Rh(iii)-catalyzed heteroannular-selective heteroarylation of biaryls: facile access to heteroacenes with sulfur-embedded 5-7 ring topology.
He, Zhanhui; Yang, Li; Zhou, Menghang; Zhong, Yue; Liu, Zheng; Zhang, Ziao; Xia, Feiyang; Deng, Xuezhe; Yan, Shuang; Xu, Cheng; Zhang, Cheng; Yin, Guodong; Chemical science 17 (2026) 4594–4600; doi:10.1039/d5sc08209a

data_1576773
_publ_section_title
;
 Rh(iii)-catalyzed heteroannular-selective heteroarylation of biaryls:
 facile access to heteroacenes with sulfur-embedded 5-7 ring topology.
;
_journal_issue                   9
_journal_name_full               'Chemical science'
_journal_page_first              4594
_journal_page_last               4600
_journal_paper_doi               10.1039/d5sc08209a
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C20 H12 S2'
_chemical_formula_sum            'C20 H12 S2'
_chemical_formula_weight         316.42
_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             2023-09-06
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.04.09 svn.r3586 for OlexSys, GUI svn.r5731)
;
_audit_update_record
;
2025-03-21 deposited with the CCDC.	2026-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                106.545(4)
_cell_angle_beta                 90.845(2)
_cell_angle_gamma                103.498(4)
_cell_formula_units_Z            4
_cell_length_a                   9.7309(3)
_cell_length_b                   11.2753(6)
_cell_length_c                   14.8333(3)
_cell_measurement_reflns_used    6591
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.0550
_cell_measurement_theta_min      4.2150
_cell_volume                     1511.25(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.988
_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     20.00  60.00   0.50    0.20    --   43.99 -43.00 -30.00   80
  2  \w     33.00 110.00   0.50    0.20    --   96.32 -33.00 -30.00  154
  3  \w     75.00 168.00   0.50    0.20    --   96.32  17.00 -30.00  186
  4  \w     78.00 104.00   0.50    0.20    --   43.99  32.00-120.00   52
  5  \w     82.00 107.00   0.50    0.20    --   43.99  20.00-129.00   50
  6  \w     95.00 144.00   0.50    0.20    --   96.32  20.00-129.00   98
  7  \w     61.00 111.00   0.50    0.20    --   43.99 138.00 -30.00  100
  8  \w    131.00 158.00   0.50    0.20    --   96.32  25.00  60.00   54
  9  \w     99.00 128.00   0.50    0.20    --   96.32  25.00  60.00   58
 10  \w     45.00  70.00   0.50    0.20    --   96.32 -20.00  62.00   50
 11  \w     13.00  51.00   0.50    0.20    --   43.99 -20.00  62.00   76
 12  \w     31.00  84.00   0.50    0.20    --   43.99  32.00  90.00  106
 13  \w     34.00 101.00   0.50    0.20    --   96.32 -33.00 120.00  134
 14  \w     41.00 127.00   0.50    0.20    --   96.32 -87.00 150.00  172
 15  \w     34.00 115.00   0.50    0.20    --   96.32 -59.00 150.00  162
 16  \w     30.00 113.00   0.50    0.20    --   96.32-117.00 150.00  166
 17  \w    -27.00   9.00   0.50    0.20    --   43.99 -20.00  62.00   72
 18  \w     -6.00  51.00   0.50    0.20    --   43.99-104.00   0.00  114
 19  \w    -22.00   9.00   0.50    0.20    --   43.99 -43.00 -30.00   62
 20  \w    -64.00 -38.00   0.50    0.20    --  -42.11 -20.00  62.00   52
 21  \w      0.00  25.00   0.50    0.20    --  -42.11  43.00 -60.00   50
 22  \w     27.00  73.00   0.50    0.20    --   43.99  20.00-129.00   92
 23  \w     36.00  98.00   0.50    0.20    --   96.32 -25.00-180.00  124
 24  \w     19.00  73.00   0.50    0.20    --   43.99-104.00-150.00  108
 25  \w    -42.00 -15.00   0.50    0.20    --  -42.11  20.00-129.00   54
 26  \w    -39.00 -14.00   0.50    0.20    --  -42.11  43.00 -60.00   50
