Electrocatalytic CO<sub>2</sub> reduction to formate by a cobalt phosphino-thiolate complex.
Intrator, Jeremy A.; Velazquez, David A.; Fan, Sicheng; Mastrobattista, Ellie; Yu, Christine; Marinescu, Smaranda C.; Chemical science 15 (2024) 6385–6396; doi:10.1039/d3sc06805f

data_1570984
_publ_section_title
;
 Electrocatalytic CO<sub>2</sub> reduction to formate by a cobalt
 phosphino-thiolate complex.
;
_journal_issue                   17
_journal_name_full               'Chemical science'
_journal_page_first              6385
_journal_page_last               6396
_journal_paper_doi               10.1039/d3sc06805f
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C47 H43 Co P3 S2, C20 H40 K O8, 1[C5H12]'
_chemical_formula_sum            'C67 H83 Co K O8 P3 S2'
_chemical_formula_weight         1266.35
_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             2022-03-16
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-10-25 deposited with the CCDC.	2024-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.7350(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.11250(10)
_cell_length_b                   18.5920(2)
_cell_length_c                   36.9620(5)
_cell_measurement_reflns_used    28112
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.2470
_cell_measurement_theta_min      2.5180
_cell_volume                     6949.21(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(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 0.935
_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    -82.00  -1.00   0.50    5.00    --  -50.18 109.00 -52.00  162
  2  \w     22.00  87.00   0.50    5.00    --   50.18-109.00-148.00  130
  3  \w   -161.00 -82.00   0.50   10.00    --  -90.00-109.00-148.00  158
  4  \w    -82.00 -18.00   0.50   10.00    --  -90.00 109.00 -52.00  128
  5  \w     32.00 107.00   0.50   10.00    --  104.18-109.00-148.00  150
  6  \w    104.00 176.00   0.50   10.00    --  104.18 109.00 -52.00  144
  7  \w   -122.00 -82.00   0.50    5.00    --  -50.18 -57.00-120.00   80
  8  \w   -122.00 -82.00   0.50    5.00    --  -50.18 -57.00   0.00   80
  9  \w   -122.00 -82.00   0.50    5.00    --  -50.18 -57.00 -60.00   80
 10  \w   -122.00 -82.00   0.50    5.00    --  -50.18 -57.00 150.00   80
 11  \w   -122.00 -82.00   0.50    5.00    --  -50.18 -57.00-150.00   80
 12  \w   -122.00 -82.00   0.50    5.00    --  -50.18 -57.00 -90.00   80
 13  \w   -122.00 -87.00   0.50    5.00    --  -50.18-125.00  90.00   70
 14  \w   -161.00 -99.00   0.50   10.00    --  -90.00 -99.00-120.00  124
 15  \w   -161.00 -82.00   0.50   10.00    --  -90.00 -57.00-120.00  158
 16  \w    -84.00 -30.00   0.50   10.00    --  -90.00 125.00-180.00  108
 17  \w    -65.00 -21.00   0.50   10.00    --  -90.00  57.00 -30.00   88
 18  \w    -55.00 -29.00   0.50   10.00    --  -90.00  57.00 -60.00   52
 19  \w    -64.00 -31.00   0.50   10.00    --  -90.00  57.00  90.00   66
 20  \w   -161.00-101.00   0.50   10.00    --  -90.00 -77.00 -90.00  120
 21  \w     33.00  67.00   0.50   10.00    --  104.18 -57.00 -90.00   68
 22  \w     33.00  65.00   0.50   10.00    --  104.18 -57.00  60.00   64
 23  \w     76.00 103.00   0.50   10.00    --  104.18-125.00 -30.00   54
 24  \w     45.00 102.00   0.50   10.00    --  104.18 -99.00 -90.00  114
 25  \w    102.00 175.00   0.50   10.00    --  104.18  77.00-180.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0429739000
_diffrn_orient_matrix_UB_12      0.0152931000
_diffrn_orient_matrix_UB_13      0.0391973000
_diffrn_orient_matrix_UB_21      0.0249236000
_diffrn_orient_matrix_UB_22      0.0793565000
_diffrn_orient_matrix_UB_23      -0.0099049000
_diffrn_orient_matrix_UB_31      -0.1439588000
_diffrn_orient_matrix_UB_32      0.0183227000
_diffrn_orient_matrix_UB_33      0.0101778000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0821
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.935
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            63432
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         76.492
_diffrn_reflns_theta_min         2.660
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.080
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41998
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark black'
_exptl_crystal_density_diffrn    1.210
_exptl_crystal_description       plate
_exptl_crystal_F_000             2668
_exptl_crystal_size_max          0.58
_exptl_crystal_size_mid          0.383
_exptl_crystal_size_min          0.209
_refine_diff_density_max         1.291
_refine_diff_density_min         -1.052
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.867
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     786
_refine_ls_number_reflns         13663
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      0.867
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0618
_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^)+(0.1741P)^2^+3.1085P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1843
_refine_ls_wR_factor_ref         0.1954
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11258
_reflns_number_total             13663
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06805f2.cif
_cod_data_source_block           kcco_022422_autored
_cod_depositor_comments          'Adding full bibliography for 1570984.cif.'
_cod_database_code               1570984
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CoS2P3KC67H83O8
_shelx_estimated_absorpt_t_max   0.481
_shelx_estimated_absorpt_t_min   0.201
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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. Uiso/Uaniso restraints and constraints
Uanis(C59') \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
3. Others
 Sof(O7')=Sof(C61')=Sof(H61C)=Sof(H61D)=Sof(C60')=Sof(H60C)=Sof(H60D)=
 Sof(C62')=Sof(H62C)=Sof(H62D)=Sof(C59')=Sof(H59C)=Sof(H59D)=1-FVAR(1)
 Sof(O7)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C59)=
 Sof(H59A)=Sof(H59B)=Sof(C62)=Sof(H62A)=Sof(H62B)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C22(H22A,H22B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,
 H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B),
 C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B),
  C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C017(H01A,
 H01B), C60(H60A,H60B), C61(H61A,H61B), C59(H59A,H59B), C62(H62A,H62B),
 C61'(H61C,H61D), C60'(H60C,H60D), C62'(H62C,H62D), C59'(H59C,H59D)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  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),
  C3(H3), C4(H4), C5(H5)
4.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              61494
_shelx_fab_checksum              99165
_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 6.857
_oxdiff_exptl_absorpt_empirical_full_min 0.436