Copper-catalyzed difluoromethylation of propargylamide-substituted indoles: synthesis of mono- and bis-difluoromethylated indoloazepinone derivatives.
Hua, Hui-Liang; Zhang, Bo-Sheng; He, Yu-Tao; Qiu, Yi-Feng; Hu, Jing-Yuan; Yang, Yu-Chen; Liang, Yong-Min; Chemical communications (Cambridge, England) 52 (2016) 10396–10399; doi:10.1039/c6cc05745d

data_7124938
_publ_section_title
;
 Copper-catalyzed difluoromethylation of propargylamide-substituted
 indoles: synthesis of mono- and bis-difluoromethylated indoloazepinone
 derivatives.
;
_journal_issue                   68
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10396
_journal_page_last               10399
_journal_paper_doi               10.1039/c6cc05745d
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C24 H22 F2 N2 O3'
_chemical_formula_sum            'C24 H22 F2 N2 O3'
_chemical_formula_weight         424.44
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-09-21
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_audit_update_record
;
2016-06-14 deposited with the CCDC.
2016-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   12.2175(2)
_cell_length_b                   15.8782(3)
_cell_length_c                   22.0697(4)
_cell_measurement_reflns_used    3446
_cell_measurement_temperature    291.48(10)
_cell_measurement_theta_max      68.9050
_cell_measurement_theta_min      4.0030
_cell_volume                     4281.34(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.48(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega   24.00   65.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   90.0000 41

  2 omega   35.00  100.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  -60.0000 65

  3 omega   93.00  165.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  -60.0000 72

  4 omega   58.00   88.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -180.0000 30

  5 omega   38.00   94.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  -60.0000 56

  6 omega   41.00   66.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000    0.0000 25

  7 omega   52.00  131.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000   90.0000 79

  8 omega   37.00   81.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  120.0000 44

  9 omega   30.00   82.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000  150.0000 52

 10 omega   23.00   56.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000   60.0000 33

 11 omega  -21.00   18.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   90.0000 39

 12 omega  -67.00  -38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   90.0000 29

 13 omega  -39.00  -13.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  108.0000 -169.0000 26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0961398000
_diffrn_orient_matrix_UB_12      0.0417521000
_diffrn_orient_matrix_UB_13      0.0337526000
_diffrn_orient_matrix_UB_21      0.0759136000
_diffrn_orient_matrix_UB_22      0.0723460000
_diffrn_orient_matrix_UB_23      0.0199654000
_diffrn_orient_matrix_UB_31      -0.0298630000
_diffrn_orient_matrix_UB_32      0.0493881000
_diffrn_orient_matrix_UB_33      -0.0577413000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0194
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            9673
_diffrn_reflns_theta_full        69.71
_diffrn_reflns_theta_max         69.71
_diffrn_reflns_theta_min         4.01
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.827
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87318
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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    1.317
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         3993
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0485
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0711P)^2^+0.8709P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1263
_refine_ls_wR_factor_ref         0.1408
_reflns_number_gt                3110
_reflns_number_total             3993
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6cc05745d2.cif
_cod_data_source_block           131_1
_cod_original_cell_volume        4281.35(12)
_cod_database_code               7124938
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C17(H17A,H17B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C)
;
_olex2_submission_special_instructions 'No special instructions were received'