Aromaticity and sterics control whether a cationic olefin radical is resistant to disproportionation
Messelberger, Julian; Grünwald, Annette; Goodner, Stephen J.; Zeilinger, Florian; Pinter, Piermaria; Miehlich, Matthias E.; Heinemann, Frank W.; Hansmann, Max M.; Munz, Dominik; Chemical Science 11 (2020) 4138–4149; doi:10.1039/D0SC00699H

data_1557687
_publ_section_title
;
 Aromaticity and sterics control whether a cationic olefin radical is
 resistant to disproportionation
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              4138
_journal_page_last               4149
_journal_paper_doi               10.1039/D0SC00699H
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C25 H39 N3, C F3 O3 S'
_chemical_formula_sum            'C26 H39 F3 N3 O3 S'
_chemical_formula_weight         530.66
_chemical_properties_physical    Moisture-sensitive,Oxygen-sensitive
_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   geom
_audit_creation_date             2019-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-08 deposited with the CCDC.	2020-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.5800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.3959(4)
_cell_length_b                   8.8582(3)
_cell_length_c                   26.7626(10)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.51
_cell_measurement_theta_min      2.38
_cell_volume                     2700.58(17)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS, 2016)'
_computing_data_collection       'Bruker APEX3 (Bruker AXS, 2015)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS, 2016)'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXTL 6.12 (Bruker AXS, 2002)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa ImuS Duo Photon II CPAD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Quazar focussing montel optics'
_diffrn_radiation_source         'ImuS high brilliance micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            44464
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.700
_diffrn_reflns_theta_min         2.380
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.173
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.7205
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0795 before and 0.0555 after correction.
The Ratio of minimum to maximum transmission is 0.9659.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_description       prism
_exptl_crystal_F_000             1132
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: tetrahydrofuran, diethyl ether'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     408
_refine_ls_number_reflns         6963
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0459P)^2^+1.1702P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1005
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5762
_reflns_number_total             6963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00699h2.cif
_cod_data_source_block           jm1902
_cod_depositor_comments
;Adding full bibliography for 1557687--1557688.cif.

 Adding full bibliography for 1557687--1557688.cif.
;
_cod_database_code               1557687
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.971
_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. Uiso/Uaniso restraints and constraints
C26 \\sim C26A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
3. Others
 Sof(S1A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C26A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=1-
 FVAR(1)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(C26)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C16(H16), C17(H17), C18(H18)
4.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              40755
_olex2_submission_special_instructions 'No special instructions were received'