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_1564072
_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         'C70 H50 Cl8 N8 Ru2 S2'
_chemical_formula_sum            'C70 H50 Cl8 N8 Ru2 S2'
_chemical_formula_weight         1553.04
_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   geom
_audit_creation_date             2020-07-31
_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                90
_cell_angle_beta                 94.565(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9221(3)
_cell_length_b                   19.5861(4)
_cell_length_c                   23.0841(3)
_cell_measurement_reflns_used    36495
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      74.3200
_cell_measurement_theta_min      3.3660
_cell_volume                     6725.3(2)
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_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     84.00 178.00   0.50    0.36    --  106.13  82.00  57.00  188
  2  \w     32.00  73.00   0.50    0.36    --  106.13 -61.00 150.00   82
  3  \w     32.00  73.00   0.50    0.36    --  106.13 -61.00  60.00   82
  4  \w     42.00  73.00   0.50    0.36    --  106.13 -61.00   0.00   62
  5  \w     32.00  73.00   0.50    0.36    --  106.13 -61.00 -30.00   82
  6  \w     32.00  73.00   0.50    0.36    --  106.13 -61.00-150.00   82
  7  \w     83.00 178.00   0.50    0.36    --  106.13  30.00 -30.00  190
  8  \w    -31.00  73.00   0.50    0.09    --   42.05 -82.00 -64.00  208
  9  \w     33.00 105.00   0.50    0.36    --  106.13 -94.00 120.00  144
 10  \w     33.00 112.00   0.50    0.36    --  106.13-125.00 150.00  158
 11  \w     32.00 137.00   0.50    0.36    --  106.13 -82.00 -64.00  210
 12  \w     33.00 105.00   0.50    0.36    --  106.13 -94.00-150.00  144
 13  \w    -40.00  35.00   0.50    0.09    --  -42.05  37.00-180.00  150
 14  \w    -24.00  39.00   0.50    0.09    --  -42.05  19.00-150.00  126
 15  \w    -24.00  39.00   0.50    0.09    --  -42.05  19.00 -60.00  126
 16  \w   -116.00 -19.00   0.50    0.09    --  -42.05 -57.00 -60.00  194
 17  \w   -175.00 -80.00   0.50    0.36    -- -102.00 -82.00 -64.00  190
 18  \w    -73.00  32.00   0.50    0.09    --  -42.05  82.00  57.00  210
 19  \w   -133.00 -28.00   0.50    0.36    -- -102.00  82.00  57.00  210
 20  \w    -69.00 -28.00   0.50    0.36    -- -102.00  61.00   0.00   82
 21  \w    -69.00 -28.00   0.50    0.36    -- -102.00  61.00 120.00   82
 22  \w    -69.00 -28.00   0.50    0.36    -- -102.00  61.00 -90.00   82
 23  \w    -69.00 -28.00   0.50    0.36    -- -102.00  61.00-120.00   82
 24  \w    -69.00 -28.00   0.50    0.36    -- -102.00  61.00-180.00   82
;
_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      0.0233445000
_diffrn_orient_matrix_UB_12      0.0681688000
_diffrn_orient_matrix_UB_13      -0.0284858000
_diffrn_orient_matrix_UB_21      0.0957497000
_diffrn_orient_matrix_UB_22      -0.0035868000
_diffrn_orient_matrix_UB_23      0.0302250000
_diffrn_orient_matrix_UB_31      0.0318717000
_diffrn_orient_matrix_UB_32      -0.0390441000
_diffrn_orient_matrix_UB_33      -0.0525204000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            66360
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.973
_diffrn_reflns_theta_min         3.407
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.528
_exptl_absorpt_correction_T_max  0.157
_exptl_absorpt_correction_T_min  0.152
