Four-step electron transfer coupled spin transition in a cyano-bridged [Fe2Co2] square complex
Ikeda, Taisuke; Huang, Yu-Bo; Wu, Shu-Qi; Zheng, Wenwei; Xu, Wen-Huang; Zhang, Xiaopeng; Ji, Tianchi; Uematsu, Mikoto; Kanegawa, Shinji; Su, Sheng-Qun; Sato, Osamu; Dalton Transactions 53 (2024) 15465–15470; doi:10.1039/D4DT01581A

data_7716933
_publ_section_title
;
 Four-step electron transfer coupled spin transition in a cyano-bridged
 [Fe2Co2] square complex
;
_journal_issue                   37
_journal_name_full               'Dalton Transactions'
_journal_page_first              15465
_journal_page_last               15470
_journal_paper_doi               10.1039/D4DT01581A
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'C42 H44 B Co Fe N13, Cl O4, 17.495(C0.457 H1.372 O0.229)'
_chemical_formula_sum            'C50 H68 B Cl Co Fe N13 O8'
_chemical_formula_weight         1140.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-26
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-26 deposited with the CCDC.	2024-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.168(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5955(4)
_cell_length_b                   14.0531(3)
_cell_length_c                   23.5734(6)
_cell_measurement_reflns_used    28139
_cell_measurement_temperature    100.04(10)
_cell_measurement_theta_max      30.9970
_cell_measurement_theta_min      2.4700
_cell_volume                     5442.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.04(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.844
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -68.00 -17.00   0.50    1.08    --  -14.67 129.00 -49.00  102
  2  \w     21.00  65.00   0.50    1.08    --  -14.67  19.00-150.00   88
  3  \w     21.00  67.00   0.50    1.08    --  -14.67  19.00   0.00   92
  4  \w     21.00  49.00   0.50    1.08    --  -14.67  19.00 120.00   56
  5  \w    -55.00   8.00   0.50    1.08    --  -14.67 -57.00   0.00  126
  6  \w    -65.00  21.00   0.50    1.08    --   15.76 -38.00 -60.00  172
  7  \w     21.00  71.00   0.50    1.08    --   15.76-129.00-123.00  100
  8  \w    -20.00   5.00   0.50    1.08    --   15.76  91.00 -30.57   50
  9  \w    -22.00   3.00   0.50    1.08    --   15.76  95.00 -32.95   50
 10  \w    -22.00   4.00   0.50    1.08    --   15.76  97.00 154.75   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0384578000
_diffrn_orient_matrix_UB_12      -0.0031444000
_diffrn_orient_matrix_UB_13      -0.0096660000
_diffrn_orient_matrix_UB_21      0.0015207000
_diffrn_orient_matrix_UB_22      0.0503284000
_diffrn_orient_matrix_UB_23      -0.0018864000
_diffrn_orient_matrix_UB_31      0.0195363000
_diffrn_orient_matrix_UB_32      0.0022215000
_diffrn_orient_matrix_UB_33      0.0287736000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.844
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            59146
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.256
_diffrn_reflns_theta_min         2.480
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.685
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73238
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       prism
_exptl_crystal_F_000             2392
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.666
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         14971
_refine_ls_number_restraints     156
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0477
_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^)+(0.0634P)^2^+4.5559P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1186
_refine_ls_wR_factor_ref         0.1335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11030
_reflns_number_total             14971
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01581a2.cif
_cod_data_source_block           98_auto
_cod_depositor_comments          'Adding full bibliography for 7716933.cif.'
