Hydrogen evolution driven by heteroatoms of bidentate N-heterocyclic ligands in iron(II) complexes.
Keszei, Soma; Wang, Yiqing; Zhou, Haotian; Ollár, Tamás; Kováts, Éva; Frey, Krisztina; Tapasztó, Levente; Shen, Shaohua; Pap, József Sándor; Dalton transactions (Cambridge, England : 2003) 53 (2024) 14817–14829; doi:10.1039/d4dt02081b

data_7716825
_publ_section_title
;
 Hydrogen evolution driven by heteroatoms of bidentate N-heterocyclic
 ligands in iron(II) complexes.
;
_journal_issue                   35
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14817
_journal_page_last               14829
_journal_paper_doi               10.1039/d4dt02081b
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C26 H16 F6 Fe N4 O6 S4'
_chemical_formula_sum            'C26 H16 F6 Fe N4 O6 S4'
_chemical_formula_weight         778.52
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-15 deposited with the CCDC.	2024-08-06 downloaded from the CCDC.
;
_cell_angle_alpha                108.810(2)
_cell_angle_beta                 99.028(3)
_cell_angle_gamma                100.433(2)
_cell_formula_units_Z            4
_cell_length_a                   8.3143(3)
_cell_length_b                   18.4365(5)
_cell_length_c                   21.3177(7)
_cell_measurement_reflns_used    12037
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.7790
_cell_measurement_theta_min      3.9900
_cell_volume                     2959.58(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5908
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.974
_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    -69.00  32.00   1.00   10.00    --  -40.87  57.00-120.00  101
  2  \w    -87.00  -6.00   1.00   10.00    --  -40.87 125.00 -90.00   81
  3  \w   -115.00 -16.00   1.00   10.00    --  -40.87 -38.00  90.00   99
  4  \w   -115.00 -16.00   1.00   10.00    --  -40.87 -38.00   0.00   99
  5  \w     27.00  97.00   1.00   10.00    --   40.87-125.00-180.00   70
  6  \w     61.00 146.00   1.00   25.00    --  112.00 178.00 -90.00   85
  7  \w     36.00 109.00   1.00   25.00    --  112.00-111.00-180.00   73
  8  \w     36.00 109.00   1.00   25.00    --  112.00-111.00  30.00   73
  9  \w    104.00 178.00   1.00   25.00    --  112.00 111.00  90.00   74
 10  \w     36.00 140.00   1.00   25.00    --  112.00 -30.00 -30.00  104
 11  \w    103.00 178.00   1.00   25.00    --  112.00  77.00  30.00   75
 12  \w    104.00 178.00   1.00   25.00    --  112.00 111.00  60.00   74
 13  \w     36.00 109.00   1.00   25.00    --  112.00-111.00 -60.00   73
 14  \w    103.00 178.00   1.00   25.00    --  112.00  77.00   0.00   75
 15  \w     36.00 109.00   1.00   25.00    --  112.00-111.00 150.00   73
 16  \w     40.00 141.00   1.00   25.00    --  112.00 -61.00   0.00  101
 17  \w     36.00 109.00   1.00   25.00    --  112.00-111.00-120.00   73
 18  \w     36.00 109.00   1.00   25.00    --  112.00-111.00  60.00   73
 19  \w     86.00 178.00   1.00   25.00    --  112.00  45.00 150.00   92
 20  \w   -114.00 -13.00   1.00   10.00    --  -40.87 -57.00-120.00  101
 21  \w   -114.00 -13.00   1.00   10.00    --  -40.87 -57.00 -30.00  101
 22  \w   -115.00 -16.00   1.00   10.00    --  -40.87 -38.00 -90.00   99
 23  \w     13.00 114.00   1.00   10.00    --   40.87  57.00-150.00  101
 24  \w     13.00 114.00   1.00   10.00    --   40.87  57.00 150.00  101
 25  \w    -21.00  73.00   1.00   10.00    --   40.87 -77.00  60.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1043136000
_diffrn_orient_matrix_UB_12      0.0131067000
_diffrn_orient_matrix_UB_13      0.0545354000
_diffrn_orient_matrix_UB_21      -0.1432648000
_diffrn_orient_matrix_UB_22      -0.0706217000
_diffrn_orient_matrix_UB_23      -0.0488572000
_diffrn_orient_matrix_UB_31      0.0780796000
_diffrn_orient_matrix_UB_32      -0.0560640000
_diffrn_orient_matrix_UB_33      0.0282250000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            36054
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.536
_diffrn_reflns_theta_min         4.020
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.532
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69852
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.747
_exptl_crystal_description       plate
_exptl_crystal_F_000             1568
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.959
_refine_diff_density_min         -0.851
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     896
_refine_ls_number_reflns         12140
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0862
_refine_ls_R_factor_gt           0.0629
_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^)+(0.0857P)^2^+4.7802P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1557
_refine_ls_wR_factor_ref         0.1734
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9138
_reflns_number_total             12140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02081b2.cif
_cod_data_source_block           exp_1172_autored
_cod_depositor_comments          'Adding full bibliography for 7716825.cif.'
_cod_original_cell_volume        2959.58(17)
_cod_database_code               7716825
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Fe S4 N4 O6 F6 C26'
_chemical_oxdiff_usercomment     'SOM267 #4'
_reflns_odcompleteness_completeness 99.02
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C7A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C7) \\sim Ueq, Uanis(C7A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(Fe2) = Uanis(Fe2A)
Uanis(S1) = Uanis(S1A)
Uanis(N1) = Uanis(N1A)
Uanis(N2) = Uanis(N2A)
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C10) = Uanis(C10A)
Uanis(C11) = Uanis(C11A)
Uanis(C12) = Uanis(C12A)
Uanis(C1) = Uanis(C1A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C6) = Uanis(C6A)
Uanis(C7) = Uanis(C7A)
3. Same fragment restrains
{S1, N1, C1, C2, C3, C4, C5, C6, C7, N2, C8, C9, C10, C11, C12} sigma for 1-2:
0.02, 1-3: 0.04
as in
{S1A, N1A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, N2A, C8A, C9A, C10A, C11A, C12A}
4. Others
 Sof(Fe2A)=Sof(S1A)=Sof(N1A)=Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(N2A)=Sof(C8A)=
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=
 1-FVAR(1)
 Sof(Fe2)=Sof(S1)=Sof(N1)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(N2)=Sof(C8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C01H(H01H), C01I(H01I), C01K(H01K), C01L(H01L), C01N(H01N), C01O(H01O),
 C01P(H01P), C01R(H01R), C01S(H01S), C01V(H01V), C01Y(H01Y), C02A(H02A),
 C02D(H02D), C022(H022), C023(H023), C024(H024), C01U(H01U), C01W(H01W),
 C02B(H02B), C02G(H02G), C02I(H02I), C02J(H02J), C3(H3), C4(H4), C5(H5), C6(H6),
  C9(H9), C10(H10), C11(H11), C12(H12), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A),
 C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C021(H021), C027(H027)
;
_shelx_res_checksum              41210
_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 1.343
_oxdiff_exptl_absorpt_empirical_full_min 0.702