_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    1.534
_exptl_crystal_description       block
_exptl_crystal_F_000             3128
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.956
_refine_diff_density_min         -1.093
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     905
_refine_ls_number_reflns         13849
_refine_ls_number_restraints     1592
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.0505
_refine_ls_R_factor_gt           0.0462
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0581P)^2^+17.5521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1196
_refine_ls_wR_factor_ref         0.1228
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12126
_reflns_number_total             13849
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02407h2.cif
_cod_data_source_block           ru2c6h5cl
_cod_database_code               1564072
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ru N Cl C H S'
_shelx_estimated_absorpt_t_max   0.255
_shelx_estimated_absorpt_t_min   0.211
_diffrn_oxdiff_digest_frames
;
01c921b26bbb4da0bcd9728ec600885b14000416a36
;
_diffrn_oxdiff_digest_hkl
;
019c27702271dad4868988145634957f45f90c
;
_reflns_odcompleteness_completeness 99.89
_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
 Ru2-C53 \\sim Ru2-C53A
 with sigma of 0.02
 S1-C58 \\sim S1A-C58A
 with sigma of 0.02
 S1-C61 \\sim S1A-C61A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C54-C55 \\sim C54A-C55A
 with sigma of 0.02
 C55-C60 \\sim C55A-C60A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.02
 C60-C59 \\sim C60A-C59A
 with sigma of 0.02
 C56-C57 \\sim C56A-C57A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C59-C58 \\sim C59A-C58A
 with sigma of 0.02
 Ru2-C54 \\sim Ru2-C54A
 with sigma of 0.04
 S1-C57 \\sim S1A-C57A
 with sigma of 0.04
 S1-C59 \\sim S1A-C59A
 with sigma of 0.04
 C53-C55 \\sim C53A-C55A
 with sigma of 0.04
 C54-C60 \\sim C54A-C60A
 with sigma of 0.04
 C54-C56 \\sim C54A-C56A
 with sigma of 0.04
 C55-C57 \\sim C55A-C57A
 with sigma of 0.04
 C55-C59 \\sim C55A-C59A
 with sigma of 0.04
 C60-C56 \\sim C60A-C56A
 with sigma of 0.04
 C60-C58 \\sim C60A-C58A
 with sigma of 0.04
 C56-C58 \\sim C56A-C58A
 with sigma of 0.04
 C57-C59 \\sim C57A-C59A
 with sigma of 0.04
 C58-C61 \\sim C58A-C61A
 with sigma of 0.04
3. Rigid bond restraints
 C11, Ru1, N2, C62, N4, N8, N6, Ru2, C7, C8, C63, C21, C20, C47, C46, C34, C33,
  C53, C53A, N7, N5, N3, N1, C9, C13, C64, C22, C26, C48, C52, C39, C35, C54,
 C54A, C40, C27, C14, C1, C10, C12, C69, C65, C23, C25, C49, C51, C38, C36, C55,
  C55A, C45, C41, C28, C32, C15, C19, C6, C2, C68, C66, C24, C50, C37, C60, C56,
  C60A, C56A, C44, C42, C29, C31, C16, C18, C5, C3, Cl2, C67, Cl4, Cl8, Cl6,
 C59, C57, C59A, C57A, C43, C30, C17, C4, S2, C58, C58A, Cl7, Cl5, Cl3, Cl1,
 C70, S1, S1A, C61, C61A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C12 \\sim Ru1 \\sim N2 \\sim C62 \\sim N4 \\sim N8 \\sim N6 \\sim Ru2 \\sim C7
\\sim C8 \\sim C63 \\sim C21 \\sim C20 \\sim C47 \\sim C46 \\sim C34 \\sim C33
\\sim C53 \\sim C53A \\sim N7 \\sim N5 \\sim N3 \\sim N1 \\sim C9 \\sim C13
\\sim C64 \\sim C22 \\sim C26 \\sim C48 \\sim C52 \\sim C39 \\sim C35 \\sim C54
\\sim C54A \\sim C40 \\sim C27 \\sim C14 \\sim C1 \\sim C10 \\sim C69 \\sim C65
\\sim C23 \\sim C25 \\sim C49 \\sim C51 \\sim C38 \\sim C36 \\sim C55 \\sim
