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_1563751
_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, 2(C2 H3 N), 4(B F4)'
_chemical_formula_sum            'C76 H90 B4 F16 Fe2 N32'
_chemical_formula_weight         1910.73
_chemical_name_common
'diiron(II) helicate of ditopic 2-imidazole-triazole ligand'
_chemical_name_systematic
'Iron(II) helicate of 1,3-bis(5-(1H-imidazol-2-yl)-4-isobutyl-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             2021-02-05
_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                84.573(2)
_cell_angle_beta                 81.247(2)
_cell_angle_gamma                89.600(2)
_cell_formula_units_Z            2
_cell_length_a                   14.5969(3)
_cell_length_b                   18.8022(3)
_cell_length_c                   19.7107(3)
_cell_measurement_reflns_used    23328
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2420
_cell_measurement_theta_min      3.8520
_cell_volume                     5322.56(16)
_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 0.999
_diffrn_measured_fraction_theta_max 0.976
_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   -116.00 -18.00   1.00    3.00    --  -42.04 -38.00 120.00   98
  2  \w   -105.00 -30.00   1.00    3.00    --  -42.04 -38.00  30.00   75
  3  \w    -60.00  30.00   1.00    3.00    --  -42.04  57.00 -90.00   90
  4  \w    -92.00  -4.00   1.00    3.00    --  -42.04 125.00 -60.00   88
  5  \w     38.00  83.00   1.00    3.00    --   42.04-125.00-180.00   45
  6  \w     34.00  62.00   1.00    6.00    --  112.00 -95.00 -90.00   28
  7  \w    120.00 177.00   1.00    6.00    --  112.00  30.00  60.00   57
  8  \w     97.00 138.00   1.00    6.00    --  112.00 -77.00   0.00   41
  9  \w     48.00  98.00   1.00    6.00    --  112.00-125.00-150.00   50
 10  \w     88.00 177.00   1.00    6.00    --  112.00  45.00 -30.00   89
 11  \w     87.00 119.00   1.00    6.00    --  112.00  30.00  30.00   32
 12  \w    122.00 170.00   1.00    6.00    --  112.00  30.00  30.00   48
 13  \w     45.00 103.00   1.00    6.00    --  112.00 -61.00 -60.00   58
 14  \w    112.00 141.00   1.00    6.00    --  112.00 -61.00 -60.00   29
 15  \w     86.00 117.00   1.00    6.00    --  112.00  30.00  60.00   31
 16  \w     40.00 118.00   1.00    6.00    --  112.00-125.00-180.00   78
 17  \w     40.00 107.00   1.00    6.00    --  112.00-125.00 -90.00   67
 18  \w    108.00 135.00   1.00    6.00    --  112.00 -30.00  30.00   27
 19  \w     87.00 118.00   1.00    6.00    --  112.00-125.00  30.00   31
 20  \w     49.00 100.00   1.00    6.00    --  112.00 -61.00-120.00   51
 21  \w     50.00  85.00   1.00    6.00    --  112.00-125.00 120.00   35
 22  \w     84.00 140.00   1.00    6.00    --  112.00  30.00 120.00   56
 23  \w     47.00  80.00   1.00    6.00    --  112.00-125.00-120.00   33
 24  \w     83.00 118.00   1.00    6.00    --  112.00-125.00-120.00   35
 25  \w     74.00 102.00   1.00    6.00    --  112.00-125.00 -60.00   28
 26  \w     56.00 118.00   1.00    6.00    --  112.00-125.00  90.00   62
 27  \w     45.00  70.00   1.00    6.00    --  112.00 -61.00   0.00   25
 28  \w    107.00 139.00   1.00    6.00    --  112.00 -61.00   0.00   32
 29  \w    105.00 170.00   1.00    6.00    --  112.00  30.00 -60.00   65
 30  \w     41.00  66.00   1.00    6.00    --  112.00-125.00 -60.00   25
 31  \w     44.00  69.00   1.00    6.00    --  112.00-125.00  30.00   25
 32  \w     67.00  93.00   1.00    6.00    --  112.00 -30.00  30.00   26
 33  \w     44.00  69.00   1.00    6.00    --  112.00-125.00 -30.00   25
 34  \w     85.00 117.00   1.00    6.00    --  112.00-125.00 -30.00   32
 35  \w     93.00 118.00   1.00    6.00    --  112.00-125.00 150.00   25
 36  \w    114.00 163.00   1.00    6.00    --  112.00 125.00 -30.00   49
 37  \w     44.00  86.00   1.00    6.00    --  112.00 -77.00   0.00   42
;
_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      0.0288474000
_diffrn_orient_matrix_UB_12      -0.0402509000
_diffrn_orient_matrix_UB_13      -0.0643480000
_diffrn_orient_matrix_UB_21      0.0901724000
_diffrn_orient_matrix_UB_22      -0.0235447000
_diffrn_orient_matrix_UB_23      0.0270432000
_diffrn_orient_matrix_UB_31      -0.0493993000
_diffrn_orient_matrix_UB_32      -0.0678223000
_diffrn_orient_matrix_UB_33      0.0379224000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            57200
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.333
_diffrn_reflns_theta_min         3.854
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.877
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62155
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.192
_exptl_crystal_description       block
_exptl_crystal_F_000             1972
_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          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.273
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1230
_refine_ls_number_reflns         22044
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0681
_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^)+(0.1197P)^2^+3.8481P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1921
_refine_ls_wR_factor_ref         0.1981
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19430
_reflns_number_total             22044
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss387
_cod_database_code               1563751
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         FeBHCHN
_chemical_oxdiff_usercomment     L952
_shelx_estimated_absorpt_t_max   0.870
_shelx_estimated_absorpt_t_min   0.762
_reflns_odcompleteness_completeness 99.94
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Same fragment restrains
{C5, C6, C7, C8} sigma for 1-2: 0.0005, 1-3: 0.04
as
{C65, C66, C67, C68}
{B1, F11, F12, F13, F14} sigma for 1-2: 0.0002, 1-3: 0.0004
as
{B4, F41, F42, F43, F44}
{B1, F11, F12, F13, F14} sigma for 1-2: 0.002, 1-3: 0.004
as
{B5, F51, F52, F53, F54}
3. Others
 Fixed Sof: B4(0.5) F41(0.5) F42(0.5) F43(0.5) F44(0.5) B5(0.5) F51(0.5)
 F52(0.5) F53(0.5) F54(0.5)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C18(H18), C30(H30A), C42(H42), C54(H54), C66(H66)
4.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)
4.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N10(H10), N12(H12), N19(H19), 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), C37(H37), C38(H38), C39(H39), C47(H47), C48(H48), C49(H49),
 C50(H50), C59(H59), C61(H61), C62(H62), C63(H63), C71(H71), C72(H72)
4.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), C67(H67A,H67B,H67C), C68(H68A,
 H68B,H68C), C102(H10A,H10B,H10C), C202(H20D,H20E,H20F)
;
_shelx_res_checksum              25847
_shelx_hkl_checksum              56504
_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 1.673
_oxdiff_exptl_absorpt_empirical_full_min 0.654
_platon_squeeze_void_probe_radius 1.20