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_1566821
_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         'C30 H25 N S, C H2 Cl2'
_chemical_formula_sum            'C31 H27 Cl2 N S'
_chemical_formula_weight         516.49
_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     dual
_audit_creation_date             2021-12-24
_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                 99.9610(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.18030(10)
_cell_length_b                   7.73940(10)
_cell_length_c                   30.7513(3)
_cell_measurement_reflns_used    23944
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      73.9560
_cell_measurement_theta_min      4.4910
_cell_volume                     2620.76(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      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     58.00  86.00   1.00    1.00    --    0.00  37.00 120.00   28
  2  \w    -19.00  16.00   1.00    1.00    --    0.00  37.00  30.00   35
  3  \w     51.00  79.00   1.00    1.00    --    0.00  37.00 150.00   28
  4  \w    -19.00  27.00   1.00    1.00    --    0.00  37.00 120.00   46
  5  \w    -17.00  44.00   1.00    1.00    --    0.00  37.00 150.00   61
  6  \w     55.00  82.00   1.00    1.00    --    0.00  37.00  90.00   27
  7  \w    -13.00  69.00   1.00    1.00    --    0.00  37.00 -60.00   82
  8  \w     -8.00  35.00   1.00    1.00    --    0.00  77.00 -30.00   43
  9  \w    -23.00  29.00   1.00    1.00    --    0.00  57.00-150.00   52
 10  \w    -19.00  12.00   1.00    1.00    --    0.00  37.00  60.00   31
 11  \w     63.00  88.00   1.00    1.00    --    0.00  37.00  30.00   25
 12  \w     38.00  68.00   1.00    1.00    --    0.00  57.00-150.00   30
 13  \w    -18.00  17.00   1.00    1.00    --    0.00  37.00  90.00   35
 14  \w     53.00  86.00   1.00    1.00    --    0.00  77.00 -30.00   33
 15  \w     50.00  87.00   1.00    1.00    --    0.00  37.00  60.00   37
 16  \w     40.00 128.00   1.00    1.00    --   95.80 -82.00  30.00   88
 17  \w     64.00  89.00   1.00    1.00    --   95.80  79.00 178.69   25
 18  \w     71.00 183.00   1.00    1.00    --   95.80  58.00 169.72  112
 19  \w     66.00 185.00   1.00    1.00    --   95.80  78.00 -75.61  119
 20  \w    149.00 182.00   1.00    1.00    --   95.80  81.00 -13.58   33
 21  \w     66.00 185.00   1.00    1.00    --   95.80  75.00  80.02  119
 22  \w     70.00 110.00   1.00    1.00    --   95.80  62.00 -94.08   40
 23  \w     65.00 132.00   1.00    1.00    --   95.80  77.00  60.00   67
 24  \w     71.00  97.00   1.00    1.00    --   95.80  61.00-120.00   26
 25  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 150.00   25
 26  \w     64.00  90.00   1.00    1.00    --   95.80  82.00  90.00   26
 27  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 28  \w     73.00  99.00   1.00    1.00    --   95.80  61.00-150.00   26
 29  \w    113.00 184.00   1.00    1.00    --   95.80  61.00-150.00   71
 30  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 31  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -30.00   26
 32  \w      6.00 120.00   1.00    1.00    --   95.80 -82.00 -60.00  114
 33  \w     63.00  98.00   1.00    1.00    --   95.80  81.00 -13.58   35
 34  \w      7.00 128.00   1.00    1.00    --   95.80 -82.00 120.00  121
 35  \w     45.00  78.00   1.00    1.00    --   95.80 -82.00 -30.00   33
 36  \w     66.00  91.00   1.00    1.00    --   95.80  74.00 -94.18   25
 37  \w     63.00 177.00   1.00    1.00    --   95.80  81.00  40.46  114
 38  \w     13.00  40.00   1.00    1.00    --   95.80 -82.00 -30.00   27
 39  \w     75.00 116.00   1.00    1.00    --   95.80  45.00-150.00   41
 40  \w     99.00 125.00   1.00    1.00    --   95.80 -82.00 -30.00   26
 41  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 150.00   25
 42  \w     76.00 181.00   1.00    1.00    --   95.80  45.00-120.00  105
 43  \w     76.00 149.00   1.00    1.00    --   95.80  45.00 -90.00   73
 44  \w    154.00 185.00   1.00    1.00    --   95.80  45.00 -90.00   31
 45  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 46  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -90.00   25
 47  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 48  \w     75.00 166.00   1.00    1.00    --   95.80  45.00 -30.00   91
 49  \w     77.00 181.00   1.00    1.00    --   95.80  45.00   0.00  104