C55A \\sim C45 \\sim C41 \\sim C28 \\sim C32 \\sim C15 \\sim C19 \\sim C6 \\sim
C2 \\sim C11 \\sim C68 \\sim C66 \\sim C24 \\sim C50 \\sim C37 \\sim C60 \\sim
C56 \\sim C60A \\sim C56A \\sim C44 \\sim C42 \\sim C29 \\sim C31 \\sim C16
\\sim C18 \\sim C5 \\sim C3 \\sim Cl2 \\sim C67 \\sim Cl4 \\sim Cl8 \\sim Cl6
\\sim C59 \\sim C57 \\sim C59A \\sim C57A \\sim C43 \\sim C30 \\sim C17 \\sim
C4 \\sim S2 \\sim C58 \\sim C58A \\sim Cl7 \\sim Cl5 \\sim Cl3 \\sim Cl1 \\sim
C70 \\sim S1 \\sim S1A \\sim C61 \\sim C61A: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(C7) \\sim Ueq, Uanis(Ru1) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C62)
\\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(N8) \\sim Ueq, Uanis(N6) \\sim Ueq,
Uanis(Ru2) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(N5)
\\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C53A) \\sim Ueq,
Uanis(N7) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C64) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C40) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C28) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C55) \\sim Ueq,
Uanis(C55A) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C66) \\sim Ueq,
Uanis(C24) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C44) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C60A) \\sim Ueq, Uanis(C56A) \\sim Ueq, Uanis(Cl8) \\sim Ueq,
Uanis(Cl2) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C59A)
\\sim Ueq, Uanis(C57A) \\sim Ueq, Uanis(S2) \\sim Ueq, Uanis(Cl1) \\sim Ueq,
Uanis(Cl3) \\sim Ueq, Uanis(Cl7) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C58A)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(S1A) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C61A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C53) \\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C55A) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C60A) \\sim Ueq,
Uanis(C60) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C59A) \\sim Ueq, Uanis(C58A)
\\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C57A) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C56A) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(S1A) \\sim Ueq, Uanis(S1)
\\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C61A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Others
 Sof(C53A)=Sof(C54A)=Sof(C55A)=Sof(C60A)=Sof(H60A)=Sof(C59A)=Sof(H59A)=
 Sof(C58A)=Sof(C57A)=Sof(H57A)=Sof(C56A)=Sof(H56A)=Sof(S1A)=Sof(C61A)=Sof(H61D)=
 Sof(H61E)=Sof(H61F)=1-FVAR(1)
 Sof(S1)=Sof(C53)=Sof(C54)=Sof(C55)=Sof(C60)=Sof(H60)=Sof(C56)=Sof(H56)=
 Sof(C57)=Sof(H57)=Sof(C59)=Sof(H59)=Sof(C58)=Sof(C61)=Sof(H61A)=Sof(H61B)=
 Sof(H61C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C48(H48), C46(H46), C7(H7), C33(H33), C6(H6), C2(H2), C28(H28), C9(H9),
 C32(H32), C45(H45), C39(H39), C5(H5), C13(H13), C35(H35), C20(H20), C49(H49),
 C29(H29), C3(H3), C16(H16), C41(H41), C12(H12), C15(H15), C22(H22), C26(H26),
 C25(H25), C36(H36), C38(H38), C42(H42), C19(H19), C10(H10), C44(H44), C51(H51),
  C52(H52), C31(H31), C69(H69), C68(H68), C18(H18), C65(H65), C23(H23),
 C66(H66), C60(H60), C56(H56), C57(H57), C59(H59), C60A(H60A), C59A(H59A),
 C57A(H57A), C56A(H56A)
6.b Idealised Me refined as rotating group:
 C70(H70A,H70B,H70C), C61(H61A,H61B,H61C), C61A(H61D,H61E,H61F)
;
_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 1.277
_oxdiff_exptl_absorpt_empirical_full_min 0.788