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_1568767
_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         'C16 H18 N2 O2 S'
_chemical_formula_sum            'C16 H18 N2 O2 S'
_chemical_formula_weight         302.38
_chemical_name_systematic
'ethyl 3-phenyl-5-(pyrrolidin-1-yl)isothiazole-4-carboxylate'
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-10-12
_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                 100.2575(19)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.0494(2)
_cell_length_b                   10.37004(19)
_cell_length_c                   26.5033(5)
_cell_measurement_reflns_used    61003
_cell_measurement_temperature    99.9(3)
_cell_measurement_theta_max      45.2090
_cell_measurement_theta_min      1.8830
_cell_volume                     2988.28(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.617
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f   -350.17   9.83   1.50   40.00  -7.62 -25.77 -30.17    --   240
  2  \w      1.55  99.05   1.50   40.00    --   57.99-101.76-144.21   65
  3  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27  72.26   66
  4  \w     -5.24  50.26   1.50   40.00    --   26.32  80.15  11.44   37
  5  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27 -29.74   66
  6  \w   -106.28   1.72   1.50   40.00    --  -25.77 -73.76 178.75   72
  7  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27 123.26   66
  8  \w   -106.28   1.72   1.50   40.00    --  -25.77 -73.76  76.75   72
  9  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27 -83.74   66
 10  \w   -106.28   1.72   1.50   40.00    --  -25.77 -73.76 -79.25   72
 11  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27 174.26   66
 12  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27  21.26   66
 13  \w    -92.78  18.22   1.50   40.00    --  -10.77 -73.76  25.75   74
 14  \w    -56.95  42.05   1.50   40.00    --  -25.77  83.27-134.74   66
 15  \w    -92.78  18.22   1.50   40.00    --  -10.77 -73.76-154.25   74
 16  \w   -106.28   1.72   1.50   40.00    --  -25.77 -73.76  25.75   72
 17  \f   -333.16  26.84   1.50   40.00   4.41 -25.77 -76.41    --   240
 18  \w    -92.78  18.22   1.50   40.00    --  -10.77 -73.76 115.75   74
 19  \w   -106.28   1.72   1.50   40.00    --  -25.77 -73.76 127.75   72
 20  \w    -92.78  18.22   1.50   40.00    --  -10.77 -73.76 -64.25   74
 21  \w    -24.76  86.24   1.50   40.00    --    4.23  73.76 -25.75   74
 22  \w   -106.28   1.72   1.50   40.00    --  -25.77 -73.76-130.25   72
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0221087000
_diffrn_orient_matrix_UB_12      -0.0226085000
_diffrn_orient_matrix_UB_13      -0.0219416000
_diffrn_orient_matrix_UB_21      0.0417160000
_diffrn_orient_matrix_UB_22      -0.0414674000
_diffrn_orient_matrix_UB_23      0.0157407000
_diffrn_orient_matrix_UB_31      -0.0450058000
_diffrn_orient_matrix_UB_32      -0.0495046000
_diffrn_orient_matrix_UB_33      -0.0031849000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0738
_diffrn_reflns_av_unetI/netI     0.0690
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.617
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            187266
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.617
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         45.848
_diffrn_reflns_theta_min         1.897
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.223
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85468
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (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    1.344
_exptl_crystal_description       plate
_exptl_crystal_F_000             1280
_exptl_crystal_recrystallization_method 'grown from n-hexane solution'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.110
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         15899
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.1463
_refine_ls_R_factor_gt           0.0927
_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^)+(0.0407P)^2^+5.3860P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1795
_refine_ls_wR_factor_ref         0.1954
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10679
_reflns_number_total             15899
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy00290j2.cif
_cod_data_source_block           bam22_s2527_fr233_autored
_cod_depositor_comments
'Adding full bibliography for 1568765--1568768.cif.'
_cod_original_cell_volume        2988.29(10)
_cod_database_code               1568767
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H18 N2 O2 S'
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.916
_reflns_odcompleteness_completeness 99.97
_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:
 C13(H13A,H13B), C19(H19A,H19B), C20(H20A,H20B), C25(H25A,H25B), C27(H27A,
 H27B), C18(H18A,H18B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B),
 C31(H31A,H31B)
2.b Aromatic/amide H refined with riding coordinates:
 C33(H33), C35(H35), C36(H36), C38(H38), C40(H40), C26(H26), C28(H28),
 C30(H30), C32(H32), C34(H34)
2.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              52317
_olex2_submission_original_sample_id BAM_9a
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.854
_oxdiff_exptl_absorpt_empirical_full_min 0.412