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_4125619
_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 H40 Co N3 P2, 2(C F3 O3 S)'
_chemical_formula_sum            'C39 H40 Co F6 N3 O6 P2 S2'
_chemical_formula_weight         945.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-04-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.477(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.560(3)
_cell_length_b                   11.5161(8)
_cell_length_c                   21.158(3)
_cell_measurement_reflns_used    5775
_cell_measurement_temperature    298.6
_cell_measurement_theta_max      32.3761
_cell_measurement_theta_min      3.3784
_cell_volume                     8459.8(15)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_reduction
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_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      298.6
_diffrn_detector_area_resol_mean 15.9653
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   35.00   60.50   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4051  179.0000 -180.0000 34

  2 omega  -39.00   53.25   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4051  -77.0000 -120.0000 123

  3 omega  -12.00   14.25   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4051  -77.0000  120.0000 35

  4 omega  -93.25   -1.00   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -27.2801  -37.0000 -120.0000 123

  5 omega  -28.00   -1.00   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -27.2801  -77.0000  -90.0000 36

  6 omega  -80.00    1.00   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -27.2801  120.0000  124.0000 108

  7 omega   13.00   39.25   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -27.2801   77.0000  -30.0000 35

  8 omega  -94.00    1.25   0.7500    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -27.2801  -77.0000 -150.0000 127
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0024411000
_diffrn_orient_matrix_UB_12      0.0004551000
_diffrn_orient_matrix_UB_13      -0.0324069000
_diffrn_orient_matrix_UB_21      -0.0201337000
_diffrn_orient_matrix_UB_22      -0.0070958000
_diffrn_orient_matrix_UB_23      -0.0113852000
_diffrn_orient_matrix_UB_31      -0.0023720000
_diffrn_orient_matrix_UB_32      0.0611980000
_diffrn_orient_matrix_UB_33      -0.0011119000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            30598
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.713
_diffrn_reflns_theta_max         24.713
_diffrn_reflns_theta_min         3.385
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81035
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.485
_exptl_crystal_description       prism
_exptl_crystal_F_000             3888
_exptl_crystal_size_max          0.568
_exptl_crystal_size_mid          0.394
_exptl_crystal_size_min          0.201
_refine_diff_density_max         1.638
_refine_diff_density_min         -0.767
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     651
_refine_ls_number_reflns         7206
_refine_ls_number_restraints     361
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.1002
_refine_ls_R_factor_gt           0.0787
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1378P)^2^+30.3425P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2202
_refine_ls_wR_factor_ref         0.2438
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5371
_reflns_number_total             7206
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b11474_si_004.cif
_cod_data_source_block           p300
_cod_depositor_comments
'Adding full bibliography for 4125618--4125621.cif.'
_cod_original_cell_volume        8459.7(14)
_cod_database_code               4125619
_chemical_oxdiff_formula         'Co S F3 P2 N2 O3 C50 H50'
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.707
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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
 C19-C24
 1.37 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S3 \\sim O3S3 \\sim O1S3 \\sim O2S3 \\sim F1S3 \\sim F2S3 \\sim F3S3 \\sim F3S2
\\sim C2S \\sim O1S2 \\sim O2S2 \\sim O3S2 \\sim F1S2 \\sim F2S2 \\sim S2:
within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.005
C1S \\sim S1 \\sim O1S1 \\sim O2S1 \\sim O3S1 \\sim O4S1 \\sim O5S1 \\sim O6S1
\\sim F1S1 \\sim F2S1 \\sim F3S1 \\sim F4S1: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.01
C19 \\sim C24A \\sim C24 \\sim C23 \\sim C23A \\sim C22 \\sim C22A \\sim C21
\\sim C21A \\sim C20 \\sim C20A: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(C24A)=Sof(H24A)=Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=
 Sof(H21A)=Sof(C20A)=Sof(H20A)=1-FVAR(1)
 Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=
 Sof(C24)=Sof(H24)=FVAR(1)
 Sof(S3)=Sof(F1S3)=Sof(F2S3)=Sof(F3S3)=Sof(O1S3)=Sof(O2S3)=Sof(O3S3)=1-FVAR(2)
 Sof(S2)=Sof(F1S2)=Sof(F2S2)=Sof(F3S2)=Sof(O1S2)=Sof(O2S2)=Sof(O3S2)=FVAR(2)
 Fixed Sof: F1S1(0.75) F2S1(0.75) F3S1(0.75) F4S1(0.75) O1S1(0.5) O2S1(0.5)
 O3S1(0.5) O4S1(0.5) O5S1(0.5) O6S1(0.5)
5.a :
 S2(F1S2,F2S2,F3S2,O1S2,O2S2,O3S2), S3(F1S3,F2S3,F3S3,O1S3,O2S3,O3S3)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C35(H35), C24A(H24A), C23A(H23A), C22A(H22A), C21A(H21A), C20A(H20A)
5.d Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2010-10-15
_olex2_submission_special_instructions 'No special instructions were received'