Copper-catalyzed direct C–H arylselenation of 4-nitro-pyrazoles and other heterocycles with selenium powder and aryl iodides. Access to unsymmetrical heteroaryl selenides
Jakubczyk, Michał; Mkrtchyan, Satenik; Madura, Izabela D.; Marek, Paulina H.; Iaroshenko, Viktor O.; RSC Advances 9 (2019) 25368–; doi:10.1039/C9RA05004C

data_7233379
_publ_section_title
;
 Copper-catalyzed direct C--H arylselenation of 4-nitro-pyrazoles and
 other heterocycles with selenium powder and aryl iodides. Access to
 unsymmetrical heteroaryl selenides
;
_journal_issue                   44
_journal_name_full               'RSC Advances'
_journal_page_first              25368
_journal_paper_doi               10.1039/C9RA05004C
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C17 H14 F3 N3 Se'
_chemical_formula_sum            'C17 H14 F3 N3 Se'
_chemical_formula_weight         396.27
_chemical_name_systematic
;
3-methyl-1-phenyl-4-((3-trifluoromethyl)phenyl)selanyl)-1H-pyrazol-5-amine
;
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-13
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-13 deposited with the CCDC.    2019-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.937(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7537(2)
_cell_length_b                   23.2453(8)
_cell_length_c                   12.4112(5)
_cell_measurement_reflns_used    3724
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.4900
_cell_measurement_theta_min      4.2390
_cell_volume                     1659.73(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3347
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_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     53.00  99.00   1.00   40.00    --   13.11-179.00 150.00   46
  2  \w     -4.00  53.00   1.00   40.00    --   13.11 -99.00 -90.00   57
  3  \w     -9.00  77.00   1.00   40.00    --   13.11  38.00  60.00   86
  4  \w    -51.00  -7.00   1.00   40.00    --   13.11 -77.00 150.00   44
  5  \w     -1.00  25.00   1.00   40.00    --   13.11 -99.00   0.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0266362000
_diffrn_orient_matrix_UB_12      0.0046303000
_diffrn_orient_matrix_UB_13      -0.0549115000
_diffrn_orient_matrix_UB_21      -0.0801654000
_diffrn_orient_matrix_UB_22      -0.0218176000
_diffrn_orient_matrix_UB_23      -0.0153702000
_diffrn_orient_matrix_UB_31      -0.0897990000
_diffrn_orient_matrix_UB_32      0.0208299000
_diffrn_orient_matrix_UB_33      -0.0038719000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9856
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.496
_diffrn_reflns_theta_max         25.496
_diffrn_reflns_theta_min         3.283
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.296
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.586
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.393
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         3036
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0287P)^2^+0.8550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0670
_refine_ls_wR_factor_ref         0.0711
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2535
_reflns_number_total             3036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ra05004c2.cif
_cod_data_source_block           5d
_cod_original_cell_volume        1659.73(10)
_cod_database_code               7233379
_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. Restrained distances
 F2A-C21 = F2-C21 = F3A-C21 = F3-C21 = F1A-C21 = F1-C21
 1.32 with sigma of 0.005
 N3-H3B = N3-H3A
 0.82 with sigma of 0.05
 N3-H3A = N3-H3B
 0.88 with sigma of 0.05
 F2-F1 \\sim F2-F3 \\sim F1-F3 \\sim F3A-F2A \\sim F3A-F1A \\sim F2A-F1A
 with sigma of 0.01
 C21-C19 \\sim C21-F2 \\sim C21-F1 \\sim C21-F3 \\sim C21-F3A \\sim C21-F2A
\\sim C21-F1A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C21, F3, F1, F2, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C21, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(1)
 Sof(F2)=Sof(F1)=Sof(F3)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C16(H16), C9(H9), C13(H13), C18(H18), C17(H17), C12(H12), C10(H10),
 C11(H11)
5.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              78652
_olex2_date_sample_data_collection 2018-03-06
_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 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.874