 27  \w    -62.00  18.00   0.50    0.20    --  -42.11  77.00 -30.00  160
 28  \w    -61.00 -35.00   0.50    0.20    --  -94.45  59.00  30.00   52
 29  \w    -59.00 -27.00   0.50    0.20    --  -94.45  96.00  60.00   64
 30  \w    -91.00 -37.00   0.50    0.20    --  -42.11 138.00  60.00  108
 31  \w    -50.00 -21.00   0.50    0.20    --  -94.45  96.00 120.00   58
 32  \w    -97.00 -72.00   0.50    0.20    --  -42.11 -20.00  62.00   50
 33  \w   -109.00 -61.00   0.50    0.20    --  -94.45  25.00  90.00   96
 34  \w   -118.00 -26.00   0.50    0.20    --  -94.45  68.00 120.00  184
 35  \w   -108.00 -65.00   0.50    0.20    --  -94.45  96.00 120.00   86
 36  \w   -134.00 -76.00   0.50    0.20    --  -94.45 -20.00  62.00  116
 37  \w    -90.00 -65.00   0.50    0.20    --  -42.11-138.00 150.00   50
 38  \w   -102.00 -77.00   0.50    0.20    --  -42.11-138.00  30.00   50
 39  \w   -158.00 -70.00   0.50    0.20    --  -94.45 -68.00  30.00  176
 40  \w    -76.00 -37.00   0.50    0.20    --  -94.45  50.00 -30.00   78
 41  \w   -107.00 -79.00   0.50    0.20    --  -94.45  50.00 -30.00   56
 42  \w   -127.00 -53.00   0.50    0.20    --  -94.45 145.00 -90.00  148
 43  \w    -66.00 -41.00   0.50    0.20    --  -94.45 145.00 -60.00   50
 44  \w   -109.00 -65.00   0.50    0.20    --  -94.45 117.00-120.00   88
 45  \w    -98.00 -27.00   0.50    0.20    --  -94.45 117.00 -90.00  142
 46  \w    -93.00 -55.00   0.50    0.20    --  -94.45  20.00-129.00   76
 47  \w   -115.00 -90.00   0.50    0.20    --  -94.45 145.00 -60.00   50
 48  \w     76.00 102.00   0.50    0.20    --   43.99 138.00 120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0545915000
_diffrn_orient_matrix_UB_12      0.1460212000
_diffrn_orient_matrix_UB_13      0.0236382000
_diffrn_orient_matrix_UB_21      -0.1527867000
_diffrn_orient_matrix_UB_22      0.0113658000
_diffrn_orient_matrix_UB_23      -0.0152180000
_diffrn_orient_matrix_UB_31      -0.0196713000
_diffrn_orient_matrix_UB_32      0.0139392000
_diffrn_orient_matrix_UB_33      0.1050616000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9924
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.233
_diffrn_reflns_theta_min         4.222
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.109
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81039
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.957
_refine_diff_density_min         -0.641
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.270
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     398
_refine_ls_number_reflns         9924
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.270
_refine_ls_R_factor_all          0.1036
_refine_ls_R_factor_gt           0.0993
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2737
_refine_ls_wR_factor_ref         0.2849
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8718
_reflns_number_total             9924
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9885\% 
 around [0.00 1.00 -0.00] (reciprocal) or [0.26 0.94 0.21] (direct)
;
_cod_data_source_file            d5sc08209a2.cif
_cod_data_source_block           l-1_twin1_hklf4
_cod_original_cell_volume        1511.24(11)
_cod_database_code               1576773
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.456
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.552(2)
 0.448(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23), C24(H24), C25(H25),
  C30(H30), C31(H31), C32(H32), C33(H33), C36(H36), C37(H37), C38(H38), C39(H39)
;
_shelx_res_checksum              19587
_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 1.659
_oxdiff_exptl_absorpt_empirical_full_min 0.348
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2