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_1576768
_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         'C21 H16 S2'
_chemical_formula_sum            'C21 H16 S2'
_chemical_formula_weight         332.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-13
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.04.09 svn.r3586 for OlexSys, GUI svn.r5731)
;
_audit_update_record
;
2023-07-15 deposited with the CCDC.	2026-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.7590(2)
_cell_length_b                   15.6784(3)
_cell_length_c                   20.0594(4)
_cell_measurement_reflns_used    6797
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.9590
_cell_measurement_theta_min      4.0970
_cell_volume                     3383.70(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_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     10.00  36.00   0.50    0.20    --   43.86 -36.00  43.00   52
  2  \w     22.00  47.00   0.50    0.20    --   43.86-116.00 -30.00   50
  3  \w     53.00  79.00   0.50    0.27    --   96.32-116.00 -30.00   52
  4  \w     29.00  88.00   0.50    0.27    --   96.32 -33.00-120.00  118
  5  \w     50.00 103.00   0.50    0.27    --   96.32 -88.00-138.00  106
  6  \w     49.00  74.00   0.50    0.20    --   43.86-165.00-177.00   50
  7  \w     30.00 111.00   0.50    0.27    --   96.32-117.00-120.00  162
  8  \w     92.00 164.00   0.50    0.27    --   96.32  33.00 -30.00  144
  9  \w     91.00 117.00   0.50    0.27    --   96.32 116.00  58.00   52
 10  \w     61.00 106.00   0.50    0.20    --   43.86 138.00  90.00   90
 11  \w    -50.00  -3.00   0.50    0.20    --  -41.99 116.00  58.00   94
 12  \w    -35.00  24.00   0.50    0.20    --  -41.99  88.00 -21.00  118
 13  \w    -68.00 -26.00   0.50    0.20    --  -41.99 -54.00-120.00   84
 14  \w    -51.00  10.00   0.50    0.20    --  -41.99  36.00-159.00  122
 15  \w    -26.00  -1.00   0.50    0.20    --   43.86 -88.00-138.00   50
 16  \w     57.00  90.00   0.50    0.20    --   43.86  36.00-159.00   66
 17  \w    107.00 151.00   0.50    0.27    --   96.32  36.00-159.00   88
 18  \w     74.00  99.00   0.50    0.20    --   43.86 165.00-153.00   50
 19  \w    -92.00 -67.00   0.50    0.20    --  -41.99 -36.00  43.00   50
 20  \w    -88.00 -63.00   0.50    0.20    --  -41.99-138.00  30.00   50
 21  \w   -150.00 -81.00   0.50    0.27    --  -94.45 -33.00 120.00  138
 22  \w     68.00  94.00   0.50    0.27    --   96.32 -96.00 150.00   52
 23  \w    -98.00 -73.00   0.50    0.20    --  -41.99 -54.00-120.00   50
 24  \w   -133.00-108.00   0.50    0.27    --  -94.45 -88.00-138.00   50
 25  \w    -98.00 -50.00   0.50    0.27    --  -94.45  36.00-159.00   96
;
_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      -0.0350688000
_diffrn_orient_matrix_UB_12      0.0153946000
_diffrn_orient_matrix_UB_13      -0.0734954000
_diffrn_orient_matrix_UB_21      0.0558841000
_diffrn_orient_matrix_UB_22      -0.0872020000
_diffrn_orient_matrix_UB_23      -0.0188176000
_diffrn_orient_matrix_UB_31      -0.1270741000
_diffrn_orient_matrix_UB_32      -0.0425588000
_diffrn_orient_matrix_UB_33      0.0120339000
_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  0.0523
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11547
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.158
_diffrn_reflns_theta_min         4.408
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.799
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13616
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.305
_exptl_crystal_description       block
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.460
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.065
_refine_ls_extinction_coef       0.0009(2)
_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   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         3071
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0570
_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^)+(0.1135P)^2^+0.3338P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1651
_refine_ls_wR_factor_ref         0.1711
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2628
_reflns_number_total             3071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08209a2.cif
_cod_data_source_block           c-h-o-n-s-2
_cod_database_code               1576768
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.679
_shelx_estimated_absorpt_t_min   0.604
_diffrn_oxdiff_digest_frames
;
0164890bd080b491127d57a5ca719f9b3b00040ff4f
;
_diffrn_oxdiff_digest_hkl
;
0136f5a8e9db3997fe6d75be51f4706388c0dd
;
_reflns_odcompleteness_completeness 99.85
_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:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C10(H10), C11(H11), C12(H12),
 C16(H16), C17(H17), C18(H18), C19(H19), C21(H21)
2.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              44822
_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 3.788
_oxdiff_exptl_absorpt_empirical_full_min 0.463