cis-3-Azido-2-methoxyindolines as safe and stable precursors to overcome the instability of fleeting 3-azidoindoles
Yamashiro, Toshiki; Abe, Takumi; Tanioka, Masaru; Kamino, Shinichiro; Sawada, Daisuke; Chemical Communications  (2021) –; doi:10.1039/D1CC06033C

data_7129307
_publ_section_title
;
 &#x000D; cis-3-Azido-2-methoxyindolines as safe and stable precursors to
 overcome the instability of fleeting 3-azidoindoles
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06033C
_journal_year                    2021
_chemical_formula_moiety         'C16 H16 N4 O3 S'
_chemical_formula_sum            'C16 H16 N4 O3 S'
_chemical_formula_weight         344.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-19
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-09-03 deposited with the CCDC.	2021-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.10420(10)
_cell_length_b                   8.55940(10)
_cell_length_c                   21.00970(10)
_cell_measurement_reflns_used    39280
_cell_measurement_temperature    103.15
_cell_measurement_theta_max      68.1890
_cell_measurement_theta_min      2.4350
_cell_volume                     3255.69(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      103.15
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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     73.00 108.00   0.50    0.20    --   40.40  77.00 120.00   70
  2  \w     15.00  69.00   0.50    0.20    --   40.40  77.00 -90.00  108
  3  \w     14.00  49.00   0.50    0.20    --   40.40  77.00 -30.00   70
  4  \w     83.00 109.00   0.50    0.20    --   40.40  77.00 -90.00   52
  5  \w     76.00 108.00   0.50    0.20    --   40.40  77.00-120.00   64
  6  \w     68.00  96.00   0.50    0.20    --   40.40  77.00-180.00   56
  7  \w     14.00  61.00   0.50    0.20    --   40.40  77.00-180.00   94
  8  \w     15.00  49.00   0.50    0.20    --   40.40  77.00-120.00   68
  9  \w     21.00  65.00   0.50    0.20    --   40.40  63.00 -90.00   88
 10  \w     84.00 109.00   0.50    0.20    --   40.40  63.00 -90.00   50
 11  \w     66.00 106.00   0.50    0.20    --   40.40  37.00-120.00   80
 12  \w     60.00 109.00   0.50    0.20    --   40.40  77.00 -30.00   98
 13  \w     21.00  95.00   0.50    0.20    --   40.40  50.00  90.00  148
 14  \w     14.00  70.00   0.50    0.20    --   40.40  77.00 120.00  112
 15  \w     18.00  84.00   0.50    0.20    --   40.40  63.00  30.00  132
 16  \w     25.00  57.00   0.50    0.20    --   40.40  37.00-120.00   64
 17  \w    -12.00  42.00   0.50    0.20    --   40.40 -37.00-120.00  108
 18  \w    -19.00   6.00   0.50    0.20    --   40.40 -50.00 -30.00   50
 19  \w     11.00  53.00   0.50    0.20    --   40.40 -50.00 -30.00   84
 20  \w    117.00 160.00   0.50    0.20    --   96.04 140.00-140.00   86
 21  \w     92.00 117.00   0.50    0.20    --   96.04 129.00  46.00   50
 22  \w     38.00  64.00   0.50    0.20    --   96.04 -59.00 120.00   52
 23  \w     43.00  96.00   0.50    0.20    --   96.04 -77.00 120.00  106
 24  \w     28.00  69.00   0.50    0.20    --   96.04 -59.00 -30.00   82
 25  \w     27.00 106.00   0.50    0.20    --   96.04 -77.00-120.00  158
 26  \w     28.00  72.00   0.50    0.20    --   96.04 -77.00-180.00   88
 27  \w     34.00  82.00   0.50    0.20    --   96.04 -68.00 -60.00   96
