Reversible Binding of Dinitrogen on a Thiolate-Bridged Cobalt-Ruthenium Complex Supported by a Flexible Bidentate Phosphine Ligand
Dong, Wenjing; Yang, Dawei; Mei, Tao; Wang, Baomin; Qu, Jingping; Dalton Transactions  (2022) –; doi:10.1039/D2DT01534J

data_7710431
_publ_section_title
;
 Reversible Binding of Dinitrogen on a Thiolate-Bridged Cobalt-Ruthenium
 Complex Supported by a Flexible Bidentate Phosphine Ligand
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01534J
_journal_year                    2022
_chemical_formula_moiety
'1(C H2 Cl2), C40 H47 Cl Co N2 P2 Ru S3, C24 H20 B'
_chemical_formula_sum            'C65 H69 B Cl3 Co N2 P2 Ru S3'
_chemical_formula_weight         1313.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2022-05-31 deposited with the CCDC.	2022-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.294(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0693(9)
_cell_length_b                   14.2710(10)
_cell_length_c                   35.980(3)
_cell_measurement_reflns_used    9952
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      28.208
_cell_measurement_theta_min      2.212
_cell_volume                     6187.0(8)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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      200.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0857
_diffrn_reflns_av_unetI/netI     0.0771
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            59823
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.980
_diffrn_source                   'sealed tube'
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.836
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6303
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1534 before and 0.0839 after correction.
The Ratio of minimum to maximum transmission is 0.8452.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dull dark black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.410
_exptl_crystal_description       block
_exptl_crystal_F_000             2712
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   0.7457
_exptl_transmission_factor_min   0.6303
_refine_diff_density_max         1.015
_refine_diff_density_min         -1.081
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.164
_refine_ls_hydrogen_treatment    'riding mode'
_refine_ls_matrix_type           full
_refine_ls_number_parameters     964
_refine_ls_number_reflns         10888
_refine_ls_number_restraints     1125
_refine_ls_restrained_S_all      1.284
_refine_ls_R_factor_all          0.1330
_refine_ls_R_factor_gt           0.0932
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0277P)^2^+53.4898P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1776
_refine_ls_wR_factor_ref         0.1882
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7782
_reflns_number_total             10888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01534j2.cif
_cod_data_source_block           1_CCDC3
_cod_original_cell_volume        6186.9(8)
_cod_database_code               7710431
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Ru1-P2 \\sim Ru1A-P2
 with sigma of 0.02
 C3-C1 \\sim C3A-C1A
 with sigma of 0.04
 Ru1-S2 \\sim Ru1A-S2A
 with sigma of 0.02
 C4-C1 \\sim C4A-C1A
 with sigma of 0.04
 Ru1-P1 \\sim Ru1A-P1
 with sigma of 0.02
 Co1-S2 \\sim Co1A-S2A
 with sigma of 0.02
 C5-C2 \\sim C5A-C2A
