The effect of the C5-substituent on regioselectivity in the Rh(i)-catalyzed intermolecular transannulation of 1,2,3-thiadiazoles with phenylacetylene
Tokareva, Marina A.; Pernik, Indrek; Messerle, Barbara A.; Glukhareva, Tatiana V.; Keaveney, Sinead T.; Catalysis Science & Technology 13 (2023) 2772–2782; doi:10.1039/D3CY00290J

data_1568766
_publ_section_title
;
 The effect of the C5-substituent on regioselectivity in the
 Rh(i)-catalyzed intermolecular transannulation of 1,2,3-thiadiazoles with
 phenylacetylene
;
_journal_issue                   9
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2772
_journal_page_last               2782
_journal_paper_doi               10.1039/D3CY00290J
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         '0.5(C18 H14 N2 O4 S)'
_chemical_formula_sum            'C9 H7 N O2 S0.5'
_chemical_formula_weight         177.19
_chemical_name_systematic
'ethyl 5-(4-nitrophenyl)-3-phenylisothiazole-4-carboxylate'
_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             2022-11-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2022-11-15 deposited with the CCDC.	2023-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                100.966(4)
_cell_angle_beta                 100.107(4)
_cell_angle_gamma                93.879(4)
_cell_formula_units_Z            4
_cell_length_a                   8.8717(4)
_cell_length_b                   8.9788(4)
_cell_length_c                   10.5747(4)
_cell_measurement_reflns_used    8921
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      29.1690
_cell_measurement_theta_min      2.3210
_cell_volume                     809.68(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2930
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.897
_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    -47.00  21.00   1.00    2.00    --  -11.94  77.00 120.00   68
  2  \w    -15.00  30.00   1.00    2.00    --  -11.94 -99.00 -60.00   45
  3  \w    -68.00  26.00   1.00    2.00    --   14.91 -19.00 150.00   94
  4  \w    -14.00  92.00   1.00    2.00    --   14.91  38.00 -30.00  106
  5  \w     37.00 105.00   1.00    2.00    --   14.91-178.00-180.00   68
  6  \w    -36.00 -11.00   1.00    2.00    --  -11.94 -73.00 -15.00   25
  7  \w    -42.00  23.00   1.00    2.00    --  -11.94 -77.00  30.00   65
  8  \w    -47.00  21.00   1.00    2.00    --  -11.94  77.00 -90.00   68
  9  \w    -47.00  21.00   1.00    2.00    --  -11.94  77.00 -60.00   68
 10  \w    -42.00  50.00   1.00    2.00    --   14.91 -77.00-120.00   92
 11  \w    -15.00  57.00   1.00    2.00    --   14.91 -99.00  30.00   72
 12  \w    -14.00  92.00   1.00    2.00    --   14.91  38.00-150.00  106
;
_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      0.0376761000
_diffrn_orient_matrix_UB_12      -0.0195849000
_diffrn_orient_matrix_UB_13      -0.0538129000
_diffrn_orient_matrix_UB_21      -0.0111070000
_diffrn_orient_matrix_UB_22      -0.0781176000
_diffrn_orient_matrix_UB_23      0.0030736000
_diffrn_orient_matrix_UB_31      -0.0715859000
_diffrn_orient_matrix_UB_32      -0.0078313000
_diffrn_orient_matrix_UB_33      -0.0440648000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0267
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.897
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            18033
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.504
_diffrn_reflns_theta_min         1.999
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.226
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.372
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.67a (Rigaku Oxford Diffraction, 2022)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.454
_exptl_crystal_description       block
_exptl_crystal_F_000             368
_exptl_crystal_preparation
'transannulation of ethyl 5-(4-nitrophenyl)-1,2,3-thiadiazole-4-carboxylate with benzonitrile'
_exptl_crystal_recrystallization_method 'n--hexane solution at rt'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.263
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         4052
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0386
_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^)+(0.0344P)^2^+0.3207P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0845
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3468
_reflns_number_total             4052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy00290j2.cif
_cod_data_source_block           bam22_s2609_sn981
_cod_depositor_comments
'Adding full bibliography for 1568765--1568768.cif.'
_cod_original_formula_sum        'C9 H7 N O2 S0.50'
_cod_database_code               1568766
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H14 N2 O4 S1'
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.919
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C18(H18), C14(H14), C4(H4), C17(H17), C16(H16),
 C15(H15)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
;
_shelx_res_checksum              51576
_olex2_submission_original_sample_id 9y
_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 1.341
_oxdiff_exptl_absorpt_empirical_full_min 0.860