Leveraging the Halo-Nazarov Cyclization for the Chemodivergent Assembly of Functionalized Haloindenes and Indanones.
Holt, Connor; Alachouzos, Georgios; Frontier, Alison J.; Journal of the American Chemical Society 141 (2019) 5461–5469; doi:10.1021/jacs.9b00198

data_4128369
_publ_section_title
;
 Leveraging the Halo-Nazarov Cyclization for the Chemodivergent Assembly
 of Functionalized Haloindenes and Indanones.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5461
_journal_page_last               5469
_journal_paper_doi               10.1021/jacs.9b00198
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C19 H19 Br O2'
_chemical_formula_sum            'C19 H19 Br O2'
_chemical_formula_weight         359.25
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-05-30
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.0573(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.76362(14)
_cell_length_b                   21.0599(4)
_cell_length_c                   9.84571(14)
_cell_measurement_reflns_used    19584
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      77.6120
_cell_measurement_theta_min      4.2270
_cell_volume                     1600.80(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.989
_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   -121.00 -65.00   0.50    0.05    --  -49.75-134.00-162.00  112
  2  \w    -98.00 -15.00   0.50    0.05    --  -49.75 134.00 -94.00  166
  3  \w   -121.00 -63.00   0.50    0.05    --  -49.75-136.00  18.00  116
  4  \w    -99.00 -16.00   0.50    0.05    --  -49.75 136.00  83.00  166
  5  \w     38.00 102.00   0.50    0.05    --   49.75-136.00  18.00  128
  6  \w     36.00 100.00   0.50    0.05    --   49.75-134.00-162.00  128
  7  \w   -156.00 -65.00   0.50    0.13    --  -84.25-134.00-162.00  182
  8  \w    -98.00 -15.00   0.50    0.13    --  -84.25 134.00 -94.00  166
  9  \w   -156.00 -63.00   0.50    0.13    --  -84.25-136.00  18.00  186
 10  \w     85.00 178.00   0.50    0.13    --  105.75 136.00  83.00  186
 11  \w     38.00 125.00   0.50    0.13    --  105.75-136.00  18.00  174
 12  \w     36.00 123.00   0.50    0.13    --  105.75-134.00-162.00  174
 13  \w     86.00 178.00   0.50    0.13    --  105.75 134.00 -94.00  184
 14  \w    -57.00  22.00   0.50    0.05    --  -49.75  38.00 -30.00  158
 15  \w   -121.00 -42.00   0.50    0.05    --  -49.75 -38.00-120.00  158
 16  \w   -121.00 -70.00   0.50    0.05    --  -49.75-125.00 -90.00  102
 17  \w   -121.00 -70.00   0.50    0.05    --  -49.75-125.00-120.00  102
 18  \w    -23.00  57.00   0.50    0.05    --   49.75 -19.00-120.00  160
 19  \w    -62.00 -12.00   0.50    0.13    --  -84.25  15.00 -30.00  100
 20  \w    -99.00 -16.00   0.50    0.13    --  -84.25 136.00  83.00  166
 21  \w     34.00  72.00   0.50    0.13    --  105.75 -30.00 -60.00   76
 22  \w     33.00  82.00   0.50    0.13    --  105.75 -15.00   0.00   98
 23  \w     97.00 178.00   0.50    0.13    --  105.75  45.00   0.00  162
 24  \w     34.00 109.00   0.50    0.13    --  105.75 -94.00  30.00  150
 25  \w     34.00  72.00   0.50    0.13    --  105.75 -30.00  30.00   76
 26  \w     34.00  90.00   0.50    0.13    --  105.75 -45.00-180.00  112
 27  \w     34.00  72.00   0.50    0.13    --  105.75 -30.00-180.00   76
 28  \w     34.00  72.00   0.50    0.13    --  105.75 -30.00  60.00   76
 29  \w     34.00 154.00   0.50    0.13    --  105.75   0.00   0.00  240
 30  \w     34.00 116.00   0.50    0.13    --  105.75-125.00 150.00  164
 31  \w     34.00 120.00   0.50    0.13    --  105.75 -61.00   0.00  172
 32  \w     34.00  72.00   0.50    0.13    --  105.75 -30.00 -30.00   76
 33  \w     34.00  72.00   0.50    0.13    --  105.75 -30.00 120.00   76
 34  \w     34.00 109.00   0.50    0.13    --  105.75 -94.00 -60.00  150
 35  \w     34.00 120.00   0.50    0.13    --  105.75 -61.00-180.00  172
 36  \w     34.00 127.00   0.50    0.13    --  105.75 -77.00 150.00  186
 37  \w     34.00 109.00   0.50    0.13    --  105.75 -94.00   0.00  150
 38  \w     34.00 110.00   0.50    0.13    --  105.75-100.00-125.66  152
 39  \w     92.00 178.00   0.50    0.13    --  105.75 125.00-120.00  172
 40  \w     33.00  82.00   0.50    0.13    --  105.75 -15.00-180.00   98
 41  \w     33.00  82.00   0.50    0.13    --  105.75 -15.00-150.00   98
 42  \w     34.00 109.00   0.50    0.13    --  105.75 -94.00 -30.00  150
 43  \w     34.00 109.00   0.50    0.13    --  105.75 -94.00-180.00  150
 44  \w     43.00 109.00   0.50    0.13    --  105.75 -94.00 -90.00  132
 45  \w     34.00  65.00   0.50    0.13    --  105.75 -15.00  90.00   62
 46  \w     35.00  66.00   0.50    0.13    --  105.75 -30.00   0.00   62
 47  \w     41.00  86.00   0.50    0.13    --  105.75 -45.00   0.00   90
 48  \w     41.00  66.00   0.50    0.13    --  105.75 -15.00 120.00   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      -0.1530983000
_diffrn_orient_matrix_UB_12      0.0464146000
_diffrn_orient_matrix_UB_13      -0.0275312000
_diffrn_orient_matrix_UB_21      0.1252678000
_diffrn_orient_matrix_UB_22      0.0565696000
_diffrn_orient_matrix_UB_23      0.0246027000
_diffrn_orient_matrix_UB_31      0.0260628000
_diffrn_orient_matrix_UB_32      0.0009555000
_diffrn_orient_matrix_UB_33      -0.1529175000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0679
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            38321
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.951
_diffrn_reflns_theta_min         4.198
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.530
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89582
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.491
_exptl_crystal_description       needle
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.116
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.057
_refine_diff_density_max         1.106
_refine_diff_density_min         -1.441
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         3393
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0659P)^2^+2.1530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1158
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3251
_reflns_number_total             3393
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b00198_si_004.cif
_cod_data_source_block           froga06
_cod_database_code               4128369
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C19H19O2Br
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.685
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              40933
_shelx_hkl_checksum              62415
_olex2_submission_original_sample_id froga06
_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 1.473
_oxdiff_exptl_absorpt_empirical_full_min 0.758