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_4128403
_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         'C11 H13 N O2'
_chemical_formula_sum            'C11 H13 N O2'
_chemical_formula_weight         191.22
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-12-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.565(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7035(5)
_cell_length_b                   7.6414(3)
_cell_length_c                   10.7527(4)
_cell_measurement_reflns_used    3309
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      29.0680
_cell_measurement_theta_min      3.2660
_cell_volume                     959.77(7)
_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 2018/2 (Sheldrick, 2018)'
_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 0.872
_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    -56.00  34.00   1.00   20.00    --   11.66 -57.00   0.00   90
  2  \w    -16.00  75.00   1.00   20.00    --   11.66  77.00 -90.00   91
  3  \w    -15.00  85.00   1.00   20.00    --   11.66  57.00 150.00  100
;
_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      0.0457566000
_diffrn_orient_matrix_UB_12      0.0606978000
_diffrn_orient_matrix_UB_13      -0.0017008000
_diffrn_orient_matrix_UB_21      0.0398899000
_diffrn_orient_matrix_UB_22      -0.0698853000
_diffrn_orient_matrix_UB_23      0.0047422000
_diffrn_orient_matrix_UB_31      -0.0021230000
_diffrn_orient_matrix_UB_32      -0.0065696000
_diffrn_orient_matrix_UB_33      -0.0659021000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.872
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6932
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.580
_diffrn_reflns_theta_min         3.186
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.091
_exptl_absorpt_correction_T_max  0.994
_exptl_absorpt_correction_T_min  0.969
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.20a (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       lath
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.641
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.059
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.167
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.005(2)
_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   1.082
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         2354
_refine_ls_number_restraints     400
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0544
_refine_ls_R_factor_gt           0.0429
_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^)+(0.0424P)^2^+0.3429P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1072
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1981
_reflns_number_total             2354
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02569_si_007.cif
_cod_data_source_block           koz-01-549
_cod_database_code               4128403
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C11 H13 N1 O2'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 H2B-O1B_$1
 1.9 with sigma of 0.01
 C2A-C3A \\sim C2B-C3B
 with sigma of 0.02
 C8A-C9A \\sim C8B-C9B
 with sigma of 0.02
 N1A-C9A \\sim N1B-C9B
 with sigma of 0.02
 N1A-C1A \\sim N1B-C1B
 with sigma of 0.02
 C2A-C1A \\sim C2B-C1B
 with sigma of 0.02
 C10A-C1A \\sim C1B-C10B
 with sigma of 0.02
 C10A-C11A \\sim C11B-C10B
 with sigma of 0.02
 O2A-C11A \\sim O2B-C11B
 with sigma of 0.02
 O1A-C9A \\sim O1B-C9B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C2A \\sim C2B \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim
C7A \\sim C8A \\sim C8B \\sim C3B \\sim C4B \\sim C5B \\sim C6B \\sim C7B \\sim
C9A \\sim C9B \\sim C10A \\sim C10B \\sim C11A \\sim C11B \\sim N1A \\sim N1B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1A) = Uanis(O1B)
Uanis(O2A) = Uanis(O2B)
4. Others
 Sof(O1B)=Sof(O2B)=Sof(H2B)=Sof(N1B)=Sof(H1B)=Sof(C1B)=Sof(H1BA)=Sof(C2B)=
 Sof(H2BA)=Sof(H2BB)=Sof(C8B)=Sof(C3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=
 Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C9B)=Sof(C10B)=Sof(H10C)=Sof(H10D)=
 Sof(C11B)=Sof(H11C)=Sof(H11D)=1-FVAR(1)
 Sof(O1A)=Sof(O2A)=Sof(H2A)=Sof(N1A)=Sof(H1A)=Sof(C1A)=Sof(H1AA)=Sof(C2A)=
 Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(C9A)=Sof(C10A)=Sof(H10A)=Sof(H10B)=
 Sof(C11A)=Sof(H11A)=Sof(H11B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1A(H1AA), C1B(H1BA)
5.b Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB), C10A(H10A,H10B), C10B(H10C,H10D), C11A(H11A,
 H11B), C11B(H11C,H11D)
5.c Aromatic/amide H refined with riding coordinates:
 N1B(H1B), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C4B(H4B), C5B(H5B),
 C6B(H6B), C7B(H7B)
5.d Fitted hexagon refined as free rotating group:
 C8B(C3B,C4B,C5B,C6B,C7B)
5.e Idealised tetrahedral OH refined as rotating group:
 O2A(H2A), O2B(H2B)
;
_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 1.427
_oxdiff_exptl_absorpt_empirical_full_min 0.763