 28  \w     -3.00  34.00   0.50    0.20    --   40.40-104.00  60.00   74
 29  \w     22.00  78.00   0.50    0.20    --   40.40-129.00 -27.00  112
 30  \w     42.00  68.00   0.50    0.20    --   40.40-104.00  60.00   52
 31  \w     30.00  95.00   0.50    0.20    --   40.40-140.00 159.00  130
 32  \w     83.00 115.00   0.50    0.20    --   96.04-140.00 159.00   64
 33  \w     88.00 113.00   0.50    0.20    --   96.04-129.00 -27.00   50
 34  \w    -54.00  26.00   0.50    0.20    --  -40.71  50.00  60.00  160
 35  \w    -40.00  26.00   0.50    0.20    --  -40.71  37.00 150.00  132
 36  \w    -33.00  -7.00   0.50    0.20    --  -40.71  37.00 -60.00   52
 37  \w     -4.00  25.00   0.50    0.20    --  -40.71  37.00 -60.00   58
 38  \w    -56.00  26.00   0.50    0.20    --  -40.71  50.00 -90.00  164
 39  \w    -42.00  23.00   0.50    0.20    --  -40.71  37.00-150.00  130
 40  \w    -21.00  19.00   0.50    0.20    --  -40.71  12.00 -90.00   80
 41  \w    -31.00  30.00   0.50    0.20    --  -40.71  25.00  30.00  122
 42  \w      8.00  33.00   0.50    0.20    --   40.40  94.00 124.09   50
 43  \w     11.00  36.00   0.50    0.20    --   40.40  86.00  82.34   50
 44  \w     10.00  35.00   0.50    0.20    --   40.40  87.00 124.50   50
 45  \w     11.00  36.00   0.50    0.20    --   40.40  85.00  34.26   50
 46  \w      8.00  33.00   0.50    0.20    --   40.40  92.00 -19.54   50
 47  \w     11.00  36.00   0.50    0.20    --   40.40  84.00 -64.37   50
 48  \w     11.00  38.00   0.50    0.20    --   40.40  86.00-173.14   54
 49  \w     68.00 119.00   0.50    0.20    --   96.04  80.00 -77.79  102
 50  \w     69.00  96.00   0.50    0.20    --   96.04  79.00 -39.65   54
 51  \w     69.00  94.00   0.50    0.20    --   96.04  77.00 120.00   50
 52  \w     69.00  95.00   0.50    0.20    --   96.04  77.00  90.00   52
 53  \w     69.00  94.00   0.50    0.20    --   96.04  77.00  60.00   50
 54  \w    132.00 165.00   0.50    0.20    --   96.04  77.00  30.00   66
 55  \w    140.00 165.00   0.50    0.20    --   96.04  77.00 -30.00   50
 56  \w    135.00 161.00   0.50    0.20    --   96.04  77.00 -60.00   52
 57  \w     69.00  95.00   0.50    0.20    --   96.04  77.00  30.00   52
 58  \w     69.00  94.00   0.50    0.20    --   96.04  77.00 -30.00   50
 59  \w     70.00 103.00   0.50    0.20    --   96.04  73.00 -50.32   66
 60  \w     69.00  94.00   0.50    0.20    --   96.04  77.00 -60.00   50
 61  \w     72.00 145.00   0.50    0.20    --   96.04  68.00 -90.00  146
 62  \w     69.00  94.00   0.50    0.20    --   96.04  77.00-150.00   50
 63  \w    -66.00 -41.00   0.50    0.20    --  -40.71 140.00-140.00   50
 64  \w    -65.00 -39.00   0.50    0.20    --  -40.71 129.00  46.00   52
 65  \w    -45.00 -20.00   0.50    0.20    --  -40.71 104.00 150.00   50
 66  \w    -78.00 -53.00   0.50    0.20    --  -40.71 104.00 150.00   50
 67  \w   -126.00 -74.00   0.50    0.20    --  -96.35 144.00  60.00  104
 68  \w   -126.00 -41.00   0.50    0.20    --  -96.35 144.00 150.00  170
 69  \w    -97.00 -72.00   0.50    0.20    --  -96.35 129.00  46.00   50
 70  \w    -77.00 -38.00   0.50    0.20    --  -96.35 138.00 -35.96   78
 71  \w   -122.00 -82.00   0.50    0.20    --  -96.35 138.00 -35.96   80
 72  \w    -82.00 -54.00   0.50    0.20    --  -96.35 140.00-140.00   56
 73  \w   -102.00 -46.00   0.50    0.20    --  -96.35  96.00-120.00  112
