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_1563752
_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
'2(C72 H78 Fe2 N24 O6), 8(B F4), 11(C H3 N O2)'
_chemical_formula_sum            'C155 H189 B8 F32 Fe4 N59 O34'
_chemical_formula_weight         4340.52
_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             2021-06-16
_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                92.820(2)
_cell_angle_beta                 101.815(2)
_cell_angle_gamma                93.092(2)
_cell_formula_units_Z            1
_cell_length_a                   12.7611(3)
_cell_length_b                   15.2423(5)
_cell_length_c                   25.9116(7)
_cell_measurement_reflns_used    18125
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.8640
_cell_measurement_theta_min      3.6920
_cell_volume                     4916.7(2)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1725
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.848
_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    -15.00  14.00   1.00   27.50    --   -9.35 -99.00   0.00   29
  2  \w    -23.00   4.00   1.00   27.50    --   -9.35  38.00  30.00   27
  3  \w    -30.00  19.00   1.00   27.50    --   -9.35  77.00 -30.00   49
  4  \w    -11.00  20.00   1.00   27.50    --   -9.35  77.00  30.00   31
  5  \w    -41.00  12.00   1.00   27.50    --   -9.35 -77.00 150.00   53
  6  \w    -41.00  20.00   1.00   27.50    --   -9.35  77.00 -90.00   61
  7  \w      4.00  30.00   1.00   27.50    --   -9.35  38.00-120.00   26
  8  \w    -63.00  33.00   1.00   27.50    --    9.98 -38.00  60.00   96
  9  \w    -53.00   3.00   1.00   27.50    --    9.98 -38.00 150.00   56
;
_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      0.0172718000
_diffrn_orient_matrix_UB_12      0.0437001000
_diffrn_orient_matrix_UB_13      -0.0039786000
_diffrn_orient_matrix_UB_21      0.0341731000
_diffrn_orient_matrix_UB_22      0.0029372000
_diffrn_orient_matrix_UB_23      0.0254102000
_diffrn_orient_matrix_UB_31      0.0421004000
_diffrn_orient_matrix_UB_32      -0.0161793000
_diffrn_orient_matrix_UB_33      -0.0111171000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.848
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            59625
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.848
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.464
_diffrn_reflns_theta_min         3.231
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.403
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87861
_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    1.466
_exptl_crystal_description       block
_exptl_crystal_F_000             2236
_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         1.285
_refine_diff_density_min         -0.656
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1434
_refine_ls_number_reflns         23153
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0892
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0557P)^2^+11.6123P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1520
_refine_ls_wR_factor_ref         0.1701
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17379
_reflns_number_total             23153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01458g2.cif
_cod_data_source_block           ss711-nome
_cod_database_code               1563752
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHNBFFeO
_chemical_oxdiff_usercomment     M389
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.965
_reflns_odcompleteness_completeness 99.76
_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. Rigid body (RIGU) restrains
 O600, O601, N600, C600, H60A, H60B, H60C
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
3. Others
 Fixed Sof: H29A(0.7) H29B(0.7) H29C(0.3) H29D(0.3) C30A(0.7) H30A(0.7)
 C30B(0.3) H30B(0.3) C31A(0.7) H31A(0.7) H31B(0.7) H31C(0.7) C31B(0.3)
 H31D(0.3) H31E(0.3) H31F(0.3) C32A(0.7) H32A(0.7) H32B(0.7) H32C(0.7)
 C32B(0.3) H32D(0.3) H32E(0.3) H32F(0.3) F22(0.8) F23(0.8) F24(0.8) F25(0.2)
 F26(0.2) F27(0.2) F44(0.5) F42(0.5) F43(0.5) F47(0.5) F45(0.5) F46(0.5)
 O600(0.5) O601(0.5) N600(0.5) C600(0.5) H60A(0.5) H60B(0.5) H60C(0.5)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C18(H18), C30A(H30A), C30B(H30B), C42(H42), C54(H54), C66(H66)
4.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C17(H17A,H17B), C29(H29A,H29B), C29(H29C,H29D), C41(H41A,H41B),
 C53(H53A,H53B), C65(H65A,H65B)
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), C35(H35), C36(H36), C37(H37), C39(H39), C47(H47), C48(H48),
  C49(H49), C50(H50), C59(H59), C60(H60), C61(H61), 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),
 C31A(H31A,H31B,H31C), C31B(H31D,H31E,H31F), C32A(H32A,H32B,H32C), C32B(H32D,
 H32E,H32F), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C55(H55A,H55B,H55C),
 C56(H56A,H56B,H56C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C100(H10A,H10B,
 H10C), C200(H20D,H20E,H20F), C300(H30C,H30D,H30E), C400(H40A,H40B,H40C),
 C500(H50A,H50B,H50C), C600(H60A,H60B,H60C)
;
_shelx_res_checksum              79456
_shelx_hkl_checksum              75482
_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 1.322
_oxdiff_exptl_absorpt_empirical_full_min 0.629