Electrocatalytic Water Oxidation by heteroleptic Ruthenium complexes of 2,6-bis(benzimidazolyl) pyridine Scaffold: A mechanistic investigation
Khan, Sahanwaj; Sengupta, Swaraj; Khan, Mohammad adnan; Sk, Md Palashuddin; Naskar, Subhendu; Dalton Transactions  (2023) –; doi:10.1039/D3DT00128H

data_7712896
_publ_section_title
;
 Electrocatalytic Water Oxidation by heteroleptic Ruthenium complexes of
 2,6-bis(benzimidazolyl) pyridine Scaffold: A mechanistic investigation
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00128H
_journal_year                    2023
_chemical_formula_moiety         'C30 H28 N7 O3 Ru S, F6 P, C2 H6 O S'
_chemical_formula_sum            'C32 H34 F6 N7 O4 P Ru S2'
_chemical_formula_weight         890.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2022-02-01
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2022-11-28 deposited with the CCDC.	2023-04-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.989(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0563(8)
_cell_length_b                   20.5315(13)
_cell_length_c                   15.021(2)
_cell_measurement_reflns_used    6838
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      28.9210
_cell_measurement_theta_min      3.7480
_cell_volume                     3407.7(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      298.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4324
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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     -1.00  79.00   1.00   35.26    --   10.07  57.00  90.00   80
  2  \w    -59.00  23.00   1.00   35.26    --   10.07 -57.00 -60.00   82
  3  \w     -9.00  16.00   1.00   35.26    --  -10.22 -99.00  90.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0267998000
_diffrn_orient_matrix_UB_12      -0.0241233000
_diffrn_orient_matrix_UB_13      0.0271793000
_diffrn_orient_matrix_UB_21      0.0256172000
_diffrn_orient_matrix_UB_22      -0.0248077000
_diffrn_orient_matrix_UB_23      -0.0266453000
_diffrn_orient_matrix_UB_31      0.0529840000
_diffrn_orient_matrix_UB_32      -0.0002224000
_diffrn_orient_matrix_UB_33      0.0285473000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15683
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        24.996
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_min         3.362
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.714
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14868
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.736
_exptl_crystal_description       plate
_exptl_crystal_F_000             1808
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.577
_refine_diff_density_min         -0.480
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     530
_refine_ls_number_reflns         5952
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0440P)^2^+3.1961P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0891
_refine_ls_wR_factor_ref         0.0950
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5104
_reflns_number_total             5952
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00128h2.cif
_cod_data_source_block           ru_4_4dmei
_cod_original_cell_volume        3407.8(6)
_cod_database_code               7712896
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H01M,H01N,H01O} of C01H, {H01G,H01H,H01I} of C01B, All
  N(H) groups
 At 1.5 times of:
  All C(H,H) groups, {H01A,H01B,H01C} of C010, {H01J,H01K,H01L} of C01G,
  {H01S,H01T,H01U} of C01E, {H01P,H01Q,H01R} of C01D, {H01D,H01E,H01F} of C018
2. Restrained distances
 C0B-C016
 1.9 with sigma of 0.02
 C01H-H01N
 1.09 with sigma of 0.02
 C01B-C01H
 3 with sigma of 0.02
 H01N-H01H
 2.5 with sigma of 0.02
3. Rigid bond restraints
 C01G, C01B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C00V, C015, C01A, C01C, C017, C00U
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C01B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C01A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C00X) = Uanis(C014) = Uanis(C00Z) = Uanis(N00L)
Uiso(H01H) = Uiso(H01M)
Uiso(H01G) = Uiso(H01N)
Uiso(H01I) = Uiso(H01O)
Uiso(H0BA) = Uiso(H01O)
Uiso(H01E) = Uiso(H01D) = Uiso(H01F) = Uiso(H01Q) = Uiso(H01R) = Uiso(H01P)
Uiso(H01A) = Uiso(H01B) = Uiso(H01C) = Uiso(H01U) = Uiso(H01T) = Uiso(H01S)
Uiso(H017) = Uiso(H01O) = Uiso(H01M) = Uiso(H01N)
5. Others
 Fixed Sof: F00C(0.5) F00M(0.5) F00S(0.5) F00W(0.5) F00Y(0.5) F012(0.5)
 H01G(0.5) H01H(0.5) H01J(0.5) H01N(0.5) F00X(0.5) F00D(0.5) F0(0.5) F00T(0.5)
 F00Z(0.5) F00N(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 N00B(H00B), N00E(H00E), C00K(H00K), C00O(H00O), C00T(H00T), C00X(H00X),
 C011(H011), C013(H013), C015(H015), C017(H017)
6.b Idealised Me refined as rotating group:
 C010(H01A,H01B,H01C), C018(H01D,H01E,H01F), C01B(H01G,H01H,H01I), C01D(H01P,
 H01Q,H01R), C01E(H01S,H01T,H01U), C0B(H0BA,H0BB,H0BC), C01G(H01J,H01K,H01L),
 C01H(H01M,H01N,H01O)
;
_olex2_date_sample_data_collection 2019-11-07
_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 6.070
_oxdiff_exptl_absorpt_empirical_full_min 0.424