Two Co(ii)/Ni(ii) complexes based on nitrogenous heterocyclic ligands as high-performance electrocatalysts for the hydrogen evolution reaction
Li, Rong-Fang; Zhang, Heng; Hong, Man-Zhou; Shi, Jing-Ge; Liu, Xin-Fang; Feng, Xun; Dalton Transactions  (2022) –; doi:10.1039/D1DT03814A

data_7709556
_publ_section_title
;
 Two Co(ii)/Ni(ii) complexes based on nitrogenous heterocyclic ligands as
 high-performance electrocatalysts for the hydrogen evolution reaction
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT03814A
_journal_year                    2022
_chemical_formula_moiety         'C24 H18 N4 Ni O10, 1.5(H2 O)'
_chemical_formula_sum            'C24 H21 N4 Ni O11.5'
_chemical_formula_weight         608.16
_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             2021-08-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6383)
;
_audit_update_record
;
2021-10-11 deposited with the CCDC.	2022-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                89.868(3)
_cell_angle_beta                 78.515(3)
_cell_angle_gamma                71.739(3)
_cell_formula_units_Z            2
_cell_length_a                   8.6837(3)
_cell_length_b                   9.7983(4)
_cell_length_c                   15.5846(6)
_cell_measurement_reflns_used    7986
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.8060
_cell_measurement_theta_min      4.1050
_cell_volume                     1231.45(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0584
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.856
_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    -17.00  10.00   1.00    5.00    --  -13.49 -99.00-120.00   27
  2  \w    -78.00   0.00   1.00    5.00    --  -13.49 -38.00  90.00   78
  3  \w    -11.00  22.00   1.00    5.00    --  -13.49 -99.00  30.00   33
  4  \w     -2.00  82.00   1.00    5.00    --   14.89  57.00   0.00   84
  5  \w     19.00  68.00   1.00    5.00    --   14.89  38.00  60.00   49
  6  \w    -20.00  54.00   1.00    5.00    --   14.89 -99.00-150.00   74
  7  \w    -50.00  42.00   1.00    5.00    --   14.89 -77.00  90.00   92
  8  \w      4.00  82.00   1.00    5.00    --   14.89  77.00-150.00   78
  9  \w    -48.00  29.00   1.00    5.00    --   14.89 -19.00-150.00   77
 10  \w    -10.00  61.00   1.00    5.00    --   14.89-111.00  12.33   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0318418000
_diffrn_orient_matrix_UB_12      -0.0474722000
_diffrn_orient_matrix_UB_13      0.0269988000
_diffrn_orient_matrix_UB_21      -0.0201435000
_diffrn_orient_matrix_UB_22      0.0496456000
_diffrn_orient_matrix_UB_23      0.0367260000
_diffrn_orient_matrix_UB_31      -0.0794713000
_diffrn_orient_matrix_UB_32      0.0334303000
_diffrn_orient_matrix_UB_33      -0.0093759000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.856
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            17924
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.856
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.562
_diffrn_reflns_theta_min         3.347
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.863
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91084
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.640
_exptl_crystal_description       block
_exptl_crystal_F_000             626
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         5380
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0272P)^2^+1.0111P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0787
_refine_ls_wR_factor_ref         0.0825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4680
_reflns_number_total             5380
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03814a2.cif
_cod_data_source_block           p4-ni
_cod_original_cell_volume        1231.45(8)
_cod_original_formula_sum        'C24 H21 N4 Ni O11.50'
_cod_database_code               7709556
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Others
 Fixed Sof: O12(0.5) H12A(0.5) H12B(0.5)
3.a Riding coordinates:
 O12(H12A,H12B)
3.b Free rotating group:
 O3(H3A,H3B)
3.c Rotating group:
 O1(H1A,H1B), O4(H4A,H4B)
3.d Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C5(H5), C7(H7), C9(H9), C10(H10A), C13(H13), C14(H14),
 C15(H15), C16(H16), C18(H18), C20(H20)
3.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O10(H10)
;
_shelx_res_checksum              82588
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.875