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_1563756
_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, 2(B F4), C2 H3 N'
_chemical_formula_sum            'C74 H87 B2 F8 N31 Ni2'
_chemical_formula_weight         1701.78
_chemical_name_common
'dinickel(II) helicate of ditopic 2-imidazole-triazole ligand'
_chemical_name_systematic
'nickel(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      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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                 96.353(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3289(4)
_cell_length_b                   22.2707(6)
_cell_length_c                   35.2655(11)
_cell_measurement_reflns_used    13232
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.3240
_cell_measurement_theta_min      3.6180
_cell_volume                     11184.6(6)
_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    'SIR2004 (Burla et al., 2007)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.978
_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   -100.00 -64.00   1.00    2.50    --  -41.54 -57.00 150.00   36
  2  \w   -114.00 -21.00   1.00    2.50    --  -41.54 -57.00-120.00   93
  3  \w   -129.00 -41.00   1.00    2.50    --  -41.54 178.00 -30.00   88
  4  \w    107.00 172.00   1.00    7.50    --  112.00 125.00 -30.00   65
  5  \w    150.00 177.00   1.00    7.50    --  112.00  61.00 -60.00   27
  6  \w     93.00 164.00   1.00    7.50    --  112.00  45.00  30.00   71
  7  \w     59.00 110.00   1.00    7.50    --  112.00 -95.00 -90.00   51
  8  \w     80.00 105.00   1.00    7.50    --  112.00 -95.00   0.00   25
  9  \w     31.00  58.00   1.00    7.50    --  112.00 -95.00   0.00   27
 10  \w     83.00 122.00   1.00    7.50    --  112.00  61.00 -60.00   39
 11  \w     61.00 139.00   1.00    7.50    --  112.00 -61.00 -90.00   78
 12  \w     85.00 112.00   1.00    7.50    --  112.00  61.00-120.00   27
 13  \w    138.00 166.00   1.00    7.50    --  112.00  61.00-120.00   28
 14  \w     41.00 100.00   1.00    7.50    --  112.00-125.00 120.00   59
 15  \w     73.00 178.00   1.00    7.50    --  112.00  15.00 -30.00  105
;
_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      -0.0621793000
_diffrn_orient_matrix_UB_12      0.0438042000
_diffrn_orient_matrix_UB_13      -0.0254246000
_diffrn_orient_matrix_UB_21      -0.0266732000
_diffrn_orient_matrix_UB_22      -0.0510819000
_diffrn_orient_matrix_UB_23      -0.0286548000
_diffrn_orient_matrix_UB_31      -0.0843617000
_diffrn_orient_matrix_UB_32      -0.0160697000
_diffrn_orient_matrix_UB_33      0.0215696000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0558
_diffrn_reflns_av_unetI/netI     0.0671
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            54658
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.665
_diffrn_reflns_theta_min         3.684
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.918
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65548
_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 violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.011
_exptl_crystal_description       plate
_exptl_crystal_F_000             3544
_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          0.04
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.005
_refine_diff_density_max         1.498
_refine_diff_density_min         -1.066
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1096
_refine_ls_number_reflns         23003
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.1472
_refine_ls_R_factor_gt           0.1241
_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^)+(0.1487P)^2^+47.8572P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3255
_refine_ls_wR_factor_ref         0.3406
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16314
_reflns_number_total             23003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss549-3-nh
_cod_database_code               1563756
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         NiCHNBF
_chemical_oxdiff_usercomment     M155
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.964
_reflns_odcompleteness_completeness 99.86
_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
2. Rigid body (RIGU) restrains
 C69, C70, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: H65a(0.7) H65b(0.7) H65c(0.3) H65d(0.3) C66(0.7) H66(0.7) C67(0.7)
 H67a(0.7) H67b(0.7) H67c(0.7) C68(0.7) H68a(0.7) H68b(0.7) H68c(0.7) C69(0.3)
 H69(0.3) C70(0.3) H70a(0.3) H70b(0.3) H70c(0.3) C71(0.3) H71a(0.3) H71b(0.3)
 H71c(0.3)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C18(H18), C30(H30a), C42(H42), C54(H54), C66(H66), C69(H69)
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), C65(H65c,H65d)
4.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), C12(H12a), C13(H13), 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), C74(H74), C75(H75)
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), C70(H70a,H70b,H70c), C71(H71a,H71b,H71c), C102(H10a,H10b,H10c)
;
_shelx_res_checksum              73163
_shelx_hkl_checksum              70164
_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 2.309
_oxdiff_exptl_absorpt_empirical_full_min 0.531