The copper-catalyzed synthesis of beta-trifluoromethylated acrylonitriles and trifluoromethyl-substituted 2H-azirines
Yu-Tao He; Qiang Wang; Jiahui Zhao; Xue-Yuan Liu; Peng-Fei Xu; Yong-Min Liang; Chem.Commun. 51 (2015) 13209–; doi:10.1039/C5cc05066A

data_7117635
_publ_section_title
;
 The copper-catalyzed synthesis of beta-trifluoromethylated acrylonitriles
 and trifluoromethyl-substituted 2H-azirines
;
_journal_name_full               Chem.Commun.
_journal_page_first              13209
_journal_paper_doi               10.1039/C5cc05066A
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C13 H15 F3 N4'
_chemical_formula_sum            'C13 H15 F3 N4'
_chemical_formula_weight         284.29
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-06-19 deposited with the CCDC.
2015-07-10 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 99.885(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.3589(5)
_cell_length_b                   8.1467(4)
_cell_length_c                   15.8924(7)
_cell_measurement_reflns_used    1125
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.6480
_cell_measurement_theta_min      4.0930
_cell_volume                     1448.81(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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      N~2~
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega   56.00   87.50   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   57.0000  -90.0000 21

  2 omega   47.00   96.50   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000 -180.0000 33

  3 omega   44.00   71.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000   30.0000 18

  4 omega  -48.00   30.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -57.0000  150.0000 52

  5 omega  -20.00   23.50   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -99.0000   30.0000 29
;
_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      -0.0356551000
_diffrn_orient_matrix_UB_12      0.0556823000
_diffrn_orient_matrix_UB_13      -0.0277673000
_diffrn_orient_matrix_UB_21      0.0424639000
_diffrn_orient_matrix_UB_22      -0.0016906000
_diffrn_orient_matrix_UB_23      -0.0279142000
_diffrn_orient_matrix_UB_31      -0.0307499000
_diffrn_orient_matrix_UB_32      -0.0668987000
_diffrn_orient_matrix_UB_33      -0.0223964000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            5607
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.47
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.108
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82197
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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    1.303
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.026(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     233
_refine_ls_number_reflns         2830
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.1207
_refine_ls_R_factor_gt           0.0637
_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^)+(0.0691P)^2^+0.3381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1508
_refine_ls_wR_factor_ref         0.1959
_reflns_number_gt                1506
_reflns_number_total             2830
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5cc05066a2.cif
_cod_data_source_block           wangqiang0312
_cod_original_cell_volume        1448.80(11)
_cod_database_code               7117635
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Uiso/Uaniso restraints and constraints
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C3')
\\sim Ueq, Uanis(C1') \\sim Ueq, Uanis(C2') \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: F2'(0.3) F3'(0.3) C1'(0.4) H1'A(0.4) H1'B(0.4) H1'C(0.4) C2'(0.4)
 H2'A(0.4) H2'B(0.4) H2'C(0.4) C3'(0.4) H3'A(0.4) H3'B(0.4) H3'C(0.4) C9(0.6)
 H9A(0.6) H9B(0.6) H9C(0.6) F3(0.7) F2(0.7) C8(0.6) H8A(0.6) H8B(0.6) H8C(0.6)
 C10(0.6) H10A(0.6) H10B(0.6) H10C(0.6)
4.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5)
4.c Idealised Me refined as rotating group:
 C1'(H1'A,H1'B,H1'C), C2'(H2'A,H2'B,H2'C), C3'(H3'A,H3'B,H3'C), C9(H9A,H9B,
 H9C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C)
;
_olex2_date_sample_data_collection 2015-03-13
_olex2_submission_special_instructions 'No special instructions were received'