 with sigma of 0.04
 Ru1-S1 \\sim Ru1A-S1A
 with sigma of 0.02
 Ru1-Cl1 \\sim Ru1A-Cl1A
 with sigma of 0.02
 Co1-S1 \\sim Co1A-S1A
 with sigma of 0.02
 Ru1-N1 \\sim Ru1A-N1A
 with sigma of 0.02
 C8-C2 \\sim C8A-C2A
 with sigma of 0.04
 Co1-S3 \\sim Co1A-S3A
 with sigma of 0.02
 C1-C10 \\sim C1A-C10A
 with sigma of 0.04
 S3-C1 \\sim S3A-C1A
 with sigma of 0.04
 C3-C5 \\sim C3A-C5A
 with sigma of 0.04
 C1-C7 \\sim C1A-C7A
 with sigma of 0.04
 S3-C4 \\sim S3A-C4A
 with sigma of 0.04
 C3-C8 \\sim C3A-C8A
 with sigma of 0.02
 C4-C9 \\sim C4A-C9A
 with sigma of 0.02
 C3-C9 \\sim C3A-C9A
 with sigma of 0.04
 S2-C14 \\sim S2A-C14A
 with sigma of 0.02
 C5-C10 \\sim C5A-C10A
 with sigma of 0.02
 C4-C5 \\sim C4A-C5A
 with sigma of 0.04
 S1-C11 \\sim S1A-C11A
 with sigma of 0.02
 C1-C6 \\sim C1A-C6A
 with sigma of 0.02
 C2-C7 \\sim C2A-C7A
 with sigma of 0.02
 S3-C13 \\sim S3A-C13A
 with sigma of 0.02
 Ru1-Co1 \\sim Ru1A-Co1A
 with sigma of 0.04
 S3-C3 \\sim S3A-C3A
 with sigma of 0.04
 S3-C12 \\sim S3A-C12A
 with sigma of 0.02
 N2-N1 \\sim N2A-N1A
 with sigma of 0.02
 S3-C5 \\sim S3A-C5A
 with sigma of 0.04
 S3-C2 \\sim S3A-C2A
 with sigma of 0.04
 Co1-C3 \\sim Co1A-C3A
 with sigma of 0.04
 S3-C11 \\sim S3A-C11A
 with sigma of 0.04
 Co1-C4 \\sim Co1A-C4A
 with sigma of 0.04
 Co1-C5 \\sim Co1A-C5A
 with sigma of 0.04
 Co1-C8 \\sim Co1A-C8A
 with sigma of 0.04
 Co1-C1 \\sim Co1A-C1A
 with sigma of 0.04
 C3-C4 \\sim C3A-C4A
 with sigma of 0.04
 Co1-C2 \\sim Co1A-C2A
 with sigma of 0.04
 Co1-C9 \\sim Co1A-C9A
 with sigma of 0.04
 Co1-C10 \\sim Co1A-C10A
 with sigma of 0.04
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C14-C13 \\sim C14A-C13A
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.04
 C13-C12 \\sim C13A-C12A
 with sigma of 0.04
 Co1-C11 \\sim Co1A-C11A
 with sigma of 0.04
 C3-C7 \\sim C3A-C7A
 with sigma of 0.04
 Cl1-N1 \\sim Cl1A-N1A
 with sigma of 0.04
 Co1-C14 \\sim Co1A-C14A
 with sigma of 0.04
 Ru1-N2 \\sim Ru1A-N2A
 with sigma of 0.04
 Co1-C13 \\sim Co1A-C13A
 with sigma of 0.04
 Ru1-C11 \\sim Ru1A-C11A
 with sigma of 0.04
 Co1-C6 \\sim Co1A-C6A
 with sigma of 0.04
 Co1-C12 \\sim Co1A-C12A
 with sigma of 0.04
 Ru1-C14 \\sim Ru1A-C14A
 with sigma of 0.04
 Co1-C7 \\sim Co1A-C7A
 with sigma of 0.04
 C4-C8 \\sim C4A-C8A
 with sigma of 0.04
 C4-C2 \\sim C4A-C2A
 with sigma of 0.04
 C4-C10 \\sim C4A-C10A
 with sigma of 0.04
 S3-C14 \\sim S3A-C14A
 with sigma of 0.04
 C5-C1 \\sim C5A-C1A
 with sigma of 0.04
 C5-C9 \\sim C5A-C9A
 with sigma of 0.04
 C5-C6 \\sim C5A-C6A
 with sigma of 0.04
 C1-C2 \\sim C1A-C2A
 with sigma of 0.04
 S2-C3 \\sim S2A-C3A
 with sigma of 0.04
 S2-C4 \\sim S2A-C4A
 with sigma of 0.04
 S2-C5 \\sim S2A-C5A
 with sigma of 0.04
 S2-C1 \\sim S2A-C1A
 with sigma of 0.04
 C2-C6 \\sim C2A-C6A
 with sigma of 0.04
 S2-C2 \\sim S2A-C2A
 with sigma of 0.04
 S1-C3 \\sim S1A-C3A
 with sigma of 0.04
 S1-C4 \\sim S1A-C4A
 with sigma of 0.04
 S1-C5 \\sim S1A-C5A
 with sigma of 0.04
 S1-C1 \\sim S1A-C1A
 with sigma of 0.04
 S1-C2 \\sim S1A-C2A
 with sigma of 0.04
 P2-S2 \\sim P2-S2A
 with sigma of 0.04
 P2-S1 \\sim P2-S1A
 with sigma of 0.04
 P2-Cl1 \\sim P2-Cl1A
 with sigma of 0.04
 P2-N1 \\sim P2-N1A
 with sigma of 0.04
 S2-P1 \\sim S2A-P1
 with sigma of 0.04
 S2-S1 \\sim S2A-S1A
 with sigma of 0.04
 S2-Cl1 \\sim S2A-Cl1A
 with sigma of 0.04
 S2-S3 \\sim S2A-S3A
 with sigma of 0.04
 S2-N1 \\sim S2A-N1A
