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_7710873
_publ_section_title
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 Mixed-valence {FeII2FeIII4} hexanuclear complexes with thermally induced
 Fe(III) spin crossover behavior
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_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02041F
_journal_year                    2022
_chemical_formula_moiety         'C102 H106 B2 Fe6 N34 O2, 6(Cl O4)'
_chemical_formula_sum            'C102 H106 B2 Cl6 Fe6 N34 O26'
_chemical_formula_weight         2793.62
_chemical_name_systematic        3-100K
_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             2021-12-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
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2021-12-07 deposited with the CCDC.	2022-07-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.145(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.824(3)
_cell_length_b                   21.984(3)
_cell_length_c                   23.864(3)
_cell_measurement_reflns_used    9874
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      29.39
_cell_measurement_theta_min      2.48
_cell_volume                     12922(3)
_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)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0501
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            43829
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.451
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.860
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'metallic light black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       block
_exptl_crystal_F_000             5728
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.571
_refine_diff_density_min         -1.253
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     796
_refine_ls_number_reflns         11351
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0947
_refine_ls_R_factor_gt           0.0710
_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^)+(0.0868P)^2^+132.9609P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1854
_refine_ls_wR_factor_ref         0.2085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8756
_reflns_number_total             11351
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02041f2.cif
_cod_data_source_block           mo_150418g_0m_sq
_cod_database_code               7710873
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.847
_shelx_estimated_absorpt_t_min   0.783
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O6) \\sim Ueq, Uanis(O12) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 B1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C22(H22A,H22B), C16(H16A,H16B), C40(H40A,H40B), C39(H39A,
 H39B), C51(H51A,H51B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C12(H12), C14(H14), C8(H8), C10(H10), C33(H33), C32(H32),
 C31(H31), C30(H30), C24(H24), C25(H25), C26(H26), C27(H27), C18(H18), C19(H19),
  C20(H20), C21(H21), C45(H45), C44(H44), C43(H43), C42(H42), C37(H37),
 C36(H36), C35(H35), C34(H34), C47(H47), C48(H48), C49(H49), C50(H50)
3.d Tetrahedral OH refined with riding coordinates:
 O1(H1A)
3.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              84501
_shelx_fab_checksum              17524
_platon_squeeze_special_details
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A solvent mask was calculated and 276 electrons were 
found in a volume of 1504\%A^3^ in 5 voids per unit cell. 
This is consistent with the presence of 
2.0[CH3CH2OH], 1.75[], 1[], 0.25[], 1[CH3OH] per Asymmetric Unit 
which account for 280 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'