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_1550678
_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         'C34 H52 N2'
_chemical_formula_sum            'C34 H52 N2'
_chemical_formula_weight         488.77
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-29
_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                 96.938(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1760(14)
_cell_length_b                   15.7667(14)
_cell_length_c                   12.4170(9)
_cell_measurement_reflns_used    8213
_cell_measurement_temperature    120.01(2)
_cell_measurement_theta_max      28.9110
_cell_measurement_theta_min      3.2560
_cell_volume                     2949.3(4)
_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      120.01(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -25.00  51.00   1.00  159.48    --    3.60  57.00-120.00   76
  2  \w    -84.00  17.00   1.00  159.48    --    3.60 -57.00-150.00  101
  3  \w      5.00  39.00   1.00  159.48    --    3.60  38.00 120.00   34
  4  \w    -72.00 -26.00   1.00  159.48    --   -3.90 -77.00  60.00   46
  5  \w    -42.00  33.00   1.00  159.48    --   -3.90 -82.00 -90.00   75
  6  \w    -51.00  -6.00   1.00  159.48    --   -3.90 -82.00   0.00   45
;
_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      0.0330687000
_diffrn_orient_matrix_UB_12      0.0145069000
_diffrn_orient_matrix_UB_13      -0.0311538000
_diffrn_orient_matrix_UB_21      -0.0239301000
_diffrn_orient_matrix_UB_22      0.0386214000
_diffrn_orient_matrix_UB_23      -0.0103376000
_diffrn_orient_matrix_UB_31      0.0233985000
_diffrn_orient_matrix_UB_32      0.0180114000
_diffrn_orient_matrix_UB_33      0.0472592000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1013
_diffrn_reflns_av_unetI/netI     0.0703
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            32924
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.500
_diffrn_reflns_theta_min         2.704
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.063
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.553
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.112
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         6102
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1182
_refine_ls_R_factor_gt           0.0907
_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^)+(0.0548P)^2^+8.1032P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2111
_refine_ls_wR_factor_ref         0.2237
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4594
_reflns_number_total             6102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05477k2.cif
_cod_data_source_block           aj0212
_cod_database_code               1550678
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C22H24N2
_reflns_odcompleteness_completeness 99.73
_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:
 C8(H8), C21(H21), C28(H28)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C9(H9), C7(H7), C20(H20), C10(H10), C16(H16), C19(H19), C17(H17),
 C18(H18)
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C22(H22A,H22B,H22C), C26(H26A,H26B,H26C), C23(H23A,H23B,
 H23C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C34(H34A,H34B,H34C), C24(H24A,
 H24B,H24C), C32(H32A,H32B,H32C), C25(H25A,H25B,H25C), C33(H33A,H33B,H33C),
 C31(H31A,H31B,H31C)
;
_shelx_res_checksum              53832
_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 2.673
_oxdiff_exptl_absorpt_empirical_full_min 0.568