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_1563754
_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
'C78 H96 Fe2 N30, C4 H10 O, 6(C2 H3 N), 4(B F4)'
_chemical_formula_sum            'C94 H124 B4 F16 Fe2 N36 O'
_chemical_formula_weight         2233.22
_chemical_name_common
'diiron(II) helicate of ditopic 4-N-Me-imidazole-triazole ligand'
_chemical_name_systematic
'Iron(II) helicate of 1,3-Bis(4-isobutyl-5-(1-methyl-1H-imidazol-4-yl)-4H-1,2,4-triazol-3-yl)benzene'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-30
_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                66.217(2)
_cell_angle_beta                 73.980(2)
_cell_angle_gamma                74.493(2)
_cell_formula_units_Z            2
_cell_length_a                   17.7970(4)
_cell_length_b                   18.8632(5)
_cell_length_c                   19.2290(3)
_cell_measurement_reflns_used    25100
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.9860
_cell_measurement_theta_min      3.9910
_cell_volume                     5587.6(2)
_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 5.1725
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.977
_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   -128.00-100.00   1.00    2.50    --  -41.79 178.00 150.00   28
  2  \w   -118.00 -10.00   1.00    2.50    --  -41.79 -77.00-180.00  108
  3  \w   -101.00 -18.00   1.00    2.50    --  -41.79 -57.00  30.00   83
  4  \w     -7.00  29.00   1.00    2.50    --  -41.79  57.00 -60.00   36
  5  \w    -68.00 -33.00   1.00    2.50    --  -41.79  57.00-180.00   35
  6  \w    -96.00 -34.00   1.00    2.50    --  -41.79 178.00 150.00   62
  7  \w     60.00 131.00   1.00    2.50    --   41.79 178.00  60.00   71
  8  \w     90.00 117.00   1.00    5.00    --  112.00-125.00 120.00   27
  9  \w     42.00 141.00   1.00    5.00    --  112.00 -61.00   0.00   99
 10  \w     40.00 138.00   1.00    5.00    --  112.00 -77.00 150.00   98
 11  \w     76.00 118.00   1.00    5.00    --  112.00-125.00-180.00   42
 12  \w    140.00 176.00   1.00    5.00    --  112.00  77.00   0.00   36
 13  \w     42.00  68.00   1.00    5.00    --  112.00-125.00-180.00   26
 14  \w     36.00 140.00   1.00    5.00    --  112.00 -30.00 -30.00  104
 15  \w     39.00 118.00   1.00    5.00    --  112.00-125.00 -30.00   79
 16  \w    146.00 174.00   1.00    5.00    --  112.00 125.00  90.00   28
 17  \w    145.00 178.00   1.00    5.00    --  112.00  45.00 -30.00   33
 18  \w    102.00 130.00   1.00    5.00    --  112.00 125.00  90.00   28
 19  \w     41.00  90.00   1.00    5.00    --  112.00 -45.00 150.00   49
 20  \w     88.00 167.00   1.00    5.00    --  112.00  61.00 150.00   79
 21  \w     93.00 118.00   1.00    5.00    --  112.00-125.00-120.00   25
 22  \w     89.00 116.00   1.00    5.00    --  112.00  45.00 -30.00   27
 23  \w     31.00  93.00   1.00    5.00    --  112.00 -95.00   0.00   62
 24  \w     93.00 118.00   1.00    5.00    --  112.00-125.00  60.00   25
 25  \w     44.00  75.00   1.00    5.00    --  112.00-125.00 -60.00   31
 26  \w     53.00 178.00   1.00    5.00    --  112.00   0.00 120.00  125
;
_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      0.0508628000
_diffrn_orient_matrix_UB_12      -0.0827162000
_diffrn_orient_matrix_UB_13      0.0126396000
_diffrn_orient_matrix_UB_21      -0.0753942000
_diffrn_orient_matrix_UB_22      -0.0343550000
_diffrn_orient_matrix_UB_23      0.0175125000
_diffrn_orient_matrix_UB_31      0.0101575000
_diffrn_orient_matrix_UB_32      0.0142177000
_diffrn_orient_matrix_UB_33      -0.0865339000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            49438
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.467
_diffrn_reflns_theta_min         4.001
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54489
_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    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             2328
_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: MeCN by diethylether ether vapour diffusion'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.941
_refine_diff_density_min         -0.921
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1404
_refine_ls_number_reflns         22943
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0722
_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^)+(0.1205P)^2^+9.5459P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2104
_refine_ls_wR_factor_ref         0.2137
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21296
_reflns_number_total             22943
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss300-1
_cod_original_cell_volume        5587.7(2)
_cod_database_code               1563754
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         FeCHNBFO
_chemical_oxdiff_usercomment     L756
_shelx_estimated_absorpt_t_max   0.784
_shelx_estimated_absorpt_t_min   0.601
_reflns_odcompleteness_completeness 99.79
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C19(H19), C33(H33), C45(H45), C59(H59), C71(H71)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6a,H6b), C18(H18a,H18b), C32(H32a,H32b), C44(H44a,H44b), C58(H58a,H58b),
 C70(H70a,H70b), C112(H11d,H11e), C113(H11f,H11g)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C12(H12), C13(H13), C14(H14), C15(H15), C24(H24), C26(H26),
 C27(H27), C29(H29), C38(H38), C39(H39), C40(H40), C41(H41), C50(H50), C52(H52),
  C53(H53), C55(H55), C64(H64), C65(H65), C66(H66), C67(H67), C76(H76), C78(H78)
2.d Idealised Me refined as rotating group:
 C2(H2a,H2b,H2c), C8(H8a,H8b,H8c), C9(H9a,H9b,H9c), C25(H25a,H25b,H25c),
 C28(H28a,H28b,H28c), C34(H34a,H34b,H34c), C35(H35a,H35b,H35c), C46(H46a,H46b,
 H46c), C47(H47a,H47b,H47c), C51(H51a,H51b,H51c), C54(H54a,H54b,H54c), C60(H60a,
 H60b,H60c), C61(H61a,H61b,H61c), C72(H72a,H72b,H72c), C73(H73a,H73b,H73c),
 C77(H77a,H77b,H77c), C111(H11a,H11b,H11c), C114(H11h,H11i,H11j), C102(H10a,
 H10b,H10c), C202(H20d,H20e,H20f), C302(H30a,H30b,H30c), C402(H40a,H40b,H40c),
 C502(H50a,H50b,H50c), C602(H60d,H60e,H60f), C21(H21a,H21b,H21c), C20(H20a,H20b,
 H20c)
;
_shelx_res_checksum              98013
_shelx_hkl_checksum              65824
_olex2_date_sample_data_collection 2018-11-03
_olex2_submission_original_sample_id SS300
_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 1.516
_oxdiff_exptl_absorpt_empirical_full_min 0.667