Control of Dominant Conduction Orbitals by Peripheral Substituents in Paddle-Wheel Diruthenium Alkynyl Molecular Junctions
Ogawa, Shiori; Chattopadhyay, Swarup; Tanaka, Yuya; Ohto, Tatsuhiko; Tada, Tomofumi; Tada, Hirokazu; Fujii, Shintaro; Nishino, Tomoaki; Akita, Munetaka; Chemical Science  (2021) –; doi:10.1039/D1SC02407H

data_1564071
_publ_section_title
;
 Control of Dominant Conduction Orbitals by Peripheral Substituents in
 Paddle-Wheel Diruthenium Alkynyl Molecular Junctions
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02407H
_journal_year                    2021
_chemical_formula_moiety         'C78 H50 F24 N8 Ru2 S2'
_chemical_formula_sum            'C78 H50 F24 N8 Ru2 S2'
_chemical_formula_weight         1821.52
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-07
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-01-19 deposited with the CCDC.	2021-07-02 downloaded from the CCDC.
;
_cell_angle_alpha                68.497(5)
_cell_angle_beta                 86.771(4)
_cell_angle_gamma                67.279(5)
_cell_formula_units_Z            1
_cell_length_a                   12.3318(7)
_cell_length_b                   13.7567(8)
_cell_length_c                   15.6187(9)
_cell_measurement_reflns_used    7630
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      72.7370
_cell_measurement_theta_min      3.9080
_cell_volume                     2262.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.954
_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     21.00 115.00   0.50    0.22    --   41.93  57.00  90.00  188
  2  \w     67.00 112.00   0.50    0.22    --   41.93  77.00-120.00   90
  3  \w     13.00  66.00   0.50    0.22    --   41.93  77.00-120.00  106
  4  \w     89.00 145.00   0.50    0.90    --  106.13 108.00  61.00  112
  5  \w    -34.00  26.00   0.50    0.22    --   41.93 -37.00 120.00  120
  6  \w    -36.00  25.00   0.50    0.22    --   41.93 -19.00 150.00  122
  7  \w     79.00 160.00   0.50    0.90    --  106.13 125.00 120.00  162
  8  \w     84.00 166.00   0.50    0.90    --  106.13  45.00  60.00  164
  9  \w    116.00 177.00   0.50    0.90    --  106.13  45.00 -60.00  122
 10  \w     84.00 161.00   0.50    0.90    --  106.13  45.00-150.00  154
 11  \w     45.00  70.00   0.50    0.90    --  106.13 -61.00-180.00   50
 12  \w     41.00  73.00   0.50    0.90    --  106.13 -61.00-120.00   64
 13  \w     45.00  71.00   0.50    0.90    --  106.13 -61.00 -30.00   52
 14  \w     35.00  72.00   0.50    0.90    --  106.13 -61.00 120.00   74
 15  \w     51.00 112.00   0.50    0.90    --  106.13-125.00 -90.00  122
 16  \w     35.00 109.00   0.50    0.90    --  106.13-125.00-150.00  148
 17  \w     59.00  85.00   0.50    0.90    --  106.13-125.00-180.00   52
 18  \w     76.00 102.00   0.50    0.90    --  106.13 -94.00-150.00   52
 19  \w     82.00 108.00   0.50    0.90    --  106.13-108.00 -34.00   52
 20  \w     46.00  78.00   0.50    0.90    --  106.13-108.00 -34.00   64
 21  \w     33.00  64.00   0.50    0.90    --  106.13 -94.00-150.00   62
 22  \w     10.00  43.00   0.50    0.22    --   41.93-108.00 -34.00   66
 23  \w     81.00 107.00   0.50    0.90    --  106.13-111.00 134.79   52
 24  \w    -15.00  34.00   0.50    0.22    --  -41.93  19.00 -90.00   98
 25  \w     -8.00  20.00   0.50    0.22    --  -41.93  57.00 -30.00   56
 26  \w    -63.00 -18.00   0.50    0.22    --  -41.93  57.00 -30.00   90
 27  \w   -100.00 -28.00   0.50    0.90    -- -102.00  77.00  90.00  144
 28  \w    -66.00 -30.00   0.50    0.90    -- -102.00  61.00  30.00   72
 29  \w   -109.00 -36.00   0.50    0.90    -- -102.00 125.00 -90.00  146
 30  \w   -107.00 -74.00   0.50    0.90    -- -102.00 109.00   1.52   66
 31  \w    -98.00 -67.00   0.50    0.90    -- -102.00 108.00  61.00   62
 32  \w    -39.00 -12.00   0.50    0.22    --  -41.93 108.00  61.00   54
 33  \w    -86.00 -46.00   0.50    0.22    --  -41.93 108.00  61.00   80
 34  \w   -109.00 -57.00   0.50    0.90    -- -102.00 125.00  60.00  104
 35  \w    -53.00 -28.00   0.50    0.90    -- -102.00 125.00  60.00   50
 36  \w   -171.00 -94.00   0.50    0.90    -- -102.00 -45.00  30.00  154
 37  \w   -174.00 -87.00   0.50    0.90    -- -102.00 -94.00   0.00  174
 38  \w   -114.00 -84.00   0.50    0.90    -- -102.00-108.00 -34.00   60
 39  \w   -157.00-130.00   0.50    0.90    -- -102.00 -45.00-120.00   54