 74  \w   -110.00 -69.00   0.50    0.20    --  -96.35 115.00 -37.69   82
 75  \w    -94.00 -29.00   0.50    0.20    --  -96.35  77.00  90.00  130
 76  \w    -67.00 -41.00   0.50    0.20    --  -96.35  59.00  90.00   52
 77  \w    -69.00 -37.00   0.50    0.20    --  -96.35  59.00-150.00   64
 78  \w    -57.00 -13.00   0.50    0.20    --  -40.71 -79.00-143.63   88
 79  \w    -64.00 -20.00   0.50    0.20    --  -40.71 -77.00 -90.00   88
 80  \w   -106.00 -79.00   0.50    0.20    --  -40.71 -77.00 -90.00   54
 81  \w   -109.00 -64.00   0.50    0.20    --  -40.71 -63.00   0.00   90
 82  \w   -108.00 -57.00   0.50    0.20    --  -40.71 -77.00  90.00  102
 83  \w   -107.00 -81.00   0.50    0.20    --  -40.71 -63.00 120.00   52
 84  \w    -52.00 -23.00   0.50    0.20    --  -40.71 -63.00 120.00   58
 85  \w    -59.00 -25.00   0.50    0.20    --  -40.71 -37.00 150.00   68
 86  \w   -106.00 -79.00   0.50    0.20    --  -40.71 -37.00 150.00   54
 87  \w    -43.00 -18.00   0.50    0.20    --  -40.71 -63.00   0.00   50
 88  \w    -50.00 -25.00   0.50    0.20    --  -40.71 -37.00 -40.02   50
 89  \w    -73.00 -27.00   0.50    0.20    --  -40.71 -37.00 -90.00   92
 90  \w   -101.00 -76.00   0.50    0.20    --  -40.71 -37.00 -40.02   50
 91  \w    -52.00 -27.00   0.50    0.20    --  -40.71 -37.00  60.00   50
 92  \w   -126.00 -98.00   0.50    0.20    --  -96.35-129.00 -27.00   56
 93  \w   -137.00-112.00   0.50    0.20    --  -96.35-140.00 159.00   50
 94  \w   -133.00 -69.00   0.50    0.20    --  -96.35 -79.00 176.32  128
 95  \w   -143.00 -68.00   0.50    0.20    --  -96.35 -80.00 141.64  150
 96  \w   -164.00 -68.00   0.50    0.20    --  -96.35 -80.00 -18.22  192
 97  \w   -164.00 -68.00   0.50    0.20    --  -96.35 -80.00 -97.90  192
 98  \w   -143.00 -69.00   0.50    0.20    --  -96.35 -79.00-128.15  148
 99  \w    -94.00 -69.00   0.50    0.20    --  -96.35 -79.00-105.17   50
100  \w   -164.00 -69.00   0.50    0.20    --  -96.35 -78.00 -73.66  190
101  \w   -164.00-108.00   0.50    0.20    --  -96.35 -77.00 -60.00  112
102  \w   -135.00-103.00   0.50    0.20    --  -96.35 -77.00-120.00   64
103  \w   -163.00-138.00   0.50    0.20    --  -96.35 -77.00-120.00   50
104  \w    -98.00 -69.00   0.50    0.20    --  -96.35 -78.00  -9.61   58
105  \w    -94.00 -69.00   0.50    0.20    --  -96.35 -77.00 -90.00   50
106  \w   -163.00 -69.00   0.50    0.20    --  -96.35 -77.00  60.00  188
107  \w   -165.00 -69.00   0.50    0.20    --  -96.35 -79.00 130.04  192
108  \w    -96.00 -69.00   0.50    0.20    --  -96.35 -77.00 150.00   54
109  \w    -94.00 -69.00   0.50    0.20    --  -96.35 -77.00 120.00   50
110  \w   -163.00 -69.00   0.50    0.20    --  -96.35 -79.00 162.96  188
111  \w   -150.00-123.00   0.50    0.20    --  -96.35 -77.00 120.00   54
112  \w   -163.00 -69.00   0.50    0.20    --  -96.35 -77.00   0.00  188
113  \w    -94.00 -69.00   0.50    0.20    --  -96.35 -77.00  94.92   50
114  \w    -94.00 -69.00   0.50    0.20    --  -96.35 -77.00  30.00   50
115  \w   -145.00-119.00   0.50    0.20    --  -96.35 -77.00  94.92   52
116  \w   -148.00-123.00   0.50    0.20    --  -96.35 -77.00 -90.00   50
117  \w   -100.00 -69.00   0.50    0.20    --  -96.35 -77.00-180.00   62
118  \w   -155.00 -69.00   0.50    0.20    --  -96.35 -77.00-150.00  172
