Remarkable Stability of a Molecular Ruthenium Complex in PEM Water Electrolysis
Bellini, Marco; Bösken, Jonas; Bartoli, Francesco; Miller, Hamish; Thöny, Debora; Poggini, Lorenzo; Wörle, Michael; Oberhauser, Werner; Gamboa-Carballo, Juan José; Lavacchi, Alessandro; Krumeich, Frank; Grützmacher, Hansjörg; Vizza, Francesco; Chemical Science  (2022) –; doi:10.1039/D1SC07234J

data_1566537
_publ_section_title
;
 Remarkable Stability of a Molecular Ruthenium Complex in PEM Water
 Electrolysis
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC07234J
_journal_year                    2022
_chemical_formula_moiety         'C38 H36 N3 Ru2, F6 P, 3(C2 H3 N)'
_chemical_formula_sum            'C44 H45 F6 N6 P Ru2'
_chemical_formula_weight         1004.97
_chemical_name_systematic        '[Ru2(NCCH3)(u-H)(Me2dad)(dbcot)2]PF6'
_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             2021-03-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-03-31 deposited with the CCDC.	2022-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.846(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6141(2)
_cell_length_b                   12.2041(2)
_cell_length_c                   27.4630(5)
_cell_measurement_reflns_used    24915
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.1200
_cell_measurement_theta_min      2.2530
_cell_volume                     4177.47(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0839
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.941
_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    -86.00  12.00   1.00   30.00    --  -16.59 -77.00 120.00   98
  2  \w    -85.00   2.00   1.00   30.00    --  -16.59 -57.00   0.00   87
  3  \w    -80.00  -5.00   1.00   30.00    --  -16.59 138.00-153.28   75
  4  \w    -85.00   2.00   1.00   30.00    --  -16.59 -57.00-150.00   87
  5  \w    -35.00  52.00   1.00   30.00    --  -16.59  57.00 -90.00   87
  6  \w    -85.00   2.00   1.00   30.00    --  -16.59 -57.00 -90.00   87
  7  \w    -52.00  46.00   1.00   30.00    --   17.06 -77.00   0.00   98
  8  \w    -25.00  58.00   1.00   30.00    --   17.06 -99.00-180.00   83
  9  \w    -25.00  58.00   1.00   30.00    --   17.06 -99.00  90.00   83
 10  \w    -25.00  24.00   1.00   30.00    --  -16.59 -99.00   0.00   49
 11  \w    -21.00  89.00   1.00   30.00    --   17.06  19.00   0.00  110
 12  \w    -25.00  58.00   1.00   30.00    --   17.06 -99.00  30.00   83
 13  \w    -25.00  58.00   1.00   30.00    --   17.06 -99.00-120.00   83
 14  \w     34.00  91.00   1.00   30.00    --   17.06 179.00 -90.00   57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0102491000
_diffrn_orient_matrix_UB_12      0.0369858000
_diffrn_orient_matrix_UB_13      0.0186486000
_diffrn_orient_matrix_UB_21      0.0160927000
_diffrn_orient_matrix_UB_22      0.0444416000
_diffrn_orient_matrix_UB_23      -0.0138348000
_diffrn_orient_matrix_UB_31      -0.0535782000
_diffrn_orient_matrix_UB_32      0.0062821000
_diffrn_orient_matrix_UB_33      -0.0120003000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            105357
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.276
_diffrn_reflns_theta_min         1.690
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.828
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85410
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.598
_exptl_crystal_description       block
_exptl_crystal_F_000             2032
_exptl_crystal_recrystallization_method
'The crystals were obtained by layering an acetonitrile solution of the complex with diisopropyl ether.'
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.11
_refine_diff_density_max         1.031
_refine_diff_density_min         -1.005
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.232
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     542
_refine_ls_number_reflns         10726
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.232
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0462
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0249P)^2^+10.7410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8852
_reflns_number_total             10726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07234j2.cif
_cod_data_source_block           exp_5227
_cod_database_code               1566537
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H30Ru2PF6
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.687
_reflns_odcompleteness_completeness 99.96
_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 C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C13(H13), C14(H14), C21(H21), C22(H22),
 C29(H29), C30(H30)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C16(H16), C17(H17), C18(H18), C19(H19),
 C24(H24), C25(H25), C26(H26), C27(H27), C32(H32), C33(H33), C34(H34), C35(H35)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C38(H38A,H38B,H38C), C44(H44A,H44B,H44C),
 C42(H42A,H42B,H42C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              86679
_shelx_hkl_checksum              48141
_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 1.254
_oxdiff_exptl_absorpt_empirical_full_min 0.908