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_4128106
_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_formula_moiety         'C13 H25 N2, C2 H3 N3, C2 H2 N3'
_chemical_formula_sum            'C17 H30 N8'
_chemical_formula_weight         346.49
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-08
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                86.497(4)
_cell_angle_beta                 82.129(4)
_cell_angle_gamma                67.729(5)
_cell_formula_units_Z            2
_cell_length_a                   9.6261(5)
_cell_length_b                   10.3410(5)
_cell_length_c                   10.5880(6)
_cell_measurement_reflns_used    6025
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      29.2840
_cell_measurement_theta_min      3.3380
_cell_volume                     966.10(9)
_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    'ShelXT (Sheldrick, 2015)'
_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 0.893
_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    -12.00  83.00   1.00    5.00    --   10.84  38.00-120.00   95
  2  \w    -21.00  85.00   1.00    5.00    --   10.84  77.00 -30.00  106
  3  \w    -63.00  42.00   1.00    5.00    --   10.84 -77.00  90.00  105
  4  \w    -32.00  63.00   1.00    5.00    --   -9.43  38.00 -60.00   95
  5  \w    -82.00  13.00   1.00    5.00    --   -9.43 -38.00 -30.00   95
  6  \w    -85.00 -39.00   1.00    5.00    --   -9.43 155.00 -44.94   46
  7  \w    -20.00  51.00   1.00    5.00    --   10.84 -99.00-120.00   71
;
_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      -0.0540148000
_diffrn_orient_matrix_UB_12      0.0300405000
_diffrn_orient_matrix_UB_13      -0.0433568000
_diffrn_orient_matrix_UB_21      0.0329496000
_diffrn_orient_matrix_UB_22      -0.0613869000
_diffrn_orient_matrix_UB_23      -0.0372810000
_diffrn_orient_matrix_UB_31      -0.0493409000
_diffrn_orient_matrix_UB_32      -0.0286975000
_diffrn_orient_matrix_UB_33      0.0361160000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.893
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            17272
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.666
_diffrn_reflns_theta_min         2.867
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.191
_exptl_crystal_description       block
_exptl_crystal_F_000             376
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of dichloromethane and pentane  by vapour diffusion'
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.371
_exptl_crystal_size_min          0.193
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.217
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4894
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0510
_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^)+(0.0394P)^2^+0.3811P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1219
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3871
_reflns_number_total             4894
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02786_si_002.cif
_cod_data_source_block           gl19001
_cod_original_cell_volume        966.11(9)
_cod_database_code               4128106
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H60 N16 '
_chemical_oxdiff_usercomment     '@ 120 K PMDBDH123Trz'
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.960
_reflns_odcompleteness_completeness 99.85
_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 C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-C2 \\sim C3A-C2 \\sim C2-C15 \\sim C2-C15A
 with sigma of 0.02
 C2-C1A \\sim C2-C1
 with sigma of 0.02
3. Others
 Sof(H4BC)=Sof(H4BD)=Sof(H14C)=Sof(H14D)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(H4AA)=Sof(H4AB)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C3)=
 Sof(H3A)=Sof(H3B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C4(H4AA,H4AB), C4(H4BC,H4BD), C14(H14A,H14B), C14(H14C,H14D), C15(H15A,H15B),
 C3(H3A,H3B), C3A(H3AA,H3AB), C15A(H15C,H15D)
4.b Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC)
4.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C24(H24), C25(H25)
4.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C7(H7A,H7B,H7C), C12(H12A,H12B,H12C), C6(H6A,H6B,H6C),
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              31599
_shelx_hkl_checksum              93447
_olex2_date_sample_submission    2019-01-07
_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 PMCBCH123Trz
_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 1.286
_oxdiff_exptl_absorpt_empirical_full_min 0.800