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_1550680
_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
'4(C F3 O3 S), 2(C F3.5 O3 S), 4(C21 H34 N), 2(C24 H33 N)'
_chemical_formula_sum            'C138 H202 F19 N6 O18 S6'
_chemical_formula_weight         2786.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-I 2y'
_space_group_name_H-M_alt        'I 1 2/m 1'
_symmetry_space_group_name_Hall  '-I 2y'
_symmetry_space_group_name_H-M   'I 1 2/m 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-16 deposited with the CCDC.    2019-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.509(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.9188(12)
_cell_length_b                   10.3807(6)
_cell_length_c                   35.7997(16)
_cell_measurement_reflns_used    9888
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.6270
_cell_measurement_theta_min      2.9340
_cell_volume                     6970.4(7)
_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 0.998
_diffrn_measured_fraction_theta_max 0.995
_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    -84.00 -57.00   1.00  144.49    --    3.60 -53.00  63.00   27
  2  \w     14.00  40.00   1.00  144.49    --    3.60  53.00-151.00   26
  3  \w    -58.00 -33.00   1.00  144.49    --   -3.90 -53.00  63.00   25
  4  \w      2.00  27.00   1.00  144.49    --   -3.90  53.00-151.00   25
  5  \w     10.00  35.00   1.00  144.49    --    3.60 -82.00 -60.00   25
  6  \w    -51.00  93.00   1.00  144.49    --    3.60  19.00   0.00  144
  7  \w    -26.00   0.00   1.00  144.49    --   -3.90  57.00 120.00   26
  8  \w    -30.00  18.00   1.00  144.49    --   -3.90 -82.00  90.00   48
  9  \w    -34.00  21.00   1.00  144.49    --   -3.90 -77.00 150.00   55
 10  \w    -60.00 -13.00   1.00  144.49    --   -3.90 -82.00  30.00   47
;
_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      0.0333059000
_diffrn_orient_matrix_UB_12      0.0311503000
_diffrn_orient_matrix_UB_13      0.0048304000
_diffrn_orient_matrix_UB_21      0.0133668000
_diffrn_orient_matrix_UB_22      -0.0309506000
_diffrn_orient_matrix_UB_23      -0.0152994000
_diffrn_orient_matrix_UB_31      -0.0119725000
_diffrn_orient_matrix_UB_32      0.0523476000
_diffrn_orient_matrix_UB_33      -0.0119143000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1046
_diffrn_reflns_av_unetI/netI     0.0686
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            47739
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.499
_diffrn_reflns_theta_min         2.583
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.189
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30974
_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    1.328
_exptl_crystal_description       plate
_exptl_crystal_F_000             2966
_exptl_crystal_size_max          0.498
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.097
_refine_diff_density_max         1.107
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         7598
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.182
_refine_ls_R_factor_all          0.1916
_refine_ls_R_factor_gt           0.1590
_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^)+(0.1332P)^2^+107.6142P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3767
_refine_ls_wR_factor_ref         0.3960
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5704
_reflns_number_total             7598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05477k2.cif
_cod_data_source_block           aj0254
_cod_database_code               1550680
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C19H18N2F3O3S
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.912
_reflns_odcompleteness_completeness 99.71
_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. Uiso/Uaniso restraints and constraints
Uanis(F01Q) \\sim Ueq: with sigma of 0.007 and sigma for terminal atoms of
0.0002
Uanis(F01D) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.002
Uanis(C01E) \\sim Ueq, Uanis(C01J) \\sim Ueq, Uanis(C01K) \\sim Ueq,
Uanis(C01O) \\sim Ueq, Uanis(C01L) \\sim Ueq, Uanis(C01P) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.002
Uanis(C01M) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.002
3. Others
 Fixed Sof: H00K(0.5) H00M(0.5) H01Y(0.5) H(0.5) F01D(0.25) F01G(0.5)
 H0AA(0.5) HE(0.5) HF(0.5) H01P(0.5) H01Q(0.5) H01D(0.5) H01E(0.5) H01F(0.5)
 F01Q(0.5) C01U(0.5) H01X(0.5) O1(0.5) O2(0.5) O1AA(0.5) O0AA(0.5) O3(0.5)
 O6(0.5) F13(0.5) F1(0.5) F0AA(0.5) F2(0.5)
4.a Riding coordinates:
 C01J(H0AA,HE,HF), C01O(H01D,H01E,H01F)
4.b Ternary CH refined with riding coordinates:
 C00D(H00D), C00N(H00N), C00P(H00P)
4.c Secondary CH2 refined with riding coordinates:
 C00Z(H00K,H00M), C010(H01Y,H), C01L(H01P,H01Q), C01S(H01S,H01T)
4.d Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00R(H00R), C00X(H00X), C016(H016), C01R(H01R), C01U(H01X)
4.e Idealised Me refined as rotating group:
 C00I(H00A,H00B,H00C), C00M(H00E,H00F,H00G), C00T(H00H,H00I,H00J), C00Y(H00O,
 H00Q,H00S), C011(H01G,H01H,H01I), C012(H01Z,HA,HB), C017(H01J,H01K,H01L),
 C01C(H01M,H01N,H01O), C01E(H01A,H01B,H01C), C01F(H01,HC,HD), C01K(H1AA,HG,HH),
 C01T(H01U,H01V,H01W)
;
_shelx_res_checksum              2820
_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 2.032
_oxdiff_exptl_absorpt_empirical_full_min 0.399