Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid.
Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques; Simon, Philippe; Fontecave, Marc; Tran, Phong D.; Derat, Etienne; Artero, Vincent; Journal of the American Chemical Society 139 (2017) 3685–3696; doi:10.1021/jacs.6b11474

data_4125618
_publ_section_title
;
 Molecular Cobalt Complexes with Pendant Amines for Selective
 Electrocatalytic Reduction of Carbon Dioxide to Formic Acid.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3685
_journal_page_last               3696
_journal_paper_doi               10.1021/jacs.6b11474
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C37 H52 Co N3 P2, 2(C F3 O3 S), 0.5(H2 O)'
_chemical_formula_sum            'C39 H53 Co F6 N3 O6.5 P2 S2'
_chemical_formula_weight         966.83
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-03-31
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.657(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.614(3)
_cell_length_b                   10.4389(9)
_cell_length_c                   42.807(7)
_cell_measurement_reflns_used    2058
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      22.9930
_cell_measurement_theta_min      2.1420
_cell_volume                     8640(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.983
_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     -4.00  95.00   1.00   30.00    --   25.56  77.00-120.00   99
  2  \w    -25.00  67.00   1.00   30.00    --   25.56 -99.00 150.00   92
  3  \w    -96.00 -19.00   1.00   30.00    --  -26.97 -57.00   0.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0037158000
_diffrn_orient_matrix_UB_12      -0.0675754000
_diffrn_orient_matrix_UB_13      0.0007250000
_diffrn_orient_matrix_UB_21      0.0300978000
_diffrn_orient_matrix_UB_22      0.0070180000
_diffrn_orient_matrix_UB_23      0.0116549000
_diffrn_orient_matrix_UB_31      -0.0206007000
_diffrn_orient_matrix_UB_32      -0.0024220000
_diffrn_orient_matrix_UB_33      0.0121014000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1116
_diffrn_reflns_av_unetI/netI     0.3041
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            19408
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.930
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.644
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92289
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent intense red'
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       plate
_exptl_crystal_F_000             4024
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.155
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.416
_refine_diff_density_min         -0.428
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.856
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     653
_refine_ls_number_reflns         8681
_refine_ls_number_restraints     282
_refine_ls_restrained_S_all      0.848
_refine_ls_R_factor_all          0.1873
_refine_ls_R_factor_gt           0.0745
_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^)+(0.0193P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1006
_refine_ls_wR_factor_ref         0.1140
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3215
_reflns_number_total             8681
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b11474_si_002.cif
_cod_data_source_block           sr2015-46_2_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 4125618--4125621.cif.'
_cod_original_cell_volume        8641(2)
_cod_original_formula_sum        'C39 H53 Co F6 N3 O6.50 P2 S2'
_cod_database_code               4125618
_chemical_oxdiff_formula         'C37 H49 Co F6 N2 O6 P2 S2'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
F1S2 \\sim F2S2 \\sim F3S2 \\sim F4S2 \\sim F5S2 \\sim F6S2 \\sim C2S \\sim
C3S: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C6 \\sim C6B \\sim C7 \\sim C7B \\sim C8 \\sim C8B \\sim C9 \\sim C9B \\sim C10
\\sim C10B \\sim C11 \\sim C11B: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.01
C41 \\sim C41B \\sim C42 \\sim C42B: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.01
3. Others
 Sof(H5BC)=Sof(H5BD)=Sof(C6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=
 Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=1-FVAR(1)
 Sof(H5AA)=Sof(H5AB)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=FVAR(1)
 Sof(F4S2)=Sof(F5S2)=Sof(F6S2)=Sof(C3S)=1-FVAR(2)
 Sof(F1S2)=Sof(F2S2)=Sof(F3S2)=Sof(C2S)=FVAR(2)
 Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(3)
 Sof(C41B)=Sof(C42B)=Sof(H42D)=Sof(H42E)=Sof(H42F)=FVAR(3)
 Fixed Sof: H1C(0.5) H1D(0.5)
4.a Free rotating group:
 O1(H1C,H1D)
4.b Ternary CH refined with riding coordinates:
 C12(H12), C25(H25)
4.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5AA,H5AB), C5(H5BC,
 H5BD), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B),
 C17(H17A,H17B), C18(H18A,H18B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B),
  C29(H29A,H29B), C30(H30A,H30B)
4.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C7B(H7B), C8(H8), C8B(H8B), C9(H9), C9B(H9B), C10(H10), C10B(H10B),
 C11(H11), C11B(H11B), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
 C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
4.e Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C42B(H42D,H42E,H42F)
;
_shelx_shelxl_version_number     2014/7
_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 1.113
_oxdiff_exptl_absorpt_empirical_full_min 0.910
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -178.6587\% 
 around [0.94 -0.00 -0.34] (reciprocal) or [1.00 -0.00 0.00] (direct)
;