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_7710871
_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
'C104 H110 B2 Fe6 N34 O2, 4(Cl O4), 2(Cl0.579 O2.159), 2(Cl0.421 O1.841)'
_chemical_formula_sum            'C104 H110 B2 Cl6 Fe6 N34 O26'
_chemical_formula_weight         2821.67
_chemical_name_systematic        1-150K
_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             2021-07-08
_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                 96.654(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.019(3)
_cell_length_b                   22.076(3)
_cell_length_c                   24.338(3)
_cell_measurement_reflns_used    9902
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.26
_cell_measurement_theta_min      2.16
_cell_volume                     13352(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      150
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_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  0.0557
_diffrn_reflns_av_unetI/netI     0.0577
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            57305
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.916
_diffrn_reflns_theta_min         1.439
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.833
_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    1.404
_exptl_crystal_description       block
_exptl_crystal_F_000             5792
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.153
_refine_diff_density_min         -0.708
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         15884
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0828
_refine_ls_R_factor_gt           0.0544
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0897P)^2^+19.5719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1471
_refine_ls_wR_factor_ref         0.1692
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11145
_reflns_number_total             15884
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02041f2.cif
_cod_data_source_block           181116d-1_sq
_cod_database_code               7710871
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.851
_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
 Cl1-O2
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl1 \\sim O2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(O5A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Cl1, O2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl1A)=Sof(O5A)=Sof(O3)=Sof(O2A)=Sof(O4A)=1-FVAR(1)
 Sof(Cl1)=Sof(O2)=Sof(O4)=Sof(O5)=Sof(O3A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 B028(H028)
6.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C39(H39A,H39B), C40(H40A,H40B), C22(H22A,H22B), C46(H46A,
 H46B), C16(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C14(H14), C10(H10), C6(H6), C8(H8), C33(H33), C12(H12), C27(H27),
 C45(H45), C21(H21), C34(H34), C42(H42), C32(H32), C18(H18), C20(H20), C44(H44),
  C26(H26), C30(H30), C51(H51), C35(H35), C37(H37), C43(H43), C19(H19),
 C31(H31), C24(H24), C50(H50), C36(H36), C48(H48), C25(H25), C49(H49)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              62971
_shelx_fab_checksum              73842
_platon_squeeze_special_details
;
A solvent mask was calculated and 540 electrons were 
found in a volume of 1688\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
7.5[CH3OH] per Asymmetric Unit 
which account for 540 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'