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_1566822
_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         'C52 H47 N S'
_chemical_formula_sum            'C52 H47 N S'
_chemical_formula_weight         717.96
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-20 deposited with the CCDC.	2022-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   36.5917(5)
_cell_length_b                   36.5917(5)
_cell_length_c                   17.7385(3)
_cell_measurement_reflns_used    27436
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      74.2230
_cell_measurement_theta_min      3.7240
_cell_volume                     20569.0(5)
_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      170.00(10)
_diffrn_detector                 'CCD plate'
_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    -62.00 -24.00   1.00    1.00    --    0.00 -57.00  90.00   38
  2  \w    -88.00  28.00   1.00    1.00    --    0.00 -77.00-150.00  116
  3  \w    -57.00  22.00   1.00    1.00    --    0.00 -19.00 -60.00   79
  4  \w     36.00  84.00   1.00    1.00    --    0.00  57.00 -60.00   48
  5  \w      6.00  32.00   1.00    1.00    --    0.00  38.00-120.00   26
  6  \w     44.00 120.00   1.00    2.00    --   95.80 -61.00 120.00   76
  7  \w     80.00 128.00   1.00    2.00    --   95.80 -82.00   0.00   48
  8  \w     23.00 116.00   1.00    2.00    --   95.80 -45.00 -30.00   93
  9  \w     58.00  97.00   1.00    2.00    --   95.80 -82.00  90.00   39
 10  \w     58.00 101.00   1.00    2.00    --   95.80 -82.00-150.00   43
 11  \w     13.00  68.00   1.00    2.00    --   95.80 -82.00   0.00   55
 12  \w     70.00 107.00   1.00    2.00    --   95.80  15.00  30.00   37
 13  \w    135.00 185.00   1.00    2.00    --   95.80  15.00  30.00   50
 14  \w     21.00 128.00   1.00    2.00    --   95.80 -82.00 120.00  107
 15  \w      6.00  37.00   1.00    2.00    --   95.80 -82.00-150.00   31
 16  \w     31.00 104.00   1.00    2.00    --   95.80 -30.00 -30.00   73
 17  \w     32.00 114.00   1.00    2.00    --   95.80 -30.00-180.00   82
 18  \w     71.00  96.00   1.00    2.00    --   95.80 -82.00-120.00   25
 19  \w    105.00 179.00   1.00    2.00    --   95.80  30.00 -90.00   74
 20  \w    121.00 183.00   1.00    2.00    --   95.80  30.00 -60.00   62
 21  \w     34.00 125.00   1.00    2.00    --   95.80 -82.00 -60.00   91
 22  \w     78.00 125.00   1.00    2.00    --   95.80 -82.00 -90.00   47
 23  \w      6.00  42.00   1.00    2.00    --   95.80 -61.00-180.00   36
;
_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      0.0098775000
_diffrn_orient_matrix_UB_12      0.0113761000
_diffrn_orient_matrix_UB_13      -0.0840035000
_diffrn_orient_matrix_UB_21      0.0416967000
_diffrn_orient_matrix_UB_22      -0.0003503000
_diffrn_orient_matrix_UB_23      0.0088293000
_diffrn_orient_matrix_UB_31      -0.0228500000
_diffrn_orient_matrix_UB_32      -0.0472733000
_diffrn_orient_matrix_UB_33      -0.0202450000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            67250
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.076
_diffrn_reflns_theta_max         67.076
_diffrn_reflns_theta_min         2.855
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.862
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85926
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.043
_exptl_crystal_description       block
_exptl_crystal_F_000             6876
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.038
_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     496
_refine_ls_number_reflns         8171
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0529P)^2^+23.2305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1099
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7243
_reflns_number_total             8171
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01086k2.cif
_cod_data_source_block           exp_2191
_cod_original_cell_volume        20569.0(7)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1566822
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.99
_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:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C14(H14), C16(H16), C19(H19),
 C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C29(H29), C35(H35), C36(H36),
  C38(H38), C39(H39), C46(H46), C48(H48)
2.b Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C50(H50A,H50B,H50C), C51(H51A,
 H51B,H51C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              84489
_shelx_hkl_checksum              58094
_shelx_fab_checksum              56973
_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 1.271
_oxdiff_exptl_absorpt_empirical_full_min 0.733