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_1563757
_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 H78 Fe2 N24 O6, 4(B F4), 6(C2 H3 N)'
_chemical_formula_sum            'C84 H96 B4 F16 Fe2 N30 O6'
_chemical_formula_weight         2080.84
_chemical_name_common
'diiron(II) helicate of ditopic oxazole-triazole ligand'
_chemical_name_systematic
'Iron(II) helicate of 1,3-Bis(4-isobutyl-5-(oxazol-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             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                105.634(3)
_cell_angle_beta                 91.620(2)
_cell_angle_gamma                96.749(3)
_cell_formula_units_Z            2
_cell_length_a                   14.0743(3)
_cell_length_b                   15.1211(6)
_cell_length_c                   27.2280(8)
_cell_measurement_reflns_used    10269
_cell_measurement_temperature    100(5)
_cell_measurement_theta_max      75.4370
_cell_measurement_theta_min      4.1790
_cell_volume                     5530.7(3)
_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_temperature      100(5)
_diffrn_detector_area_resol_mean 10.3449
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.966
_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   -107.00 -14.00   1.00    1.50    --  -41.79 -57.00-150.00   93
  2  \w   -129.00 -34.00   1.00    1.50    --  -41.79 178.00 -30.00   95
  3  \w    -65.00  31.00   1.00    1.50    --  -41.79  57.00   0.00   96
  4  \w    -30.00  54.00   1.00    1.50    --   41.79 -38.00  90.00   84
  5  \w     96.00 121.00   1.00    1.50    --   41.79-178.00 -30.00   25
  6  \w     44.00 139.00   1.00    3.00    --  112.00 -61.00 120.00   95
  7  \w     94.00 126.00   1.00    3.00    --  112.00 -61.00 -30.00   32
  8  \w     46.00 130.00   1.00    3.00    --  112.00-141.00  17.98   84
  9  \w     37.00 140.00   1.00    3.00    --  112.00 -30.00 -30.00  103
 10  \w    131.00 177.00   1.00    3.00    --  112.00 125.00  30.00   46
 11  \w     51.00  95.00   1.00    3.00    --  112.00-125.00 150.00   44
 12  \w     47.00  74.00   1.00    3.00    --  112.00-125.00 -90.00   27
 13  \w     85.00 112.00   1.00    3.00    --  112.00-125.00 -90.00   27
 14  \w     43.00 110.00   1.00    3.00    --  112.00 -95.00  30.00   67
 15  \w     85.00 171.00   1.00    3.00    --  112.00  30.00 -60.00   86
 16  \w    143.00 170.00   1.00    3.00    --  112.00  61.00 -60.00   27
 17  \w     86.00 113.00   1.00    3.00    --  112.00  61.00 -60.00   27
 18  \w     94.00 143.00   1.00    3.00    --  112.00 125.00 120.00   49
 19  \w    145.00 172.00   1.00    3.00    --  112.00  30.00-120.00   27
 20  \w     56.00 115.00   1.00    3.00    --  112.00-125.00  30.00   59
 21  \w     84.00 163.00   1.00    3.00    --  112.00  30.00-150.00   79
 22  \w     60.00 101.00   1.00    3.00    --  112.00-125.00-120.00   41
 23  \w     86.00 125.00   1.00    3.00    --  112.00-135.00-172.87   39
 24  \w     86.00 113.00   1.00    3.00    --  112.00  45.00  30.00   27
 25  \w    148.00 173.00   1.00    3.00    --  112.00  45.00  30.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0839
_diffrn_reflns_av_unetI/netI     0.1072
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            45905
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.934
_diffrn_reflns_theta_min         3.496
_exptl_absorpt_coefficient_mu    2.848
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56551
_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 violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       block
_exptl_crystal_F_000             2148
_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          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.880
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1337
_refine_ls_number_reflns         22571
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.1339
_refine_ls_R_factor_gt           0.0916
_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^)+(0.0644P)^2^+14.9910P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2333
_refine_ls_wR_factor_ref         0.2546
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13069
_reflns_number_total             22571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss411
_cod_database_code               1563757
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.804
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 F41, F42, F43, F44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N601, C601, C602
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 F45, F46, F47, F48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Same fragment restrains
{C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as
{C56, C57, C58, C59}
4. Others
 Fixed Sof: H17A(0.5) H17B(0.5) H17C(0.5) H17D(0.5) C18(0.5) H18(0.5) C19(0.5)
 H19A(0.5) H19B(0.5) H19C(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C21(0.5)
 H21(0.5) C22(0.5) H22A(0.5) H22B(0.5) H22C(0.5) C23(0.5) H23A(0.5) H23B(0.5)
 H23C(0.5) F41(0.5) F42(0.5) F43(0.5) F44(0.5) F45(0.5) F46(0.5) F47(0.5)
 F48(0.5)
5.a Ternary CH refined with riding coordinates:
 C6(H6), C18(H18), C21(H21), C33(H33), C45(H45), C57(H57), C69(H69)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C17(H17A,H17B), C17(H17C,H17D), C32(H32A,H32B), C44(H44A,H44B),
 C56(H56A,H56B), C68(H68A,H68B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C11(H11), C12(H12), C13(H13), C15(H15), C26(H26), C27(H27),
 C28(H28), C29(H29), C38(H38), C39(H39), C40(H40), C42(H42), C50(H50), C51(H51),
  C52(H52), C53(H53), C62(H62), C63(H63), C64(H64), C66(H66), C74(H74), C75(H75)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C58(H58A,H58B,H58C), C59(H59A,
 H59B,H59C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C102(H10A,H10B,H10C),
 C202(H20D,H20E,H20F), C302(H30A,H30B,H30C), C402(H40A,H40B,H40C), C502(H50A,
 H50B,H50C), C602(H60A,H60B,H60C)
;
_shelx_res_checksum              29282
_shelx_hkl_checksum              46736
_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
;