119  \w   -159.00-133.00   0.50    0.20    --  -96.35 -77.00-180.00   52
120  \w   -158.00 -70.00   0.50    0.20    --  -96.35 -76.00-138.60  176
121  \w    -98.00 -69.00   0.50    0.20    --  -96.35 -77.00-120.00   58
122  \w    -94.00 -69.00   0.50    0.20    --  -96.35 -77.00 -60.00   50
123  \w   -155.00 -72.00   0.50    0.20    --  -96.35 -68.00  30.00  166
124  \w   -133.00 -70.00   0.50    0.20    --  -96.35 -76.00   8.62  126
125  \w    -97.00 -71.00   0.50    0.20    --  -96.35 -72.00  78.65   52
126  \w   -137.00 -71.00   0.50    0.20    --  -96.35 -70.00  68.05  132
127  \w   -164.00 -75.00   0.50    0.20    --  -96.35 -59.00  90.00  178
128  \w   -118.00 -70.00   0.50    0.20    --  -96.35 -74.00  20.15   96
129  \w   -162.00-108.00   0.50    0.20    --  -96.35 -67.00-173.23  108
130  \w   -101.00 -72.00   0.50    0.20    --  -96.35 -68.00-180.00   58
131  \w    -97.00 -72.00   0.50    0.20    --  -96.35 -67.00-173.23   50
132  \w    -37.00 -12.00   0.50    0.20    --  -40.71 -82.00-170.06   50
133  \w    -35.00 -10.00   0.50    0.20    --  -40.71 -89.00  -9.71   50
134  \w    -34.00  -9.00   0.50    0.20    --  -40.71 -89.00  14.95   50
135  \w    -38.00 -13.00   0.50    0.20    --  -40.71 -86.00 -53.49   50
136  \w    -33.00  -8.00   0.50    0.20    --  -40.71 -93.00  83.88   50
137  \w    -34.00  -9.00   0.50    0.20    --  -40.71 -89.00  86.43   50
138  \w    -33.00  -8.00   0.50    0.20    --  -40.71 -92.00 156.38   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0142194000
_diffrn_orient_matrix_UB_12      -0.0043383000
_diffrn_orient_matrix_UB_13      -0.0722704000
_diffrn_orient_matrix_UB_21      0.0834099000
_diffrn_orient_matrix_UB_22      -0.0201678000
_diffrn_orient_matrix_UB_23      -0.0119824000
_diffrn_orient_matrix_UB_31      -0.0090263000
_diffrn_orient_matrix_UB_32      -0.1788133000
_diffrn_orient_matrix_UB_33      0.0030808000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0115
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            61402
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.499
_diffrn_reflns_theta_min         4.209
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.971
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.533
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.907
_exptl_crystal_size_mid          0.286
_exptl_crystal_size_min          0.111
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.00060(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         2986
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0294
_refine_ls_R_factor_gt           0.0287
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0401P)^2^+1.6235P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0775
_refine_ls_wR_factor_ref         0.0780
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2887
_reflns_number_total             2986
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06033c2.cif
_cod_data_source_block           exp_158
_cod_database_code               7129307
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C19(H19), C8(H8), C7(H7), C22(H22), C6(H6), C20(H20), C5(H5)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              64973
_shelx_hkl_checksum              88935
_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 2.811
_oxdiff_exptl_absorpt_empirical_full_min 0.729