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_1568950
_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 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 111.1442(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.82272(18)
_cell_length_b                   8.08217(10)
_cell_length_c                   14.6182(2)
_cell_measurement_reflns_used    10444
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.7150
_cell_measurement_theta_min      4.1360
_cell_volume                     1302.78(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 0.987
_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    -62.00  25.00   0.50    0.05    --  -47.62  54.00-163.00  174
  2  \w    -60.00 -21.00   0.50    0.10    --  -91.75  54.00-163.00   78
  3  \w    -80.00 -32.00   0.50    0.05    --  -47.62 125.00 -30.00   96
  4  \w    -50.00 -22.00   0.50    0.10    --  -91.75  45.00  30.00   56
  5  \w    -23.00  27.00   0.50    0.05    --  -47.62  19.00 -30.00  100
  6  \w     42.00  99.00   0.50    0.10    --  113.25 -94.00 -30.00  114
  7  \w     42.00  85.00   0.50    0.10    --  113.25 -94.00-180.00   86
  8  \w     58.00  94.00   0.50    0.10    --  113.25 -77.00-180.00   72
  9  \w     65.00  90.00   0.50    0.10    --  113.25 -77.00-150.00   50
 10  \w     46.00  90.00   0.50    0.10    --  113.25 -77.00   0.00   88
 11  \w     42.00  67.00   0.50    0.10    --  113.25 -61.00 -60.00   50
 12  \w     42.00  67.00   0.50    0.10    --  113.25 -61.00 -90.00   50
 13  \w     42.00  67.00   0.50    0.10    --  113.25 -61.00   0.00   50
 14  \w     43.00  69.00   0.50    0.10    --  113.25 -61.00  60.00   52
 15  \w     43.00  98.00   0.50    0.10    --  113.25 -77.00  90.00  110
 16  \w     49.00  90.00   0.50    0.10    --  113.25-125.00 150.00   82
 17  \w     58.00 105.00   0.50    0.10    --  113.25 -77.00 120.00   94
 18  \w     60.00  86.00   0.50    0.05    --   47.62  19.00   0.00   52
 19  \w    133.00 175.00   0.50    0.10    --  113.25  61.00 -90.00   84
 20  \w    129.00 155.00   0.50    0.10    --  113.25  61.00   0.00   52
 21  \w    130.00 174.00   0.50    0.10    --  113.25  61.00  60.00   88
 22  \w    144.00 171.00   0.50    0.10    --  113.25  61.00  90.00   54
 23  \w    149.00 176.00   0.50    0.10    --  113.25  61.00 150.00   54
 24  \w    101.00 148.00   0.50    0.10    --  113.25  30.00   0.00   94
 25  \w    129.00 177.00   0.50    0.10    --  113.25  30.00 120.00   96
 26  \w    103.00 146.00   0.50    0.10    --  113.25  30.00 -60.00   86
 27  \w    122.00 175.00   0.50    0.10    --  113.25  45.00-120.00  106
 28  \w     99.00 178.00   0.50    0.10    --  113.25  54.00-163.00  158
 29  \w     84.00 109.00   0.50    0.05    --   47.62  54.00-163.00   50
 30  \w    118.00 148.00   0.50    0.10    --  113.25  30.00 -90.00   60
 31  \w    150.00 175.00   0.50    0.10    --  113.25  30.00 -30.00   50
 32  \w    101.00 148.00   0.50    0.10    --  113.25  30.00 -30.00   94
 33  \w    101.00 132.00   0.50    0.10    --  113.25  30.00  30.00   62
 34  \w    151.00 178.00   0.50    0.10    --  113.25  30.00  30.00   54
 35  \w    140.00 176.00   0.50    0.10    --  113.25  30.00  90.00   72
 36  \w    102.00 127.00   0.50    0.10    --  113.25  30.00  90.00   50
 37  \w     10.00  36.00   0.50    0.05    --   47.62 -54.00  53.00   52
 38  \w   -119.00 -36.00   0.50    0.05    --  -47.62 -54.00  53.00  166
 39  \w   -144.00-119.00   0.50    0.10    --  -91.75 -54.00  53.00   50
 40  \w   -163.00-138.00   0.50    0.10    --  -91.75 -30.00   0.00   50
 41  \w   -117.00 -88.00   0.50    0.10    --  -91.75 -30.00 -60.00   58
 42  \w   -104.00 -79.00   0.50    0.10    --  -91.75 -29.00 -56.97   50
 43  \w   -105.00 -79.00   0.50    0.10    --  -91.75 -29.00-132.94   52
 44  \w   -108.00 -79.00   0.50    0.10    --  -91.75 -27.00-101.37   58
 45  \w   -115.00 -79.00   0.50    0.10    --  -91.75 -29.00-120.62   72
 46  \w   -108.00 -82.00   0.50    0.10    --  -91.75 -25.00-113.55   52
 47  \w   -108.00 -79.00   0.50    0.10    --  -91.75 -27.00 -83.57   58
 48  \w   -103.00 -78.00   0.50    0.10    --  -91.75 -20.00 -63.23   50
 49  \w    -85.00 -35.00   0.50    0.05    --  -47.62 -19.00 -90.00  100
 50  \w    115.00 143.00   0.50    0.10    --  113.25 125.00 -90.00   56
 51  \w    120.00 152.00   0.50    0.10    --  113.25 125.00-120.00   64
;
_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      -0.1290381000
_diffrn_orient_matrix_UB_12      -0.0719649000
_diffrn_orient_matrix_UB_13      -0.0305685000
_diffrn_orient_matrix_UB_21      -0.0387575000
_diffrn_orient_matrix_UB_22      0.1023765000
_diffrn_orient_matrix_UB_23      -0.0952645000
_diffrn_orient_matrix_UB_31      0.0369707000
_diffrn_orient_matrix_UB_32      -0.1438290000
_diffrn_orient_matrix_UB_33      -0.0524822000
_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  0.0319
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            17052
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.158
_diffrn_reflns_theta_min         4.148
_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    0.592
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.608
_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    1.230
_exptl_crystal_description       irregular
_exptl_crystal_F_000             520
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.225
_refine_diff_density_min         -0.310
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         2813
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0401
_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^)+(0.0549P)^2^+0.3649P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1052
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2620
_reflns_number_total             2813
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06999g2.cif
_cod_data_source_block           jw722a
_cod_depositor_comments
'Adding full bibliography for 1568950--1568954.cif.'
_cod_original_cell_volume        1302.78(4)
_cod_database_code               1568950
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H19NO
_chemical_oxdiff_usercomment     ZTP-3-143-major
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.887
_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:
 C7(H7), C8(H8), C9(H9), C10(H10)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              95196
_shelx_hkl_checksum              80411
_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-major
_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 0.869