Mechanistic insights into photocatalysis and over two days of stable H2 generation in electrocatalysis by a molecular cobalt catalyst immobilized on TiO2
Weder, Nicola; Probst, Benjamin; Sévery, Laurent; Fernández-Terán, Ricardo J.; Beckord, Jan; Blacque, Olivier; Tilley, S. David; Hamm, Peter; Osterwalder, Jürg; Alberto, Roger; Catalysis Science & Technology 10 (2020) 2549–2560; doi:10.1039/D0CY00330A

data_1557724
_publ_section_title
;
 Mechanistic insights into photocatalysis and over two days of stable H2
 generation in electrocatalysis by a molecular cobalt catalyst immobilized
 on TiO2
;
_journal_issue                   8
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2549
_journal_page_last               2560
_journal_paper_doi               10.1039/D0CY00330A
_journal_volume                  10
_journal_year                    2020
_chemical_formula_moiety         'C24 H20 Br2 Co N4 O2, 2(C H4 O)'
_chemical_formula_sum            'C26 H28 Br2 Co N4 O4'
_chemical_formula_weight         679.27
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-10-08 deposited with the CCDC.	2020-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.751(1)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.0833(1)
_cell_length_b                   11.8214(1)
_cell_length_c                   13.6272(1)
_cell_measurement_reflns_used    16539
_cell_measurement_temperature    160(1)
_cell_measurement_theta_max      78.7740
_cell_measurement_theta_min      4.9410
_cell_volume                     1295.61(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.13a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.13a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.13a (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (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(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_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     36.00 124.00   0.50    3.00    --   50.71  57.00 -30.00  176
  2  \w     99.00 178.00   0.50   12.00    --  107.75 111.00-120.00  158
  3  \w     95.00 178.00   0.50   12.00    --  107.75  15.00-120.00  166
  4  \w     95.00 178.00   0.50   12.00    --  107.75  15.00 -60.00  166
  5  \w     95.00 178.00   0.50   12.00    --  107.75  15.00   0.00  166
  6  \w     95.00 178.00   0.50   12.00    --  107.75  15.00-150.00  166
  7  \w     91.00 178.00   0.50   12.00    --  107.75  61.00  30.00  174
  8  \w     94.00 178.00   0.50   12.00    --  107.75  30.00  30.00  168
  9  \w     94.00 178.00   0.50   12.00    --  107.75  30.00 120.00  168
 10  \w     94.00 178.00   0.50   12.00    --  107.75  45.00  30.00  168
 11  \w     94.00 178.00   0.50   12.00    --  107.75  30.00  90.00  168
 12  \w     94.00 178.00   0.50   12.00    --  107.75  30.00  60.00  168
 13  \w     94.00 178.00   0.50   12.00    --  107.75  45.00  60.00  168
 14  \w     92.00 178.00   0.50   12.00    --  107.75  58.00  80.00  172
 15  \w     31.00 108.00   0.50   12.00    --  107.75 -94.00-180.00  154
 16  \w     29.00  69.00   0.50   12.00    --  107.75 -30.00-150.00   80
 17  \w     32.00  77.00   0.50   12.00    --  107.75 -45.00-150.00   90
 18  \w     34.00 130.00   0.50   12.00    --  107.75 -77.00-150.00  192
 19  \w     31.00 115.00   0.50   12.00    --  107.75-111.00-180.00  168
 20  \w     32.00  77.00   0.50   12.00    --  107.75 -45.00-180.00   90
 21  \w     29.00  69.00   0.50   12.00    --  107.75 -30.00 -90.00   80
 22  \w     31.00 108.00   0.50   12.00    --  107.75 -94.00-150.00  154
 23  \w     31.00 115.00   0.50   12.00    --  107.75-111.00 -60.00  168
 24  \w     32.00  77.00   0.50   12.00    --  107.75 -45.00  60.00   90
 25  \w     31.00 115.00   0.50   12.00    --  107.75-111.00  60.00  168
 26  \w     32.00  77.00   0.50   12.00    --  107.75 -45.00 150.00   90
 27  \w     29.00  69.00   0.50   12.00    --  107.75 -30.00 150.00   80
 28  \w     31.00 108.00   0.50   12.00    --  107.75 -94.00  90.00  154
 29  \w     28.00 124.00   0.50    3.00    --   50.71  77.00-120.00  192
 30  \w     28.00 124.00   0.50    3.00    --   50.71  77.00-180.00  192
 31  \w    -63.00  27.00   0.50    3.00    --  -50.71  38.00 -90.00  180
 32  \w    -66.00  22.00   0.50    3.00    --  -50.71  57.00   0.00  176
 33  \w    -63.00  27.00   0.50    3.00    --  -50.71  38.00-180.00  180
 34  \w    -90.00  -9.00   0.50   12.00    --  -86.25 111.00 -30.00  162
 35  \w   -128.00 -39.00   0.50    3.00    --  -50.71 -38.00  30.00  178
 36  \w   -127.00 -82.00   0.50    3.00    --  -50.71 -99.00-120.00   90
 37  \w   -127.00 -82.00   0.50    3.00    --  -50.71 -99.00-180.00   90
 38  \w   -162.00 -73.00   0.50   12.00    --  -86.25 -45.00  60.00  178
 39  \w   -160.00 -72.00   0.50   12.00    --  -86.25 -55.00 105.43  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0781732000
_diffrn_orient_matrix_UB_12      0.0724497000
_diffrn_orient_matrix_UB_13      -0.0772511000
_diffrn_orient_matrix_UB_21      -0.1588910000
_diffrn_orient_matrix_UB_22      0.0725191000
_diffrn_orient_matrix_UB_23      -0.0139004000
_diffrn_orient_matrix_UB_31      0.0730712000
_diffrn_orient_matrix_UB_32      0.0804787000
_diffrn_orient_matrix_UB_33      0.0821273000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26383
_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         74.501
_diffrn_reflns_theta_min         4.963
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.148
_exptl_absorpt_correction_T_max  0.863
_exptl_absorpt_correction_T_min  0.477
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.13a (Rigaku Oxford Diffraction, 2015)
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            red
_exptl_crystal_density_diffrn    1.741
_exptl_crystal_description       needle
_exptl_crystal_F_000             682
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.952
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         2644
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0513P)^2^+1.6856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0928
_refine_ls_wR_factor_ref         0.0942
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2495
_reflns_number_total             2644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy00330a2.cif
_cod_data_source_block           Co(II)-9
_cod_depositor_comments
;Adding full bibliography for 1557722--1557724.cif.

 Adding full bibliography for 1557722--1557724.cif.
;
_cod_database_code               1557724
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.305
_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, All O(H,H) groups
2. Restrained distances
 O1-H1 = O2-H2A
 0.82 with sigma of 0.005
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9)
3.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              70285