Amine-catalyzed and functional group-controlled chemo- and regioselective synthesis of multi-functionalized CF3-benzene via a metal-free process
Peng, Fu; Zhao, Qian; Huang, Wei; Liu, Shuai-Jiang; Zhong, Ya-Jun; Mao, Qing; Zhang, Nan; He, Gu; Han, Bo; Green Chemistry  (2019) –; doi:10.1039/C9GC02694K

data_7234747
_publ_section_title
;
 Amine-catalyzed and functional group-controlled chemo- and regioselective
 synthesis of multi-functionalized CF3-benzene via a metal-free process
;
_journal_name_full               'Green Chemistry'
_journal_paper_doi               10.1039/C9GC02694K
_journal_year                    2019
_chemical_formula_moiety         'C22 H15 Br N O2'
_chemical_formula_sum            'C22 H15 Br N O2'
_chemical_formula_weight         405.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-02-20 deposited with the CCDC.    2019-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.675(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.8840(6)
_cell_length_b                   7.2300(2)
_cell_length_c                   32.8613(11)
_cell_measurement_reflns_used    4245
_cell_measurement_temperature    292.4(5)
_cell_measurement_theta_max      72.3090
_cell_measurement_theta_min      5.3720
_cell_volume                     3773.6(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      air
_diffrn_ambient_temperature      292.4(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000   60.0000 94

  2 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000   90.0000 94

  3 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000   30.0000 74

  4 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000 -150.0000 74

  5 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000 -180.0000 84

  6 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000   30.0000 94

  7 omega   40.00   98.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -150.0000 58

  8 omega  100.00  178.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 78

  9 omega   39.00  109.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -120.0000 70

 10 omega   38.00   91.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 53

 11 omega   38.00   91.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 53

 12 omega   40.00   98.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

 13 omega   40.00   98.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 58

 14 omega   41.00  126.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000 -120.0000 85

 15 omega   39.00  177.00   1.0000    3.0200
omega____ theta____ kappa____ phi______ frames
    -      108.0000    0.0000  120.0000 138

 16 omega  -33.00   23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -38.0000  120.0000 56

 17 omega   18.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   38.0000  -60.0000 88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0810389000
_diffrn_orient_matrix_UB_12      0.0795430000
_diffrn_orient_matrix_UB_13      -0.0184419000
_diffrn_orient_matrix_UB_21      -0.0352519000
_diffrn_orient_matrix_UB_22      -0.0366985000
_diffrn_orient_matrix_UB_23      -0.0431493000
_diffrn_orient_matrix_UB_31      -0.0397794000
_diffrn_orient_matrix_UB_32      0.1942416000
_diffrn_orient_matrix_UB_33      -0.0005976000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0337
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            10640
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.534
_diffrn_reflns_theta_min         5.385
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41109
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_description       block
_exptl_crystal_F_000             1640
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.473
_refine_diff_density_min         -0.750
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3658
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0582
_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^)+(0.1151P)^2^+1.7496P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1593
_refine_ls_wR_factor_ref         0.1688
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3126
_reflns_number_total             3658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9gc02694k2.cif
_cod_data_source_block           lq-hb-zq-02061
_cod_original_cell_volume        3773.5(2)
_cod_database_code               7234747
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.62
_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 C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C9(H9), C5(H5), C1(H1), C19(H19), C2(H2), C15(H15), C18(H18),
 C17(H17), C16(H16), C21(H21)
2.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_olex2_submission_special_instructions 'No special instructions were received'