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_7712895
_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         'C26 H20 F0.5 N7 O3 Ru S, F6 P, C2 H6 O S'
_chemical_formula_sum            'C28 H26 F6.5 N7 O4 P Ru S2'
_chemical_formula_weight         844.22
_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     dual
_audit_creation_date             2022-02-14
_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                 92.084(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0467(3)
_cell_length_b                   20.0220(7)
_cell_length_c                   14.8502(4)
_cell_measurement_reflns_used    10291
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      29.3240
_cell_measurement_theta_min      3.8030
_cell_volume                     3282.35(17)
_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    'ShelXT (Sheldrick, 2015)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -12.00  21.00   1.00   52.91    --   10.07  38.00 150.00   33
  2  \w    -16.00  12.00   1.00   52.91    --   10.07 -99.00   0.00   28
  3  \w     -3.00  80.00   1.00   52.91    --   10.07  38.00-180.00   83
  4  \w    -13.00  29.00   1.00   52.91    --  -10.22 -99.00 -60.00   42
;
_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      0.0387454000
_diffrn_orient_matrix_UB_12      -0.0093748000
_diffrn_orient_matrix_UB_13      -0.0348721000
_diffrn_orient_matrix_UB_21      0.0017001000
_diffrn_orient_matrix_UB_22      -0.0331511000
_diffrn_orient_matrix_UB_23      0.0168297000
_diffrn_orient_matrix_UB_31      -0.0512054000
_diffrn_orient_matrix_UB_32      -0.0082381000
_diffrn_orient_matrix_UB_33      -0.0280520000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0188
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            15099
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         3.347
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76318
_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    1.708
_exptl_crystal_description       plate
_exptl_crystal_F_000             1698
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.178
_refine_diff_density_min         -1.600
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         5753
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0394
_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^)+(0.0478P)^2^+6.5282P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0979
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5108
_reflns_number_total             5753
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00128h2.cif
_cod_data_source_block           ru4f
_cod_original_formula_sum        'C28 H26 F6.50 N7 O4 P Ru S2'
_cod_database_code               7712895
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C24 H17 F8 N7 O2 Ru S P'
_reflns_odcompleteness_completeness 99.70
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F2-C30
 1.4 with sigma of 0.02
 F0AA-C45
 1.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C48) = Uanis(C46)
Uanis(F6) = Uanis(F0AA)
Uanis(F6) = Uanis(F2)
Uanis(C43) = Uanis(C48) = Uanis(C47) = Uanis(C46) = Uanis(C45) = Uanis(C44)
4. Others
 Sof(F9B)=1-FVAR(1)
 Sof(F9A)=FVAR(1)
 Sof(F11B)=1-FVAR(2)
 Sof(F11A)=FVAR(2)
 Sof(F10B)=1-FVAR(3)
 Sof(F10A)=FVAR(3)
 Sof(F8B)=1-FVAR(4)
 Sof(F8A)=FVAR(4)
 Fixed Sof: O2B(0.75) O2A(0.25) F0AA(0.25) F2(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 N27(H27), N42(H42), C39(H39), C37(H37), C38(H38), C22(H22), C19(H19),
 C20(H20), C31(H31)
5.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_olex2_date_sample_data_collection 2019-10-25
_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 1.215
_oxdiff_exptl_absorpt_empirical_full_min 0.806