Synthesis of spiropyrans <i>via</i> Ru(II)-catalyzed coupling of 3-aryl-2<i>H</i>-benzo[<i>b</i>][1,4]oxazines with benzoquinones.
Wen, Mengke; Zhang, Mengying; Gu, Fan; Geng, Yuehua; Liu, Xiangyang; Wu, Qingnan; Yang, Xifa; Organic & biomolecular chemistry 22 (2024) 998–1009; doi:10.1039/d3ob01971c

data_7159738
_publ_section_title
;
 Synthesis of spiropyrans <i>via</i> Ru(II)-catalyzed coupling of
 3-aryl-2<i>H</i>-benzo[<i>b</i>][1,4]oxazines with benzoquinones.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              998
_journal_page_last               1009
_journal_paper_doi               10.1039/d3ob01971c
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C24 H23 Br Cl N O Ru, C H2 Cl2'
_chemical_formula_sum            'C25 H25 Br Cl3 N O Ru'
_chemical_formula_weight         642.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/ccdc.csd.cc2h8mkz
_audit_creation_date             2022-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-10-19 deposited with the CCDC.	2023-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.437(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2824(2)
_cell_length_b                   9.8025(2)
_cell_length_c                   26.5730(5)
_cell_measurement_reflns_used    3770
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.5890
_cell_measurement_theta_min      4.4050
_cell_volume                     2649.39(9)
_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    'ShelXS (Sheldrick, 2008)'
_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 0.997
_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    -78.00 -53.00   1.00    2.50    --  -33.50 145.00-116.00   25
  2  \w    -44.00 -18.00   1.00    2.50    --  -33.50 145.00-116.00   26
  3  \w   -102.00 -17.00   1.00    2.50    --  -33.50 -57.00-180.00   85
  4  \w    -15.00  59.00   1.00    2.50    --   36.47 -37.00   0.00   74
  5  \w     80.00 106.00   1.00    2.50    --   36.47 178.00  90.00   26
  6  \w     28.00  54.00   1.00    2.50    --   36.47 -57.00 120.00   26
  7  \w    -32.00  13.00   1.00    2.50    --   36.47 -57.00 120.00   45
  8  \w      1.00  77.00   1.00    2.50    --   36.47 -99.00 -90.00   76
  9  \w     65.00  91.00   1.00    2.50    --   36.47  57.00  60.00   26
 10  \w    116.00 174.00   1.00    4.50    --  108.00 110.00  -6.00   58
 11  \w     51.00 108.00   1.00    4.50    --  108.00 -94.00  90.00   57
 12  \w    121.00 173.00   1.00    4.50    --  108.00  45.00 -90.00   52
 13  \w     93.00 178.00   1.00    4.50    --  108.00  45.00 150.00   85
 14  \w     37.00 120.00   1.00    4.50    --  108.00 -30.00-150.00   83
 15  \w     90.00 175.00   1.00    4.50    --  108.00  45.00  30.00   85
 16  \w     47.00  85.00   1.00    4.50    --  108.00-111.00  60.00   38
 17  \w     79.00 104.00   1.00    4.50    --  108.00 -94.00 -60.00   25
 18  \w     46.00 100.00   1.00    4.50    --  108.00 -94.00 -90.00   54
 19  \w    101.00 127.00   1.00    4.50    --  108.00 111.00 -30.00   26
;
_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      -0.0111864000
_diffrn_orient_matrix_UB_12      -0.0906548000
_diffrn_orient_matrix_UB_13      0.0465208000
_diffrn_orient_matrix_UB_21      0.0366365000
_diffrn_orient_matrix_UB_22      0.1228023000
_diffrn_orient_matrix_UB_23      0.0354590000
_diffrn_orient_matrix_UB_31      -0.1464954000
_diffrn_orient_matrix_UB_32      0.0376773000
_diffrn_orient_matrix_UB_33      -0.0035664000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            10551
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.363
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.476
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59211
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.612
_exptl_crystal_description       block
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.842
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.131
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4718
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0717P)^2^+2.3020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1227
_refine_ls_wR_factor_ref         0.1332
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3951
_reflns_number_total             4718
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01971c2.cif
_cod_data_source_block           202208151
_cod_depositor_comments
'Adding full bibliography for 7159736--7159738.cif.'
_cod_original_cell_volume        2649.39(10)
_cod_database_code               7159738
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N2S1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.451
_shelx_estimated_absorpt_t_min   0.296
_reflns_odcompleteness_completeness 99.70
_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. Restrained distances
 Cl2-C25
 1.78 with sigma of 0.02
 C25-Cl3
 1.78 with sigma of 0.02
 C25A-Cl3A
 1.78 with sigma of 0.02
 C25A-Cl2A
 1.78 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl3) \\sim Ueq, Uanis(Cl3A) \\sim Ueq, Uanis(Cl2A) \\sim Ueq, Uanis(Cl2)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25A) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C25) = Uanis(C25A)
Uanis(Cl3) = Uanis(Cl3A)
Uanis(Cl2) = Uanis(Cl2A)
4. Others
 Sof(Cl2A)=Sof(Cl3A)=Sof(C25A)=Sof(H25C)=Sof(H25D)=1-FVAR(1)
 Sof(Cl2)=Sof(Cl3)=Sof(C25)=Sof(H25A)=Sof(H25B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C21(H21)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C25(H25A,H25B), C25A(H25C,H25D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19)
5.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              71048
_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 1.606
_oxdiff_exptl_absorpt_empirical_full_min 0.762