Copper-Catalyzed Electrochemical Selective Bromination Of 8-Aminoquinoline Amide Using NH4Br as the Brominating Reagent.
Yang, Xiang; Yang, Qi-Liang; Wang, Xiang-Yang; Xu, Haohan; Mei, Tian-Sheng; Huang, Yan; Fang, Ping; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b03223

data_4037893
_publ_section_title
;
 Copper-Catalyzed Electrochemical Selective Bromination Of
 8-Aminoquinoline Amide Using NH4Br as the Brominating Reagent.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03223
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C14 H9 Br N2 O S'
_chemical_formula_sum            'C14 H9 Br N2 O S'
_chemical_formula_weight         333.20
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.9080(2)
_cell_length_b                   14.0311(5)
_cell_length_c                   18.5729(6)
_cell_measurement_reflns_used    9307
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.99
_cell_measurement_theta_min      3.44
_cell_volume                     1279.02(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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      169.96
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            11457
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.962
_diffrn_reflns_theta_min         3.435
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.960
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6070
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1335 before and 0.0794 after correction. The Ratio of minimum to maximum transmission is 0.8085. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.730
_exptl_crystal_description       needle
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 882 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.071(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         2397
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0303
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0273P)^2^+1.0939P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0730
_refine_ls_wR_factor_ref         0.0748
_reflns_Friedel_coverage         0.670
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                2283
_reflns_number_total             2397
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03223_si_003.cif
_cod_data_source_block           mj19369_0m
_cod_database_code               4037893
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.742
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 C15-C14 = C15-C11
 1.39 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C11 \\sim S1A \\sim C13: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C14 \\sim C15 \\sim C11: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C12 \\sim C13 \\sim C11: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(S1A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Fixed Sof: S1(0.75) S1A(0.25) H14(0.75) H14A(0.25) H13A(0.25) H13(0.75)
 C12(0.75) H12(0.75) C15(0.25) H15(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 N2(H2), C7(H7), C6(H6), C3(H3), C1(H1), C14(H14), C14(H14A), C2(H2A),
 C13(H13A), C13(H13), C12(H12), C15(H15)
;
_shelx_res_checksum              78110
_shelx_hkl_checksum              2494
_olex2_submission_special_instructions 'No special instructions were received'