Influence of <i>N</i>-Substitution on the Formation and Oxidation of NHC-CAAC-Derived Triazaalkenes.
Mandal, Debdeep; Dolai, Ramapada; Kumar, Ravi; Suhr, Simon; Chrysochos, Nicolas; Kalita, Pankaj; Narayanan, Ramakirushnan Suriya; Rajaraman, Gopalan; Schulzke, Carola; Sarkar, Biprajit; Chandrasekhar, Vadapalli; Jana, Anukul; The Journal of organic chemistry 84 (2019) 8899–8909; doi:10.1021/acs.joc.9b00774

data_4034174
_publ_section_title
;
 Influence of <i>N</i>-Substitution on the Formation and Oxidation of
 NHC-CAAC-Derived Triazaalkenes.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8899
_journal_page_last               8909
_journal_paper_doi               10.1021/acs.joc.9b00774
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C18 H33 N3'
_chemical_formula_sum            'C18 H33 N3'
_chemical_formula_weight         291.47
_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
_audit_creation_date             2017-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.535(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3035(9)
_cell_length_b                   9.3897(4)
_cell_length_c                   12.7018(6)
_cell_measurement_reflns_used    5358
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.2430
_cell_measurement_theta_min      3.1170
_cell_volume                     1809.43(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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    -32.00  42.00   0.50   28.84    --    3.60 -82.00   0.00  148
  2  \w    -73.00 -14.00   0.50   28.84    --    3.60 -57.00  30.00  118
  3  \w     -2.00  31.00   0.50   28.84    --    3.60 -57.00  30.00   66
  4  \w      3.00  52.00   0.50   28.84    --    3.60  57.00 120.00   98
  5  \w     65.00  92.00   0.50   28.84    --    3.60  57.00 120.00   54
  6  \w     13.00  78.00   0.50   28.84    --   -3.90  19.00 -60.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0167672000
_diffrn_orient_matrix_UB_12      0.0699531000
_diffrn_orient_matrix_UB_13      -0.0092048000
_diffrn_orient_matrix_UB_21      0.0435043000
_diffrn_orient_matrix_UB_22      0.0275150000
_diffrn_orient_matrix_UB_23      0.0091452000
_diffrn_orient_matrix_UB_31      0.0038017000
_diffrn_orient_matrix_UB_32      -0.0071405000
_diffrn_orient_matrix_UB_33      -0.0548033000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0562
_diffrn_reflns_av_unetI/netI     0.0428
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            16018
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.500
_diffrn_reflns_theta_min         2.706
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.063
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
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    1.070
_exptl_crystal_description       plate
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.884
_exptl_crystal_size_mid          0.58
_exptl_crystal_size_min          0.157
_refine_diff_density_max         0.322
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         3726
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0562P)^2^+1.1852P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1343
_refine_ls_wR_factor_ref         0.1425
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2901
_reflns_number_total             3726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00774_si_002.cif
_cod_data_source_block           aj0117
_cod_database_code               4034174
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C21 H24 N3'
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.946
_reflns_odcompleteness_completeness 99.54
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C8(H8A,H8B,H8C), C10(H10A,H10B,
 H10C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C13(H13A,H13B,H13C), C14(H14A,
 H14B,H14C), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              92464
_shelx_hkl_checksum              3354
_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 3.077
_oxdiff_exptl_absorpt_empirical_full_min 0.342