 40  \w   -128.00 -81.00   0.50    0.90    -- -102.00 -45.00-120.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0534407000
_diffrn_orient_matrix_UB_12      0.0474442000
_diffrn_orient_matrix_UB_13      -0.1008724000
_diffrn_orient_matrix_UB_21      0.1159146000
_diffrn_orient_matrix_UB_22      -0.0771779000
_diffrn_orient_matrix_UB_23      -0.0241524000
_diffrn_orient_matrix_UB_31      -0.0472630000
_diffrn_orient_matrix_UB_32      -0.0945280000
_diffrn_orient_matrix_UB_33      0.0243419000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0427
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            25560
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.882
_diffrn_reflns_theta_min         3.757
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.948
_exptl_absorpt_correction_T_max  0.674
_exptl_absorpt_correction_T_min  0.516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_description       irregular
_exptl_crystal_F_000             910
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         5.063
_refine_diff_density_min         -1.238
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.326
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         9320
_refine_ls_number_restraints     863
_refine_ls_restrained_S_all      1.297
_refine_ls_R_factor_all          0.1125
_refine_ls_R_factor_gt           0.1068
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2854
_refine_ls_wR_factor_ref         0.2940
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7800
_reflns_number_total             9320
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02407h2.cif
_cod_data_source_block           200106_so58
_cod_original_cell_volume        2262.7(2)
_cod_database_code               1564071
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Ru2CHNS
_diffrn_oxdiff_digest_frames
;
0105ad1a2205b286ee0997dd45dfecd24c0380872c1
;
_diffrn_oxdiff_digest_hkl
;
01f0faf1dfe74585d35b4417bffb8e939cee26
;
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C7-F2
 1.35 with sigma of 0.02
 C7-F3
 1.35 with sigma of 0.02
 C7-F1
 1.35 with sigma of 0.02
 C15-F8
 1.35 with sigma of 0.02
 C15-F7
 1.35 with sigma of 0.02
 C15-F9
 1.35 with sigma of 0.02
 C22-F4
 1.35 with sigma of 0.02
 C22-F6
 1.35 with sigma of 0.02
 C22-F5
 1.35 with sigma of 0.02
 C30-F10
 1.35 with sigma of 0.02
 C30-F11
 1.35 with sigma of 0.02
 C30-F12
 1.35 with sigma of 0.02
 S1-C39
 1.82 with sigma of 0.02
 S1-C39 \\sim S1-C39A
 with sigma of 0.02
3. Rigid bond restraints
 S1, Ru1, C31, N1, N3, C32, C8, C1, C16, C23, C33, N2, C6, C2, C17, C21, N4,
 C34, C38, C9, C5, C3, C18, C20, C24, C35, C37, C14, C10, C4, C19, C29, C25,
 C36, C13, C11, C7, C22, C28, C26, C12, F1, F2, F3, F5, F6, F4, C27, C39, C39A,
 C15, C30, F9, F8, F7, F11, F12, F10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C36 \\sim Ru1 \\sim C31 \\sim N1 \\sim N3 \\sim C32 \\sim C8 \\sim C1 \\sim C16
\\sim C23 \\sim C33 \\sim N2 \\sim C6 \\sim C2 \\sim C17 \\sim C21 \\sim N4
\\sim C34 \\sim C38 \\sim C9 \\sim C5 \\sim C3 \\sim C18 \\sim C20 \\sim C24
\\sim C35 \\sim C37 \\sim C14 \\sim C10 \\sim C4 \\sim C19 \\sim C29 \\sim C25
\\sim C13 \\sim C11 \\sim C7 \\sim C22 \\sim C28 \\sim C26 \\sim S1 \\sim C12
\\sim F1 \\sim F2 \\sim F3 \\sim F5 \\sim F6 \\sim F4 \\sim C27 \\sim C39 \\sim
C39A \\sim C15 \\sim C30 \\sim F9 \\sim F8 \\sim F7 \\sim F11 \\sim F12 \\sim
F10: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(S1) \\sim Ueq, Uanis(Ru1) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(N1)
\\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C1) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(F1) \\sim Ueq,
Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim
Ueq, Uanis(F4) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C39A) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(F9)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F10) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
5. Others
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=1-FVAR(1)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C17(H17), C8(H8), C23(H23), C14(H14), C10(H10), C29(H29), C6(H6), C13(H13),
 C28(H28), C21(H21), C18(H18), C25(H25), C26(H26), C2(H2), C11(H11), C5(H5),
 C20(H20), C3(H3), C35(H35), C34(H34), C38(H38), C37(H37)
6.b Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C39A(H39D,H39E,H39F)
;
_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 1.489
_oxdiff_exptl_absorpt_empirical_full_min 0.636