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_7233382
_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         'C16 H14 Br N3 Se'
_chemical_formula_sum            'C16 H14 Br N3 Se'
_chemical_formula_weight         407.17
_chemical_name_systematic
;
4-((2-bromophenyl)selanyl)-3-methyl-1-phenyl-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                 91.719(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.4439(4)
_cell_length_b                   26.1410(11)
_cell_length_c                   12.8829(4)
_cell_measurement_reflns_used    5377
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.5040
_cell_measurement_theta_min      4.0550
_cell_volume                     3179.0(2)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -58.00  70.00   1.00   50.00    --  -11.40  19.00-120.00  128
  2  \w    -18.00  86.00   1.00   50.00    --   11.71  57.00  60.00  104
  3  \w    -77.00 -32.00   1.00   50.00    --   11.71 179.00-150.00   45
  4  \w    -87.00   1.00   1.00   50.00    --  -11.40 -38.00  90.00   88
  5  \w     -4.00  54.00   1.00   50.00    --   11.71 -99.00  60.00   58
;
_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      -0.0510002000
_diffrn_orient_matrix_UB_12      0.0198080000
_diffrn_orient_matrix_UB_13      0.0031692000
_diffrn_orient_matrix_UB_21      -0.0537500000
_diffrn_orient_matrix_UB_22      -0.0185099000
_diffrn_orient_matrix_UB_23      0.0071753000
_diffrn_orient_matrix_UB_31      0.0123034000
_diffrn_orient_matrix_UB_32      0.0012725000
_diffrn_orient_matrix_UB_33      0.0545299000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0735
_diffrn_reflns_av_unetI/netI     0.0655
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            33276
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.499
_diffrn_reflns_theta_max         26.499
_diffrn_reflns_theta_min         3.259
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.872
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56112
_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            colourless
_exptl_crystal_density_diffrn    1.701
_exptl_crystal_description       needle
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.425
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         6587
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0859
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0233P)^2^+0.4132P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0647
_refine_ls_wR_factor_ref         0.0772
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4331
_reflns_number_total             6587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ra05004c2.cif
_cod_data_source_block           5i
_cod_database_code               7233382
_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
 N3A-H3AA = N3A-H3AB = N3-H3B = N3-H3A
 0.82 with sigma of 0.05
3.a Aromatic/amide H refined with riding coordinates:
 C9A(H9A), C16(H16), C13A(H13A), C16A(H16A), C10A(H10A), C9(H9), C13(H13),
 C11A(H11A), C17(H17), C17A(H17A), C10(H10), C12(H12), C12A(H12A), C11(H11),
 C19(H19), C19A(H19A), C18(H18), C18A(H18A)
3.b Idealised Me refined as rotating group:
 C7A(H7AA,H7AB,H7AC), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              86350
_olex2_date_sample_data_collection 2018-03-12
_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 1.793
_oxdiff_exptl_absorpt_empirical_full_min 0.769