The electron-donating effect of methyl in pyridine-2-thiol cobalt complexes regulating electrocatalytic reduction of CO<sub>2</sub>.
Guo, Shipeng; Liu, Yipei; Lin, Chenchen; Xie, Lingfeng; Yi, Xiaoyi; He, Piao; Dalton transactions (Cambridge, England : 2003) 54 (2025) 17078–17082; doi:10.1039/d5dt01953b

data_7719901
_publ_section_title
;
 The electron-donating effect of methyl in pyridine-2-thiol cobalt
 complexes regulating electrocatalytic reduction of CO<sub>2</sub>.
;
_journal_issue                   46
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              17078
_journal_page_last               17082
_journal_paper_doi               10.1039/d5dt01953b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '8(C22 H20 Co N4 S2), 4(Cl4 Co), 4(C H2 Cl2)'
_chemical_formula_sum            'C180 H168 Cl24 Co12 N32 S16'
_chemical_formula_weight         4850.37
_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             2024-04-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2024-04-28 deposited with the CCDC.	2025-11-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.161(9)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   14.193(4)
_cell_length_b                   15.635(5)
_cell_length_c                   27.301(7)
_cell_measurement_reflns_used    7155
_cell_measurement_temperature    301.00
_cell_measurement_theta_max      21.035
_cell_measurement_theta_min      2.201
_cell_volume                     5944(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      301.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  bruker
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0822
_diffrn_reflns_av_unetI/netI     0.0596
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            68334
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.541
_diffrn_reflns_theta_min         1.958
_diffrn_source_current           1.6
_diffrn_source_power             0.08
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.274
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5900
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1560 before and 0.0950 after correction.
The Ratio of minimum to maximum transmission is 0.7913.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       block
_exptl_crystal_F_000             2460
_refine_diff_density_max         1.015
_refine_diff_density_min         -1.065
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         13660
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.1617
_refine_ls_R_factor_gt           0.1008
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1044P)^2^+22.6934P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2370
_refine_ls_wR_factor_ref         0.2838
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7761
_reflns_number_total             13660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01953b2.cif
_cod_data_source_block           mo_240411lu_lgpz090169_zcs_0m
_cod_database_code               7719901
_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
 Cl1-C01X = Cl-C01X
 1.79 with sigma of 0.01
 ClA-Cl1A
 2.924 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl1A \\sim C01Y \\sim ClA: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
4. Others
 Sof(ClA)=Sof(C01Y)=Sof(Cl1A)=1-FVAR(1)
 Sof(Cl)=Sof(Cl1)=Sof(C01X)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C01X(H01Z,H01)
5.b Aromatic/amide H refined with riding coordinates:
 C00N(H00N), C00O(H00O), C00P(H00P), C00T(H00T), C00V(H00V), C00W(H00W),
 C00X(H00X), C00Z(H00Z), C011(H011), C012(H012), C014(H014), C015(H015),
 C017(H017), C018(H018), C01A(H01A), C01B(H01B), C01C(H01M), C01D(H01D),
 C01E(H01E), C01F(H01F), C01G(H01N), C01H(H01H), C01I(H01O), C01J(H01P),
 C01K(H01Q), C01L(H01R), C01N(H01S), C01Q(H01W)
5.c Idealised Me refined as rotating group:
 C01O(H01T,H01U,H01V), C01R(H01C,H01G,H01I), C01S(H01J,H01K,H01L), C01V(H01X,
 H01Y,H)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              649
_shelx_fab_checksum              43086
_olex2_submission_special_instructions 'No special instructions were received'