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_1557723
_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, 0.5(C2 H4 O6 S2), C2 H6 O S, H2 O'
_chemical_formula_sum            'C27 H30 Br2 Co N4 O7 S2'
_chemical_formula_weight         805.42
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-20
_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                107.981(3)
_cell_angle_beta                 96.136(3)
_cell_angle_gamma                103.720(3)
_cell_formula_units_Z            2
_cell_length_a                   8.1545(3)
_cell_length_b                   11.7917(5)
_cell_length_c                   16.3115(4)
_cell_measurement_reflns_used    10672
_cell_measurement_temperature    160(1)
_cell_measurement_theta_max      78.4
_cell_measurement_theta_min      2.9
_cell_volume                     1421.47(10)
_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 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    -73.00  21.00   0.50    8.00    --  -51.81  77.00   0.00  188
  2  \w    -77.00 -11.00   0.50   32.00    --  -86.25  45.00 -30.00  132
  3  \w    -90.00 -10.00   0.50   32.00    --  -86.25 111.00  60.00  160
  4  \w    -95.00  -9.00   0.50    8.00    --  -51.81 125.00 120.00  172
  5  \w   -131.00 -43.00   0.50    8.00    --  -51.81 -19.00 120.00  176
  6  \w   -127.00 -82.00   0.50    8.00    --  -51.81 -99.00  90.00   90
  7  \w   -127.00 -82.00   0.50    8.00    --  -51.81 -99.00   0.00   90
  8  \w   -127.00 -82.00   0.50    8.00    --  -51.81 -99.00 -60.00   90
  9  \w   -124.00 -38.00   0.50    8.00    --  -51.81 -57.00-150.00  172
 10  \w   -126.00 -70.00   0.50    8.00    --  -51.81-125.00-180.00  112
 11  \w     35.00 129.00   0.50   32.00    --  107.75 -77.00  90.00  188
 12  \w     72.00 105.00   0.50   32.00    --  107.75 -94.00  90.00   66
 13  \w     71.00 113.00   0.50   32.00    --  107.75-111.00  60.00   84
 14  \w     57.00 106.00   0.50   32.00    --  107.75-111.00  90.00   98
 15  \w     38.00  69.00   0.50   32.00    --  107.75 -94.00  90.00   62
 16  \w     32.00  77.00   0.50   32.00    --  107.75 -45.00 150.00   90
 17  \w     41.00  67.00   0.50   32.00    --  107.75 -30.00  90.00   52
 18  \w     45.00  70.00   0.50   32.00    --  107.75 -15.00  30.00   50
 19  \w     83.00 117.00   0.50   32.00    --  107.75 -15.00  30.00   68
 20  \w    106.00 174.00   0.50   32.00    --  107.75  15.00  30.00  136
 21  \w    121.00 171.00   0.50   32.00    --  107.75  30.00  60.00  100
 22  \w     98.00 178.00   0.50   32.00    --  107.75  15.00 -60.00  160
 23  \w     83.00 117.00   0.50   32.00    --  107.75 -61.00 -60.00   68
 24  \w     82.00 114.00   0.50   32.00    --  107.75-111.00 -90.00   64
 25  \w     69.00 115.00   0.50   32.00    --  107.75-111.00-180.00   92
 26  \w     45.00 127.00   0.50   32.00    --  107.75 -77.00 -60.00  164
 27  \w     48.00  97.00   0.50   32.00    --  107.75 -94.00 -90.00   98
 28  \w     46.00 108.00   0.50   32.00    --  107.75 -94.00 -60.00  124
 29  \w     38.00  65.00   0.50   32.00    --  107.75 -61.00 -60.00   54
 30  \w     34.00  61.00   0.50   32.00    --  107.75 -30.00-120.00   54
 31  \w     34.00  74.00   0.50   32.00    --  107.75 -45.00 -60.00   80
 32  \w     32.00  69.00   0.50   32.00    --  107.75 -30.00   0.00   74
 33  \w     33.00  66.00   0.50   32.00    --  107.75 -30.00 -60.00   66
 34  \w     34.00  66.00   0.50   32.00    --  107.75 -30.00 -30.00   64
 35  \w     33.00  71.00   0.50   32.00    --  107.75 -94.00-120.00   76
 36  \w     32.00 102.00   0.50   32.00    --  107.75 -94.00-180.00  140
 37  \w     38.00  79.00   0.50   32.00    --  107.75-111.00 -90.00   82
 38  \w     35.00  72.00   0.50   32.00    --  107.75 -45.00  60.00   74
 39  \w     32.00  71.00   0.50   32.00    --  107.75 -45.00  90.00   78
 40  \w     36.00  62.00   0.50   32.00    --  107.75 -30.00 120.00   52
 41  \w     35.00  66.00   0.50   32.00    --  107.75 -30.00 150.00   62
;
_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      -0.0183580000
_diffrn_orient_matrix_UB_12      0.1329698000
_diffrn_orient_matrix_UB_13      0.0295080000
_diffrn_orient_matrix_UB_21      -0.1876882000
_diffrn_orient_matrix_UB_22      -0.0512202000
_diffrn_orient_matrix_UB_23      0.0077570000
_diffrn_orient_matrix_UB_31      0.0612257000
_diffrn_orient_matrix_UB_32      0.0154552000
_diffrn_orient_matrix_UB_33      0.0965306000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            21345
_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         74.504
_diffrn_reflns_theta_min         2.904
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.878
_exptl_absorpt_correction_T_max  0.877
_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            colourless
_exptl_crystal_density_diffrn    1.882
_exptl_crystal_description       needle
_exptl_crystal_F_000             810
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.287
_refine_diff_density_min         -0.724
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     400
_refine_ls_number_reflns         5801
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0412
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0510P)^2^+3.0667P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1032
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4879
_reflns_number_total             5801
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy00330a2.cif
_cod_data_source_block           Co(III)-9
_cod_depositor_comments
;Adding full bibliography for 1557722--1557724.cif.

 Adding full bibliography for 1557722--1557724.cif.
;
_cod_original_cell_volume        1421.47(9)
_cod_database_code               1557723
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.410
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 O7-H7A
 0.82 with sigma of 0.01
 O7-H7B
 0.82 with sigma of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C14(H14), C15(H15), C16(H16),
 C19(H19), C20(H20), C21(H21)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C)
3.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2A)
;
_shelx_res_checksum              40958