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_1568765
_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         'C17 H19 N O2 S'
_chemical_formula_sum            'C17 H19 N O2 S'
_chemical_formula_weight         301.39
_chemical_name_systematic
'ethyl 4-phenyl-2-(pyrrolidin-1-yl)thiophene-3-carboxylate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-15
_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                90
_cell_angle_beta                 100.851(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8925(4)
_cell_length_b                   7.8461(2)
_cell_length_c                   15.2747(5)
_cell_measurement_reflns_used    11358
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.4400
_cell_measurement_theta_min      2.9160
_cell_volume                     1517.50(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2930
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.971
_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   -131.00  51.00   1.00    2.50    --  -40.07   0.00  90.00  182
  2  \w     61.00 131.00   1.00    2.50    --   40.07 178.00-180.00   70
  3  \w     61.00 131.00   1.00    2.50    --   40.07 178.00 -30.00   70
  4  \w     61.00 131.00   1.00    2.50    --   40.07 178.00  90.00   70
  5  \w     58.00 130.00   1.00    2.50    --   40.07-178.00 -90.00   72
  6  \w     28.00  57.00   1.00   10.00    --  107.94 -30.00  90.00   29
  7  \w     28.00  57.00   1.00   10.00    --  107.94 -30.00-150.00   29
  8  \w     32.00  93.00   1.00   10.00    --  107.94 -61.00 -60.00   61
  9  \w     29.00 109.00   1.00   10.00    --  107.94-112.00 -60.00   80
 10  \w     31.00  72.00   1.00   10.00    --  107.94 -45.00   0.00   41
 11  \w     28.00  57.00   1.00   10.00    --  107.94 -30.00  60.00   29
 12  \w     32.00  93.00   1.00   10.00    --  107.94 -61.00   0.00   61
 13  \w     28.00  57.00   1.00   10.00    --  107.94 -30.00   0.00   29
 14  \w     29.00 109.00   1.00   10.00    --  107.94-112.00  30.00   80
 15  \w     28.00  57.00   1.00   10.00    --  107.94 -30.00 -30.00   29
 16  \w     74.00 178.00   1.00   10.00    --  107.94  30.00 -30.00  104
 17  \w     74.00 178.00   1.00   10.00    --  107.94  30.00-120.00  104
 18  \w     28.00  57.00   1.00   10.00    --  107.94 -30.00  30.00   29
 19  \w     23.00 106.00   1.00   10.00    --  107.94 -95.00-180.00   83
 20  \w     32.00  93.00   1.00   10.00    --  107.94 -61.00  30.00   61
 21  \w     31.00  72.00   1.00   10.00    --  107.94 -45.00-180.00   41
 22  \w     26.00 126.00   1.00   10.00    --  107.94 -77.00-150.00  100
 23  \w     31.00  72.00   1.00   10.00    --  107.94 -45.00 -60.00   41
 24  \w     29.00 109.00   1.00   10.00    --  107.94-112.00 150.00   80
 25  \w   -116.00  -9.00   1.00    2.50    --  -40.07 -57.00 -90.00  107
 26  \w   -116.00  -9.00   1.00    2.50    --  -40.07 -57.00-180.00  107
 27  \w   -116.00  -9.00   1.00    2.50    --  -40.07 -57.00   0.00  107
 28  \w    -22.00  37.00   1.00    2.50    --  -40.07  38.00-120.00   59
 29  \w   -116.00  -9.00   1.00    2.50    --  -40.07 -57.00  90.00  107
 30  \w     76.00 178.00   1.00   10.00    --  107.94  61.00 150.00  102
 31  \w     31.00 178.00   1.00   10.00    --  107.94  15.00 120.00  147
 32  \w     76.00 178.00   1.00   10.00    --  107.94  61.00  90.00  102
 33  \w     79.00 178.00   1.00   10.00    --  107.94  45.00 -90.00   99
 34  \w     76.00 157.00   1.00   10.00    --  107.94  61.00-180.00   81
 35  \w     79.00 178.00   1.00   10.00    --  107.94  45.00   0.00   99
;
_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      0.1190548000
_diffrn_orient_matrix_UB_12      0.0201793000
_diffrn_orient_matrix_UB_13      0.0008521000
_diffrn_orient_matrix_UB_21      -0.0250491000
_diffrn_orient_matrix_UB_22      0.0830523000
_diffrn_orient_matrix_UB_23      -0.0930615000
_diffrn_orient_matrix_UB_31      -0.0017460000
_diffrn_orient_matrix_UB_32      0.1766447000
_diffrn_orient_matrix_UB_33      0.0435522000
_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  0.0437
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            13345
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.564
_diffrn_reflns_theta_min         6.266
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.922
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.634
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       plate
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.319
_exptl_crystal_size_mid          0.244
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2926
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0467P)^2^+1.4490P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2827
_reflns_number_total             2926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy00290j2.cif
_cod_data_source_block           bam22_s2419_sn917
_cod_depositor_comments
'Adding full bibliography for 1568765--1568768.cif.'
_cod_database_code               1568765
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C13 H20 N5 O2 S1'
_reflns_odcompleteness_completeness 98.07
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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:
 C3(H3A,H3B), C8(H8A,H8B), C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B)
2.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C17(H17), C16(H16), C15(H15), C14(H14)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              57737
_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 3.712
_oxdiff_exptl_absorpt_empirical_full_min 0.604