Mixed-valence {FeII2FeIII4} hexanuclear complexes with thermally induced Fe(III) spin crossover behavior
Jia, Shuwen; Fan, Lingyue; Zheng, Chun-Yang; Jin, Sai; Li, Dongfeng; Dalton Transactions  (2022) –; doi:10.1039/D2DT02041F

data_7710870
_publ_section_title
;
 Mixed-valence {FeII2FeIII4} hexanuclear complexes with thermally induced
 Fe(III) spin crossover behavior
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02041F
_journal_year                    2022
_chemical_formula_moiety
'C104 H110 B2 Fe6 N34 O2, 2(Cl0.926 O4), 4(Cl O4)'
_chemical_formula_sum            'C100 H106 B2 Cl5.84 Fe6 N38 O26'
_chemical_formula_weight         2819.97
_chemical_name_systematic        1-298K
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-09-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-07 deposited with the CCDC.	2022-07-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.334(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.421(5)
_cell_length_b                   22.267(4)
_cell_length_c                   24.753(5)
_cell_measurement_reflns_used    9965
_cell_measurement_temperature    298
_cell_measurement_theta_max      27.4950
_cell_measurement_theta_min      2.1814
_cell_volume                     13926(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            72480
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.609
_diffrn_reflns_theta_min         1.423
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.796
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             5781
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.991
_refine_diff_density_min         -0.919
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     807
_refine_ls_number_reflns         21208
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1083
_refine_ls_R_factor_gt           0.0630
_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^)+(0.1097P)^2^+14.3972P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1770
_refine_ls_wR_factor_ref         0.2104
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12737
_reflns_number_total             21208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02041f2.cif
_cod_data_source_block           mo_150508b_0m_sq
_cod_original_cell_volume        13926(4)
_cod_database_code               7710870
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.796
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-O8 = Cl2-O6 = Cl2-O7 = Cl2-O9 = Cl1-O2 = Cl1-O3 = Cl1-O5 = Cl1-O4 = Cl3-
 O10 = Cl3-O13 = Cl3-O11 = Cl3-O12
 1.44 with sigma of 0.01
 O6-O8 = O6-O7 = O6-O9 = O8-O7 = O8-O9 = O7-O9
 2.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 B1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C39(H39A,H39B), C40(H40A,H40B), C46(H46A,H46B), C22(H22A,
 H22B), C16(H16A,H16B)
4.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C8(H8), C4(H4), C6(H6), C12(H12), C10(H10), C27(H27), C33(H33),
 C45(H45), C34(H34), C51(H51), C18(H18), C21(H21), C26(H26), C50(H50), C30(H30),
  C37(H37), C20(H20), C35(H35), C48(H48), C32(H32), C19(H19), C31(H31),
 C49(H49), C42(H42), C36(H36), C24(H24), C44(H44), C43(H43), C25(H25)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C7(H7A,H7B,H7C), C11(H11A,H11B,H11C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              5235
_shelx_fab_checksum              78354
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'