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_7233384
_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         'C19 H19 N3 O2 Se'
_chemical_formula_sum            'C19 H19 N3 O2 Se'
_chemical_formula_weight         400.33
_chemical_name_systematic
;
1-(4-ethylbenzyl)-4-nitro-3-(p-tolylselanyl)pyridine
;
_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   geom
_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                 95.860(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.8207(3)
_cell_length_b                   36.9783(15)
_cell_length_c                   10.4021(6)
_cell_measurement_reflns_used    3030
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.9650
_cell_measurement_theta_min      4.0650
_cell_volume                     1844.60(17)
_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 0.921
_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    -95.00  18.00   0.50   25.00    --  -16.04 -77.00  60.00  226
  2  \w    -92.00  10.00   0.50   25.00    --  -16.04 -38.00 -30.00  204
  3  \w    -10.00  92.00   0.50   25.00    --   16.36  38.00-180.00  204
  4  \w   -106.00 -34.00   0.50   25.00    --  -16.04-179.00 -30.00  144
  5  \w    -90.00 -38.00   0.50   25.00    --  -16.04 -57.00-150.00  104
  6  \w     56.00 106.00   0.50   25.00    --   16.36 179.00 -60.00  100
;
_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      -0.0266328000
_diffrn_orient_matrix_UB_12      -0.0029882000
_diffrn_orient_matrix_UB_13      -0.0675066000
_diffrn_orient_matrix_UB_21      -0.1453496000
_diffrn_orient_matrix_UB_22      0.0013402000
_diffrn_orient_matrix_UB_23      0.0047388000
_diffrn_orient_matrix_UB_31      0.0060608000
_diffrn_orient_matrix_UB_32      0.0188984000
_diffrn_orient_matrix_UB_33      -0.0110114000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0730
_diffrn_reflns_av_unetI/netI     0.0819
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.921
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -53
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            25566
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         31.428
_diffrn_reflns_theta_min         3.306
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.052
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91974
_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            yellowish
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       trapezoid
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         5610
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1563
_refine_ls_R_factor_gt           0.0516
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0363P)^2^+0.2825P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0916
_refine_ls_wR_factor_ref         0.1214
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2524
_reflns_number_total             5610
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ra05004c2.cif
_cod_data_source_block           1c
_cod_original_cell_volume        1844.63(17)
_cod_database_code               7233384
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.534
_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. Restrained distances
 Se1A-Se1
 1 with sigma of 0.004
 N3A-C20 \\sim N3-C20
 with sigma of 0.002
 O2A-N3A \\sim O2-N3 \\sim O1A-N3A \\sim O1-N3
 with sigma of 0.002
 Se1A-C4 \\sim Se1-C4
 with sigma of 0.015
 Se1A-C12 \\sim Se1-C12
 with sigma of 0.015
3. Uiso/Uaniso restraints and constraints
N3A \\sim N3: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.005
Se1A \\sim Se1: within 2A with sigma of 0.009 and sigma for terminal atoms of
0.002
4. Others
 Sof(O2A)=Sof(N3A)=Sof(O1A)=1-FVAR(1)
 Sof(O1)=Sof(N3)=Sof(O2)=FVAR(1)
 Sof(Se1A)=1-FVAR(2)
 Sof(Se1)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C24(H24A,H24B)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C17(H17), C3(H3), C16(H16), C13(H13),
 C14(H14)
5.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              91291
_olex2_date_sample_data_collection 2018-04-03
_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 1.225
_oxdiff_exptl_absorpt_empirical_full_min 0.822