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_1568951
_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 H19 N O'
_chemical_formula_sum            'C16 H19 N O'
_chemical_formula_weight         241.32
_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             2022-07-05
_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                 107.5140(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.0584(2)
_cell_length_b                   6.13979(7)
_cell_length_c                   13.79498(19)
_cell_measurement_reflns_used    11062
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.3760
_cell_measurement_theta_min      2.8620
_cell_volume                     1297.07(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.60a (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 0.990
_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    -26.00  23.00   0.50    0.05    --   47.62 -19.00 120.00   98
  2  \w     -2.00  23.00   0.50    0.05    --   47.62 -19.00   0.00   50
  3  \w    -18.00  15.00   0.50    0.05    --   47.62 -19.00 -30.00   66
  4  \w     43.00  68.00   0.50    0.21    --  113.25-125.00-120.00   50
  5  \w     73.00 108.00   0.50    0.21    --  113.25-125.00-120.00   70
  6  \w     68.00  97.00   0.50    0.21    --  113.25-149.00-121.00   58
  7  \w     44.00  89.00   0.50    0.21    --  113.25-125.00-180.00   90
  8  \w     55.00  80.00   0.50    0.05    --   47.62-149.00-121.00   50
  9  \w     43.00  69.00   0.50    0.21    --  113.25-125.00   0.00   52
 10  \w     51.00  76.00   0.50    0.21    --  113.25-123.00  41.00   50
 11  \w     42.00  69.00   0.50    0.21    --  113.25-125.00 150.00   54
 12  \w     55.00  92.00   0.50    0.05    --   47.62-123.00  41.00   74
 13  \w     43.00  68.00   0.50    0.21    --  113.25 -94.00  30.00   50
 14  \w     79.00 104.00   0.50    0.21    --  113.25 -94.00  30.00   50
 15  \w     73.00 100.00   0.50    0.21    --  113.25 -94.00 -30.00   54
 16  \w     79.00 104.00   0.50    0.21    --  113.25 -94.00-150.00   50
 17  \w     44.00 104.00   0.50    0.21    --  113.25-102.00-170.31  120
 18  \w     42.00  67.00   0.50    0.21    --  113.25 -94.00-150.00   50
 19  \w     43.00  68.00   0.50    0.21    --  113.25 -94.00 -90.00   50
 20  \w     73.00 104.00   0.50    0.21    --  113.25 -94.00 -90.00   62
 21  \w     42.00  68.00   0.50    0.21    --  113.25 -94.00 -30.00   52
 22  \w     42.00 103.00   0.50    0.21    --  113.25 -94.00  60.00  122
 23  \w     74.00 102.00   0.50    0.21    --  113.25 -94.00  90.00   56
 24  \w     70.00 103.00   0.50    0.21    --  113.25 -94.00 120.00   66
 25  \w     44.00  69.00   0.50    0.21    --  113.25 -94.00  90.00   50
 26  \w     74.00 104.00   0.50    0.21    --  113.25 -94.00   0.00   60
 27  \w     78.00 104.00   0.50    0.21    --  113.25 -94.00 -60.00   52
 28  \w     51.00  98.00   0.50    0.21    --  113.25 -94.00-120.00   94
 29  \w     42.00  69.00   0.50    0.21    --  113.25 -61.00-180.00   54
 30  \w     42.00  67.00   0.50    0.21    --  113.25 -61.00-120.00   50
 31  \w     42.00  68.00   0.50    0.21    --  113.25 -61.00 -90.00   52
 32  \w     45.00  70.00   0.50    0.21    --  113.25 -61.00 -60.00   50
 33  \w     42.00  69.00   0.50    0.21    --  113.25 -61.00  30.00   54
 34  \w     42.00  68.00   0.50    0.21    --  113.25 -61.00  90.00   52
 35  \w    109.00 134.00   0.50    0.21    --  113.25  30.00-120.00   50
 36  \w    144.00 170.00   0.50    0.21    --  113.25  61.00-180.00   52
 37  \w    128.00 178.00   0.50    0.21    --  113.25  77.00-150.00  100
 38  \w    142.00 175.00   0.50    0.21    --  113.25  61.00-120.00   66
 39  \w    122.00 176.00   0.50    0.21    --  113.25  45.00 -60.00  108
 40  \w    131.00 157.00   0.50    0.21    --  113.25  45.00   0.00   52
 41  \w    130.00 176.00   0.50    0.21    --  113.25  61.00   0.00   92
 42  \w    122.00 175.00   0.50    0.21    --  113.25  45.00  60.00  106
