Regiodivergent (3 + 2) annulation reactions of oxyallyl cations.
Protich, Zachary; Lowder, Leah L.; Hughes, Russell P.; Wu, Jimmy; Chemical science 14 (2023) 5196–5203; doi:10.1039/d2sc06999g

data_1568952
_publ_section_title
;
 Regiodivergent (3 + 2) annulation reactions of oxyallyl cations.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              5196
_journal_page_last               5203
_journal_paper_doi               10.1039/d2sc06999g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C16 H18 Br N O'
_chemical_formula_sum            'C16 H18 Br N O'
_chemical_formula_weight         320.22
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-28
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-21 deposited with the CCDC.	2023-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.5354(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.68696(11)
_cell_length_b                   6.65657(6)
_cell_length_c                   15.48510(13)
_cell_measurement_reflns_used    14864
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.2500
_cell_measurement_theta_min      2.8720
_cell_volume                     1382.32(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.59a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.59a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.59a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.977
_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    130.00 177.00   0.50    0.05    --  113.25 125.00 -90.00   94
  2  \w     -5.00  40.00   0.50    0.05    --   47.62 -37.00-150.00   90
  3  \w    -25.00   0.00   0.50    0.05    --   47.62  -9.00 -42.00   50
  4  \w    -26.00  20.00   0.50    0.05    --   47.62 -19.00 150.00   92
  5  \w     45.00  71.00   0.50    0.05    --  113.25 -77.00  60.00   52
  6  \w     44.00  70.00   0.50    0.05    --  113.25 -61.00  90.00   52
  7  \w     42.00  67.00   0.50    0.05    --  113.25 -61.00   0.00   50
  8  \w     42.00  68.00   0.50    0.05    --  113.25 -61.00 -30.00   52
  9  \w     43.00  68.00   0.50    0.05    --  113.25 -61.00 -60.00   50
 10  \w     42.00  90.00   0.50    0.05    --  113.25 -77.00 -90.00   96
 11  \w     42.00  67.00   0.50    0.05    --  113.25 -61.00-120.00   50
 12  \w     53.00 102.00   0.50    0.05    --  113.25 -94.00-150.00   98
 13  \w     76.00 105.00   0.50    0.05    --  113.25-108.00-142.87   58
 14  \w     43.00  71.00   0.50    0.05    --  113.25-108.00-142.87   56
 15  \w     42.00  68.00   0.50    0.05    --  113.25 -94.00-120.00   52
 16  \w     79.00 104.00   0.50    0.05    --  113.25 -94.00-120.00   50
 17  \w     67.00 104.00   0.50    0.05    --  113.25 -94.00 -90.00   74
 18  \w    130.00 176.00   0.50    0.05    --  113.25  61.00   0.00   92
 19  \w    152.00 177.00   0.50    0.05    --  113.25  61.00 -90.00   50
 20  \w    134.00 178.00   0.50    0.05    --  113.25  61.00  30.00   88
 21  \w    141.00 171.00   0.50    0.05    --  113.25  45.00  60.00   60
 22  \w    145.00 172.00   0.50    0.05    --  113.25  61.00 120.00   54
 23  \w    152.00 178.00   0.50    0.05    --  113.25  45.00 150.00   52
 24  \w    103.00 129.00   0.50    0.05    --  113.25  32.00 -54.70   52
 25  \w    101.00 174.00   0.50    0.05    --  113.25  30.00 -30.00  146
 26  \w    101.00 140.00   0.50    0.05    --  113.25  30.00 -90.00   78
 27  \w    101.00 127.00   0.50    0.05    --  113.25  30.00 -60.00   52
 28  \w    102.00 154.00   0.50    0.05    --  113.25  30.00-120.00  104
 29  \w    137.00 176.00   0.50    0.05    --  113.25  45.00-150.00   78
 30  \w    144.00 170.00   0.50    0.05    --  113.25  30.00-180.00   52
 31  \w    102.00 133.00   0.50    0.05    --  113.25  30.00-180.00   62
 32  \w    102.00 133.00   0.50    0.05    --  113.25  30.00-150.00   62
 33  \w    151.00 178.00   0.50    0.05    --  113.25  30.00 -90.00   54
 34  \w    106.00 132.00   0.50    0.05    --  113.25  30.00 150.00   52
 35  \w    111.00 159.00   0.50    0.05    --  113.25   9.00 131.00   96
 36  \w     30.00  56.00   0.50    0.05    --   47.62   9.00 131.00   52
 37  \w     75.00 100.00   0.50    0.05    --   47.62   9.00 131.00   50
 38  \w     36.00  80.00   0.50    0.05    --   47.62  30.00 -55.06   88
 39  \w     44.00  72.00   0.50    0.05    --   47.62  19.00-150.00   56
