Extended phenothiazines: synthesis, photophysical and redox properties, and efficient photocatalytic oxidative coupling of amines
Zhou, Jun; Mao, Lijun; Wu, Meng-Xiang; Peng, Zhiyong; Yang, Yiming; Zhou, Manfei; Zhao, Xiao-Li; Shi, Xueliang; Yang, Hai-Bo; Chemical Science  (2022) –; doi:10.1039/D2SC01086K

data_1566823
_publ_section_title
;
 Extended phenothiazines: synthesis, photophysical and redox properties,
 and efficient photocatalytic oxidative coupling of amines
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01086K
_journal_year                    2022
_chemical_formula_moiety         'C74 H69 N S'
_chemical_formula_sum            'C74 H69 N S'
_chemical_formula_weight         1004.36
_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     dual
_audit_creation_date             2022-01-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-21 deposited with the CCDC.	2022-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                106.660(2)
_cell_angle_beta                 90.552(2)
_cell_angle_gamma                96.116(2)
_cell_formula_units_Z            2
_cell_length_a                   7.16900(10)
_cell_length_b                   17.2492(3)
_cell_length_c                   25.1684(5)
_cell_measurement_reflns_used    24472
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      74.0300
_cell_measurement_theta_min      3.6530
_cell_volume                     2962.06(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -89.00 -49.00   1.00    1.00    --    0.00 -63.00 -50.00   40
  2  \w    -25.00  25.00   1.00    1.00    --    0.00  63.00  86.00   50
  3  \w      6.00 120.00   1.00    2.00    --   95.80 -63.00 -50.00  114
  4  \w     71.00 143.00   1.00    2.00    --   95.80  63.00  86.00   72
  5  \w    -20.00  23.00   1.00    1.00    --    0.00 -57.00  30.00   43
  6  \w     -3.00  24.00   1.00    1.00    --    0.00 -63.00 -50.00   27
  7  \w     34.00  84.00   1.00    1.00    --    0.00  37.00-120.00   50
  8  \w    -38.00  16.00   1.00    1.00    --    0.00 -57.00-120.00   54
  9  \w    -19.00  62.00   1.00    1.00    --    0.00  37.00   0.00   81
 10  \w    -24.00   8.00   1.00    1.00    --    0.00  19.00-150.00   32
 11  \w     55.00  86.00   1.00    1.00    --    0.00  37.00  60.00   31
 12  \w     -5.00  22.00   1.00    1.00    --    0.00  37.00-120.00   27
 13  \w     32.00  84.00   1.00    1.00    --    0.00  19.00-150.00   52
 14  \w    -30.00  12.00   1.00    1.00    --    0.00  77.00  30.00   42
 15  \w     30.00  58.00   1.00    1.00    --    0.00  77.00  30.00   28
 16  \w     -7.00  51.00   1.00    1.00    --    0.00  37.00  60.00   58
 17  \w    -82.00 -57.00   1.00    1.00    --    0.00 -57.00-120.00   25
 18  \w    -89.00 -33.00   1.00    1.00    --    0.00 -57.00  30.00   56
 19  \w    149.00 175.00   1.00    2.00    --   95.80  81.00  45.96   26
 20  \w     71.00 185.00   1.00    2.00    --   95.80  58.00  51.24  114
 21  \w     63.00  88.00   1.00    2.00    --   95.80  81.00  45.96   25
 22  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 150.00   26
 23  \w    107.00 133.00   1.00    2.00    --   95.80  82.00 -90.00   26
 24  \w    154.00 180.00   1.00    2.00    --   95.80  77.00-180.00   26
 25  \w    133.00 159.00   1.00    2.00    --   95.80  82.00   0.00   26
 26  \w     63.00 102.00   1.00    2.00    --   95.80  82.00 -90.00   39
 27  \w     65.00 115.00   1.00    2.00    --   95.80  77.00 120.00   50
 28  \w     70.00 185.00   1.00    2.00    --   95.80  64.00   4.70  115
 29  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-162.44   25
 30  \w     75.00 184.00   1.00    2.00    --   95.80  45.00 -30.00  109
 31  \w    157.00 185.00   1.00    2.00    --   95.80  61.00 -30.00   28
 32  \w     64.00 104.00   1.00    2.00    --   95.80  80.00 163.55   40
 33  \w    142.00 174.00   1.00    2.00    --   95.80  80.00 163.55   32
 34  \w     66.00 185.00   1.00    2.00    --   95.80  74.00-126.48  119
 35  \w     72.00 185.00   1.00    2.00    --   95.80  56.00 110.33  113
 36  \w    122.00 148.00   1.00    2.00    --   95.80  82.00-150.00   26
 37  \w     63.00  88.00   1.00    2.00    --   95.80  82.00-150.00   25
 38  \w     65.00  94.00   1.00    2.00    --   95.80  77.00-120.00   29
 39  \w     65.00 136.00   1.00    2.00    --   95.80  77.00-180.00   71
 40  \w     99.00 124.00   1.00    2.00    --   95.80  77.00 -60.00   25
