Dual vicinal functionalisation of heterocycles <i>via</i> an interrupted Pummerer coupling/[3,3]-sigmatropic rearrangement cascade.
Šiaučiulis, Mindaugas; Sapmaz, Selma; Pulis, Alexander P.; Procter, David J.; Chemical science 9 (2018) 754–759; doi:10.1039/c7sc04723a

data_1548110
_publ_section_title
;
 Dual vicinal functionalisation of heterocycles <i>via</i> an interrupted
 Pummerer coupling/[3,3]-sigmatropic rearrangement cascade.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              754
_journal_page_last               759
_journal_paper_doi               10.1039/c7sc04723a
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C14 H15 N O S'
_chemical_formula_sum            'C14 H15 N O S'
_chemical_formula_weight         245.33
_chemical_name_systematic        '2-Allyl-3-(allylsulfinyl)-1H-indole '
_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             2017-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-08-24 deposited with the CCDC.
2017-11-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.633(11)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.7719(16)
_cell_length_b                   8.1203(7)
_cell_length_c                   19.0328(19)
_cell_measurement_reflns_used    3373
_cell_measurement_temperature    150
_cell_measurement_theta_max      25.0250
_cell_measurement_theta_min      3.5250
_cell_volume                     2570.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_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      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1636
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     24.00  76.00   1.00   40.00    --   11.54  77.00 -30.00   52
  2  \w    -66.00 -32.00   1.00   40.00    --   11.54 178.00-150.00   34
  3  \w    -76.00  34.00   1.00   40.00    --  -12.00 -19.00  60.00  110
  4  \w   -101.00 -54.00   1.00   40.00    --  -12.00-178.00 -30.00   47
  5  \w    -41.00  77.00   1.00   40.00    --  -12.00   0.00-150.00  118
  6  \w    -87.00 -57.00   1.00   40.00    --  -12.00-178.00-120.00   30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0126996000
_diffrn_orient_matrix_UB_12      -0.0817549000
_diffrn_orient_matrix_UB_13      -0.0028362000
_diffrn_orient_matrix_UB_21      -0.0319146000
_diffrn_orient_matrix_UB_22      -0.0093171000
_diffrn_orient_matrix_UB_23      -0.0348938000
_diffrn_orient_matrix_UB_31      0.0252814000
_diffrn_orient_matrix_UB_32      0.0293340000
_diffrn_orient_matrix_UB_33      -0.0189619000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0941
_diffrn_reflns_av_unetI/netI     0.0930
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22982
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         3.325
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.235
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93232
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear grayish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   grayish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       needle
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.276
_exptl_crystal_size_mid          0.049
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.289
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         4690
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1032
_refine_ls_R_factor_gt           0.0532
_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^)+(0.0259P)^2^+0.4696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.1068
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3004
_reflns_number_total             4690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc04723a2.cif
_cod_data_source_block           odjp5
_cod_depositor_comments
;

2019-01-24
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 1548110--1548111.cif.
;
_cod_original_cell_volume        2570.5(4)
_cod_original_formula_moiety     '2(C14 H15 N O S)'
_cod_original_formula_sum        'C28 H30 N2 O2 S2'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     490.66
_cod_database_code               1548110
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         C14H15NOS
_reflns_odcompleteness_completeness 99.63
_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, All N(H) groups
2. Restrained distances
 C27-H00X \\sim C28-HA \\sim C28-H00Z \\sim C24-H00V \\sim C25-H \\sim C25-H00Y
\\sim C14-H00M \\sim C14-
 H00J \\sim C13-H00N \\sim C11-H00F \\sim C11-H00H \\sim C10-H00G
 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C9(H00B,H00C), C12(H00D,H00E), C23(H00P,H00Q), C26(H00S,H00T)
3.b Aromatic/amide H refined with riding coordinates:
 N1(H005), N2(H006), C5(H00A), C10(H00G), C4(H00I), C2(H00K), C3(H00L),
 C19(H00O), C13(H00N), C16(H00R), C17(H00U), C24(H00V), C18(H00W), C27(H00X)
3.c X=CH2 refined with riding coordinates:
 C11(H00F,H00H), C14(H00J,H00M), C25(H00Y,H), C28(H00Z,HA)
;
_shelx_res_checksum              52967
_olex2_date_sample_data_collection 2017-05-30
_olex2_submission_original_sample_id
'Sulfenylation Product - diallylsulfoxide/indole'
_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 1.077
_oxdiff_exptl_absorpt_empirical_full_min 0.937