 40  \w    -80.00 -30.00   0.50    0.05    --  -47.62 125.00-150.00  100
 41  \w    -82.00 -57.00   0.50    0.05    --  -91.75 125.00-180.00   50
 42  \w    -63.00 -36.00   0.50    0.05    --  -47.62 -31.00-128.18   54
 43  \w    -64.00 -35.00   0.50    0.05    --  -47.62 -31.00 -95.99   58
 44  \w    -75.00 -42.00   0.50    0.05    --  -47.62 -29.00-153.78   66
 45  \w    -76.00 -42.00   0.50    0.05    --  -47.62  -9.00 -42.00   68
 46  \w    -25.00  22.00   0.50    0.05    --  -47.62   9.00 131.00   94
 47  \w    -81.00 -36.00   0.50    0.05    --  -47.62 -29.00 168.38   90
 48  \w   -114.00 -87.00   0.50    0.05    --  -47.62 -29.00 168.38   54
 49  \w    -98.00 -36.00   0.50    0.05    --  -47.62 -29.00 124.62  124
 50  \w   -123.00 -97.00   0.50    0.05    --  -91.75 -31.00 139.65   52
 51  \w   -126.00 -91.00   0.50    0.05    --  -91.75 -30.00 124.84   70
 52  \w   -116.00 -90.00   0.50    0.05    --  -91.75 -30.00 -90.00   52
 53  \w   -113.00 -88.00   0.50    0.05    --  -91.75 -30.00-120.00   50
 54  \w   -115.00 -90.00   0.50    0.05    --  -91.75 -30.00-175.88   50
 55  \w   -117.00 -91.00   0.50    0.05    --  -91.75 -30.00-180.00   52
 56  \w   -107.00 -81.00   0.50    0.05    --  -91.75 -29.00 135.75   52
 57  \w   -107.00 -82.00   0.50    0.05    --  -91.75 -29.00 143.28   50
 58  \w   -106.00 -81.00   0.50    0.05    --  -91.75 -29.00 151.42   50
 59  \w   -105.00 -79.00   0.50    0.05    --  -91.75 -29.00 160.10   52
 60  \w   -104.00 -79.00   0.50    0.05    --  -91.75 -29.00-156.98   50
 61  \w   -104.00 -79.00   0.50    0.05    --  -91.75 -28.00-176.79   50
 62  \w   -104.00 -79.00   0.50    0.05    --  -91.75 -29.00-161.78   50
 63  \w   -112.00 -79.00   0.50    0.05    --  -91.75 -28.00-152.49   66
 64  \w   -104.00 -79.00   0.50    0.05    --  -91.75 -29.00-136.65   50
 65  \w   -144.00-119.00   0.50    0.05    --  -91.75  -9.00 -42.00   50
;
_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      -0.0358484000
_diffrn_orient_matrix_UB_12      -0.0194052000
_diffrn_orient_matrix_UB_13      0.0878080000
_diffrn_orient_matrix_UB_21      0.1089726000
_diffrn_orient_matrix_UB_22      -0.0188681000
_diffrn_orient_matrix_UB_23      0.0496619000
_diffrn_orient_matrix_UB_31      0.0059392000
_diffrn_orient_matrix_UB_32      0.2298677000
_diffrn_orient_matrix_UB_33      0.0115137000
_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  0.0267
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            19284
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.122
_diffrn_reflns_theta_min         3.296
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    3.972
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.421
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.59a (Rigaku Oxford Diffraction, 2022)
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    1.539
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.354
_exptl_crystal_size_mid          0.205
_exptl_crystal_size_min          0.172
_refine_diff_density_max         0.556
_refine_diff_density_min         -0.620
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         2959
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0278
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0328P)^2^+1.3770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0715
_refine_ls_wR_factor_ref         0.0719
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2910
_reflns_number_total             2959
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06999g2.cif
_cod_data_source_block           jw622b
_cod_depositor_comments
'Adding full bibliography for 1568950--1568954.cif.'
_cod_database_code               1568952
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H19NO
_chemical_oxdiff_usercomment     ZTP-3-187-minor
_shelx_estimated_absorpt_t_max   0.548
_shelx_estimated_absorpt_t_min   0.334
_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:
 C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              84205
_shelx_hkl_checksum              11956
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id ZTP-3-187-minor
_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 1.194
_oxdiff_exptl_absorpt_empirical_full_min 0.908