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_1563753
_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), 4(C H3 N O2)'
_chemical_formula_sum            'C76 H90 B4 F16 Fe2 N28 O14'
_chemical_formula_weight         2078.69
_chemical_name_systematic        '[Fe2(L4OIm-meta)3](BF4)4'
_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             2021-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2021-06-17 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;
_cell_angle_alpha                93.702(3)
_cell_angle_beta                 101.308(3)
_cell_angle_gamma                93.154(3)
_cell_formula_units_Z            2
_cell_length_a                   12.9427(4)
_cell_length_b                   15.5781(6)
_cell_length_c                   26.0851(9)
_cell_measurement_reflns_used    14970
_cell_measurement_temperature    253.00(10)
_cell_measurement_theta_max      27.8460
_cell_measurement_theta_min      3.7760
_cell_volume                     5134.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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      253.00(10)
_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 0.847
_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     16.00  58.00   1.00   60.00    --   -9.35  38.00-120.00   42
  2  \w    -40.00  -4.00   1.00   60.00    --   -9.35  90.00 152.00   36
  3  \w    -20.00  27.00   1.00   60.00    --   -9.35 -90.00  38.00   47
  4  \w    -40.00  18.00   1.00   60.00    --   -9.35  77.00 -30.00   58
  5  \w    -31.00  51.00   1.00   60.00    --   -9.35  38.00-150.00   82
  6  \w    -80.00 -40.00   1.00   60.00    --   -9.35 -38.00-120.00   40
  7  \w    -31.00  -5.00   1.00   60.00    --   -9.35 -77.00 150.00   26
  8  \w    -15.00  25.00   1.00   60.00    --    9.98 -99.00  90.00   40
  9  \w    -10.00  16.00   1.00   60.00    --    9.98  38.00  30.00   26
;
_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      0.0176564000
_diffrn_orient_matrix_UB_12      0.0433417000
_diffrn_orient_matrix_UB_13      -0.0020059000
_diffrn_orient_matrix_UB_21      0.0333365000
_diffrn_orient_matrix_UB_22      0.0004957000
_diffrn_orient_matrix_UB_23      0.0251004000
_diffrn_orient_matrix_UB_31      0.0414176000
_diffrn_orient_matrix_UB_32      -0.0145974000
_diffrn_orient_matrix_UB_33      -0.0118105000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0573
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.847
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            57448
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.847
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.296
_diffrn_reflns_theta_min         3.294
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.380
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70863
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             2140
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Nitromethane'
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.012
_refine_diff_density_max         1.204
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1413
_refine_ls_number_reflns         23784
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.1189
_refine_ls_R_factor_gt           0.0871
_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^)+(0.1282P)^2^+11.1090P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2495
_refine_ls_wR_factor_ref         0.2745
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16561
_reflns_number_total             23784
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss711-253k
_cod_database_code               1563753
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHNBFFeO
_chemical_oxdiff_usercomment     M390
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.967
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_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. Same fragment restrains
{C18, C19, C20} sigma for 1-2: 0.02, 1-3: 0.04
as
{C31A, C31B, C32B}
{F11, F12, F13, F14, B1} sigma for 1-2: 0.02, 1-3: 0.04
as
{F31, F32, F33, F34, B3}
{O300, O301, N300, C300} sigma for 1-2: 0.02, 1-3: 0.04
as
{O500, O501, N500, C500}
3. Others
 Fixed Sof: C4AA(0.6) H4AA(0.6) H29A(0.6) H29B(0.6) H29C(0.4) H29D(0.4)
 C30A(0.6) H30A(0.6) C30B(0.4) H30B(0.4) C31A(0.6) H31A(0.6) H31B(0.6)
 H31C(0.6) C31B(0.4) H31D(0.4) H31E(0.4) H31F(0.4) C32B(0.4) H32A(0.4)
 H32B(0.4) H32C(0.4) C32A(0.6) H32D(0.6) H32E(0.6) H32F(0.6) H42A(0.7)
 H42B(0.7) H42C(0.3) H42D(0.3) H54A(0.7) H54B(0.7) H54C(0.3) H54D(0.3)
 C55A(0.4) H55A(0.4) C56A(0.6) H56A(0.6) H56B(0.6) H56C(0.6) C56B(0.4)
 H56D(0.4) H56E(0.4) H56F(0.4) C57A(0.6) H57A(0.6) H57B(0.6) H57C(0.6)
 C57B(0.4) H57D(0.4) H57E(0.4) H57F(0.4) F42(0.5) F43(0.5) F44(0.5) F45(0.5)
 F46(0.5) F47(0.5) O400(0.5) O401(0.5) N400(0.5) C400(0.5) H40A(0.5) H40B(0.5)
 H40C(0.5) O500(0.5) O501(0.5) N500(0.5) C500(0.5) H50A(0.5) H50B(0.5)
 H50C(0.5) C43A(0.7) H43A(0.7) C45A(0.7) H45A(0.7) H45B(0.7) H45C(0.7)
 C44A(0.7) H44A(0.7) H44B(0.7) H44C(0.7) C43B(0.3) H43B(0.3) C44B(0.3)
 H44D(0.3) H44E(0.3) H44F(0.3) C45B(0.3) H45D(0.3) H45E(0.3) H45F(0.3)
4.a Ternary CH refined with riding coordinates:
 C4AA(H4AA), C6(H6), C18(H18), C30A(H30A), C30B(H30B), C55A(H55A), C67(H67),
 C43A(H43A), C43B(H43B)
4.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C17(H17A,H17B), C29(H29A,H29B), C29(H29C,H29D), C42(H42A,H42B),
 C42(H42C,H42D), C54(H54A,H54B), C54(H54C,H54D), C66(H66A,H66B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C11(H11), C12(H12), C13(H13), C15(H15), C23(H23), C24(H24),
 C25(H25), C26(H26), C36(H36), C37(H37), C38(H38), C40(H40), C48(H48), C49(H49),
  C50(H50), C51(H51), C60(H60), C61(H61), C62(H62), C64(H64), C72(H72), C73(H73)
4.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C31A(H31A,H31B,H31C), C31B(H31D,H31E,H31F), C32B(H32A,H32B,H32C), C32A(H32D,
 H32E,H32F), C56A(H56A,H56B,H56C), C56B(H56D,H56E,H56F), C57A(H57A,H57B,H57C),
 C57B(H57D,H57E,H57F), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C100(H10A,H10B,
 H10C), C200(H20D,H20E,H20F), C300(H30C,H30D,H30E), C400(H40A,H40B,H40C),
 C500(H50A,H50B,H50C), C45A(H45A,H45B,H45C), C44A(H44A,H44B,H44C), C44B(H44D,
 H44E,H44F), C45B(H45D,H45E,H45F)
;
_shelx_res_checksum              59102
_shelx_hkl_checksum              9976
_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 1.464
_oxdiff_exptl_absorpt_empirical_full_min 0.717
_platon_squeeze_void_probe_radius 1.20