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_1573723
_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 H44 Co N8 Re2, 5(F6 P)'
_chemical_formula_sum            'C54 H44 Co F30 N8 P5 Re2'
_chemical_formula_weight         1961.15
_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             2023-01-11
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-10-16 deposited with the CCDC.	2025-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.142(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1888(5)
_cell_length_b                   21.4924(7)
_cell_length_c                   24.0881(7)
_cell_measurement_reflns_used    12361
_cell_measurement_temperature    160.0(1)
_cell_measurement_theta_max      67.2880
_cell_measurement_theta_min      4.1250
_cell_volume                     6119.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (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 0.998
_diffrn_measured_fraction_theta_max 0.933
_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    -62.00 -35.00   0.50    8.00    --  -50.88  97.00 -67.00   54
  2  \w    -29.00  12.00   0.50    8.00    --  -50.88  97.00 -67.00   82
  3  \w     -5.00  29.00   0.50    8.00    --   50.88 -97.00-175.00   68
  4  \w    -79.00 -47.00   0.50   32.00    --  -90.00  97.00 -67.00   64
  5  \w   -153.00-127.00   0.50   32.00    --  -90.00 -97.00-175.00   52
  6  \w     68.00 103.00   0.50   32.00    --  111.50 -97.00-175.00   70
  7  \w    -21.00  23.00   0.50    8.00    --  -50.88  19.00  60.00   88
  8  \w    -40.00  14.00   0.50    8.00    --  -50.88  38.00-180.00  108
  9  \w    -26.00  23.00   0.50    8.00    --  -50.88  19.00 -60.00   98
 10  \w    -15.00  15.00   0.50    8.00    --  -50.88  19.00  30.00   60
 11  \w    -11.00  26.00   0.50    8.00    --   50.88 -19.00  60.00   74
 12  \w   -161.00-127.00   0.50   32.00    --  -90.00 -57.00  90.00   68
 13  \w   -161.00-136.00   0.50   32.00    --  -90.00 -77.00-120.00   50
 14  \w   -150.00-123.00   0.50   32.00    --  -90.00 -99.00  90.00   54
 15  \w   -159.00-129.00   0.50   32.00    --  -90.00 -57.00-180.00   60
 16  \w   -156.00-127.00   0.50   32.00    --  -90.00 -99.00 120.00   58
 17  \w    -66.00 -40.00   0.50   32.00    --  -90.00  57.00 -60.00   52
 18  \w   -161.00-127.00   0.50   32.00    --  -90.00 -57.00 -60.00   68
 19  \w   -153.00-128.00   0.50   32.00    --  -90.00 -57.00 -30.00   50
 20  \w   -155.00-120.00   0.50   32.00    --  -90.00 -99.00 150.00   70
 21  \w   -159.00-132.00   0.50   32.00    --  -90.00 -77.00 -90.00   54
 22  \w   -161.00-118.00   0.50   32.00    --  -90.00 -38.00-150.00   86
 23  \w    -55.00 -29.00   0.50   32.00    --  -90.00  57.00 -90.00   52
 24  \w    119.00 176.00   0.50   32.00    --  111.50 125.00-120.00  114
 25  \w     42.00 101.00   0.50   32.00    --  111.50 -99.00-120.00  118
 26  \w     56.00 105.00   0.50   32.00    --  111.50 -77.00-180.00   98
 27  \w     44.00 109.00   0.50   32.00    --  111.50-125.00   0.00  130
 28  \w    127.00 173.00   0.50   32.00    --  111.50  57.00-150.00   92
 29  \w    137.00 177.00   0.50   32.00    --  111.50  57.00  60.00   80
 30  \w    112.00 178.00   0.50   32.00    --  111.50  97.00 -67.00  132
 31  \w    -55.00 -30.00   0.50    8.00    --  -50.88  97.00 -67.00   50
 32  \w   -123.00 -43.00   0.50    8.00    --  -50.88 -19.00-120.00  160
 33  \w   -123.00 -43.00   0.50    8.00    --  -50.88 -19.00  90.00  160
 34  \w   -123.00 -43.00   0.50    8.00    --  -50.88 -19.00 -60.00  160
 35  \w   -123.00 -43.00   0.50    8.00    --  -50.88 -19.00-180.00  160
 36  \w   -123.00 -56.00   0.50    8.00    --  -50.88 -19.00 120.00  134
 37  \w   -123.00 -43.00   0.50    8.00    --  -50.88 -19.00   0.00  160
;
_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      0.1025308000
_diffrn_orient_matrix_UB_12      -0.0361399000
_diffrn_orient_matrix_UB_13      -0.0101466000
_diffrn_orient_matrix_UB_21      -0.0334763000
_diffrn_orient_matrix_UB_22      -0.0567810000
_diffrn_orient_matrix_UB_23      0.0313011000
_diffrn_orient_matrix_UB_31      -0.0731184000
_diffrn_orient_matrix_UB_32      -0.0246152000
_diffrn_orient_matrix_UB_33      -0.0571779000
_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  0.0850
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            51004
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.451
_diffrn_reflns_theta_min         2.794
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.185
_exptl_absorpt_correction_T_max  0.924
_exptl_absorpt_correction_T_min  0.477
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.75a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    2.129
_exptl_crystal_description       plate
_exptl_crystal_F_000             3784
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         4.988
_refine_diff_density_min         -4.812
_refine_diff_density_rms         0.220
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.451
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     879
_refine_ls_number_reflns         12523
_refine_ls_number_restraints     574
_refine_ls_restrained_S_all      1.429
_refine_ls_R_factor_all          0.1623
_refine_ls_R_factor_gt           0.1195
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3572
_refine_ls_wR_factor_ref         0.3996
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7663
_reflns_number_total             12523
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cy01282h2.cif
_cod_data_source_block           '[4](PF6)5'
_cod_depositor_comments
'Adding full bibliography for 1573721--1573724.cif.'
_cod_database_code               1573723
_shelx_estimated_absorpt_t_max   0.793
_shelx_estimated_absorpt_t_min   0.407
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Restrained distances
 C52-C51 = C51-C50 = C50-C49 = C54-C49 = C54-C53 = C53-C52
 1.39 with sigma of 0.01
 C45-C44 = C44-C43 = C48-C43 = C48-C47 = C47-C46 = C46-C45
 1.39 with sigma of 0.01
 F28-F26
 2.3 with sigma of 0.01
 C5-C4 \\sim C5-C6 \\sim C1-C6 \\sim C1-C2 \\sim C2-C3 \\sim C3-C4
 with sigma of 0.01
 C9-C8 \\sim C9-C10 \\sim C11-C10 \\sim C12-C11 \\sim C12-C7 \\sim C8-C7
 with sigma of 0.01
 P5-F25 \\sim P5-F26 \\sim P5-F27 \\sim P5-F28 \\sim P5-F30 \\sim P5-F29
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
N8 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48: within 3A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C49 \\sim C54: within 3A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 3A
F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17 \\sim F18: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
F7 \\sim F8 \\sim F9 \\sim F10 \\sim F11 \\sim F12: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
F25 \\sim F26 \\sim F27 \\sim F28 \\sim F29 \\sim F30: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
4.a :
 C43(C44,C45,C46,C47,C48), C49(C50,C51,C52,C53,C54)
4.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N8(H8), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8A),
 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), C28(H28), C29(H29),
  C30(H30), C31(H31), C34(H34), C36(H36), C39(H39), C40(H40), C41(H41),
 C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50),
  C51(H51), C52(H52), C53(H53), C54(H54)
;
_shelx_res_checksum              34887
_shelx_hkl_checksum              69333