Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing chromones <i>via</i> tandem cyclization of <i>o</i>-hydroxyaryl enaminones.
Wu, Long-Hui; Liu, Xia; Liu, Zhao-Wen; Chen, Zhi-Xi; Fu, Xin-Lei; Yang, Kai; Organic & biomolecular chemistry 21 (2023) 9236–9241; doi:10.1039/d3ob01582c

data_7159662
_publ_section_title
;
 Metal-free synthesis of difluoro/trifluoromethyl carbinol-containing
 chromones <i>via</i> tandem cyclization of <i>o</i>-hydroxyaryl
 enaminones.
;
_journal_issue                   46
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9236
_journal_page_last               9241
_journal_paper_doi               10.1039/d3ob01582c
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C11 H7 Br F2 O3'
_chemical_formula_sum            'C11 H7 Br F2 O3'
_chemical_formula_weight         305.08
_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             2023-10-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-30 deposited with the CCDC.	2023-11-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.874(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4857(15)
_cell_length_b                   9.7788(14)
_cell_length_c                   9.6329(11)
_cell_measurement_reflns_used    1177
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.7230
_cell_measurement_theta_min      3.8650
_cell_volume                     1058.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0606
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.954
_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    -31.00  23.00   1.00    1.50    --   36.10 -57.00   0.00   54
  2  \w     -3.00  22.00   1.00    1.50    --   36.10 -99.00  90.00   25
  3  \w     21.00  62.00   1.00    1.50    --   36.10-125.00 120.00   41
  4  \w     34.00  88.00   1.00    1.50    --   36.10-125.00  30.00   54
  5  \w    105.00 130.00   1.00    2.00    --  108.00 -38.00  90.00   25
  6  \w     78.00 177.00   1.00    2.00    --  108.00  25.00 120.00   99
  7  \w     68.00 127.00   1.00    2.00    --  108.00 -50.00 -60.00   59
  8  \w     89.00 151.00   1.00    2.00    --  108.00  38.00-150.00   62
  9  \w     69.00 105.00   1.00    1.50    --   36.10  77.00-120.00   36
 10  \w     24.00  94.00   1.00    1.50    --   36.10  57.00 -60.00   70
 11  \w     42.00  87.00   1.00    2.00    --  108.00 -38.00  90.00   45
 12  \w     43.00 129.00   1.00    2.00    --  108.00 -63.00 150.00   86
 13  \w     41.00  82.00   1.00    2.00    --  108.00 -63.00  60.00   41
 14  \w     50.00  85.00   1.00    2.00    --  108.00 -63.00 -60.00   35
 15  \w     16.00  58.00   1.00    1.50    --   36.10  77.00-120.00   42
 16  \w    -62.00 -24.00   1.00    1.50    --  -33.50  77.00-120.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0997433000
_diffrn_orient_matrix_UB_12      -0.0820733000
_diffrn_orient_matrix_UB_13      -0.0462545000
_diffrn_orient_matrix_UB_21      -0.0702706000
_diffrn_orient_matrix_UB_22      0.0021091000
_diffrn_orient_matrix_UB_23      -0.1546749000
_diffrn_orient_matrix_UB_31      0.0624767000
_diffrn_orient_matrix_UB_32      0.1344285000
_diffrn_orient_matrix_UB_33      -0.0257632000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0527
_diffrn_reflns_av_unetI/netI     0.0722
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            3446
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.921
_diffrn_reflns_theta_min         3.933
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.554
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17997
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.914
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_refine_diff_density_max         0.798
_refine_diff_density_min         -0.981
_refine_diff_density_rms         0.177
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         1976
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0867
_refine_ls_R_factor_gt           0.0679
_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^)+(0.1105P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1727
_refine_ls_wR_factor_ref         0.2021
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1444
_reflns_number_total             1976
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01582c2.cif
_cod_data_source_block           exp_13559
_cod_depositor_comments          'Adding full bibliography for 7159662.cif.'
_cod_database_code               7159662
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 97.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C11(H11)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3A), C4(H4), C7(H7)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              11493
_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 6.268
_oxdiff_exptl_absorpt_empirical_full_min 0.430