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_1573721
_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         'C54 H42 Co N6 Re2, 4(F6 P), C4 H10 O'
_chemical_formula_sum            'C58 H52 Co F24 N6 O P4 Re2'
_chemical_formula_weight         1860.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_Hall           '-P 2a 2bc'
_space_group_name_H-M_alt        'P n n a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-27
_audit_creation_method
;
Olex2 1.5-ac6-012
(compiled 2023.08.24 svn.re1ec1418 for Rigaku Oxford Diffraction, GUI svn.r6817)
;
_audit_update_record
;
2024-10-16 deposited with the CCDC.	2025-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.3235(2)
_cell_length_b                   15.85530(10)
_cell_length_c                   17.5716(2)
_cell_measurement_reflns_used    26417
_cell_measurement_temperature    160.0(1)
_cell_measurement_theta_max      79.1060
_cell_measurement_theta_min      3.2070
_cell_volume                     6219.39(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.104a 64-bit (release 22-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-012 (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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -81.00   3.00   0.50    0.60    --  -50.11 104.00 103.00  168
  2  \w    -81.00 -20.00   0.50    1.53    --  -90.00 104.00 103.00  122
  3  \w    -51.00 -18.00   0.50    1.53    --  -90.00  45.00 -60.00   66
  4  \w    -26.00  23.00   0.50    0.60    --  -50.11  19.00 -60.00   98
  5  \w    -43.00  21.00   0.50    0.60    --  -50.11  38.00-120.00  128
  6  \w     18.00  83.00   0.50    0.60    --   50.11-104.00   1.00  130
  7  \w     41.00 105.00   0.50    1.53    --  111.50 -95.00 -60.00  128
  8  \w     42.00 107.00   0.50    1.53    --  111.50-104.00   1.00  130
  9  \w     41.00  71.00   0.50    1.53    --  111.50 -61.00 -90.00   60
 10  \w     41.00  71.00   0.50    1.53    --  111.50 -61.00 -30.00   60
 11  \w    -22.00  26.00   0.50    0.60    --   50.11 -19.00-120.00   96
 12  \w     41.00  71.00   0.50    1.53    --  111.50 -61.00   0.00   60
 13  \w     41.00  71.00   0.50    1.53    --  111.50 -61.00  30.00   60
 14  \w     41.00  71.00   0.50    1.53    --  111.50 -61.00 150.00   60
 15  \w    106.00 178.00   0.50    1.53    --  111.50 104.00 103.00  144
 16  \w    107.00 178.00   0.50    1.53    --  111.50 125.00 150.00  142
 17  \w    107.00 178.00   0.50    1.53    --  111.50 125.00 150.00  142
 18  \w    126.00 178.00   0.50    1.53    --  111.50  77.00  90.00  104
 19  \w    122.00 178.00   0.50    1.53    --  111.50  45.00  30.00  112
 20  \w    127.00 178.00   0.50    1.53    --  111.50  61.00 -30.00  102
 21  \w    127.00 178.00   0.50    1.53    --  111.50  61.00-120.00  102
 22  \w    127.00 178.00   0.50    1.53    --  111.50  61.00-150.00  102
 23  \w   -160.00 -84.00   0.50    1.53    --  -90.00-104.00   1.00  152
 24  \w   -122.00 -50.00   0.50    0.60    --  -50.11 -19.00 150.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0403585000
_diffrn_orient_matrix_UB_12      0.0360103000
_diffrn_orient_matrix_UB_13      -0.0633054000
_diffrn_orient_matrix_UB_21      -0.0526696000
_diffrn_orient_matrix_UB_22      0.0049208000
_diffrn_orient_matrix_UB_23      0.0565180000
_diffrn_orient_matrix_UB_31      0.0189372000
_diffrn_orient_matrix_UB_32      0.0900870000
_diffrn_orient_matrix_UB_33      0.0221304000
_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  0.0295
_diffrn_reflns_av_unetI/netI     0.0177
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            55816
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.499
_diffrn_reflns_theta_min         3.201
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.568
_exptl_absorpt_correction_T_max  0.631
_exptl_absorpt_correction_T_min  0.126
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
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    1.987
_exptl_crystal_description       plate
_exptl_crystal_F_000             3612
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.471
_refine_diff_density_min         -1.141
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     505
_refine_ls_number_reflns         6369
_refine_ls_number_restraints     642
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0812P)^2^+10.7434P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1351
_refine_ls_wR_factor_ref         0.1384
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5682
_reflns_number_total             6369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01282h2.cif
_cod_data_source_block           '[2](PF6)4'
_cod_depositor_comments
'Adding full bibliography for 1573721--1573724.cif.'
_cod_database_code               1573721
_shelx_estimated_absorpt_t_max   0.655
_shelx_estimated_absorpt_t_min   0.111
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C3A-C2A = C3A-C4A = C5A-C4A = C6A-C5A = C6A-C1A = C2A-C1A
 1.39 with sigma of 0.01
 C5B-C6B = C5B-C4B = C3B-C4B = C3B-C2B = C2B-C1B = C6B-C1B
 1.39 with sigma of 0.01
 F5-F6 \\sim F5-F7 \\sim F6-F7
 with sigma of 0.01
 P2-F5 \\sim P2-F6 \\sim P2-F7
 with sigma of 0.005
3. Restrained planarity
 P3, F10A, F10B, F11A, F11B, F12A, F12B, F13A, F13B
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
F10A \\sim F10B \\sim F11A \\sim F11B \\sim F12A \\sim F12B \\sim F13A \\sim
F13B: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
C1A \\sim C1B \\sim C2A \\sim C2B \\sim C3A \\sim C3B \\sim C4A \\sim C4B \\sim
C5A \\sim C5B \\sim C6A \\sim C6B: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
N1 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17: within 3A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 3A
5. Others
 Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(F13B)=1-FVAR(1)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(F13A)=FVAR(1)
 Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=1-FVAR(2)
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1B(H1B), C2A(H2A), C2B(H2B), C3A(H3A), C3B(H3B), C4A(H4A),
 C4B(H4B), C5A(H5A), C5B(H5B), C6A(H6A), C6B(H6B), C8(H8), C9(H9), C10(H10),
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C19(H19), C21(H21),
  C24(H24), C25(H25), C26(H26), C27(H27)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              40945
_shelx_hkl_checksum              28463
_shelx_fab_checksum              23890