Introduction of substituents for tuning the redox properties of benzoate-bridged paddlewheel diruthenium(II,II) complexes: what does the OH group bring?
Kosaka, Wataru; Watanabe, Yudai; Kitayama, Taku; Itoh, Chisa; Miyasaka, Hitoshi; Dalton transactions (Cambridge, England : 2003) 54 (2025) 1838–1849; doi:10.1039/d4dt03020f

data_7717938
_publ_section_title
;
 Introduction of substituents for tuning the redox properties of
 benzoate-bridged paddlewheel diruthenium(II,II) complexes: what does the
 OH group bring?
;
_journal_issue                   5
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1838
_journal_page_last               1849
_journal_paper_doi               10.1039/d4dt03020f
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C36 H32 F4 O14 Ru2, 4(C4 H8 O)'
_chemical_formula_sum            'C52 H64 F4 O18 Ru2'
_chemical_formula_weight         1255.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-08-27
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2024-12-03 deposited with the CCDC.	2024-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2350(4)
_cell_length_b                   18.3819(5)
_cell_length_c                   20.2770(6)
_cell_measurement_reflns_used    23244
_cell_measurement_temperature    93
_cell_measurement_theta_max      31.2180
_cell_measurement_theta_min      2.3640
_cell_volume                     5305.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      93
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 28.626
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -110.00  70.00   0.50    5.00    --  -20.00  45.00   0.00  360
  2  \w   -110.00  70.00   0.50    5.00    --  -20.00  45.00  90.00  360
;
_diffrn_measurement_device       'AFC10: Fixed Chi 2 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0199458000
_diffrn_orient_matrix_UB_12      0.0284546000
_diffrn_orient_matrix_UB_13      -0.0190440000
_diffrn_orient_matrix_UB_21      -0.0418196000
_diffrn_orient_matrix_UB_22      -0.0205649000
_diffrn_orient_matrix_UB_23      -0.0036497000
_diffrn_orient_matrix_UB_31      -0.0182811000
_diffrn_orient_matrix_UB_32      0.0159819000
_diffrn_orient_matrix_UB_33      0.0291440000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            42242
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.704
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63329
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.571
_exptl_crystal_description       block
_exptl_crystal_F_000             2576
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.116
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.527
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     439
_refine_ls_number_reflns         6087
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0335P)^2^+5.0549P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0781
_refine_ls_wR_factor_ref         0.0850
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4698
_reflns_number_total             6087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03020f2.cif
_cod_data_source_block           ru_3-f-4-oh
_cod_database_code               7717938
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Ru2C36H32O14F4
_reflns_odcompleteness_completeness 92.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C23-O9 \\sim C23A-O9A
 with sigma of 0.02
 C20-C21 \\sim C20-C21A
 with sigma of 0.02
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C22-O8 \\sim C22A-O8A
 with sigma of 0.02
 C24-O9 \\sim C24A-O9A
 with sigma of 0.04
 C21-O8 \\sim C21A-O8A
 with sigma of 0.04
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C19-O8 \\sim C19-O8A
 with sigma of 0.02
 C19-C22 \\sim C19-C22A
 with sigma of 0.04
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C26-O9 \\sim C26A-O9A
 with sigma of 0.02
 C20-C22 \\sim C20-C22A
 with sigma of 0.04
 C25-O9 \\sim C25A-O9A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C23-C26 \\sim C23A-C26A
 with sigma of 0.04
3. Rigid bond restraints
 C23A, C24A, C25A, C26A, O9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19, C20, C21A, C22A, O8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C23A \\sim C24A \\sim C25A \\sim C26A \\sim O9A: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 1.7A
C19 \\sim C20 \\sim C21A \\sim C22A \\sim O8A: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 1.7A
5. Others
 Sof(H4)=Sof(F1A)=1-FVAR(1)
 Sof(H6)=Sof(F1)=FVAR(1)
 Sof(H11)=Sof(F2A)=1-FVAR(2)
 Sof(H13)=Sof(F2)=FVAR(2)
 Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24C)=Sof(H24D)=Sof(C25A)=
 Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(O9A)=1-FVAR(3)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(O9)=FVAR(3)
 Sof(H19C)=Sof(H19D)=Sof(H20C)=Sof(H20D)=Sof(C21A)=Sof(H21C)=Sof(H21D)=
 Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(O8A)=1-FVAR(4)
 Sof(H19A)=Sof(H19B)=Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=
 Sof(H22A)=Sof(H22B)=Sof(O8)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), C19(H19C,H19D), C20(H20A,H20B), C20(H20C,H20D), C21(H21A,H21B),
 C21A(H21C,H21D), C22(H22A,H22B), C22A(H22C,H22D), C23(H23A,H23B), C24(H24A,
 H24B), C25(H25A,H25B), C26(H26A,H26B), C23A(H23C,H23D), C24A(H24C,H24D),
 C25A(H25C,H25D), C26A(H26C,H26D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14)
6.c Idealised tetrahedral OH refined as rotating group:
 O3(H3A), O6(H6A)
;
_shelx_res_checksum              40802
_shelx_hkl_checksum              15091
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.555
_oxdiff_exptl_absorpt_empirical_full_min 0.562