 43  \w    122.00 147.00   0.50    0.21    --  113.25  45.00 120.00   50
 44  \w    144.00 173.00   0.50    0.21    --  113.25  77.00 150.00   58
 45  \w     99.00 134.00   0.50    0.21    --  113.25 123.00 122.00   70
 46  \w    116.00 155.00   0.50    0.21    --  113.25 125.00   0.00   78
 47  \w     98.00 123.00   0.50    0.21    --  113.25 149.00 -74.00   50
 48  \w    -42.00  20.00   0.50    0.05    --  -47.62  37.00 -90.00  124
 49  \w    -50.00 -20.00   0.50    0.21    --  -91.75  45.00 -60.00   60
 50  \w    -19.00   9.00   0.50    0.05    --  -47.62  19.00 -30.00   56
 51  \w    -20.00   6.00   0.50    0.05    --  -47.62  19.00  60.00   52
 52  \w    -26.00  25.00   0.50    0.05    --  -47.62  19.00 120.00  102
 53  \w    -52.00 -27.00   0.50    0.21    --  -91.75 123.00 122.00   50
 54  \w    -82.00 -20.00   0.50    0.05    --  -47.62 123.00 122.00  124
 55  \w    -88.00 -63.00   0.50    0.05    --  -47.62 149.00 -74.00   50
 56  \w    -88.00 -63.00   0.50    0.21    --  -91.75 149.00 -74.00   50
 57  \w   -160.00-124.00   0.50    0.21    --  -91.75 -45.00 -60.00   72
 58  \w   -159.00-122.00   0.50    0.21    --  -91.75 -45.00 -30.00   74
 59  \w   -157.00-131.00   0.50    0.21    --  -91.75 -61.00   0.00   52
 60  \w   -151.00-125.00   0.50    0.21    --  -91.75 -45.00  90.00   52
 61  \w   -163.00-125.00   0.50    0.21    --  -91.75 -45.00 150.00   76
 62  \w   -140.00 -77.00   0.50    0.21    --  -91.75-123.00  41.00  126
 63  \w   -112.00 -61.00   0.50    0.05    --  -47.62-149.00-121.00  102
 64  \w   -127.00-101.00   0.50    0.21    --  -91.75-149.00-121.00   52
;
_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      0.0837300000
_diffrn_orient_matrix_UB_12      -0.0346023000
_diffrn_orient_matrix_UB_13      -0.0306284000
_diffrn_orient_matrix_UB_21      -0.0167715000
_diffrn_orient_matrix_UB_22      -0.2474029000
_diffrn_orient_matrix_UB_23      -0.0064549000
_diffrn_orient_matrix_UB_31      -0.0531942000
_diffrn_orient_matrix_UB_32      0.0235874000
_diffrn_orient_matrix_UB_33      -0.1128324000
_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  0.0363
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18674
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.865
_diffrn_reflns_theta_min         2.886
_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    0.595
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.576
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.60a (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    1.236
_exptl_crystal_description       irregular
_exptl_crystal_F_000             520
_exptl_crystal_recrystallization_method 'Used as recieved'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.057
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0014(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     167
_refine_ls_number_reflns         2798
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0500P)^2^+0.3692P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1011
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2570
_reflns_number_total             2798
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06999g2.cif
_cod_data_source_block           jw722b
_cod_depositor_comments
'Adding full bibliography for 1568950--1568954.cif.'
_cod_database_code               1568951
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H19NO
_chemical_oxdiff_usercomment     ZTP-3-143-minor
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.880
_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:
 C1(H1), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C8(H8), C9(H9), C7(H7)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              73055
_shelx_hkl_checksum              33248
_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-3-143-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 1.179
_oxdiff_exptl_absorpt_empirical_full_min 0.862