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_7709555
_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         'C48 H30 Co2 N8 O18, 4.5(H2 O)'
_chemical_formula_sum            'C48 H39 Co2 N8 O22.5'
_chemical_formula_weight         1205.73
_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             2021-01-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-10-11 deposited with the CCDC.	2022-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                96.042(2)
_cell_angle_beta                 109.872(2)
_cell_angle_gamma                90.2510(10)
_cell_formula_units_Z            2
_cell_length_a                   11.6709(2)
_cell_length_b                   15.1906(2)
_cell_length_c                   15.5405(3)
_cell_measurement_reflns_used    14812
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.6270
_cell_measurement_theta_min      3.7030
_cell_volume                     2574.32(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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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 0.996
_diffrn_measured_fraction_theta_max 0.875
_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    -27.00  48.00   1.00   10.00    --  -15.84  57.00 120.00   75
  2  \w    -31.00  -4.00   1.00   10.00    --  -15.84 128.00  45.39   27
  3  \w    -71.00 -44.00   1.00   10.00    --  -15.84 128.00  45.39   27
  4  \w    -68.00 -37.00   1.00   10.00    --  -15.84 122.00 -35.02   31
  5  \w    -72.00  -5.00   1.00   10.00    --  -15.84 129.00 166.55   67
  6  \w    -83.00   3.00   1.00   10.00    --  -15.84 -38.00 -60.00   86
  7  \w      5.00  79.00   1.00   10.00    --   16.93  57.00-180.00   74
  8  \w    -10.00  84.00   1.00   10.00    --   16.93  77.00  60.00   94
  9  \w    -51.00  33.00   1.00   10.00    --   16.93 -38.00   0.00   84
 10  \w    -49.00  44.00   1.00   10.00    --   16.93 -77.00 -60.00   93
 11  \w    -10.00  67.00   1.00   10.00    --   16.93  77.00 -90.00   77
;
_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      -0.0015166000
_diffrn_orient_matrix_UB_12      0.0146572000
_diffrn_orient_matrix_UB_13      -0.0422122000
_diffrn_orient_matrix_UB_21      0.0537352000
_diffrn_orient_matrix_UB_22      -0.0228431000
_diffrn_orient_matrix_UB_23      0.0025689000
_diffrn_orient_matrix_UB_31      -0.0359727000
_diffrn_orient_matrix_UB_32      -0.0383685000
_diffrn_orient_matrix_UB_33      -0.0244461000
_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  0.0338
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.875
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            40990
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.875
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.292
_diffrn_reflns_theta_min         3.369
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.737
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70049
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.555
_exptl_crystal_description       block
_exptl_crystal_F_000             1234
_refine_diff_density_max         0.915
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     751
_refine_ls_number_reflns         12305
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0552
_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^)+(0.0791P)^2^+3.3324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1464
_refine_ls_wR_factor_ref         0.1572
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9794
_reflns_number_total             12305
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03814a2.cif
_cod_data_source_block           lrf-p4-co
_cod_original_formula_sum        'C48 H39 Co2 N8 O22.50'
_cod_database_code               7709555
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 Co2-H18A \\sim Co2-H18B
 with sigma of 0.02
3. Others
 Fixed Sof: O3(0.5) H3A(0.5) H3B(0.5) O5(0.5) H5A(0.5) H5B(0.5) O11(0.5)
 H11A(0.5) H11B(0.5) O21(0.5) H21A(0.5) H21B(0.5) O23(0.5) H23A(0.5) H23B(0.5)
4.a Riding coordinates:
 O18(H18A,H18B), O3(H3A,H3B), O5(H5A,H5B), O11(H11A,H11B), O17(H17A,H17B),
 O19(H19A,H19B), O21(H21A,H21B), O23(H23A,H23B)
4.b Rotating group:
 O4(H4A,H4B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C9(H9), C12(H12), C16(H16), C19(H19), C20(H20), C21(H21), C22(H22),
 C26(H26), C27(H27), C29(H29), C30(H30), C34(H34), C35(H35), C36(H36), C37(H37),
  C38(H38), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48)
4.d Idealised tetrahedral OH refined as rotating group:
 O7(H7), O10(H10)
;
_shelx_res_checksum              72581
_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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.686