_cod_database_code               7716933
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'H B C N O Cl Fe Co'
_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
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 Cl1-O1 = Cl1-O3A = Cl1-O2A = Cl1-O4A = Cl1-O2B = Cl1-O3B = Cl1-O4B
 1.44 with sigma of 0.05
 C43-O5B = C43-O5A = C45A-O6A = C45B-O6B = C47A-O7A = O8A-C49A = O8C-C49C =
 C49B-O8B = C45C-O6C = C45D-O6D = O7B-C47B
 1.43 with sigma of 0.05
 O7B-C47B
 1.23 with sigma of 0.05
 C43-C44 = C46A-C45A = C46B-C45B = C46C-C45C = C46D-C45D = C48A-C47A = C49A-
 C50A = C50B-C49B = C49C-C50C = C47B-C48B
 1.53 with sigma of 0.05
 O1-O3A = O1-O4A = O1-O2A = O1-O2B = O1-O3B = O1-O4B = O3A-O4A = O3A-O2A = O4A-
 O2A = O2B-O3B = O2B-O4B = O3B-O4B
 2.325 with sigma of 0.03
 C44-O5B = C44-O5A = C46A-O6A = C46B-O6B = C46C-O6C = C46D-O6D = C48A-O7A =
 O8A-C50A = C50B-O8B = O8C-C50C = O7B-C48B
 2.45 with sigma of 0.05
3. Uiso/Uaniso restraints and constraints
C45A \\sim C45B \\sim O6C: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C46C \\sim C45D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C46A \\sim C46B \\sim C45C \\sim C46D: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(O2A) = Uanis(O2B)
Uanis(O4A) = Uanis(O4B)
Uanis(O6B) = Uanis(C45B)
Uanis(C46B) = Uanis(C45C) = Uanis(C46D)
Uanis(C46A) = Uanis(C45A)
Uanis(C47A) = Uanis(C48B)
Uanis(C48A) = Uanis(C47B)
Uanis(O8A) = Uanis(C49A)
4. Rigid body (RIGU) restrains
 C46A, C45A, O6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C46B, C45B, O6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45C, O6C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6D, C45D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45D, C46D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8A, C49A, C50A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8B, C49B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49B, C50B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(O8A)+Sof(H8A)+Sof(C50A)+Sof(H50A)+Sof(H50B)+Sof(H50C)+Sof(C49A)+
 Sof(H49A)+Sof(H49B)]+1*[Sof(O8B)+Sof(H8B)+Sof(C49B)+Sof(H49C)+Sof(H49D)+
 Sof(C50B)+Sof(H50D)+Sof(H50E)+Sof(H50F)]+1*[Sof(O8C)+Sof(H8C)+Sof(C49C)+
 Sof(H49E)+Sof(H49F)+Sof(C50C)+Sof(H50G)+Sof(H50H)+Sof(H50I)]=1 with esd of 0
 1*[Sof(C45A)+Sof(H45A)+Sof(H45B)+Sof(C46A)+Sof(H46A)+Sof(H46B)+Sof(H46C)+
 Sof(H46D)+Sof(H46E)+Sof(H46F)+Sof(O6A)+Sof(H6A)]+1*[Sof(C45B)+Sof(H45C)+
 Sof(H45D)+Sof(C46B)+Sof(H46G)+Sof(H46H)+Sof(H46I)+Sof(O6B)+Sof(H6B)]+1*
 [Sof(C45C)+Sof(H45E)+Sof(H45F)+Sof(C46C)+Sof(H46J)+Sof(H46K)+Sof(H46L)+
 Sof(O6C)+Sof(H6C)]+1*[Sof(C45D)+Sof(H45G)+Sof(H45H)+Sof(C46D)+Sof(H46M)+
