Aluminum–Catalyzed Tunable Halodefluorination of Trifluoromethyl- and Difluoroalkyl-Substituted Olefins
Liu, Zhong; Tu, Xian-Shuang; Guo, Le-Tao; Wang, Xiao-Chen; Chemical Science  (2020) –; doi:10.1039/D0SC03883K

data_1559238
_publ_section_title
;
 Aluminum--Catalyzed Tunable Halodefluorination of Trifluoromethyl- and
 Difluoroalkyl-Substituted Olefins
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03883K
_journal_year                    2020
_chemical_formula_moiety         'C15 H11 Br2 F'
_chemical_formula_sum            'C15 H11 Br2 F'
_chemical_formula_weight         370.06
_chemical_properties_physical    Heat-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-05-13 deposited with the CCDC.	2020-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                93.858(5)
_cell_angle_beta                 114.425(7)
_cell_angle_gamma                109.404(5)
_cell_formula_units_Z            2
_cell_length_a                   8.7495(5)
_cell_length_b                   9.7201(5)
_cell_length_c                   9.7633(7)
_cell_measurement_reflns_used    6017
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      28.6110
_cell_measurement_theta_min      3.6390
_cell_volume                     692.53(9)
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      294.15
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_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    -84.00  94.00   1.00   30.00    --    5.00  45.00   0.00  178
  2  \w    -97.00  81.00   1.00   30.00    --   -8.10  45.00  90.00  178
  3  \w    -95.00 -69.00   1.00   30.00    --   -8.10  45.00 120.00   26
  4  \w    -97.00 -46.00   1.00   30.00    --   -8.10  45.00 150.00   51
  5  \w     56.00  81.00   1.00   30.00    --   -8.10  45.00 150.00   25
  6  \w    -96.00  25.00   1.00   30.00    --   -8.10  45.00  30.00  121
  7  \w    -15.00  45.00   1.00   30.00    --   -8.10  45.00  90.00   60
  8  \w    -51.00  80.00   1.00   30.00    --   -8.10  45.00 120.00  131
  9  \w      4.00  80.00   1.00   30.00    --   -8.10  45.00  -5.74   76
 10  \w    -70.00 -44.00   1.00   30.00    --   -8.10  45.00  -5.74   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0209536000
_diffrn_orient_matrix_UB_12      0.0136746000
_diffrn_orient_matrix_UB_13      -0.0619252000
_diffrn_orient_matrix_UB_21      -0.0685108000
_diffrn_orient_matrix_UB_22      -0.0714596000
_diffrn_orient_matrix_UB_23      -0.0462922000
_diffrn_orient_matrix_UB_31      -0.0653588000
_diffrn_orient_matrix_UB_32      0.0324432000
_diffrn_orient_matrix_UB_33      -0.0277870000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0570
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            19699
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.273
_diffrn_reflns_theta_min         3.658
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.843
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49958
_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            colorless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.775
_exptl_crystal_description       prism
_exptl_crystal_F_000             360
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.491
_refine_diff_density_rms         0.059
_refine_ls_extinction_coef       0.0043(11)
_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   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         3400
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0355P)^2^+0.1251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0680
_refine_ls_wR_factor_ref         0.0741
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2542
_reflns_number_total             3400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03883k2.cif
_cod_data_source_block           m20190315a
_cod_original_cell_volume        692.53(8)
_cod_database_code               1559238
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.455
_shelx_estimated_absorpt_t_min   0.360
_reflns_odcompleteness_completeness 99.10
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C15(H15), C5(H5), C9(H9), C6(H6), C14(H14), C13(H13), C11(H11),
 C12(H12)
;
_shelx_res_checksum              66228
_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 2.330
_oxdiff_exptl_absorpt_empirical_full_min 0.434