Synthesis of Polycyclic Spiropyrans via Rh(III)-Catalyzed Twofold C-H Annulation of 3-aryl-2H-benzo[b][1,4]oxazines with Diazo Ketoesters
Yang, Xifa; Zhang, Jing Jing; Zhang, Mengying; Lu, Mingxin; He, Yuhao; Li, Song; fan, liangxin; Zhang, Xinle; Wu, Jia-Kai; Chemical Communications  (2022) –; doi:10.1039/D2CC00916A

data_7129876
_publ_section_title
;
 Synthesis of Polycyclic Spiropyrans via Rh(III)-Catalyzed Twofold C-H
 Annulation of 3-aryl-2H-benzo[b][1,4]oxazines with Diazo Ketoesters
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00916A
_journal_year                    2022
_chemical_formula_moiety         'C24 H20 Br N O6'
_chemical_formula_sum            'C24 H20 Br N O6'
_chemical_formula_weight         498.32
_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     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc28px30
_audit_creation_date             2021-07-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-08-28 deposited with the CCDC.	2022-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                115.315(9)
_cell_angle_beta                 103.598(7)
_cell_angle_gamma                101.463(7)
_cell_formula_units_Z            2
_cell_length_a                   10.6396(8)
_cell_length_b                   11.0916(11)
_cell_length_c                   11.1581(9)
_cell_measurement_reflns_used    2405
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.1800
_cell_measurement_theta_min      4.5230
_cell_volume                     1087.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -102.00 -15.00   1.00    1.00    --  -33.50 -57.00 -60.00   87
  2  \w     -4.00  77.00   1.00    1.00    --   36.47 -99.00 120.00   81
  3  \w     18.00 105.00   1.00    1.00    --   36.47  57.00  90.00   87
  4  \w     -4.00  77.00   1.00    1.00    --   36.47 -99.00 -30.00   81
  5  \w    -34.00  59.00   1.00    1.00    --   36.47 -37.00-180.00   93
  6  \w     57.00 110.00   1.00    1.00    --   36.47 178.00  30.00   53
  7  \w    -34.00  59.00   1.00    1.00    --   36.47 -37.00 -60.00   93
  8  \w    -33.00  65.00   1.00    1.00    --   36.47 -77.00-150.00   98
  9  \w     18.00 105.00   1.00    1.00    --   36.47  57.00-180.00   87
 10  \w     37.00 112.00   1.00    2.50    --  108.00-111.00-120.00   75
 11  \w     43.00 125.00   1.00    2.50    --  108.00 -61.00-150.00   82
 12  \w    145.00 174.00   1.00    2.50    --  108.00  61.00-150.00   29
 13  \w     57.00 118.00   1.00    2.50    --  108.00 -77.00 120.00   61
 14  \w    128.00 155.00   1.00    2.50    --  108.00  30.00  30.00   27
 15  \w     40.00 106.00   1.00    2.50    --  108.00-111.00 120.00   66
 16  \w     75.00 112.00   1.00    2.50    --  108.00-111.00 -30.00   37
 17  \w     52.00  96.00   1.00    2.50    --  108.00 -94.00  30.00   44
 18  \w     86.00 137.00   1.00    2.50    --  108.00  30.00 120.00   51
 19  \w     38.00 124.00   1.00    2.50    --  108.00 -30.00 120.00   86
 20  \w     39.00 106.00   1.00    2.50    --  108.00 -45.00  60.00   67
 21  \w     47.00 141.00   1.00    2.50    --  108.00 -15.00 -90.00   94
 22  \w     40.00  66.00   1.00    2.50    --  108.00-111.00 -30.00   26
 23  \w     41.00 127.00   1.00    2.50    --  108.00 -61.00 -60.00   86
 24  \w     63.00 168.00   1.00    2.50    --  108.00  15.00 -30.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0323910000
_diffrn_orient_matrix_UB_12      -0.1363764000
_diffrn_orient_matrix_UB_13      -0.0254505000
_diffrn_orient_matrix_UB_21      -0.0827271000
_diffrn_orient_matrix_UB_22      -0.0212342000
_diffrn_orient_matrix_UB_23      0.0899716000
_diffrn_orient_matrix_UB_31      -0.1311923000
_diffrn_orient_matrix_UB_32      -0.0875036000
_diffrn_orient_matrix_UB_33      -0.1344888000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0429
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7827
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.064
_diffrn_reflns_theta_max         67.064
_diffrn_reflns_theta_min         4.548
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.936
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.521
_exptl_crystal_description       block
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.551
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         3878
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0692P)^2^+0.2797P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1411
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2925
_reflns_number_total             3878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00916a2.cif
_cod_data_source_block           202106187
_cod_original_cell_volume        1087.78(18)
_cod_database_code               7129876
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O5N2S1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.758
_shelx_estimated_absorpt_t_min   0.651
_reflns_odcompleteness_completeness 99.97
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C13(H13), C14(H14), C15(H15), C16(H16)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C24(H24A,H24B,
 H24C)
;
_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 1.223
_oxdiff_exptl_absorpt_empirical_full_min 0.873