 Sof(H46N)+Sof(H46O)+Sof(O6D)+Sof(H6D)]=1 with esd of 0
 Sof(O2B)=Sof(O4B)=Sof(O3B)=1-FVAR(1)
 Sof(O3A)=Sof(O4A)=Sof(O2A)=FVAR(1)
 Sof(H43A)=Sof(H43B)=Sof(O5A)=Sof(H5A)=1-FVAR(2)
 Sof(H43C)=Sof(H43D)=Sof(O5B)=Sof(H5B)=FVAR(2)
 Sof(O7B)=Sof(H7B)=Sof(C47B)=Sof(H47C)=Sof(H47D)=Sof(C48B)=Sof(H48D)=Sof(H48E)=
 Sof(H48F)=1-FVAR(3)
 Sof(O7A)=Sof(H7A)=Sof(C47A)=Sof(H47A)=Sof(H47B)=Sof(C48A)=Sof(H48A)=Sof(H48B)=
 Sof(H48C)=FVAR(3)
 Sof(O8A)=Sof(H8A)=Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C49A)=Sof(H49A)=
 Sof(H49B)=FVAR(4)
 Sof(O8B)=Sof(H8B)=Sof(C49B)=Sof(H49C)=Sof(H49D)=Sof(C50B)=Sof(H50D)=Sof(H50E)=
 Sof(H50F)=FVAR(5)
 Sof(O8C)=Sof(H8C)=Sof(C49C)=Sof(H49E)=Sof(H49F)=Sof(C50C)=Sof(H50G)=Sof(H50H)=
 Sof(H50I)=FVAR(6)
 Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(H46D)=Sof(H46E)=Sof(H46F)=0.5*FVAR(8)
 Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(C46A)=Sof(O6A)=Sof(H6A)=FVAR(7)
 Sof(C45B)=Sof(H45C)=Sof(H45D)=Sof(C46B)=Sof(H46G)=Sof(H46H)=Sof(H46I)=
 Sof(O6B)=Sof(H6B)=FVAR(8)
 Sof(C45C)=Sof(H45E)=Sof(H45F)=Sof(C46C)=Sof(H46J)=Sof(H46K)=Sof(H46L)=
 Sof(O6C)=Sof(H6C)=FVAR(9)
 Sof(C45D)=Sof(H45G)=Sof(H45H)=Sof(C46D)=Sof(H46M)=Sof(H46N)=Sof(H46O)=
 Sof(O6D)=Sof(H6D)=FVAR(10)
6.a Ternary CH refined with riding coordinates:
 B1(H1A)
6.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C13(H13A,H13B), C14(H14A,H14B), C21(H21A,H21B), C35(H35A,
 H35B), C15(H15A,H15B), C45A(H45A,H45B), C45B(H45C,H45D), C45C(H45E,H45F),
 C45D(H45G,H45H), C43(H43A,H43B), C43(H43C,H43D), C49A(H49A,H49B), C47A(H47A,
 H47B), C49B(H49C,H49D), C47B(H47C,H47D), C49C(H49E,H49F)
6.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C32(H32), C30(H30), C29(H29), C23(H23), C24(H24), C25(H25),
 C26(H26), C17(H17), C18(H18), C19(H19), C20(H20), C37(H37), C38(H38), C40(H40),
  C41(H41), C6(H6), C5(H5), C4(H4), C1(H1), C2(H2), C3(H3), C9(H9), C8(H8),
 C7(H7)
6.d Disordered Me refined with riding coordinates:
 C46A(H46A,H46B,H46C,H46D,H46E,H46F)
6.e Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C42(H42A,H42B,H42C), C46B(H46G,H46H,H46I), C46C(H46J,
 H46K,H46L), C46D(H46M,H46N,H46O), C44(H44A,H44B,H44C), C50A(H50A,H50B,H50C),
 C48A(H48A,H48B,H48C), C50B(H50D,H50E,H50F), C48B(H48D,H48E,H48F), C50C(H50G,
 H50H,H50I)
6.f Idealised tetrahedral OH refined as rotating group:
 O6A(H6A), O6B(H6B), O6C(H6C), O6D(H6D), O5A(H5A), O5B(H5B), O8A(H8A),
 O7A(H7A), O8B(H8B), O7B(H7B), O8C(H8C)
;
_shelx_res_checksum              64913
_shelx_hkl_checksum              91819
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.209
_oxdiff_exptl_absorpt_empirical_full_min 0.436