 50  \w     71.00 109.00   1.00    1.00    --   95.80  61.00 120.00   38
 51  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 120.00   25
 52  \w     71.00  96.00   1.00    1.00    --   95.80  61.00 -30.00   25
 53  \w     70.00  96.00   1.00    1.00    --   95.80  62.00 130.56   26
 54  \w     92.00 117.00   1.00    1.00    --   95.80 -77.00-180.00   25
 55  \w     44.00  76.00   1.00    1.00    --   95.80 -77.00-180.00   32
 56  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 57  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 58  \w     10.00  38.00   1.00    1.00    --   95.80 -77.00-180.00   28
 59  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 60  \w      6.00 110.00   1.00    1.00    --   95.80 -82.00-150.00  104
 61  \w     70.00 115.00   1.00    1.00    --   95.80  62.00  37.28   45
 62  \w     71.00 179.00   1.00    1.00    --   95.80  59.00 145.58  108
 63  \w    150.00 175.00   1.00    1.00    --   95.80  71.00-113.72   25
 64  \w     67.00  92.00   1.00    1.00    --   95.80  71.00-113.72   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      -0.0849553000
_diffrn_orient_matrix_UB_12      -0.0277582000
_diffrn_orient_matrix_UB_13      -0.0445176000
_diffrn_orient_matrix_UB_21      0.0817627000
_diffrn_orient_matrix_UB_22      0.1170369000
_diffrn_orient_matrix_UB_23      -0.0228582000
_diffrn_orient_matrix_UB_31      0.0752421000
_diffrn_orient_matrix_UB_32      -0.1586751000
_diffrn_orient_matrix_UB_33      -0.0090769000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0599
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            56983
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         4.027
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.118
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36980
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.654
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         4679
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0534
_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^)+(0.0625P)^2^+3.0924P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4398
_reflns_number_total             4679
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01086k2.cif
_cod_data_source_block           exp_2506
_cod_database_code               1566821
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.476
_shelx_estimated_absorpt_t_min   0.400
_reflns_odcompleteness_completeness 99.98
_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
 C27-C1AA
 1.52 with sigma of 0.01
 C27-C29
 1.52 with sigma of 0.01
 C27-C2AA
 1.52 with sigma of 0.01
 C27-C30
 1.52 with sigma of 0.01
 C27-C0AA
 1.52 with sigma of 0.01
 C27-C28
 1.52 with sigma of 0.01
3. Rigid bond restraints
 C1AA, C27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C27, C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C27, C2AA
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C27, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C27, C0AA
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C28, C27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C27 \\sim C28: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C28 \\sim C27: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C27 \\sim C1AA: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C27 \\sim C29: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C27 \\sim C2AA: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C27 \\sim C30: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C27 \\sim C0AA: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
5. Others
 Fixed Sof: C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C29(0.5) H29A(0.5)
 H29B(0.5) H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5) C0AA(0.5) H0AA(0.5)
 H0AB(0.5) H0AC(0.5) C2AA(0.5) H2AA(0.5) H2AB(0.5) H2AC(0.5) C1AA(0.5)
 H1AA(0.5) H1AB(0.5) H1AC(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C10(H10), C12(H12), C15(H15),
 C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25), C26(H26)
6.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C0AA(H0AA,H0AB,
 H0AC), C2AA(H2AA,H2AB,H2AC), C1AA(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              17755
_shelx_hkl_checksum              84812
_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 2.045
_oxdiff_exptl_absorpt_empirical_full_min 0.468