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_4128397
_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_absolute_configuration rmad
_chemical_formula_moiety         'C16 H15 N O'
_chemical_formula_sum            'C16 H15 N O'
_chemical_formula_weight         237.29
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.952(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1246(2)
_cell_length_b                   6.02431(18)
_cell_length_c                   23.2712(5)
_cell_measurement_reflns_used    5739
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.3770
_cell_measurement_theta_min      3.8360
_cell_volume                     1255.91(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 (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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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  29.00   1.00    1.00    --  -43.13  19.00 120.00  111
  2  \w    -42.00 -16.00   1.00    1.00    --  -43.13 -57.00  30.00   26
  3  \w    -53.00 -12.00   1.00    1.00    --  -43.13 -77.00  30.00   41
  4  \w   -118.00 -11.00   1.00    1.00    --  -43.13 -77.00 -30.00  107
  5  \w     23.00  87.00   1.00    1.00    --   43.13-125.00-180.00   64
  6  \w     18.00  72.00   1.00    1.00    --   43.13  19.00  60.00   54
  7  \w     31.00 106.00   1.00    2.57    --  105.68 -94.00 -30.00   75
  8  \w     23.00  52.00   1.00    2.57    --  105.68 -94.00  30.00   29
  9  \w     75.00 102.00   1.00    2.57    --  105.68  67.00 -29.94   27
 10  \w     73.00  99.00   1.00    2.57    --  105.68  77.00 -90.00   26
 11  \w     76.00 103.00   1.00    2.57    --  105.68  77.00 -30.00   27
 12  \w     69.00 109.00   1.00    2.57    --  105.68 -94.00  30.00   40
 13  \w     80.00 106.00   1.00    2.57    --  105.68  45.00 -30.00   26
 14  \w     73.00  99.00   1.00    2.57    --  105.68  77.00 -60.00   26
 15  \w    126.00 154.00   1.00    2.57    --  105.68  77.00  60.00   28
 16  \w    152.00 178.00   1.00    2.57    --  105.68  63.00  36.33   26
 17  \w     77.00 103.00   1.00    2.57    --  105.68  61.00 -60.00   26
 18  \w    118.00 156.00   1.00    2.57    --  105.68  61.00   0.00   38
 19  \w     77.00 110.00   1.00    2.57    --  105.68  61.00  60.00   33
 20  \w     34.00 131.00   1.00    2.57    --  105.68 -45.00   0.00   97
 21  \w     76.00 103.00   1.00    2.57    --  105.68  77.00  60.00   27
 22  \w     79.00 114.00   1.00    2.57    --  105.68  61.00   0.00   35
 23  \w     77.00 103.00   1.00    2.57    --  105.68  61.00 -90.00   26
 24  \w     74.00  99.00   1.00    2.57    --  105.68  77.00  30.00   25
 25  \w     73.00  99.00   1.00    2.57    --  105.68  77.00   0.00   26
 26  \w     78.00 103.00   1.00    2.57    --  105.68  61.00  30.00   25
 27  \w    110.00 175.00   1.00    2.57    --  105.68  77.00 -60.00   65
 28  \w     76.00 103.00   1.00    2.57    --  105.68  63.00  36.33   27
 29  \w     80.00 177.00   1.00    2.57    --  105.68  45.00  30.00   97
 30  \w     75.00 102.00   1.00    2.57    --  105.68  77.00-120.00   27
 31  \w     77.00 104.00   1.00    2.57    --  105.68  60.00  17.25   27
 32  \w     78.00 103.00   1.00    2.57    --  105.68  61.00 -30.00   25
 33  \w     79.00 106.00   1.00    2.57    --  105.68  61.00  90.00   27
 34  \w     74.00 101.00   1.00    2.57    --  105.68  77.00  90.00   27
 35  \w     81.00 147.00   1.00    2.57    --  105.68  39.00 -56.06   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1664523000
_diffrn_orient_matrix_UB_12      -0.0223997000
_diffrn_orient_matrix_UB_13      0.0030895000
_diffrn_orient_matrix_UB_21      -0.0403457000
_diffrn_orient_matrix_UB_22      0.0001792000
_diffrn_orient_matrix_UB_23      -0.0673586000
_diffrn_orient_matrix_UB_31      0.0144292000
_diffrn_orient_matrix_UB_32      -0.2548557000
_diffrn_orient_matrix_UB_33      -0.0003314000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            11961
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.632
_diffrn_reflns_theta_min         3.870
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.613
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.689
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       prism
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.629
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.148
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1675 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(17)
_refine_ls_extinction_coef       0.0023(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         4637
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0381
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0535P)^2^+0.1327P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0955
_reflns_Friedel_coverage         0.686
_reflns_Friedel_fraction_full    0.875
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                4329
_reflns_number_total             4637
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02569_si_010.cif
_cod_data_source_block           koz-01-521
_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        1255.91(6)
_cod_database_code               4128397
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C16 H15 N1 O1'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 N2-H2 \\sim N1-H1
 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C1(H1A), C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C25(H25A,H25B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
 C20(H20), C22(H22), C23(H23), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32)
3.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C26(H26A,H26B,H26C)
;
_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 1.487
_oxdiff_exptl_absorpt_empirical_full_min 0.811