Zinc Acetate-Promoted Buchwald-Hartwig Couplings of Heteroaromatic Amines.
Ayothiraman, Rajaram; Rangaswamy, Sundaramurthy; Maity, Prantik; Simmons, Eric M.; Beutner, Gregory L.; Janey, Jacob; Treitler, Daniel S.; Eastgate, Martin D.; Vaidyanathan, Rajappa; The Journal of organic chemistry 82 (2017) 7420–7427; doi:10.1021/acs.joc.7b01101

data_4032735
_publ_section_title
;
 Zinc Acetate-Promoted Buchwald-Hartwig Couplings of Heteroaromatic
 Amines.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7420
_journal_page_last               7427
_journal_paper_doi               10.1021/acs.joc.7b01101
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C22 H24 N4 O8 Zn2'
_chemical_formula_sum            'C22 H24 N4 O8 Zn2'
_chemical_formula_weight         603.19
_chemical_name_systematic        '7-azainzole zinc acetate dimer'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-04-25
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.12.12 svn.r3370 for OlexSys, GUI svn.r5282)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.063(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8444(9)
_cell_length_b                   8.1601(4)
_cell_length_c                   15.9017(8)
_cell_measurement_reflns_used    2478
_cell_measurement_temperature    296
_cell_measurement_theta_max      22.84
_cell_measurement_theta_min      2.71
_cell_volume                     2433.8(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8994
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         2.172
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.026
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4980
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1004 before and 0.0497 after correction. The Ratio of minimum to maximum transmission is 0.6679. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_description       plate
_exptl_crystal_F_000             1232
_exptl_crystal_preparation
'In N2 filled glove box, 500 mg of 7-azainzole dissolved in 7 mL of toluene in 20 mL vial, followed by 0.5 equiv of Zn(OAc)2. The reaction mixture was heated at 90 C for 4h to get a clear solution which was cooled slowly to give crystalline 7-azainzole zinc acetate dimer (compound-15).'
_exptl_crystal_recrystallization_method
'Crystallized directly from reaction mixture in toluene'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.005
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     169
_refine_ls_number_reflns         2153
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0557P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0969
_refine_ls_wR_factor_ref         0.1018
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1774
_reflns_number_total             2153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01101_si_001.cif
_cod_data_source_block           Compound-15
_cod_database_code               4032735
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.631
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C3(H3), C5(H5)
2.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
;
_olex2_exptl_crystal_mounting_method
'Thick plate shaped (Rhombus-like) colourless crystal mounted on a nylon cryoloop with paratone oil.'
_olex2_submission_original_sample_id '7-azainzole zinc acetate dimer'
_olex2_submission_special_instructions 'No special instructions were received'