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_1557722
_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         'C36 H46 N4 O6 P2'
_chemical_formula_sum            'C36 H46 N4 O6 P2'
_chemical_formula_weight         692.71
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-08 deposited with the CCDC.	2020-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                96.9776(19)
_cell_angle_beta                 99.2858(19)
_cell_angle_gamma                104.161(2)
_cell_formula_units_Z            2
_cell_length_a                   9.4370(2)
_cell_length_b                   10.4908(3)
_cell_length_c                   18.5143(4)
_cell_measurement_reflns_used    19683
_cell_measurement_temperature    160(1)
_cell_measurement_theta_max      32.6700
_cell_measurement_theta_min      2.5450
_cell_volume                     1728.97(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_area_resol_mean 10.4498
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -44.00  52.00   0.60   15.00    --  -17.65  57.00 -60.00  160
  2  \w    -25.00  21.20   0.60   15.00    --  -17.65 -99.00-150.00   77
  3  \w    -25.00  21.20   0.60   15.00    --  -17.65 -99.00  90.00   77
  4  \w    -25.00  21.20   0.60   15.00    --  -17.65 -99.00 150.00   77
  5  \w    -55.00  50.00   0.60   15.00    --   18.44 -77.00 -30.00  175
  6  \w    -52.00  44.00   0.60   15.00    --   18.44 -57.00-180.00  160
  7  \w     -4.00  90.20   0.60   15.00    --   18.44  38.00 120.00  157
  8  \w    -25.00  21.20   0.60   15.00    --  -17.65 -99.00 -60.00   77
  9  \w    -90.00   4.20   0.60   15.00    --  -17.65 -38.00 150.00  157
 10  \w     -8.00  88.00   0.60   15.00    --   18.44  57.00   0.00  160
 11  \w    -25.00   0.20   0.60   15.00    --   18.44 -99.00 120.00   42
 12  \w    -54.00  34.80   0.60   15.00    --   18.44 -38.00  60.00  148
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0674679000
_diffrn_orient_matrix_UB_12      0.0448547000
_diffrn_orient_matrix_UB_13      -0.0032541000
_diffrn_orient_matrix_UB_21      -0.0327922000
_diffrn_orient_matrix_UB_22      0.0045972000
_diffrn_orient_matrix_UB_23      -0.0365263000
_diffrn_orient_matrix_UB_31      -0.0250660000
_diffrn_orient_matrix_UB_32      0.0545057000
_diffrn_orient_matrix_UB_33      0.0143556000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            34712
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.607
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.178
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_correction_T_min  0.945
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.331
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.025
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     439
_refine_ls_number_reflns         6339
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0387
_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^)+(0.0385P)^2^+1.6306P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0937
_refine_ls_wR_factor_ref         0.0974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5660
_reflns_number_total             6339
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cy00330a2.cif
_cod_data_source_block           4
_cod_depositor_comments
;Adding full bibliography for 1557722--1557724.cif.

 Adding full bibliography for 1557722--1557724.cif.
;
_cod_original_cell_volume        1728.96(7)
_cod_database_code               1557722
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.924
_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
2.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C31(H31A,
 H31B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B)
2.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)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              96485
_olex2_date_sample_data_collection 2018-10-16
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.233
_oxdiff_exptl_absorpt_empirical_full_min 0.796