 41  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -60.00   25
 42  \w      6.00 128.00   1.00    2.00    --   95.80 -82.00 150.00  122
 43  \w     65.00  90.00   1.00    2.00    --   95.80  77.00  90.00   25
 44  \w     64.00  89.00   1.00    2.00    --   95.80  79.00  70.13   25
 45  \w     74.00 120.00   1.00    2.00    --   95.80  61.00  30.00   46
 46  \w    126.00 151.00   1.00    2.00    --   95.80  61.00  30.00   25
 47  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 150.00   25
 48  \w     71.00 135.00   1.00    2.00    --   95.80  61.00-150.00   64
 49  \w     35.00 105.00   1.00    2.00    --   95.80 -82.00-120.00   70
 50  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  30.00   26
 51  \w    122.00 184.00   1.00    2.00    --   95.80  52.00 -79.38   62
 52  \w    130.00 177.00   1.00    2.00    --   95.80  82.00 120.00   47
 53  \w     75.00 139.00   1.00    2.00    --   95.80  45.00-180.00   64
 54  \w    147.00 179.00   1.00    2.00    --   95.80  45.00-180.00   32
 55  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-150.00   25
 56  \w     65.00 130.00   1.00    2.00    --   95.80  77.00  60.00   65
 57  \w     63.00  88.00   1.00    2.00    --   95.80  82.00-120.00   25
 58  \w     71.00  97.00   1.00    2.00    --   95.80  61.00 -30.00   26
 59  \w      7.00 128.00   1.00    2.00    --   95.80 -82.00 -60.00  121
 60  \w     65.00  91.00   1.00    2.00    --   95.80  77.00   0.00   26
 61  \w     64.00  89.00   1.00    2.00    --   95.80  79.00 102.51   25
 62  \w     72.00  97.00   1.00    2.00    --   95.80  61.00   0.00   25
 63  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -30.00   26
 64  \w     63.00  88.00   1.00    2.00    --   95.80  82.00  90.00   25
 65  \w     73.00  99.00   1.00    2.00    --   95.80  52.00 -79.38   26
 66  \w     75.00 154.00   1.00    2.00    --   95.80  45.00   0.00   79
 67  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 120.00   26
 68  \w     68.00  94.00   1.00    2.00    --   95.80  68.00 -82.73   26
 69  \w     25.00 113.00   1.00    2.00    --   95.80 -82.00  90.00   88
 70  \w     63.00  89.00   1.00    2.00    --   95.80  82.00  30.00   26
 71  \w     78.00 127.00   1.00    2.00    --   95.80 -82.00  60.00   49
 72  \w     63.00  88.00   1.00    2.00    --   95.80  82.00   0.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1502747000
_diffrn_orient_matrix_UB_12      0.0496414000
_diffrn_orient_matrix_UB_13      0.0443815000
_diffrn_orient_matrix_UB_21      0.0362634000
_diffrn_orient_matrix_UB_22      -0.0781568000
_diffrn_orient_matrix_UB_23      0.0145032000
_diffrn_orient_matrix_UB_31      0.1513079000
_diffrn_orient_matrix_UB_32      -0.0152630000
_diffrn_orient_matrix_UB_33      -0.0436971000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0607
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            74173
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.670
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.799
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58292
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.126
_exptl_crystal_description       block
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.255
_refine_diff_density_min         -0.890
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         10555
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0547
_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^)+(0.0609P)^2^+1.9740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1406
_refine_ls_wR_factor_ref         0.1453
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9254
_reflns_number_total             10555
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01086k2.cif
_cod_data_source_block           exp_2547
_cod_database_code               1566823
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.63
_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 Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C12(H12), C14(H14), C20(H20), C21(H21), C23(H23), C24(H24),
 C30(H30), C32(H32), C40(H40), C42(H42), C48(H48), C52(H52), C53(H53), C54(H54),
  C55(H55), C59(H59), C62(H62), C66(H66), C67(H67), C68(H68), C69(H69), C73(H73)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              57609
_shelx_hkl_checksum              43536
_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 1.765
_oxdiff_exptl_absorpt_empirical_full_min 0.600