Direct Access to 2-Aryl Substituted Pyrrolinium Salts for Carbon Centre Based Radicals without Pyrrolidine-2-Ylidene alias cyclic(Alkyl)(Amino)Carbene (CAAC) as a Precursor
Mandal, Debdeep; Sobottka, Sebastian; Dolai, Ramapada; Maiti, Avijit; Dhara, Debabrata; Kalita, Pankaj; Narayanan, Ramakirushnan Surya; Chandrasekhar, Vadapalli; Sarkar, Biprajit; Jana, Anukul; Chemical Science  (2019) –; doi:10.1039/C8SC05477K

data_1550677
_publ_section_title
;
 Direct Access to 2-Aryl Substituted Pyrrolinium Salts for Carbon Centre
 Based Radicals without Pyrrolidine-2-Ylidene alias
 cyclic(Alkyl)(Amino)Carbene (CAAC) as a Precursor
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC05477K
_journal_year                    2019
_chemical_formula_moiety         'C F3 O3 S, C19 H30 N'
_chemical_formula_sum            'C20 H30 F3 N O3 S'
_chemical_formula_weight         421.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2018-09-16 deposited with the CCDC.    2019-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.540(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.4373(11)
_cell_length_b                   8.2621(2)
_cell_length_c                   15.8008(6)
_cell_measurement_reflns_used    10965
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.9170
_cell_measurement_theta_min      3.0870
_cell_volume                     4356.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.979
_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     53.00  93.00   0.50    6.12    --    7.20  77.00  30.00   80
  2  \w     69.00  96.00   0.50    6.12    --    7.20  77.00-180.00   54
  3  \w     52.00  90.00   0.50    6.12    --    7.20  77.00 120.00   76
  4  \w    -75.00  43.00   0.50    6.12    --    7.20 -77.00 150.00  236
  5  \w    -61.00 -35.00   0.50    6.12    --   -7.60 -82.00 120.00   52
  6  \w    -75.00  -8.00   0.50    6.12    --   -7.60 -77.00-120.00  134
  7  \w     28.00  61.00   0.50    6.12    --   -7.60  57.00  30.00   66
  8  \w    -37.00  13.00   0.50    6.12    --   -7.60  57.00  30.00  100
  9  \w    -50.00   4.00   0.50    6.12    --   -7.60 -82.00-150.00  108
 10  \w    -60.00  31.00   0.50    6.12    --   -7.60 -82.00 -30.00  182
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0129961000
_diffrn_orient_matrix_UB_12      -0.0618465000
_diffrn_orient_matrix_UB_13      0.0129805000
_diffrn_orient_matrix_UB_21      -0.0066694500
_diffrn_orient_matrix_UB_22      0.0515392500
_diffrn_orient_matrix_UB_23      0.0321602000
_diffrn_orient_matrix_UB_31      -0.0154326000
_diffrn_orient_matrix_UB_32      0.0298386000
_diffrn_orient_matrix_UB_33      -0.0286335000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0851
_diffrn_reflns_av_unetI/netI     0.0589
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26737
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.500
_diffrn_reflns_theta_min         2.832
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.193
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54553
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_description       plate
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.327
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.856
_refine_diff_density_min         -0.327
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         4422
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0588
_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^)+(0.0371P)^2^+13.4559P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1463
_refine_ls_wR_factor_ref         0.1517
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3766
_reflns_number_total             4422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05477k2.cif
_cod_data_source_block           aj0300
_cod_database_code               1550677
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C20H30F3N1O3S1
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.918
_reflns_odcompleteness_completeness 97.47
_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:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C9(H9), C6(H6), C7(H7)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C14(H14A,H14B,H14C), C18(H18A,H18B,
 H18C), C15(H15A,H15B,H15C), C19(H19A,H19B,H19C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              93614
_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 3.502
_oxdiff_exptl_absorpt_empirical_full_min 0.361