Nitrogen-interrupted <i>halo</i>-Prins/<i>halo</i>-Nazarov fragment coupling cascade for the synthesis of indolines.
Milosavljevic, Aleksa; Holt, Connor; Frontier, Alison J.; Chemical science 14 (2023) 5431–5437; doi:10.1039/d3sc00986f

data_1568947
_publ_section_title
;
 Nitrogen-interrupted <i>halo</i>-Prins/<i>halo</i>-Nazarov fragment
 coupling cascade for the synthesis of indolines.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              5431
_journal_page_last               5437
_journal_paper_doi               10.1039/d3sc00986f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C21 H22 I N O3 S'
_chemical_formula_sum            'C21 H22 I N O3 S'
_chemical_formula_weight         495.35
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-11-26
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-07 deposited with the CCDC.	2023-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                77.386(3)
_cell_angle_beta                 82.198(3)
_cell_angle_gamma                89.881(2)
_cell_formula_units_Z            4
_cell_length_a                   10.9449(2)
_cell_length_b                   13.1560(5)
_cell_length_c                   14.6317(6)
_cell_measurement_reflns_used    17099
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.0350
_cell_measurement_theta_min      3.4510
_cell_volume                     2036.12(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_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   -119.00 -31.00   0.50    1.92    --  -47.31 -62.00-162.00  176
  2  \w    -64.00  25.00   0.50    1.92    --  -47.31  62.00 -24.00  178
  3  \w    -24.00  64.00   0.50    1.92    --   47.31 -62.00-162.00  176
  4  \w     31.00 120.00   0.50    1.92    --   47.31  62.00 -24.00  178
  5  \w    -86.00 -13.00   0.50    1.92    --  -47.31 125.00-120.00  146
  6  \w    -14.00  28.00   0.50    1.92    --  -47.31  19.00-120.00   84
  7  \w    -38.00  26.00   0.50    1.92    --  -47.31  38.00 -60.00  128
  8  \w    -27.00  18.00   0.50    1.92    --   47.31 -19.00 -90.00   90
  9  \w    -27.00  18.00   0.50    1.92    --   47.31 -19.00  30.00   90
 10  \w     -1.00  80.00   0.50    1.92    --   47.31 -99.00 -60.00  162
 11  \w     34.00  93.00   0.50    1.92    --   47.31-125.00-150.00  118
 12  \w     33.00 120.00   0.50    1.92    --   47.31  57.00 -90.00  174
 13  \w     25.00 105.00   0.50    1.92    --   47.31  77.00 150.00  160
 14  \w     25.00 120.00   0.50    1.92    --   47.31  77.00  60.00  190
 15  \w    -74.00 -19.00   0.50    7.66    --  -91.75  62.00 -24.00  110
 16  \w   -163.00 -75.00   0.50    7.66    --  -91.75 -62.00-162.00  176
 17  \w    -47.00 -20.00   0.50    7.66    --  -91.75  45.00-180.00   54
 18  \w    -85.00 -22.00   0.50    7.66    --  -91.75 125.00 -90.00  126
 19  \w    -72.00 -19.00   0.50    7.66    --  -91.75  61.00 150.00  106
 20  \w    -47.00 -20.00   0.50    7.66    --  -91.75  45.00  90.00   54
 21  \w    -47.00 -20.00   0.50    7.66    --  -91.75  45.00 -30.00   54
 22  \w     97.00 178.00   0.50    7.66    --  113.25  62.00 -24.00  162
 23  \w     42.00  78.00   0.50    7.66    --  113.25 -62.00-162.00   72
 24  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00-120.00  128
 25  \w    101.00 178.00   0.50    7.66    --  113.25  30.00 -60.00  154
 26  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00-150.00  128
 27  \w    100.00 178.00   0.50    7.66    --  113.25  15.00  60.00  156
 28  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00 -30.00  128
 29  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00 120.00  128
 30  \w     42.00  76.00   0.50    7.66    --  113.25 -61.00 -30.00   68
 31  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00-180.00  128
 32  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00 -60.00  128
 33  \w     97.00 178.00   0.50    7.66    --  113.25  61.00-150.00  162
 34  \w     42.00  76.00   0.50    7.66    --  113.25 -61.00  90.00   68
 35  \w    101.00 178.00   0.50    7.66    --  113.25  30.00 120.00  154
 36  \w    101.00 178.00   0.50    7.66    --  113.25  45.00-180.00  154
 37  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00  60.00  128
 38  \w    101.00 178.00   0.50    7.66    --  113.25  45.00   0.00  154
 39  \w     42.00  76.00   0.50    7.66    --  113.25 -61.00   0.00   68
 40  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00  90.00  128
 41  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00 -90.00  128
 42  \w    101.00 178.00   0.50    7.66    --  113.25  45.00  60.00  154
 43  \w     44.00 111.00   0.50    7.66    --  113.25-125.00-180.00  134
 44  \w     43.00 106.00   0.50    7.66    --  113.25-102.00 170.18  126
 45  \w     42.00 106.00   0.50    7.66    --  113.25 -94.00  30.00  128
 46  \w     97.00 178.00   0.50    7.66    --  113.25  61.00-120.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1378929000
_diffrn_orient_matrix_UB_12      -0.0208452000
_diffrn_orient_matrix_UB_13      0.0043858000
_diffrn_orient_matrix_UB_21      -0.0020313000
_diffrn_orient_matrix_UB_22      0.0610038000
_diffrn_orient_matrix_UB_23      0.0788156000
_diffrn_orient_matrix_UB_31      -0.0344727000
_diffrn_orient_matrix_UB_32      -0.1012476000
_diffrn_orient_matrix_UB_33      0.0750782000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.075
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            60921
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.720
_diffrn_reflns_theta_min         3.444
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.488
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59652
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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    1.616
_exptl_crystal_description       needle
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.106
_exptl_crystal_size_mid          0.026
_exptl_crystal_size_min          0.019
_refine_diff_density_max         2.278
_refine_diff_density_min         -1.940
_refine_diff_density_rms         0.172
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     492
_refine_ls_number_reflns         13917
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0819
_refine_ls_R_factor_gt           0.0655
_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^)+(0.1270P)^2^+3.1279P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1814
_refine_ls_wR_factor_ref         0.1963
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10953
_reflns_number_total             13917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00986f2.cif
_cod_data_source_block           froam04
_cod_depositor_comments
'Adding full bibliography for 1568947--1568949.cif.'
_cod_database_code               1568947
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.784
_shelx_estimated_absorpt_t_min   0.329
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7586(10)
 0.2414(10)
2. 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, All O(H) groups
3.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C26(H26), C3(H3), C4(H4), C5(H5)
3.b Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C18(H18A,H18B), C19(H19A,
 H19B), C20(H20A,H20B)
3.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36),
 C37(H37), C38(H38), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C17(H17)
3.d Idealised Me refined as rotating group:
 C42(H42A,H42C,H42B), C21(H21A,H21B,H21C)
3.e Idealised tetrahedral OH refined as rotating group:
 O4(H4A), O1(H1)
;
_shelx_res_checksum              40089
_shelx_hkl_checksum              16751
_olex2_submission_original_sample_id froam04
_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 1.580
_oxdiff_exptl_absorpt_empirical_full_min 0.705