Metal-free allylic C–H nitrogenation, oxygenation, and carbonation of alkenes by thianthrenation
Liu, Ming-Shang; Du, Hai-Wu; Shu, Wei; Chemical Science 13 (2022) 1003–1008; doi:10.1039/D1SC06577G

data_1565819
_publ_section_title
;
 Metal-free allylic C--H nitrogenation, oxygenation, and carbonation of
 alkenes by thianthrenation
;
_journal_issue                   4
_journal_name_full               'Chemical Science'
_journal_page_first              1003
_journal_page_last               1008
_journal_paper_doi               10.1039/D1SC06577G
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H24 O3'
_chemical_formula_sum            'C24 H24 O3'
_chemical_formula_weight         360.43
_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
_audit_creation_date             2021-09-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2021-09-17 deposited with the CCDC.	2021-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.230(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.0869(3)
_cell_length_b                   17.6346(9)
_cell_length_c                   17.8806(9)
_cell_measurement_reflns_used    9905
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      68.12
_cell_measurement_theta_min      2.47
_cell_volume                     1917.85(17)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0868
_diffrn_reflns_av_unetI/netI     0.0677
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_number            7046
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.332
_diffrn_reflns_theta_min         2.473
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  0.896
_exptl_absorpt_correction_T_min  0.745
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1406 before and 0.1026 after correction.
 
For component 2:
 wR2(int) was 0.1518 before and 0.1023 after correction.
 The Ratio of minimum to maximum transmission is 0.74.

Final HKLF 4 output contains 49362 reflections, Rint = 0.0992
 (29844 with I > 3sig(I), Rint = 0.0868)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       prism
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 2481 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.11(16)
_refine_ls_extinction_coef       0.013(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     530
_refine_ls_number_reflns         7046
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0778
_refine_ls_R_factor_gt           0.0680
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1402P)^2^+0.0550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1896
_refine_ls_wR_factor_ref         0.2070
_reflns_Friedel_coverage         0.929
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                5883
_reflns_number_total             7046
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06577g2.cif
_cod_data_source_block           cxy3383_0m_4
_cod_depositor_comments
'Adding full bibliography for 1565818--1565820.cif.'
_cod_database_code               1565819
_shelx_shelxl_version_number     2016/6
_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
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 C14-C21 \\sim C14A-C21A
 with sigma of 0.04
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C15-C16 \\sim C15A-C16A
 with sigma of 0.02
 C13-C15 \\sim C13A-C15A
 with sigma of 0.04
 C16-C21 \\sim C16A-C21A
 with sigma of 0.04
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C16-C17 \\sim C16A-C17A
 with sigma of 0.02
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 C15-C17 \\sim C15A-C17A
 with sigma of 0.04
 C17-C22 \\sim C17A-C22A
 with sigma of 0.04
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C14-C22 \\sim C14A-C22A
 with sigma of 0.02
 C17-C21 \\sim C17A-C21A
 with sigma of 0.02
 C11-C13 \\sim C11-C13A
 with sigma of 0.04
 C13-C22 \\sim C13A-C22A
 with sigma of 0.04
 C14-C16 \\sim C14A-C16A
 with sigma of 0.04
 C15-C22 \\sim C15A-C22A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C22A) = Uanis(C22)
Uanis(C12) = Uanis(C12A)
Uanis(C17A) = Uanis(C17)
Uanis(C14) = Uanis(C14A)
Uanis(C15A) = Uanis(C15)
Uanis(C13A) = Uanis(C13)
Uanis(C21A) = Uanis(C21)
Uanis(C16A) = Uanis(C16)
4. Others
 Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=
 Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C17A)=Sof(H17A)=Sof(C16A)=
 Sof(H16A)=Sof(C15A)=Sof(H15A)=1-FVAR(1)
 Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C21)=Sof(H21)=Sof(C22)=
 Sof(H22)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C8(H8)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C13(H13A,H13B), C13A(H13C,H13D)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C11(H11), C11(H11A), C12(H12), C15(H15), C16(H16),
 C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C24(H24), C12A(H12A),
 C22A(H22A), C21A(H21A), C17A(H17A), C16A(H16A), C15A(H15A)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              49365
_shelx_hkl_checksum              33011
_olex2_submission_special_instructions 'No special instructions were received'