Solvent-Controlled, Site-Selective N-Alkylation Reactions of Azolo-Fused Ring Heterocycles at N1-, N2-, and N3-Positions, Including Pyrazolo[3,4- d]pyrimidines, Purines, [1,2,3]Triazolo[4,5]pyridines, and Related Deaza-Compounds.
Bookser, Brett C.; Weinhouse, Michael I.; Burns, Aaron C.; Valiere, Andrew N.; Valdez, Lino J.; Stanczak, Pawel; Na, Jim; Rheingold, Arnold L.; Moore, Curtis E.; Dyck, Brian; The Journal of organic chemistry 83 (2018) 6334–6353; doi:10.1021/acs.joc.8b00540

data_4035860
_publ_section_title
;
 Solvent-Controlled, Site-Selective N-Alkylation Reactions of Azolo-Fused
 Ring Heterocycles at N1-, N2-, and N3-Positions, Including Pyrazolo[3,4-
 d]pyrimidines, Purines, [1,2,3]Triazolo[4,5]pyridines, and Related
 Deaza-Compounds.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6334
_journal_page_last               6353
_journal_paper_doi               10.1021/acs.joc.8b00540
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C6 H5 Cl N4'
_chemical_formula_sum            'C6 H5 Cl N4'
_chemical_formula_weight         168.59
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-08-22
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.08.19 svn.r3327 for OlexSys, GUI svn.r5215)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.162(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   3.9913(2)
_cell_length_b                   6.7117(3)
_cell_length_c                   13.3807(7)
_cell_measurement_reflns_used    997
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      67.868
_cell_measurement_theta_min      6.670
_cell_volume                     355.65(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.939
_diffrn_measured_fraction_theta_max 0.937
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.939
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            2096
_diffrn_reflns_point_group_measured_fraction_full 0.939
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.210
_diffrn_reflns_theta_min         6.669
_diffrn_source                   'rotating anode'
_diffrn_source_target            Mo
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.203
_exptl_absorpt_correction_T_max  0.3200
_exptl_absorpt_correction_T_min  0.1847
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1021 before and 0.0462 after correction.
The Ratio of minimum to maximum transmission is 0.5772.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_description       plate
_exptl_crystal_F_000             172
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.47
_refine_diff_density_max         0.689
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     101
_refine_ls_number_reflns         608
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.199
_refine_ls_R_factor_all          0.0850
_refine_ls_R_factor_gt           0.0787
_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^)+(0.1567P)^2^+0.1472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2115
_refine_ls_wR_factor_ref         0.2229
_reflns_Friedel_coverage         0.000
_reflns_number_gt                521
_reflns_number_total             608
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00540_si_006.cif
_cod_data_source_block           Dart170
_cod_database_code               4035860
_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. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: Cl1(0.5) C1(0.5) H1(0.5) N4(0.5) N3(0.5) C5(0.5) C3(0.5) C2(0.5)
 H2(0.5) N2(0.5) N1(0.5) C4(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2)
4.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C)
;
_shelx_res_checksum              26386
_shelx_hkl_checksum              96531
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'