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_7714965
_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                111.734(7)
_cell_angle_beta                 93.802(7)
_cell_angle_gamma                106.978(6)
_cell_formula_units_Z            1
_cell_length_a                   11.1025(17)
_cell_length_b                   16.132(3)
_cell_length_c                   17.708(3)
_cell_measurement_reflns_used    9903
_cell_measurement_temperature    298
_cell_measurement_theta_max      59.71
_cell_measurement_theta_min      2.38
_cell_volume                     2762.9(8)
_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      298
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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  0.0776
_diffrn_reflns_av_unetI/netI     0.0551
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_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            48878
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        52.094
_diffrn_reflns_theta_max         52.094
_diffrn_reflns_theta_min         3.769
_diffrn_source_current           3.57
_diffrn_source_power             0.2497215
_diffrn_source_voltage           69.95
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.479
_exptl_absorpt_correction_T_max  0.7517
_exptl_absorpt_correction_T_min  0.4570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1423 before and 0.1090 after correction.
The Ratio of minimum to maximum transmission is 0.6080.
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    1.232
_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         0.549
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.072
_refine_ls_extinction_coef       0.0094(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     748
_refine_ls_number_reflns         9293
_refine_ls_number_restraints     265
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0688
_refine_ls_R_factor_gt           0.0615
_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^)+(0.1176P)^2^+1.1423P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1779
_refine_ls_wR_factor_ref         0.1850
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7929
_reflns_number_total             9293
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03208f2.cif
_cod_data_source_block           1-8CH3OH-298K
_cod_depositor_comments
'Adding full bibliography for 7714965--7714970.cif.'
_cod_original_cell_volume        2763.0(8)
_cod_database_code               7714965
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.701
_shelx_estimated_absorpt_t_min   0.642
_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
 Cl1-O4 \\sim Cl1-O2 \\sim Cl1-O3 \\sim Cl1-O1
 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. Rigid bond restraints
 N9, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Cl1A \\sim O1A \\sim O2A \\sim O3A \\sim O4A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Cl1 \\sim O1 \\sim O2 \\sim O3 \\sim O4: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C36) \\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.001
Uanis(C26) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.01
Uanis(C24) \\sim Ueq, Uanis(C25A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3A) \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(O1A)
\\sim Ueq, Uanis(Cl1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O1) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(O4) \\sim
Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O4A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 Cl1A, O1A, O2A, O3A, O4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, O1, O2, O3, O4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C24A)=Sof(H24A)=
 Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(C27A)=Sof(C26A)=Sof(H26A)=Sof(C25A)=
 Sof(H25A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=1-FVAR(1)
 Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=
 Sof(C28)=Sof(C29)=Sof(H29)=FVAR(1)
 Sof(Cl1A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=1-FVAR(2)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 B1(H1)
7.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C19(H19C,H19D), C30(H30A,H30B), C31(H31A,
 H31B), C37(H37A,H37B), C38(H38A,H38B)
7.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C15(H15), C16(H16), C32(H32), C33(H33), C34(H34), C35(H35),
  C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48),
 C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C29(H29),
 C21A(H21A), C24A(H24A), C23A(H23A), C26A(H26A), C25A(H25A), C28A(H28A),
 C29A(H29A)
7.d Fitted hexagon refined as free rotating group:
 C24A(C23A,C22A,C27A,C26A,C25A)
;
_shelx_res_checksum              65665
_shelx_fab_checksum              3028
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'