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_1568768
_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 H21 N O2 S'
_chemical_formula_sum            'C17 H21 N O2 S'
_chemical_formula_weight         303.428
_chemical_name_systematic
'ethyl 2-(cyclopentanecarbonothioyl)-3-phenylbutanoate'
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-10
_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                 91.380(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7409(1)
_cell_length_b                   7.7066(1)
_cell_length_c                   21.1913(2)
_cell_measurement_reflns_used    14017
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.4090
_cell_measurement_theta_min      4.1570
_cell_volume                     1590.35(3)
_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  'olex2.refine 1.3 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5861
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.9940
_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     -5.00  43.00   1.00    1.00    --  -40.07  19.00  60.00   48
  2  \w     -5.00  43.00   1.00    1.00    --  -40.07  19.00 -90.00   48
  3  \w     -5.00  43.00   1.00    1.00    --  -40.07  19.00 -30.00   48
  4  \w     -5.00  43.00   1.00    1.00    --  -40.07  19.00-150.00   48
  5  \w     -5.00  43.00   1.00    1.00    --  -40.07  19.00 -60.00   48
  6  \w     -5.00  43.00   1.00    1.00    --  -40.07  19.00-180.00   48
  7  \w    -21.00  37.00   1.00    1.00    --  -40.07  38.00  30.00   58
  8  \w     61.00 131.00   1.00    1.00    --   40.07 178.00  30.00   70
  9  \w     26.00  96.00   1.00    1.00    --   40.07-124.00-165.00   70
 10  \w     58.00 130.00   1.00    1.00    --   40.07-178.00-180.00   72
 11  \w     31.00 109.00   1.00    1.00    --  107.62-112.00  60.00   78
 12  \w     74.00 178.00   1.00    1.00    --  107.62  30.00 -30.00  104
 13  \w     31.00 109.00   1.00    1.00    --  107.62-112.00-120.00   78
 14  \w     31.00  72.00   1.00    1.00    --  107.62 -45.00 -60.00   41
 15  \w     31.00 109.00   1.00    1.00    --  107.62-112.00-150.00   78
 16  \w     31.00  72.00   1.00    1.00    --  107.62 -45.00-150.00   41
 17  \w     28.00  57.00   1.00    1.00    --  107.62 -30.00   0.00   29
 18  \w     31.00 109.00   1.00    1.00    --  107.62-112.00   0.00   78
 19  \w     31.00  72.00   1.00    1.00    --  107.62 -45.00-180.00   41
 20  \w     28.00  57.00   1.00    1.00    --  107.62 -30.00  30.00   29
 21  \w     23.00 106.00   1.00    1.00    --  107.62 -95.00  90.00   83
 22  \w    104.00 166.00   1.00    1.00    --  107.62 112.00-120.00   62
 23  \w     28.00  57.00   1.00    1.00    --  107.62 -30.00 150.00   29
 24  \w     31.00  72.00   1.00    1.00    --  107.62 -45.00  90.00   41
 25  \w     30.00 178.00   1.00    1.00    --  107.62  15.00  60.00  148
 26  \w     61.00 143.00   1.00    1.00    --  107.62 178.00  30.00   82
 27  \w     76.00 176.00   1.00    1.00    --  107.62  61.00-180.00  100
 28  \w     76.00 176.00   1.00    1.00    --  107.62  61.00  30.00  100
 29  \w     76.00 176.00   1.00    1.00    --  107.62  61.00 -90.00  100
 30  \w     76.00 176.00   1.00    1.00    --  107.62  61.00-150.00  100
 31  \w     76.00 176.00   1.00    1.00    --  107.62  61.00  90.00  100
 32  \w     78.00 178.00   1.00    1.00    --  107.62  45.00  90.00  100
 33  \w     76.00 176.00   1.00    1.00    --  107.62  61.00 -30.00  100
 34  \w     76.00 160.00   1.00    1.00    --  107.62  61.00-120.00   84
 35  \w     76.00 176.00   1.00    1.00    --  107.62  61.00 150.00  100
;
_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      0.1228095000
_diffrn_orient_matrix_UB_12      0.0377771000
_diffrn_orient_matrix_UB_13      -0.0423490000
_diffrn_orient_matrix_UB_21      -0.0890517000
_diffrn_orient_matrix_UB_22      -0.0441771000
_diffrn_orient_matrix_UB_23      -0.0589076000
_diffrn_orient_matrix_UB_31      -0.0446623000
_diffrn_orient_matrix_UB_32      0.1912933000
_diffrn_orient_matrix_UB_33      -0.0052203000
_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  0.0349
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9940
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            21419
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9940
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         72.42
_diffrn_reflns_theta_min         4.17
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72383
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.67a (Rigaku Oxford Diffraction, 2022)
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    1.267
_exptl_crystal_description       plate
_exptl_crystal_F_000             651.148
_exptl_crystal_recrystallization_method
'recrystallation from ethyl acetate and hexane'
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.3457
_refine_diff_density_min         -0.1819
_refine_diff_density_rms         0.0493
_refine_ls_d_res_high            0.8087
_refine_ls_d_res_low             10.5926
_refine_ls_goodness_of_fit_ref   1.0802
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    33
_refine_ls_number_parameters     192
_refine_ls_number_reflns         3130
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0802
_refine_ls_R_factor_all          0.0351
_refine_ls_R_factor_gt           0.0330
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1184
_refine_ls_wR_factor_ref         0.1224
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -12
_reflns_limit_k_max              9
_reflns_limit_k_min              0
_reflns_limit_l_max              26
_reflns_limit_l_min              -9
_reflns_number_gt                2933
_reflns_number_total             3130
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3cy00290j2.cif
_cod_data_source_block           bam22_s2580_sn950
_cod_depositor_comments
'Adding full bibliography for 1568765--1568768.cif.'
_cod_original_sg_symbol_Hall     '-P 2ybc (x-z,y,z)'
_cod_database_code               1568768
_chemical_oxdiff_formula         C17H18N1S1O3
_chemical_oxdiff_usercomment     10b
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C11(H11a,H11b), C16(H16a,H16b), C12(H12a,H12b), C14(H14a,H14b), C13(H13a,H13b)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C3(H3), C2(H2), C1(H1)
2.c Idealised Me refined as rotating group:
 C8(H8a,H8b,H8c), C17(H17a,H17b,H17c)
;
_olex2_submission_original_sample_id BAM_10a
_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 1.306
_oxdiff_exptl_absorpt_empirical_full_min 0.696