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_1565818
_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_formula_moiety         'C16 H24 N, B F4'
_chemical_formula_sum            'C16 H24 B F4 N'
_chemical_formula_weight         317.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           45
_space_group_name_Hall           'I 2 -2c'
_space_group_name_H-M_alt        'I b a 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-09-16 deposited with the CCDC.	2021-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            24
_cell_length_a                   26.2135(15)
_cell_length_b                   48.489(3)
_cell_length_c                   7.7284(5)
_cell_measurement_reflns_used    9132
_cell_measurement_temperature    100
_cell_measurement_theta_max      69.20
_cell_measurement_theta_min      3.21
_cell_volume                     9823.3(10)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_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 0.998
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_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  0.0749
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       58
_diffrn_reflns_limit_k_min       -58
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            42810
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.194
_diffrn_reflns_theta_min         3.212
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.11
_diffrn_source_power             0.0555
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.894
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6121
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1309 before and 0.0863 after correction.
The Ratio of minimum to maximum transmission is 0.8128.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             4032
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.456
_refine_diff_density_min         -0.233
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.59(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         8964
_refine_ls_number_restraints     208
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0580
_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^)+(0.1008P)^2^+7.1303P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1544
_refine_ls_wR_factor_ref         0.1580
_reflns_Friedel_coverage         0.849
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                8264
_reflns_number_total             8964
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06577g2.cif
_cod_data_source_block           cxy3292
_cod_depositor_comments
'Adding full bibliography for 1565818--1565820.cif.'
_cod_database_code               1565818
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.41(15)
 0.59(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups, All N(H,H,H,H) groups
3. Restrained distances
 C34-C33 = C38A-C33A = C34A-C33A = C38-C33 = C35A-C34A = C38-C37 = C37-C36 =
 C36A-C35A = C36-C35 = C37A-C36A = C35-C34 = C38A-C37A
 1.54 with sigma of 0.02
 N3-C33 \\sim N3-C33A
 with sigma of 0.02
 C34-C33 \\sim C34A-C33A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C37-C36 \\sim C37A-C36A
 with sigma of 0.02
 C37-C38 \\sim C37A-C38A
 with sigma of 0.02
 C37-C33 \\sim C37A-C33A
 with sigma of 0.04
 C33-C38 \\sim C33A-C38A
 with sigma of 0.02
 C36-C38 \\sim C36A-C38A
 with sigma of 0.04
 C36-C35 \\sim C36A-C35A
 with sigma of 0.02
 C37-C35 \\sim C37A-C35A
 with sigma of 0.04
 C33-C35 \\sim C33A-C35A
 with sigma of 0.04
 N3-C34 \\sim N3-C34A
 with sigma of 0.04
 N3-C38 \\sim N3-C38A
 with sigma of 0.04
 C34-C36 \\sim C34A-C36A
 with sigma of 0.04
 C34-C38 \\sim C34A-C38A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C34 \\sim C37 \\sim C33 \\sim C36 \\sim C38 \\sim C35 \\sim C38A \\sim C37A
\\sim C36A \\sim C35A \\sim C34A \\sim C33A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C36A) = Uanis(C36)
Uanis(C34A) = Uanis(C38)
Uanis(C38A) = Uanis(C34)
Uanis(C33) = Uanis(C33A)
Uanis(C37) = Uanis(C35A)
Uanis(C35) = Uanis(C37A)
5. Others
 Sof(H3BC)=Sof(H3BD)=Sof(C33A)=Sof(H33A)=Sof(C38A)=Sof(H38C)=Sof(H38D)=
 Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C35A)=
 Sof(H35C)=Sof(H35D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=1-FVAR(1)
 Sof(H3AA)=Sof(H3AB)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(C33)=Sof(H33)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C38)=Sof(H38A)=Sof(H38B)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C17(H17), C33(H33), C33A(H33A)
6.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C7(H7A,H7B), C2(H2A,H2B), C10(H10A,H10B), C6(H6A,H6B), C3(H3A,
 H3B), C5(H5A,H5B), C4(H4A,H4B), N2(H2C,H2D), C18(H18A,H18B), C22(H22A,H22B),
 C23(H23A,H23B), C19(H19A,H19B), C20(H20A,H20B), C26(H26A,H26B), C21(H21A,H21B),
  N3(H3AA,H3AB), N3(H3BC,H3BD), C39(H39A,H39B), C42(H42A,H42B), C34(H34A,H34B),
 C37(H37A,H37B), C36(H36A,H36B), C38(H38A,H38B), C35(H35A,H35B), C38A(H38C,
 H38D), C37A(H37C,H37D), C36A(H36C,H36D), C35A(H35C,H35D), C34A(H34C,H34D)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C8(H8), C9(H9), C13(H13), C16(H16), C14(H14), C15(H15), C24(H24),
 C28(H28), C25(H25), C32(H32), C29(H29), C30(H30), C31(H31), C40(H40), C41(H41),
  C44(H44), C48(H48), C46(H46), C45(H45), C47(H47)
;
_shelx_res_checksum              28203
_shelx_hkl_checksum              55872
_olex2_submission_special_instructions 'No special instructions were received'