Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C-H Functionalizations.
Ozols, Kristers; Jang, Yun-Suk; Cramer, Nicolai; Journal of the American Chemical Society 141 (2019) 5675–5680; doi:10.1021/jacs.9b02569

data_4128399
_publ_section_title
;
 Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly
 Enantioselective 3d-Metal-Catalyzed C-H Functionalizations.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5675
_journal_page_last               5680
_journal_paper_doi               10.1021/jacs.9b02569
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C33 H29 Co I2 O3, C7 H8'
_chemical_formula_sum            'C40 H37 Co I2 O3'
_chemical_formula_weight         878.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.7262(16)
_cell_angle_gamma                90
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_cell_length_a                   7.74793(11)
_cell_length_b                   12.5796(2)
_cell_length_c                   18.6446(3)
_cell_measurement_reflns_used    19489
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      32.0090
_cell_measurement_theta_min      3.1120
_cell_volume                     1791.09(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.938
_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    -12.00  92.00   1.00    3.00    --   19.91  77.00-120.00  104
  2  \w      8.00  96.00   1.00    3.00    --   19.91  77.00  90.00   88
  3  \w    -53.00  48.00   1.00    3.00    --   19.91 -57.00 -30.00  101
  4  \w     -5.00  90.00   1.00    3.00    --   19.91  77.00   0.00   95
  5  \w     -6.00  71.00   1.00    3.00    --   19.91-116.00  98.95   77
  6  \w    -42.00  52.00   1.00    3.00    --   19.91 -77.00-120.00   94
  7  \w    -26.00  52.00   1.00    3.00    --  -20.22  38.00 150.00   78
  8  \w    -92.00 -27.00   1.00    3.00    --  -20.22 -38.00 150.00   65
  9  \w    -97.00 -56.00   1.00    3.00    --  -20.22 155.00  72.04   41
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0028346000
_diffrn_orient_matrix_UB_12      0.0465477000
_diffrn_orient_matrix_UB_13      -0.0216383000
_diffrn_orient_matrix_UB_21      -0.0926390000
_diffrn_orient_matrix_UB_22      -0.0034186000
_diffrn_orient_matrix_UB_23      -0.0078453000
_diffrn_orient_matrix_UB_31      -0.0059106000
_diffrn_orient_matrix_UB_32      0.0316499000
_diffrn_orient_matrix_UB_33      0.0309826000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            41182
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.966
_diffrn_reflns_theta_min         2.667
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.239
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.180
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.20a (Rigaku Oxford Diffraction, 2018)
 Numerical absorption correction based on Gaussian integration over
 a multifaceted crystal model/Empirical absorption correction using
 spherical harmonics as implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_density_diffrn    1.629
_exptl_crystal_description       prism
_exptl_crystal_F_000             868
_exptl_crystal_size_max          0.628
_exptl_crystal_size_mid          0.353
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.262
_refine_diff_density_min         -1.278
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Flack x determined using 4491 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     461
_refine_ls_number_reflns         12268
_refine_ls_number_restraints     235
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0268P)^2^+1.0742P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0659
_refine_ls_wR_factor_ref         0.0698
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.880
_reflns_number_gt                10952
_reflns_number_total             12268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02569_si_004.cif
_cod_data_source_block           koz-01-433
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_cell_volume        1791.10(5)
_cod_database_code               4128399
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C40 H37 O3 Co1 I2'
_reflns_odcompleteness_completeness 99.93
_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
 C40A-C34A
 1.5 with sigma of 0.02
 C34B-C40B
 1.5 with sigma of 0.02
 C39A-C40A \\sim C40A-C35A
 with sigma of 0.02
 C39B-C40B \\sim C40B-C35B
 with sigma of 0.02
3. Restrained planarity
 C34A, C35A, C36A, C37A, C38A, C39A, C40A
 with sigma of 0.1
 C34B, C39B, C38B, C37B, C36B, C35B, C40B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C34A \\sim C35A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim
C34B \\sim C35B \\sim C36B \\sim C37B \\sim C38B \\sim C39B \\sim C40B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C34B)=Sof(C39B)=Sof(H39B)=Sof(C38B)=Sof(H38B)=Sof(C37B)=Sof(H37B)=
 Sof(C36B)=Sof(H36B)=Sof(C35B)=Sof(H35B)=Sof(C40B)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=1-FVAR(1)
 Sof(C34A)=Sof(C39A)=Sof(H39A)=Sof(C38A)=Sof(H38A)=Sof(C37A)=Sof(H37A)=
 Sof(C36A)=Sof(H36A)=Sof(C35A)=Sof(H35A)=Sof(C40A)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C6(H6)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C30(H30A,H30B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C22(H22),
 C23(H23), C24(H24), C25(H25), C27(H27), C39A(H39A), C38A(H38A), C37A(H37A),
 C36A(H36A), C35A(H35A), C39B(H39B), C38B(H38B), C37B(H37B), C36B(H36B),
 C35B(H35B)
6.d Fitted hexagon refined as free rotating group:
 C34A(C39A,C38A,C37A,C36A,C35A), C34B(C39B,C38B,C37B,C36B,C35B)
6.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C40A(H40A,H40B,H40C), C40B(H40D,H40E,H40F)
;
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.398
_oxdiff_exptl_absorpt_empirical_full_min 0.786