An unprecedented intramolecular to intermolecular mechanistic switch in 1,1-diaminoazines leading to differential product formation during the I<sub>2</sub>-induced tandem oxidative transformation.
Kathuria, Deepika; Gupta, Pankaj; Chourasiya, Sumit S.; Sahoo, Subash C.; Beifuss, Uwe; Chakraborti, Asit K.; Bharatam, Prasad V.; Organic & biomolecular chemistry 17 (2019) 4129–4138; doi:10.1039/c9ob00610a

data_7156771
_publ_section_title
;
 An unprecedented intramolecular to intermolecular mechanistic switch in
 1,1-diaminoazines leading to differential product formation during the
 I<sub>2</sub>-induced tandem oxidative transformation.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4129
_journal_page_last               4138
_journal_paper_doi               10.1039/c9ob00610a
_journal_volume                  17
_journal_year                    2019
_chemical_compound_source        synthesized
_chemical_formula_moiety         'C15 H11 F2 N5'
_chemical_formula_sum            'C15 H11 F2 N5'
_chemical_formula_weight         299.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_primary     direct
_audit_creation_date             2018-05-11
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.02.24 svn.r3390 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_audit_update_record
;
2018-05-12 deposited with the CCDC.    2019-03-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.481(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.282(2)
_cell_length_b                   3.7619(2)
_cell_length_c                   35.085(3)
_cell_measurement_reflns_used    2948
_cell_measurement_temperature    293
_cell_measurement_theta_max      20.1920
_cell_measurement_theta_min      3.3670
_cell_volume                     3333.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      293
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.99
_diffrn_measured_fraction_theta_max 0.99
_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    -50.00  -8.00   0.50   50.00    --  -10.10 113.00 -83.00   84
  2  \w     25.00  50.00   0.50   50.00    --   10.38-113.00-175.00   50
  3  \w     34.00  59.00   0.50   50.00    --  -10.10  19.00  60.00   50
  4  \w    -22.00   9.00   0.50   50.00    --  -10.10  19.00  90.00   62
  5  \w    -57.00 -31.00   0.50   50.00    --  -10.10 125.00-150.00   52
  6  \w    -18.00  11.00   0.50   50.00    --  -10.10  19.00  60.00   58
  7  \w    -79.00 -19.00   0.50   50.00    --  -10.10 -19.00 -90.00  120
  8  \w     15.00  40.00   0.50   50.00    --  -10.10  19.00  90.00   50
  9  \w    -50.00  16.00   0.50   50.00    --   10.38 -38.00-120.00  132
 10  \w    -12.00  74.00   0.50   50.00    --   10.38  77.00  90.00  172
 11  \w    -29.00  -3.00   0.50   50.00    --   10.38 -38.00  90.00   52
 12  \w    -32.00  -4.00   0.50   50.00    --   10.38 124.00-102.62   56
 13  \w      3.00  57.00   0.50   50.00    --   10.38-125.00 -90.00  108
 14  \w     23.00  56.00   0.50   50.00    --   10.38-125.00  30.00   66
 15  \w      6.00  72.00   0.50   50.00    --   10.38  38.00-180.00  132
 16  \w      6.00  31.00   0.50   50.00    --   10.38  57.00 150.00   50
 17  \w    -18.00  18.00   0.50   50.00    --   10.38 -99.00-150.00   72
 18  \w    -29.00  -4.00   0.50   50.00    --   10.38 127.00 104.87   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1031
_diffrn_reflns_av_unetI/netI     0.1281
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            19238
_diffrn_reflns_theta_full        27.05
_diffrn_reflns_theta_max         27.052
_diffrn_reflns_theta_min         3.23
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.091
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.1925
_exptl_crystal_description       rod
_exptl_crystal_F_000             1232.6371
_exptl_crystal_recrystallization_method slowevaporation
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.4869
_refine_diff_density_min         -0.5001
_refine_diff_density_rms         0.1046
_refine_ls_d_res_high            0.7687
_refine_ls_d_res_low             6.3146
_refine_ls_goodness_of_fit_ref   0.9196
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    21
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3650
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.9196
_refine_ls_R_factor_all          0.2008
_refine_ls_R_factor_gt           0.0700
_refine_ls_shift/su_max          0.0000
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0919P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1632
_refine_ls_wR_factor_ref         0.2208
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              32
_reflns_limit_h_min              0
_reflns_limit_k_max              4
_reflns_limit_k_min              0
_reflns_limit_l_max              44
_reflns_limit_l_min              -44
_reflns_number_gt                1166
_reflns_number_total             3650
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            c9ob00610a2.cif
_cod_data_source_block           niper-5
_cod_depositor_comments          'Adding full bibliography for 7156771.cif.'
_cod_database_code               7156771
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C007(H007), C00A(H00A), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H),
 C00I(H00I), C00J(H00J), C00M(H00M)
2.b X=CH2 refined with riding coordinates:
 N00B(H00b,H00c)
;
_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
;