What Are the Radical Intermediates in Oxidative N-Heterocyclic Carbene Organocatalysis?
Regnier, Vianney; Romero, Erik A.; Molton, Florian; Jazzar, Rodolphe; Bertrand, Guy; Martin, David; Journal of the American Chemical Society 141 (2019) 1109–1117; doi:10.1021/jacs.8b11824

data_4133622
_publ_section_title
;
 What Are the Radical Intermediates in Oxidative N-Heterocyclic Carbene
 Organocatalysis?
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1109
_journal_page_last               1117
_journal_paper_doi               10.1021/jacs.8b11824
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Cl, C H Cl3, C37 H46 N O'
_chemical_formula_sum            'C38 H47 Cl4 N O'
_chemical_formula_weight         675.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-07-20
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.9668(11)
_cell_length_b                   16.6522(12)
_cell_length_c                   25.8421(19)
_cell_measurement_reflns_used    9939
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      25.25
_cell_measurement_theta_min      2.33
_cell_volume                     7301.3(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0379
_diffrn_reflns_av_unetI/netI     0.0454
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            41165
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.396
_diffrn_reflns_theta_min         1.455
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.354
_exptl_absorpt_correction_T_max  0.4901
_exptl_absorpt_correction_T_min  0.4515
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0607 before and 0.0470 after correction. The Ratio of minimum to maximum transmission is 0.9212. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_description       block
_exptl_crystal_F_000             2864
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.399
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 4309 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.010(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     840
_refine_ls_number_reflns         12530
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0290P)^2^+1.9746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0699
_refine_ls_wR_factor_ref         0.0749
_reflns_Friedel_coverage         0.827
_reflns_Friedel_fraction_full    0.869
_reflns_Friedel_fraction_max     0.865
_reflns_number_gt                10972
_reflns_number_total             12530
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11824_si_002.cif
_cod_data_source_block           2f-cation
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/saulius/struct/COD-crude-data/automatic-downloads/DataCite-retrospective/ACS/depositions/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_database_code               4133622
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.923
_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
 Cl7-C38 \\sim Cl4-C39 \\sim Cl8-C38 \\sim Cl3-C39 \\sim Cl6-C38 \\sim Cl5-C39
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C38) = Uanis(C39)
4. Others
 Sof(Cl4)=Sof(Cl5)=Sof(C39)=Sof(H39)=Sof(Cl3)=1-FVAR(1)
 Sof(Cl6)=Sof(Cl7)=Sof(Cl8)=Sof(C38)=Sof(H38)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C35A(H35A), C32(H32), C35(H35), C32A(H32A), C40(H40), C39(H39), C38(H38)
5.b Secondary CH2 refined with riding coordinates:
 C24(H24C,H24D), C22A(H22A,H22B), C22(H22C,H22D), C18A(H18A,H18B), C24A(H24A,
 H24B), C18(H18C,H18D)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C6(H6), C30A(H30A), C3A(H3A), C10A(H10A), C7A(H7A), C3(H3),
 C29A(H29A), C16(H16), C8A(H8A), C28A(H28A), C13A(H13A), C12A(H12A), C30(H30),
 C14(H14), C7(H7), C10(H10), C13(H13), C8(H8), C28(H28), C29(H29), C6A(H6A),
 C16A(H16A), C9(H9), C14A(H14A), C15(H15), C9A(H9A), C15A(H15A)
5.d Idealised Me refined as rotating group:
 C21A(H21A,H21B,H21C), C36A(H36A,H36B,H36C), C37(H37D,H37E,H37F), C25(H25D,
 H25E,H25F), C20A(H20A,H20B,H20C), C37A(H37A,H37B,H37C), C33(H33D,H33E,H33F),
 C20(H20D,H20E,H20F), C34(H34D,H34E,H34F), C21(H21D,H21E,H21F), C36(H36D,H36E,
 H36F), C23A(H23A,H23B,H23C), C23(H23D,H23E,H23F), C34A(H34A,H34B,H34C),
 C33A(H33A,H33B,H33C), C25A(H25A,H25B,H25C)
;
_shelx_res_checksum              52575
_shelx_hkl_checksum              53929
_olex2_submission_special_instructions 'No special instructions were received'