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_1568953
_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 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2022-06-14
_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                 101.3867(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.88043(12)
_cell_length_b                   10.96832(16)
_cell_length_c                   14.65499(19)
_cell_measurement_reflns_used    12002
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.7790
_cell_measurement_theta_min      4.0450
_cell_volume                     1399.35(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(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 0.972
_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    -66.00 -31.00   0.50    0.05    --  -91.75  57.00-180.00   70
  2  \w    -67.00 -33.00   0.50    0.05    --  -91.75  57.00 -90.00   68
  3  \w    -27.00  22.00   0.50    0.05    --  -47.62  19.00 -90.00   98
  4  \w    -22.00  26.00   0.50    0.05    --  -47.62  37.00 -60.00   96
  5  \w    -26.00   8.00   0.50    0.05    --  -47.62  19.00  60.00   68
  6  \w    -25.00  39.00   0.50    0.05    --   47.62 -37.00  30.00  128
  7  \w    -23.00  41.00   0.50    0.05    --   47.62 -37.00 -30.00  128
  8  \w     -6.00  19.00   0.50    0.05    --   47.62 -19.00-150.00   50
  9  \w     -8.00  24.00   0.50    0.05    --   47.62 -19.00-120.00   64
 10  \w     48.00 104.00   0.50    0.05    --  107.19 -99.00  90.00  112
 11  \w     67.00  92.00   0.50    0.05    --  107.19-157.00 178.00   50
 12  \w     68.00 115.00   0.50    0.05    --   47.62-157.00 178.00   94
 13  \w     68.00 101.00   0.50    0.05    --  107.19 -99.00 120.00   66
 14  \w     52.00 100.00   0.50    0.05    --  107.19-125.00   0.00   96
 15  \w     47.00 101.00   0.50    0.05    --  107.19 -99.00   0.00  108
 16  \w     63.00  98.00   0.50    0.05    --  107.19-118.00 -26.00   70
 17  \w     42.00  69.00   0.50    0.05    --  107.19 -99.00  60.00   54
 18  \w     38.00  63.00   0.50    0.05    --   47.62-118.00 -26.00   50
 19  \w     41.00  66.00   0.50    0.05    --  107.19 -99.00-180.00   50
 20  \w     71.00 104.00   0.50    0.05    --  107.19 -99.00-180.00   66
 21  \w     39.00  99.00   0.50    0.05    --  107.19 -99.00-150.00  120
 22  \w     56.00 104.00   0.50    0.05    --  107.19 -99.00-120.00   96
 23  \w     77.00 102.00   0.50    0.05    --  107.19 -99.00  30.00   50
 24  \w     36.00  62.00   0.50    0.05    --  107.19 -99.00  30.00   52
 25  \w     37.00  62.00   0.50    0.05    --  107.19 -57.00  90.00   50
 26  \w     40.00  65.00   0.50    0.05    --  107.19 -57.00  30.00   50
 27  \w     37.00  64.00   0.50    0.05    --  107.19 -57.00   0.00   54
 28  \w     35.00  60.00   0.50    0.05    --  107.19 -57.00-180.00   50
 29  \w     92.00 117.00   0.50    0.05    --  107.19 157.00-145.00   50
 30  \w    126.00 165.00   0.50    0.05    --  107.19  77.00  30.00   78
 31  \w    106.00 149.00   0.50    0.05    --  107.19 118.00  59.00   86
 32  \w    129.00 173.00   0.50    0.05    --  107.19  57.00 120.00   88
 33  \w    -63.00 -37.00   0.50    0.05    --  -91.75 118.00  59.00   52
 34  \w    -40.00 -10.00   0.50    0.05    --  -47.62 118.00  59.00   60
 35  \w    -82.00 -56.00   0.50    0.05    --  -91.75 157.00-145.00   52
 36  \w    -82.00 -30.00   0.50    0.05    --  -91.75 125.00-150.00  104
 37  \w    -92.00 -67.00   0.50    0.05    --  -47.62 157.00-145.00   50
 38  \w   -163.00-114.00   0.50    0.05    --  -91.75 -37.00  60.00   98
 39  \w   -162.00-130.00   0.50    0.05    --  -91.75 -77.00   0.00   64
 40  \w   -161.00-126.00   0.50    0.05    --  -91.75 -77.00 -60.00   70
 41  \w   -152.00-127.00   0.50    0.05    --  -91.75 -57.00 -90.00   50
 42  \w   -154.00-128.00   0.50    0.05    --  -91.75 -77.00 -90.00   52
 43  \w   -163.00-130.00   0.50    0.05    --  -91.75 -57.00-120.00   66
 44  \w   -160.00-130.00   0.50    0.05    --  -91.75 -77.00-150.00   60
 45  \w   -160.00-134.00   0.50    0.05    --  -91.75 -57.00-180.00   52
 46  \w   -160.00-127.00   0.50    0.05    --  -91.75 -57.00-150.00   66
 47  \w   -163.00-127.00   0.50    0.05    --  -91.75 -57.00  30.00   72
 48  \w   -112.00 -86.00   0.50    0.05    --  -91.75-118.00 -26.00   52
 49  \w    -93.00 -55.00   0.50    0.05    --  -47.62-157.00 178.00   76
 50  \w    -93.00 -53.00   0.50    0.05    --  -91.75-157.00 178.00   80
;
_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      -0.0543358000
_diffrn_orient_matrix_UB_12      -0.1336394000
_diffrn_orient_matrix_UB_13      -0.0079877000
_diffrn_orient_matrix_UB_21      0.1485454000
_diffrn_orient_matrix_UB_22      -0.0391228000
_diffrn_orient_matrix_UB_23      0.0669324000
_diffrn_orient_matrix_UB_31      -0.0794300000
_diffrn_orient_matrix_UB_32      0.0184958000
_diffrn_orient_matrix_UB_33      0.0833681000
_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  0.0331
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            17600
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.789
_diffrn_reflns_theta_min         5.073
_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    3.924
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89059
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (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    1.520
_exptl_crystal_description       irregular
_exptl_crystal_F_000             656
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.179
_exptl_crystal_size_mid          0.146
_exptl_crystal_size_min          0.119
_refine_diff_density_max         0.298
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         2868
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0236
_refine_ls_R_factor_gt           0.0227
_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^)+(0.0272P)^2^+0.8835P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0575
_refine_ls_wR_factor_ref         0.0580
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2750
_reflns_number_total             2868
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06999g2.cif
_cod_data_source_block           jw622a
_cod_depositor_comments
'Adding full bibliography for 1568950--1568954.cif.'
_cod_database_code               1568953
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H18BrNO
_chemical_oxdiff_usercomment     ZTP-3-187
_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:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B)
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              23429
_shelx_hkl_checksum              60477
_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
_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 1.098
_oxdiff_exptl_absorpt_empirical_full_min 0.918