Electrocatalytic Hydrogen Evolution by a Dinuclear Copper Complex and Mechanistic Elucidation through DFT Studies
Raj, Manaswini; Makhal, Koushik; Raj, Dev; Mishra, Aman; Mallik, Bhabani S.; Padhi, Sumanta Kumar; Dalton Transactions  (2023) –; doi:10.1039/D3DT02733C

data_7713992
_publ_section_title
;
 Electrocatalytic Hydrogen Evolution by a Dinuclear Copper Complex and
 Mechanistic Elucidation through DFT Studies
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02733C
_journal_year                    2023
_chemical_formula_moiety         'C52 H32 Cu2 N8 O4, H2 O'
_chemical_formula_sum            'C52 H34 Cu2 N8 O5'
_chemical_formula_weight         977.99
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc2g05qd
_audit_creation_date             2022-07-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-05-20 deposited with the CCDC.	2023-09-19 downloaded from the CCDC.
;
_cell_angle_alpha                100.619(4)
_cell_angle_beta                 98.708(4)
_cell_angle_gamma                103.620(4)
_cell_formula_units_Z            2
_cell_length_a                   11.5122(6)
_cell_length_b                   12.5503(7)
_cell_length_c                   15.0198(7)
_cell_measurement_reflns_used    8164
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.4890
_cell_measurement_theta_min      2.5460
_cell_volume                     2029.38(19)
_computing_cell_refinement
;
'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
;
_computing_data_collection
;
'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
;
_computing_data_reduction
;
'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0303
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.9997
_diffrn_measured_fraction_theta_max 0.8748
_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    -52.00  22.00   1.00   54.00    --   13.76 -57.00  90.00   74
  2  \w    -52.00  39.00   1.00   54.00    --   13.76 -77.00   0.00   91
  3  \w    -46.00  16.00   1.00   54.00    --   13.76 -38.00 150.00   62
  4  \w     -1.00  65.00   1.00   54.00    --   13.76  57.00   0.00   66
  5  \w     -9.00  80.00   1.00   54.00    --   13.76  77.00 120.00   89
  6  \w      1.00  82.00   1.00   54.00    --   13.76  38.00 -90.00   81
  7  \w    -76.00   1.00   1.00   54.00    --  -15.95 -38.00   0.00   77
  8  \w    -80.00 -52.00   1.00   54.00    --  -15.95 143.00 107.89   28
  9  \w    -80.00 -12.00   1.00   54.00    --  -15.95 143.00-175.40   68
 10  \w    -80.00 -37.00   1.00   54.00    --  -15.95 143.00 -22.34   43
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0062910000
_diffrn_orient_matrix_UB_12      0.0587267000
_diffrn_orient_matrix_UB_13      0.0073521000
_diffrn_orient_matrix_UB_21      -0.0574897000
_diffrn_orient_matrix_UB_22      -0.0107406000
_diffrn_orient_matrix_UB_23      -0.0298544000
_diffrn_orient_matrix_UB_31      -0.0291333000
_diffrn_orient_matrix_UB_32      -0.0021226000
_diffrn_orient_matrix_UB_33      0.0382540000
_diffrn_radiation_collimation    0.3
_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  0.0449
_diffrn_reflns_av_unetI/netI     0.0640
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            33134
_diffrn_reflns_theta_full        26.0000
_diffrn_reflns_theta_max         29.42
_diffrn_reflns_theta_min         1.86
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.113
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56167
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light brown'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.6004
_exptl_crystal_description       block
_exptl_crystal_F_000             1001.7254
_exptl_crystal_size_max          25
_exptl_crystal_size_mid          22
_exptl_crystal_size_min          18
_refine_diff_density_max         0.5715
_refine_diff_density_min         -0.7252
_refine_diff_density_rms         0.1385
_refine_ls_d_res_high            0.7235
_refine_ls_d_res_low             10.9534
_refine_ls_goodness_of_fit_ref   1.0308
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    65
_refine_ls_number_parameters     607
_refine_ls_number_reflns         9807
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0308
_refine_ls_R_factor_all          0.0856
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.0000
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0468P)^2^+0.2124P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0939
_refine_ls_wR_factor_ref         0.1084
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              16
_reflns_limit_k_min              -17
_reflns_limit_l_max              20
_reflns_limit_l_min              0
_reflns_number_gt                6372
_reflns_number_total             9807
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3dt02733c2.cif
_cod_data_source_block           Copper_SBO
_cod_database_code               7713992
_chemical_oxdiff_formula         'C104 H64 As4 N20 O6 '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 O(H,H) groups
2.a Free rotating group:
 O5(H5a,H5b)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10a,H10b), C36(H36a,H36b)
2.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C45(H45), C38(H38), C15(H15), C41(H41), C46(H46),
 C23(H23), C31(H31), C21(H21), C32(H32), C39(H39), C40(H40), C22(H22), C12(H12),
  C14(H14), C6(H6), C47(H47), C49(H49), C30(H30), C4(H4), C2(H2), C5(H5),
 C48(H48), C29(H29), C28(H28), C13(H13), C3(H3)
;
_olex2_date_sample_data_collection 2018-05-07
_olex2_submission_original_sample_id Cu_SBO
_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 1.712
_oxdiff_exptl_absorpt_empirical_full_min 0.652