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_1563758
_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 N30 Ni2, 4(B F4), 4(C2 H3 N)'
_chemical_formula_sum            'C80 H96 B4 F16 N34 Ni2'
_chemical_formula_weight         1998.56
_chemical_name_common
'dinickel(II) helicate of ditopic 4-imidazole-triazole ligand'
_chemical_name_systematic
'nickel(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           73
_space_group_name_Hall           '-I 2b 2c'
_space_group_name_H-M_alt        'I b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-08-05
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.9782(4)
_cell_length_b                   29.8827(5)
_cell_length_c                   37.7594(8)
_cell_measurement_reflns_used    15262
_cell_measurement_temperature    100.02(13)
_cell_measurement_theta_max      76.3540
_cell_measurement_theta_min      3.7500
_cell_volume                     22542.5(8)
_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      100.02(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1725
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.974
_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    -80.00  37.00   1.00    4.00    --  -41.54  19.00 -60.00  117
  2  \w     58.00  89.00   1.00    4.00    --   41.54 178.00 120.00   31
  3  \w    102.00 127.00   1.00    4.00    --   41.54 178.00 120.00   25
  4  \w    112.00 152.00   1.00   12.00    --  112.00  45.00  90.00   40
  5  \w     86.00 164.00   1.00   12.00    --  112.00  45.00 -60.00   78
  6  \w     46.00 103.00   1.00   12.00    --  112.00-125.00  90.00   57
  7  \w     80.00 174.00   1.00   12.00    --  112.00  77.00 150.00   94
  8  \w     90.00 118.00   1.00   12.00    --  112.00  30.00 -90.00   28
;
_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      0.0193536000
_diffrn_orient_matrix_UB_12      -0.0230092000
_diffrn_orient_matrix_UB_13      0.0350359000
_diffrn_orient_matrix_UB_21      -0.0593054000
_diffrn_orient_matrix_UB_22      -0.0325384000
_diffrn_orient_matrix_UB_23      -0.0041758000
_diffrn_orient_matrix_UB_31      0.0453248000
_diffrn_orient_matrix_UB_32      -0.0327013000
_diffrn_orient_matrix_UB_33      -0.0204878000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0230
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            30243
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.611
_diffrn_reflns_theta_min         3.544
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.093
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44709
_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 light pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.178
_exptl_crystal_description       block
_exptl_crystal_F_000             8272
_exptl_crystal_preparation       'ligand field strength, UV-Visible spectra'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: MeCN by diethylether ether vapour diffusion'
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.009
_exptl_crystal_size_min          0.008
_refine_diff_density_max         0.978
_refine_diff_density_min         -0.641
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     623
_refine_ls_number_reflns         11551
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0772
_refine_ls_R_factor_gt           0.0679
_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^)+(0.1336P)^2^+12.8326P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2062
_refine_ls_wR_factor_ref         0.2175
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9372
_reflns_number_total             11551
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss566
_cod_database_code               1563758
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         NHCBFNi
_chemical_oxdiff_usercomment     M188
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.989
_reflns_odcompleteness_completeness 99.66
_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.a Ternary CH refined with riding coordinates:
 C6(H6), C18(H18), C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5a,H5b), C17(H17a,H17b), C29(H29a,H29b)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N10(H10), N12(H12), C1(H1), C2(H2a), C11(H11), C12(H12a), C13(H13),
 C15(H15), C23(H23), C24(H24), C25(H25), C26(H26), C35(H35), C36(H36), C37(H37)
2.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), C102(H10a,H10b,H10c), C202(H20d,H20e,
 H20f)
;
_shelx_res_checksum              26197
_shelx_hkl_checksum              14354
_platon_squeeze_void_probe_radius 1.20
_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 2.109
_oxdiff_exptl_absorpt_empirical_full_min 0.469