Electron transfer coupled spin transition in cyano-bridged mixed-valence {FeIII2FeII2} molecular squares.
Jia, Shuwen; Shang, Mengjia; Jin, Sai; Zhu, Xinrui; Cai, Yuanyuan; Li, Dongfeng; Dalton transactions (Cambridge, England : 2003) 53 (2024) 2807–2814; doi:10.1039/d3dt03208f

data_7714967
_publ_section_title
;
 Electron transfer coupled spin transition in cyano-bridged mixed-valence
 {FeIII2FeII2} molecular squares.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2807
_journal_page_last               2814
_journal_paper_doi               10.1039/d3dt03208f
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C96 H88 B2 Fe4 N26, 2(Cl O4)'
_chemical_formula_sum            'C96 H88 B2 Cl2 Fe4 N26 O8'
_chemical_formula_weight         2049.84
_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
_audit_creation_date             2023-12-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-12-28 deposited with the CCDC.	2024-01-09 downloaded from the CCDC.
;
_cell_angle_alpha                110.445(4)
_cell_angle_beta                 93.745(5)
_cell_angle_gamma                108.936(4)
_cell_formula_units_Z            1
_cell_length_a                   10.998(3)
_cell_length_b                   15.766(5)
_cell_length_c                   16.541(5)
_cell_measurement_reflns_used    3489
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.87
_cell_measurement_theta_min      2.36
_cell_volume                     2489.8(13)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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  0.0465
_diffrn_reflns_av_unetI/netI     0.0769
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16395
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        24.405
_diffrn_reflns_theta_max         24.405
_diffrn_reflns_theta_min         1.341
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.693
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5861
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             1058
_refine_diff_density_max         1.236
_refine_diff_density_min         -0.607
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     768
_refine_ls_number_reflns         8090
_refine_ls_number_restraints     421
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1257
_refine_ls_R_factor_gt           0.0886
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1408P)^2^+8.5232P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2406
_refine_ls_wR_factor_ref         0.2725
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5320
_reflns_number_total             8090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03208f2.cif
_cod_data_source_block           1-100K
_cod_depositor_comments
'Adding full bibliography for 7714965--7714970.cif.'
_cod_original_cell_volume        2489.8(12)
_cod_database_code               7714967
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   56.98
_shelx_estimated_absorpt_t_min   2.40
_olex2_refinement_description
;
1. Restrained distances
 Cl1A-O1A = Cl1A-O2A = Cl1A-O4A = Cl1A-O3A
 1.44 with sigma of 0.01
 O1-O2 = O1-O3 = O1-O4 = O2-O3 = O2-O4 = O3-O4
 2.35 with sigma of 0.02
 O1A-O2A = O1A-O3A = O1A-O4A = O2A-O3A = O2A-O4A = O3A-O4A
 2.35 with sigma of 0.02
 Cl1-O4 = Cl1-O1 = Cl1-O2 = Cl1-O3 = Cl1A-O1A = Cl1A-O2A = Cl1A-O4A = Cl1A-O3A
 1.44 with sigma of 0.01
 N8-C19 \\sim N8-C19A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C29-C23 \\sim C29A-C23A
 with sigma of 0.04
 C28-C26 \\sim C28A-C26A
 with sigma of 0.04
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 C29-C28 \\sim C29A-C28A
 with sigma of 0.02
 C20-C29 \\sim C20A-C29A
 with sigma of 0.02
 C28-C23 \\sim C28A-C23A
 with sigma of 0.02
 C28-C22 \\sim C28A-C22A
 with sigma of 0.04
 C27-C23 \\sim C27A-C23A
 with sigma of 0.04
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 C24-C22 \\sim C24A-C22A
 with sigma of 0.04
 C26-C25 \\sim C26A-C25A
 with sigma of 0.02
 C25-C24 \\sim C25A-C24A
 with sigma of 0.02
 C24-C23 \\sim C24A-C23A
 with sigma of 0.02
 C28-C27 \\sim C28A-C27A
 with sigma of 0.02
 C29-C21 \\sim C29A-C21A
 with sigma of 0.04
 C23-C22 \\sim C23A-C22A
 with sigma of 0.02
 C28-C24 \\sim C28A-C24A
 with sigma of 0.04
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C27-C25 \\sim C27A-C25A
 with sigma of 0.04
 C26-C24 \\sim C26A-C24A
 with sigma of 0.04
 C25-C23 \\sim C25A-C23A
 with sigma of 0.04
 N8-C20 \\sim N8-C20A
 with sigma of 0.04
 C19-C29 \\sim C19A-C29A
 with sigma of 0.04
 C19-C21 \\sim C19A-C21A
 with sigma of 0.04
 C23-C21 \\sim C23A-C21A
 with sigma of 0.04
 C20-C28 \\sim C20A-C28A
 with sigma of 0.04
 C20-C22 \\sim C20A-C22A
 with sigma of 0.04
 C29-C27 \\sim C29A-C27A
 with sigma of 0.04
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C20A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C22A) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq,
Uanis(C24A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C27A) \\sim Ueq,
Uanis(C25A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O3) \\sim Ueq, Uanis(O2A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O4) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O2) \\sim
Ueq, Uanis(O4) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Others
 Sof(Cl1A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=1-FVAR(1)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(1)
 Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(C29A)=Sof(H29A)=Sof(C28A)=
 Sof(C27A)=Sof(H27A)=Sof(C26A)=Sof(H26A)=Sof(C25A)=Sof(H25A)=Sof(C24A)=
 Sof(H24A)=Sof(C23A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=1-FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(C29)=Sof(H29)=Sof(C28)=Sof(C27)=
 Sof(H27)=Sof(C26)=Sof(H26)=Sof(C25)=Sof(H25)=Sof(C24)=Sof(H24)=Sof(C23)=
 Sof(C22)=Sof(H22)=Sof(C21)=Sof(H21)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 B1(H1)
5.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C30(H30A,H30B), C31(H31A,H31B), C38(H38A,H38B), C37(H37A,
 H37B), C19(H19A,H19B), C19A(H19C,H19D)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C15(H15), C16(H16), C40(H40), C41(H41), C43(H43), C44(H44),
  C45(H45), C46(H46), C48(H48), C35(H35), C34(H34), C33(H33), C32(H32),
 C29(H29), C27(H27), C26(H26), C25(H25), C24(H24), C22(H22), C21(H21),
 C29A(H29A), C27A(H27A), C26A(H26A), C25A(H25A), C24A(H24A), C22A(H22A),
 C21A(H21A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 17 electrons were 
found in a volume of 263\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[CH3OH] per Asymmetric Unit 
which account for 18 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6115
_shelx_fab_checksum              26949
_olex2_submission_special_instructions 'No special instructions were received'