 with sigma of 0.04
 S2-C13 \\sim S2A-C13A
 with sigma of 0.04
 P1-S1 \\sim P1-S1A
 with sigma of 0.04
 P1-Cl1 \\sim P1-Cl1A
 with sigma of 0.04
 P1-N1 \\sim P1-N1A
 with sigma of 0.04
 S1-Cl1 \\sim S1A-Cl1A
 with sigma of 0.04
 S1-S3 \\sim S1A-S3A
 with sigma of 0.04
 S1-N1 \\sim S1A-N1A
 with sigma of 0.04
 S1-C12 \\sim S1A-C12A
 with sigma of 0.04
 Cl2-C65 \\sim Cl3-C65
 with sigma of 0.02
 Cl2-C65 \\sim Cl2A-C65A
 with sigma of 0.02
 Cl2-Cl3 \\sim Cl2A-Cl3A
 with sigma of 0.04
 Cl3-C65 \\sim Cl3A-C65A
 with sigma of 0.02
 Cl2A-C65A \\sim Cl2B-C65B
 with sigma of 0.02
 C65A-Cl3A \\sim C65B-Cl3B
 with sigma of 0.02
 Cl2A-Cl3A \\sim Cl2B-Cl3B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Ru1 \\sim Co1 \\sim Cl1 \\sim S1 \\sim S2 \\sim S3 \\sim N1 \\sim N2 \\sim C1
\\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim
C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim Ru1A \\sim Co1A \\sim Cl1A
\\sim S1A \\sim S2A \\sim S3A \\sim N1A \\sim N2A \\sim C1A \\sim C2A \\sim C3A
\\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim
C11A \\sim C12A \\sim C13A \\sim C14A: within 2.5A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2.5A
Cl3 \\sim Cl2 \\sim C65: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C65 \\sim Cl2 \\sim Cl3 \\sim Cl3B \\sim C65B \\sim Cl2B \\sim Cl2A \\sim C65A
\\sim Cl3A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Cl2 \\sim C65 \\sim Cl3 \\sim C65A \\sim Cl2A \\sim Cl3A \\sim C65B \\sim Cl2B
\\sim Cl3B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(C65) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Cl2, Cl3, C65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2A, C65A, Cl3A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl3, Cl2, C65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C65B, Cl3B, Cl2B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 1*[Sof(Cl2)+Sof(Cl3)+Sof(C65)+Sof(H65A)+Sof(H65B)]+1*[Sof(Cl2A)+Sof(C65A)+
 Sof(H65C)+Sof(H65D)+Sof(Cl3A)]+1*[Sof(C65B)+Sof(H65E)+Sof(H65F)+Sof(Cl2B)+
 Sof(Cl3B)]=1 with esd of 0.0001
 Sof(Ru1A)=Sof(Co1A)=Sof(Cl1A)=Sof(S1A)=Sof(S2A)=Sof(S3A)=Sof(N1A)=Sof(N2A)=
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=1-FVAR(1)
 Sof(Ru1)=Sof(Co1)=Sof(Cl1)=Sof(S1)=Sof(S2)=Sof(S3)=Sof(N1)=Sof(N2)=Sof(C1)=
 Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=
 Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=FVAR(1)
 Sof(Cl2)=Sof(Cl3)=Sof(C65)=Sof(H65A)=Sof(H65B)=FVAR(2)
 Sof(Cl2A)=Sof(C65A)=Sof(H65C)=Sof(H65D)=Sof(Cl3A)=FVAR(3)
 Sof(C65B)=Sof(H65E)=Sof(H65F)=Sof(Cl2B)=Sof(Cl3B)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C27(H27A,H27B), C28(H28A,H28B), C11(H11A,H11B), C12(H12A,
 H12B), C13(H13A,H13B), C14(H14A,H14B), C11A(H11C,H11D), C12A(H12C,H12D),
 C13A(H13C,H13D), C14A(H14C,H14D), C65A(H65C,H65D), C65B(H65E,H65F)
6.b Me refined with riding coordinates:
 C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC), C10A(H10D,H10E,H10F)
6.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
  C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43),
 C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52),
  C54(H54), C55(H55), C56(H56), C57(H57), C58(H58), C60(H60), C61(H61),
 C62(H62), C63(H63), C64(H64)
6.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C)
;
_shelx_res_checksum              29175
_olex2_submission_special_instructions 'No special instructions were received'