Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp<sup>3</sup>)-H Bonds.
Wang, Yaxin; Hu, Xiafei; Morales-Rivera, Cristian A; Li, Guo-Xing; Huang, Xin; He, Gang; Liu, Peng; Chen, Gong; Journal of the American Chemical Society 140 (2018) 9678–9684; doi:10.1021/jacs.8b05753

data_4132710
_publ_section_title
;
 Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage
 of Unactivated C(sp<sup>3</sup>)-H Bonds.
;
_journal_issue                   30
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9678
_journal_page_last               9684
_journal_paper_doi               10.1021/jacs.8b05753
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C35 H44 O4'
_chemical_formula_sum            'C35 H44 O4'
_chemical_formula_weight         528.70
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-01-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1414(3)
_cell_length_b                   12.4672(4)
_cell_length_c                   21.0621(5)
_cell_measurement_reflns_used    4397
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      27.7060
_cell_measurement_theta_min      3.4260
_cell_volume                     2925.57(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2116
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -41.00  92.00   1.00    5.00    --   18.63   0.00 -60.00  133
  2  \w     63.00  88.00   1.00    5.00    --   18.63 178.00 120.00   25
  3  \w    -44.00  -2.00   1.00    5.00    --   18.63 -57.00 120.00   42
  4  \w    -95.00 -63.00   1.00    5.00    --  -19.56 178.00 -30.00   32
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0526540000
_diffrn_orient_matrix_UB_12      0.0315615000
_diffrn_orient_matrix_UB_13      -0.0032749000
_diffrn_orient_matrix_UB_21      0.0339385000
_diffrn_orient_matrix_UB_22      0.0407066000
_diffrn_orient_matrix_UB_23      -0.0151712000
_diffrn_orient_matrix_UB_31      -0.0113677000
_diffrn_orient_matrix_UB_32      -0.0241108000
_diffrn_orient_matrix_UB_33      -0.0298989000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0545
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            11601
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.025
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         3.123
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82579
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       block
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.129
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1501 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   1.4(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5154
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0451
_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^)+(0.0340P)^2^+0.1930P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0862
_refine_ls_wR_factor_ref         0.0930
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4358
_reflns_number_total             5154
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05753_si_004.cif
_cod_data_source_block           p180124d
_cod_original_cell_volume        2925.55(13)
_cod_database_code               4132710
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O'
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.977
_reflns_odcompleteness_completeness 99.71
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C17(H17), C22(H22), C18(H18), C12(H12), C26(H26), C27(H27), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C16(H16A,H16B), C10(H10A,H10B), C19(H19A,H19B), C13(H13A,
 H13B), C25(H25A,H25B), C15(H15A,H15B), C9(H9A,H9B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C5(H5), C1(H1), C33(H33), C31(H31), C34(H34), C32(H32), C2(H2),
 C3(H3), C4(H4)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C14(H14A,H14B,H14C), C28(H28A,H28B,H28C)
;
_olex2_date_sample_data_collection 2018-01-24
_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 1.147
_oxdiff_exptl_absorpt_empirical_full_min 0.784