The role of [Re(η6-arene)2]+ substituents in electro- and photocatalytic water reduction with [Co(terpy)2]3+ catalysts
Csucker, Joshua; Grundmann, Nora Sophie; Blacque, Olivier; Spingler, Bernhard; Alberto, Roger; Catalysis Science & Technology 15 (2025) 1627–1633; doi:10.1039/D4CY01282H

data_1573722
_publ_section_title
;
 The role of [Re(\h6-arene)2]+ substituents in electro- and photocatalytic
 water reduction with [Co(terpy)2]3+ catalysts
;
_journal_issue                   5
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              1627
_journal_page_last               1633
_journal_paper_doi               10.1039/D4CY01282H
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C42 H32 Co N8, 3(F6 P), 2(C2 H3 N)'
_chemical_formula_sum            'C46 H38 Co F18 N10 P3'
_chemical_formula_weight         1224.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-10-16 deposited with the CCDC.	2025-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.0770(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.7621(2)
_cell_length_b                   16.5626(2)
_cell_length_c                   20.9736(3)
_cell_measurement_reflns_used    12887
_cell_measurement_temperature    160.0(1)
_cell_measurement_theta_max      76.1240
_cell_measurement_theta_min      4.0140
_cell_volume                     5032.48(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      160.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3801
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -74.00  36.00   1.00    3.00    --  -41.01  72.00-175.00  110
  2  \w    -15.00  74.00   1.00    3.00    --   41.01 -72.00  54.00   89
  3  \w     36.00 146.00   1.00   12.00    --  113.00 -72.00  54.00  110
  4  \w    101.00 178.00   1.00   12.00    --  113.00  72.00-175.00   77
  5  \w    -67.00  35.00   1.00    3.00    --  -41.01  37.00 -60.00  102
  6  \w    -87.00 -20.00   1.00    3.00    --  -41.01 125.00 -90.00   67
  7  \w      6.00  82.00   1.00    3.00    --   41.01 -99.00 -90.00   76
  8  \w     97.00 178.00   1.00   12.00    --  113.00  45.00 -30.00   81
  9  \w     38.00 109.00   1.00   12.00    --  113.00-111.00 -30.00   71
 10  \w    115.00 178.00   1.00   12.00    --  113.00  77.00  60.00   63
 11  \w     29.00 107.00   1.00   12.00    --  113.00 -94.00 120.00   78
 12  \w    113.00 178.00   1.00   12.00    --  113.00  61.00   0.00   65
 13  \w     38.00 109.00   1.00   12.00    --  113.00-111.00  30.00   71
 14  \w    115.00 178.00   1.00   12.00    --  113.00  77.00-150.00   63
 15  \w    115.00 178.00   1.00   12.00    --  113.00  77.00 -60.00   63
 16  \w    115.00 178.00   1.00   12.00    --  113.00  77.00-120.00   63
 17  \w     38.00 109.00   1.00   12.00    --  113.00-111.00  90.00   71
 18  \w     38.00 109.00   1.00   12.00    --  113.00-111.00  60.00   71
 19  \w     38.00 109.00   1.00   12.00    --  113.00-111.00 -90.00   71
 20  \w    113.00 178.00   1.00   12.00    --  113.00  61.00 -90.00   65
 21  \w     15.00 117.00   1.00    3.00    --   41.01  37.00-150.00  102
 22  \w     15.00 117.00   1.00    3.00    --   41.01  37.00  90.00  102
 23  \w     15.00 117.00   1.00    3.00    --   41.01  37.00 150.00  102
 24  \w     15.00 117.00   1.00    3.00    --   41.01  37.00 -30.00  102
 25  \w     82.00 155.00   1.00   12.00    --  113.00  30.00 150.00   73
;
_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      0.0157655000
_diffrn_orient_matrix_UB_12      -0.0851487000
_diffrn_orient_matrix_UB_13      0.0297047000
_diffrn_orient_matrix_UB_21      0.0553500000
_diffrn_orient_matrix_UB_22      -0.0232888000
_diffrn_orient_matrix_UB_23      -0.0524815000
_diffrn_orient_matrix_UB_31      0.0893318000
_diffrn_orient_matrix_UB_32      0.0294523000
_diffrn_orient_matrix_UB_33      0.0443552000
_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  0.0380
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            27747
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.500
_diffrn_reflns_theta_min         4.054
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.602
_exptl_absorpt_correction_T_max  0.895
_exptl_absorpt_correction_T_min  0.674
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.616
_exptl_crystal_description       needle
_exptl_crystal_F_000             2472
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         5148
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0348
_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^)+(0.0424P)^2^+4.9125P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0858
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4647
_reflns_number_total             5148
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01282h2.cif
_cod_data_source_block           '[5](PF6)3'
_cod_depositor_comments
'Adding full bibliography for 1573721--1573724.cif.'
_cod_database_code               1573722
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.565
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
F8A \\sim F8B \\sim F9A \\sim F9B \\sim F10B: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
3. Others
 Sof(F10B)=1-FVAR(1)
 Sof(F8B)=Sof(F9B)=0.5*(1-FVAR(2))
 Sof(F8A)=Sof(F9A)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C9(H9), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21)
4.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              96755
_shelx_hkl_checksum              17319