H65D)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N10(H10), N12(H12), N20(H20), N22(H22), N30(H30), C1(H1), C2(H2A),
 C11(H11), C13(H13), C14(H14), C15(H15), C23(H23), C24(H24), C25(H25), C26(H26),
  C35(H35), C36(H36), C37(H37), C39(H39), C47(H47), C48(H48), C49(H49),
 C50(H50), C59(H59), C60(H60), C61(H61), C63(H63), C73(H73), C74(H74)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C68(H68A,H68B,H68C), C68(H68D,
 H68E,H68F), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              77134
_shelx_hkl_checksum              34169
_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 1.838
_oxdiff_exptl_absorpt_empirical_full_min 0.554
_platon_squeeze_void_probe_radius 1.20