A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches.
Zitzmann, Max; Hampel, Frank; Dube, Henry; Chemical science 14 (2023) 5734–5742; doi:10.1039/d2sc06939c

data_1568988
_publ_section_title
;
 A cross-conjugation approach for high-performance diaryl-hemithioindigo
 photoswitches.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              5734
_journal_page_last               5742
_journal_paper_doi               10.1039/d2sc06939c
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C23 H20 N2 O S'
_chemical_formula_sum            'C23 H20 N2 O S'
_chemical_formula_weight         372.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-08-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-12-16 deposited with the CCDC.	2023-05-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.222(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.5494(8)
_cell_length_b                   12.9584(18)
_cell_length_c                   13.437(2)
_cell_measurement_reflns_used    2364
_cell_measurement_temperature    153.00(10)
_cell_measurement_theta_max      70.0320
_cell_measurement_theta_min      3.3910
_cell_volume                     962.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      153.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6144
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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  31.00   1.00    1.00    --  -42.06  57.00 -30.00   93
  2  \w      1.00  78.00   1.00    1.00    --   42.06 -99.00  60.00   77
  3  \w      9.00 117.00   1.00    1.00    --   42.06  77.00-180.00  108
  4  \w     22.00  79.00   1.00    1.00    --   42.06  57.00 120.00   57
  5  \w     81.00 168.00   1.00    1.54    --  101.31  45.00 -60.00   87
  6  \w     25.00 101.00   1.00    1.54    --  101.31 -94.00-120.00   76
  7  \w    113.00 170.00   1.00    1.54    --  101.31 125.00 -60.00   57
  8  \w     49.00 109.00   1.00    1.54    --  101.31 -94.00 -30.00   60
  9  \w     87.00 178.00   1.00    1.54    --  101.31  30.00   0.00   91
 10  \w     29.00 116.00   1.00    1.54    --  101.31-125.00-180.00   87
 11  \w     83.00 150.00   1.00    1.54    --  101.31  45.00  60.00   67
 12  \w    100.00 175.00   1.00    1.54    --  101.31 125.00-150.00   75
 13  \w     38.00  64.00   1.00    1.54    --  101.31 -45.00 -90.00   26
 14  \w     95.00 133.00   1.00    1.54    --  101.31 125.00-180.00   38
 15  \w     44.00 121.00   1.00    1.54    --  101.31 -30.00-180.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0588927000
_diffrn_orient_matrix_UB_12      0.0365509000
_diffrn_orient_matrix_UB_13      -0.1083526000
_diffrn_orient_matrix_UB_21      -0.0612731000
_diffrn_orient_matrix_UB_22      0.1080427000
_diffrn_orient_matrix_UB_23      0.0389263000
_diffrn_orient_matrix_UB_31      0.2651626000
_diffrn_orient_matrix_UB_32      0.0338136000
_diffrn_orient_matrix_UB_33      -0.0039347000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6457
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.330
_diffrn_reflns_theta_min         3.303
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.601
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.718
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       plate
_exptl_crystal_F_000             392
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and i-Hexane  by solvent layering'
_exptl_crystal_size_max          0.239
_exptl_crystal_size_mid          0.116
_exptl_crystal_size_min          0.105
_refine_diff_density_max         0.238
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.14(7)
_refine_ls_extinction_coef       0.008(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         3595
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0930
_refine_ls_R_factor_gt           0.0816
_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^)+(0.1170P)^2^+0.7713P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2222
_refine_ls_wR_factor_ref         0.2346
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.939
_reflns_number_gt                2974
_reflns_number_total             3595
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06939c3.cif
_cod_data_source_block           21dub_mz07
_cod_depositor_comments
'Adding full bibliography for 1568986--1568991.cif.'
_cod_database_code               1568988
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H20 N2 O S'
_chemical_oxdiff_usercomment     MZ-190
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.03
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.86(7)
 0.14(7)
2. 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
3. Shared sites
{C17A, N14}
{C17, N14A}
4. Restrained distances
 N14A-C18 \\sim N14-C13
 with sigma of 0.02
 C32-C33 \\sim C16-C17
 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(S12A) = Uanis(S12)
Uanis(O20A) = Uanis(O20)
Uanis(C17) = Uanis(N14A)
Uanis(C19A) = Uanis(C19)
Uanis(C17A) = Uanis(N14)
6. Others
 Sof(H15A)=Sof(H16A)=Sof(S12A)=Sof(O20A)=Sof(N14A)=Sof(C17A)=Sof(H17A)=
 Sof(C19A)=1-FVAR(1)
 Sof(H15)=Sof(H16)=Sof(S12)=Sof(O20)=Sof(N14)=Sof(C17)=Sof(H17)=Sof(C19)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C15(H15A), C15(H15), C16(H16A), C16(H16), C22(H22), C23(H23), C25(H25),
 C26(H26), C32(H32), C33(H33), C35(H35), C36(H36), C17A(H17A), C17(H17)
7.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C37(H37A,H37B,H37C)
;
_olex2_date_sample_data_collection 2021-08-25
_olex2_diffrn_ambient_temperature_device 'Cryojet - Oxford Instruments'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in perfluoroether oil'
_olex2_submission_original_sample_id MZ190
_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 1.333
_oxdiff_exptl_absorpt_empirical_full_min 0.825