Copper-catalysed <i>N</i>-arylation of 5-aminopyrazoles: a simple route to pyrazolo[3,4-<i>b</i>]indoles.
Chatterjee, Arpita; Murmu, Chudamani; Peruncheralathan, S.; Organic & biomolecular chemistry 18 (2020) 6571–6581; doi:10.1039/d0ob00812e

data_7157641
_publ_section_title
;
 Copper-catalysed <i>N</i>-arylation of 5-aminopyrazoles: a simple route
 to pyrazolo[3,4-<i>b</i>]indoles.
;
_journal_issue                   33
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6571
_journal_page_last               6581
_journal_paper_doi               10.1039/d0ob00812e
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety         'C16 H12 Br N3'
_chemical_formula_sum            'C16 H12 Br N3'
_chemical_formula_weight         326.20
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-12-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2020-02-22 deposited with the CCDC.	2020-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.326(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.1264(10)
_cell_length_b                   19.8670(19)
_cell_length_c                   19.419(3)
_cell_measurement_reflns_used    2093
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.5230
_cell_measurement_theta_min      3.6110
_cell_volume                     2741.5(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_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    -72.00   1.00   0.50   46.00    --   -3.67 -21.00 -38.00  146
  2  \w     -8.00  65.00   0.50   46.00    --   -3.67  21.00 127.00  146
  3  \w    -20.00  32.00   0.50   46.00    --   -3.67 -99.00 150.00  104
  4  \w    -70.00   0.00   0.50   46.00    --   -3.67 -38.00 -90.00  140
  5  \w    -20.00  32.00   0.50   46.00    --   -3.67 -99.00  30.00  104
  6  \w    -20.00  29.00   0.50   46.00    --   -3.67 -99.00 -90.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0891051000
_diffrn_orient_matrix_UB_12      0.0062991000
_diffrn_orient_matrix_UB_13      0.0175182000
_diffrn_orient_matrix_UB_21      -0.0441324000
_diffrn_orient_matrix_UB_22      0.0065327000
_diffrn_orient_matrix_UB_23      0.0308601000
_diffrn_orient_matrix_UB_31      0.0083170000
_diffrn_orient_matrix_UB_32      -0.0345426000
_diffrn_orient_matrix_UB_33      0.0090833000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2166
_diffrn_reflns_av_unetI/netI     0.1452
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            27049
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.291
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.991
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.581
_exptl_crystal_description       plate
_exptl_crystal_F_000             1312
_exptl_crystal_size_max          1.0
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.637
_refine_diff_density_min         -0.820
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     363
_refine_ls_number_reflns         4819
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.125
_refine_ls_R_factor_all          0.1888
_refine_ls_R_factor_gt           0.0994
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2041
_refine_ls_wR_factor_ref         0.2384
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2570
_reflns_number_total             4819
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00812e2.cif
_cod_data_source_block           4s
_cod_depositor_comments          'Adding full bibliography for 7157641.cif.'
_cod_database_code               7157641
_chemical_oxdiff_formula         'C116 H100 Br8 N36 '
_diffrn_oxdiff_ac3_digest_frames
;
01923bd81282909ec7bf2568b0b1d318fa00025f0c0
;
_diffrn_oxdiff_ac3_digest_hkl
;
01ba173073257532f926c7f8b8870222595f92
;
_reflns_odcompleteness_completeness 99.43
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C6-C5
 1.38 with sigma of 0.002
 C5-C4
 1.38 with sigma of 0.002
 C4-C3
 1.38 with sigma of 0.002
 C3-C2
 1.38 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 C6, C5, C4, C3, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Aromatic/amide H refined with riding coordinates:
 N3(H3), N6(H6), C12(H12), C19(H19), C15(H15), C31(H31), C13(H13), C22(H22),
 C30(H30), C21(H21), C29(H29), C6(H6A), C28(H28), C14(H14), C20(H20), C3(H3A),
 C5(H5), C4(H4)
5.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              3943
_shelx_shelxl_version_number     2014/7
_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 1.452
_oxdiff_exptl_absorpt_empirical_full_min 0.624