The isomer-sensitive electrochemical HER of ruthenium(II)-hydrido complexes involving redox-active azoheteroaromatics.
Seikh, Liton; Dhara, Suman; Singh, Ajit Kumar; Singh, Aditi; Dey, Sanchaita; Indra, Arindam; Lahiri, Goutam Kumar; Dalton transactions (Cambridge, England : 2003) 53 (2024) 1746–1756; doi:10.1039/d3dt02925e

data_7714712
_publ_section_title
;
 The isomer-sensitive electrochemical HER of ruthenium(II)-hydrido
 complexes involving redox-active azoheteroaromatics.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1746
_journal_page_last               1756
_journal_paper_doi               10.1039/d3dt02925e
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C45 H41 N6 O P2 Ru, Cl O4'
_chemical_formula_sum            'C45 H41.5 Cl N6 O5 P2 Ru'
_chemical_formula_weight         944.80
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-16
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-08-15 deposited with the CCDC.	2023-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.1410(10)
_cell_length_b                   15.7359(5)
_cell_length_c                   19.1556(5)
_cell_measurement_reflns_used    8749
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.0840
_cell_measurement_theta_min      1.8600
_cell_volume                     9386.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f    -14.01 129.99   0.40    4.00   6.61  -9.84 -31.50    --   360
  2  \w   -100.81  15.59   0.40    4.00    --   -9.84 -59.25  20.08  291
  3  \f   -130.46  22.34   0.40    4.00  81.02  -9.84  31.50    --   382
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0416977000
_diffrn_orient_matrix_UB_12      0.0012212000
_diffrn_orient_matrix_UB_13      0.0139972000
_diffrn_orient_matrix_UB_21      -0.0047422000
_diffrn_orient_matrix_UB_22      0.0224931000
_diffrn_orient_matrix_UB_23      0.0043609000
_diffrn_orient_matrix_UB_31      -0.0164381000
_diffrn_orient_matrix_UB_32      -0.0033400000
_diffrn_orient_matrix_UB_33      0.0340147000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1312
_diffrn_reflns_av_unetI/netI     0.1013
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            124760
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         1.685
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.508
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68297
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic brownish brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_description       block
_exptl_crystal_F_000             3876
_exptl_crystal_size_max          0.165
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.118
_refine_diff_density_min         -0.737
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 3986 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1092
_refine_ls_number_reflns         21461
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1382
_refine_ls_R_factor_gt           0.0657
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0787P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1453
_refine_ls_wR_factor_ref         0.1783
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                11795
_reflns_number_total             21461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02925e2.cif
_cod_data_source_block           '[1a]ClO4'
_cod_depositor_comments
'Adding full bibliography for 7714712--7714715.cif.'
_cod_original_formula_sum        'C45 H41.50 Cl N6 O5 P2 Ru'
_cod_database_code               7714712
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.921
_reflns_odcompleteness_completeness 87.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.80
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(O9) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.002
Uanis(Cl2) \\sim Ueq, Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.002
Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(N6) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.001
3. Others
 Fixed Uiso: H(0.001)
4.a Aromatic/amide H refined with riding coordinates:
 C89(H89), C29(H29), C88(H88), C71(H71), C23(H23), C59(H59), C39(H39),
 C51(H51), C41(H41), C35(H35), C37(H37), C36(H36), C31(H31), C38(H38), C55(H55),
  C45(H45), C73(H73), C63(H63), C17(H17), C33(H33), C77(H77), C47(H47),
 C52(H52), C27(H27), C70(H70), C43(H43), C48(H48), C87(H87), C44(H44), C85(H85),
  C65(H65), C15(H15), C25(H25), C61(H61), C11(H11), C30(H30), C58(H58),
 C76(H76), C2(H2), C69(H69), C83(H83), C64(H64), C3(H3), C86(H86), C20(H20),
 C79(H79), C21(H21), C24(H24), C42(H42), C32(H32), C81(H81), C68(H68), C75(H75),
  C56(H56), C82(H82), C67(H67), C19(H19), C14(H14), C26(H26), C12(H12),
 C18(H18), C80(H80), C57(H57), C62(H62), C13(H13), C74(H74), C6(H6), C7(H7)
4.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C46(H46A,H46B,H46C), C53(H53A,H53B,H53C), C1(H1A,H1B,H1C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              15566
_shelx_hkl_checksum              44490
_shelx_fab_checksum              32280
_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 1.431
_oxdiff_exptl_absorpt_empirical_full_min 0.790