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_7714968
_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                111.488(5)
_cell_angle_beta                 93.295(5)
_cell_angle_gamma                106.620(4)
_cell_formula_units_Z            1
_cell_length_a                   10.9642(12)
_cell_length_b                   15.8155(19)
_cell_length_c                   17.507(2)
_cell_measurement_reflns_used    9961
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      56.98
_cell_measurement_theta_min      2.40
_cell_volume                     2661.6(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0588
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            45600
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        51.244
_diffrn_reflns_theta_max         51.244
_diffrn_reflns_theta_min         2.400
_diffrn_source_current           3.57
_diffrn_source_power             0.2497215
_diffrn_source_voltage           69.95
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.611
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.4462
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1632 before and 0.0732 after correction.
The Ratio of minimum to maximum transmission is 0.5940.
The \l/2 correction factor is Not present.
;
_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    1.279
_exptl_crystal_description       block
_exptl_crystal_F_000             1058
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.590
_refine_diff_density_min         -0.517
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         8737
_refine_ls_number_restraints     128
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0589P)^2^+1.2406P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1041
_refine_ls_wR_factor_ref         0.1074
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7559
_reflns_number_total             8737
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03208f2.cif
_cod_data_source_block           1-8CH3OH-100K
_cod_depositor_comments
'Adding full bibliography for 7714965--7714970.cif.'
_cod_database_code               7714968
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.692
_shelx_estimated_absorpt_t_min   0.632
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 Cl1A-O1A = Cl1A-O4A = Cl1A-O2A = Cl1A-O3A
 1.5 with sigma of 0.02
 Cl1-O4 = Cl1-O2 = Cl1-O3 = Cl1-O1
 1.5 with sigma of 0.02
 O1A-O2A \\sim O4A-O3A \\sim O1A-O3A \\sim O4A-O2A \\sim O1A-O4A \\sim O2A-O3A
 with sigma of 0.04
 Cl1A-O1A \\sim Cl1A-O4A \\sim Cl1A-O2A \\sim Cl1A-O3A
 with sigma of 0.02
 O4-O3 \\sim O2-O1 \\sim O4-O1 \\sim O2-O3 \\sim O4-O2 \\sim O3-O1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O4A) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C26) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C23A) \\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C28A) \\sim Ueq,
Uanis(C29A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24A) \\sim Ueq, Uanis(C28A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl1A) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(O3A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28A) \\sim Ueq, Uanis(C23A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C26A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H19C)=Sof(H19D)=Sof(C22A)=Sof(H22A)=Sof(C27A)=Sof(H27A)=Sof(C24A)=
 Sof(H24A)=Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(C23A)=Sof(C25A)=Sof(H25A)=
 Sof(C26A)=Sof(H26A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=1-FVAR(1)
 Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(C27)=Sof(C22)=Sof(C29)=Sof(H29)=Sof(C21)=
 Sof(H21)=Sof(C28)=Sof(H28)=Sof(C26)=Sof(H26)=Sof(C25)=Sof(H25)=Sof(C24)=
 Sof(H24)=Sof(C23)=Sof(H23)=FVAR(1)
 Sof(O4A)=Sof(Cl1A)=Sof(O3A)=Sof(O2A)=Sof(O1A)=1-FVAR(2)
 Sof(Cl1)=Sof(O2)=Sof(O4)=Sof(O3)=Sof(O1)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 B1(H1)
5.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C19(H19A,H19B), C19(H19C,H19D), C18(H18A,
 H18B), C38(H38A,H38B), C37(H37A,H37B)
5.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C5(H5), C7(H7), C48(H48), C32(H32), C40(H40), C43(H43),
 C4(H4), C41(H41), C33(H33), C35(H35), C16(H16), C6(H6), C34(H34), C15(H15),
 C44(H44), C46(H46), C8(H8), C45(H45), C10(H10), C12(H12), C9(H9), C29(H29),
 C21(H21), C11(H11), C28(H28), C26(H26), C25(H25), C24(H24), C23(H23),
 C22A(H22A), C27A(H27A), C24A(H24A), C29A(H29A), C25A(H25A), C26A(H26A),
 C21A(H21A)
;
_shelx_res_checksum              83176
_shelx_fab_checksum              90387
_platon_squeeze_special_details
;
A solvent mask was calculated and 131 electrons were 
found in a volume of 538\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
8[CH3OH], 2[] per Formula Unit 
which account for 144 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'