Reagent-Controlled Divergent Synthesis of 2-Amino-1,3-Benzoxazines and 2-Amino-1,3-Benzothiazines.
Putta, Venkata Pattabhi Rama Kishore; Vodnala, Nagaraju; Gujjarappa, Raghuram; Tyagi, Ujjawal; Garg, Aakriti; Gupta, Sreya; Pujar, Prasad P.; Malakar, Chandi Charan; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02384

data_4037752
_publ_section_title
;
 Reagent-Controlled Divergent Synthesis of 2-Amino-1,3-Benzoxazines and
 2-Amino-1,3-Benzothiazines.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02384
_journal_year                    2019
_chemical_formula_moiety         'C15 H11 F N2 O S'
_chemical_formula_sum            'C15 H11 F N2 O S'
_chemical_formula_weight         286.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-06-29
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_cell_angle_alpha                113.811(7)
_cell_angle_beta                 96.971(6)
_cell_angle_gamma                102.713(5)
_cell_formula_units_Z            4
_cell_length_a                   7.6249(4)
_cell_length_b                   13.6933(9)
_cell_length_c                   14.7998(12)
_cell_measurement_reflns_used    3009
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.7080
_cell_measurement_theta_min      3.6920
_cell_volume                     1340.26(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9974
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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    -10.00  95.00   1.00    1.00    --   25.57  57.00  60.00  105
  2  \w    101.00 136.00   1.00    1.00    --   66.78 111.00   0.00   35
  3  \w    124.00 172.00   1.00    1.50    --  108.00 104.00  30.00   48
  4  \w    116.00 141.00   1.00    1.00    --   66.78 111.00 -90.00   25
  5  \w    115.00 150.00   1.00    1.00    --   66.78 111.00-120.00   35
  6  \w    138.00 165.00   1.00    1.50    --  108.00  21.00 -90.00   27
  7  \w    106.00 165.00   1.00    1.50    --  108.00 -11.00-120.00   59
  8  \w    117.00 149.00   1.00    1.50    --  108.00 -77.00-180.00   32
  9  \w     95.00 134.00   1.00    1.50    --  108.00 -77.00-150.00   39
 10  \w     72.00 112.00   1.00    1.50    --  108.00-104.00 -90.00   40
 11  \w     48.00 143.00   1.00    1.50    --  108.00 -77.00 -30.00   95
 12  \w     54.00 114.00   1.00    1.50    --  108.00-116.00 133.84   60
 13  \w     44.00 108.00   1.00    1.50    --  108.00-104.00   0.00   64
 14  \w     35.00 114.00   1.00    1.00    --   66.78-111.00 -60.00   79
 15  \w     28.00  97.00   1.00    1.00    --   66.78 -61.00 -30.00   69
 16  \w     29.00  62.00   1.00    1.50    --  108.00 -11.00-120.00   33
 17  \w     28.00 100.00   1.00    1.50    --  108.00  21.00 -90.00   72
 18  \w     32.00  85.00   1.00    1.50    --  108.00 -77.00-180.00   53
 19  \w     27.00  75.00   1.00    1.50    --  108.00 -77.00-150.00   48
 20  \w     24.00 109.00   1.00    1.50    --  108.00-104.00-180.00   85
 21  \w     24.00  50.00   1.00    1.50    --  108.00-104.00 -90.00   26
 22  \w    -10.00 109.00   1.00    1.00    --   66.78 -45.00-120.00  119
 23  \w     56.00 107.00   1.00    1.00    --   66.78  61.00  60.00   51
 24  \w     72.00 172.00   1.00    1.50    --  108.00  65.00  60.00  100
 25  \w    113.00 177.00   1.00    1.50    --  108.00  77.00 150.00   64
 26  \w     74.00 176.00   1.00    1.50    --  108.00  65.00 120.00  102
 27  \w     65.00 132.00   1.00    1.00    --   66.78 178.00 -60.00   67
 28  \w     68.00 110.00   1.00    1.50    --  108.00  77.00 150.00   42
 29  \w     11.00 100.00   1.00    1.00    --   25.57  57.00 -60.00   89
 30  \w     -5.00 141.00   1.00    1.00    --   66.78  15.00-150.00  146
 31  \w     26.00  52.00   1.00    1.50    --  108.00-116.00 133.84   26
 32  \w    -17.00  88.00   1.00    1.00    --   25.57  77.00-180.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0847890000
_diffrn_orient_matrix_UB_12      -0.0290345000
_diffrn_orient_matrix_UB_13      -0.0934057000
_diffrn_orient_matrix_UB_21      -0.1457898000
_diffrn_orient_matrix_UB_22      -0.1157801000
_diffrn_orient_matrix_UB_23      -0.0535915000
_diffrn_orient_matrix_UB_31      -0.1302896000
_diffrn_orient_matrix_UB_32      0.0482617000
_diffrn_orient_matrix_UB_33      -0.0459238000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0236
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            7911
_diffrn_reflns_theta_full        66.95
_diffrn_reflns_theta_max         66.95
_diffrn_reflns_theta_min         3.69
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.231
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.427
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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_density_diffrn    1.419
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       triclinic
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.302
_exptl_crystal_size_mid          0.213
_exptl_crystal_size_min          0.154
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     361
_refine_ls_number_reflns         4695
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0517
_refine_ls_R_factor_gt           0.0408
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0600P)^2^+0.2953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1076
_refine_ls_wR_factor_ref         0.1182
_reflns_number_gt                3808
_reflns_number_total             4695
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9b02384_si_003.cif
_cod_data_source_block           sps_05_g2_rt_cu
_cod_depositor_comments
;

2020-04-07
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        1340.26(16)
_cod_original_formula_moiety     '2(C15 H11 F N2 O S)'
_cod_original_formula_sum        'C30 H22 F2 N4 O2 S2'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     572.64
_cod_database_code               4037752
_chemical_oxdiff_formula         'C60 H44 F4 N8 O4 S4'
_reflns_odcompleteness_completeness 98.28
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 N11(H11), N31(H31), C36(H36), C16(H16), C20(H20), C7(H7), C27(H27), C17(H17),
 C37(H37), C40(H40), C19(H19), C18(H18), C6(H6), C25(H25), C26(H26), C5(H5),
 C38(H38), C39(H39)
;
_olex2_date_sample_data_collection 2019-06-27
_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 1.220
_oxdiff_exptl_absorpt_empirical_full_min 0.822