Tuning intramolecular charge transfer and suppressing rotations in thianthrene derivatives for enhancement of room-temperature phosphorescence
Zeng, Huiwen; Li, Hualiu; Zhen, Peng; Zhou, Jiadong; Xu, Bingjia; Shi, Guang; Zhang, Yujian; Chi, Zhenguo; Liu, Cong; Chemical Science 16 (2025) 9169–9177; doi:10.1039/D5SC01176K

data_1574426
_publ_section_title
;
 Tuning intramolecular charge transfer and suppressing rotations in
 thianthrene derivatives for enhancement of room-temperature
 phosphorescence
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              9169
_journal_page_last               9177
_journal_paper_doi               10.1039/D5SC01176K
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '1(C22 H14 S2)'
_chemical_formula_sum            'C22 H14 S2'
_chemical_formula_weight         342.45
_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             2023-10-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-12-19 deposited with the CCDC.	2025-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.588(7)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   20.081(3)
_cell_length_b                   11.1282(17)
_cell_length_c                   29.075(5)
_cell_measurement_reflns_used    8076
_cell_measurement_temperature    197.00
_cell_measurement_theta_max      68.291
_cell_measurement_theta_min      4.252
_cell_volume                     6494.8(18)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      197.00
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            51185
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.271
_diffrn_reflns_theta_min         2.640
_diffrn_source_current           1.11
_diffrn_source_power             0.05550000000000001
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.938
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4472
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1527 before and 0.0757 after correction.
The Ratio of minimum to maximum transmission is 0.5938.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             2848
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1010
_refine_ls_number_reflns         11770
_refine_ls_number_restraints     517
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0456
_refine_ls_R_factor_gt           0.0433
_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^)+8.0034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.0995
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11290
_reflns_number_total             11770
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01176k6.cif
_cod_data_source_block           1_CCDC2
_cod_depositor_comments
'Adding full bibliography for 1574423--1574426.cif.'
_cod_original_cell_volume        6494.8(17)
_cod_database_code               1574426
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.684
_shelx_estimated_absorpt_t_min   0.564
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S1-C22 \\sim S1-C22A
 with sigma of 0.02
 C17-C22 \\sim C17-C22A
 with sigma of 0.02
 C21-C22 \\sim C21-C22A
 with sigma of 0.02
 C22-C17A \\sim C22A-C17A
 with sigma of 0.02
 C22-C21A \\sim C22A-C21A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C1A \\sim C2 \\sim C2A \\sim C3 \\sim C3A \\sim C4 \\sim C4A \\sim C5
\\sim C5A \\sim C6 \\sim C6A \\sim C7 \\sim C7A \\sim C8 \\sim C8A \\sim C9
\\sim C9A \\sim C10 \\sim C10A \\sim C11 \\sim C11A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C17A \\sim C18A \\sim C19A
\\sim C20A \\sim C21A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S2A) = Uanis(S2)
Uanis(C12A) = Uanis(C12)
Uanis(C22A) = Uanis(C22)
Uanis(C16A) = Uanis(C16)
4. Others
 Sof(S2A)=Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=
 Sof(C9A)=Sof(C10A)=Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(H13A)=Sof(C21A)=Sof(H21A)=
 Sof(C20A)=Sof(H20A)=Sof(C19A)=Sof(H19A)=Sof(C18A)=Sof(H18A)=Sof(C17A)=
 Sof(C22A)=Sof(C16A)=1-FVAR(1)
 Sof(S2)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=
 Sof(C11)=Sof(C12)=Sof(H12)=Sof(H13)=Sof(C16)=Sof(C17)=Sof(C18)=Sof(H18)=
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C1A(H1A), C2(H2), C2A(H2A), C3(H3), C3A(H3A), C4(H4), C4A(H4A),
 C6(H6), C6A(H6A), C7(H7), C7A(H7A), C8(H8), C8A(H8A), C12(H12), C12A(H12A),
 C13(H13), C13(H13A), C14(H14), C18(H18), C19(H19), C20(H20), C21(H21),
 C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C34(H34),
  C35(H35), C36(H36), C40(H40), C41(H41), C42(H42), C43(H43), C45(H45),
 C46(H46), C47(H47), C48(H48), C50(H50), C51(H51), C52(H52), C56(H56), C57(H57),
  C58(H58), C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68),
 C69(H69), C70(H70), C72(H72), C73(H73), C74(H74), C78(H78), C79(H79), C80(H80),
  C84(H84), C85(H85), C86(H86), C87(H87), C21A(H21A), C20A(H20A), C19A(H19A),
 C18A(H18A)
5.b Fitted hexagon refined as free rotating group:
 C21A(C20A,C19A,C18A,C17A,C22A)
;
_shelx_res_checksum              23680
_shelx_hkl_checksum              18654
_olex2_submission_special_instructions 'No special instructions were received'