Taming Ambident Triazole Anions: Regioselective Ion Pairing Catalyzes Direct N-Alkylation with Atypical Regioselectivity.
Dale, Harvey J. A.; Hodges, George R.; Lloyd-Jones, Guy C; Journal of the American Chemical Society 141 (2019) 7181–7193; doi:10.1021/jacs.9b02786

data_4128105
_publ_section_title
;
 Taming Ambident Triazole Anions: Regioselective Ion Pairing Catalyzes
 Direct N-Alkylation with Atypical Regioselectivity.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7181
_journal_page_last               7193
_journal_paper_doi               10.1021/jacs.9b02786
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H25 N2, C2 H2 N3'
_chemical_formula_sum            'C15 H27 N5'
_chemical_formula_weight         277.41
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             2018-08-22
_audit_creation_method
;
Olex2 1.2-beta
(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                   13.4569(4)
_cell_length_b                   12.8420(5)
_cell_length_c                   9.2876(4)
_cell_measurement_reflns_used    7290
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      29.3290
_cell_measurement_theta_min      3.7350
_cell_volume                     1605.02(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.941
_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    -20.00  30.00   1.00   15.00    --   -9.43 -99.00-180.00   50
  2  \w    -12.00  83.00   1.00   15.00    --   10.84  38.00 -30.00   95
  3  \w    -59.00  30.00   1.00   15.00    --   10.84 -57.00-180.00   89
  4  \w    -26.00  42.00   1.00   15.00    --   10.84 -77.00 120.00   68
  5  \w    -28.00  -1.00   1.00   15.00    --   10.84 -19.00 -30.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0073667000
_diffrn_orient_matrix_UB_12      0.0535690000
_diffrn_orient_matrix_UB_13      0.0152856000
_diffrn_orient_matrix_UB_21      0.0059192000
_diffrn_orient_matrix_UB_22      -0.0119165000
_diffrn_orient_matrix_UB_23      0.0740551000
_diffrn_orient_matrix_UB_31      0.0518624000
_diffrn_orient_matrix_UB_32      -0.0062701000
_diffrn_orient_matrix_UB_33      -0.0106076000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            14676
_diffrn_reflns_point_group_measured_fraction_full 0.916
_diffrn_reflns_point_group_measured_fraction_max 0.805
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.690
_diffrn_reflns_theta_min         3.101
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.072
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.594
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.148
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of dichloromethane and pentane  by vapour diffusion'
_exptl_crystal_size_max          0.423
_exptl_crystal_size_mid          0.232
_exptl_crystal_size_min          0.213
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1208 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.2(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         3649
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0470P)^2^+0.3037P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0941
_refine_ls_wR_factor_ref         0.0955
_reflns_Friedel_coverage         0.618
_reflns_Friedel_fraction_full    0.822
_reflns_Friedel_fraction_max     0.653
_reflns_number_gt                3475
_reflns_number_total             3649
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02786_si_003.cif
_cod_data_source_block           gl18003
_cod_database_code               4128105
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C15 H27 N5'
_chemical_oxdiff_usercomment     '@ 120 K PMDBDH-Trz'
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.970
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
;
_shelx_res_checksum              47890
_shelx_hkl_checksum              39978
_olex2_date_sample_data_collection 2018-08-21
_olex2_date_sample_submission    2018-08-20
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id PMDBDH-Trz
_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 1.155
_oxdiff_exptl_absorpt_empirical_full_min 0.864