(Z)-Tetrahydrothiophene and (Z)-tetrahydrothiopyran synthesis through nucleophilic substitution and intramolecular cycloaddition of alkynyl halides and EtOCS<sub>2</sub>K.
Luo, Xianglin; Li, Yibiao; Chen, Xiuwen; Song, Zhiyan; Liang, Junyi; Liao, Chunshu; Zhu, Zhongzhi; Chen, Lu; Organic & biomolecular chemistry 17 (2019) 7315–7319; doi:10.1039/c9ob01370a

data_7156971
_publ_section_title
;
 (Z)-Tetrahydrothiophene and (Z)-tetrahydrothiopyran synthesis through
 nucleophilic substitution and intramolecular cycloaddition of alkynyl
 halides and EtOCS<sub>2</sub>K.
;
_journal_issue                   31
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7315
_journal_page_last               7319
_journal_paper_doi               10.1039/c9ob01370a
_journal_volume                  17
_journal_year                    2019
_chemical_formula_moiety         'C13 H16 S'
_chemical_formula_sum            'C13 H16 S'
_chemical_formula_weight         204.32
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-02-06 deposited with the CCDC.    2019-07-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.396(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8311(9)
_cell_length_b                   7.0802(5)
_cell_length_c                   12.0660(8)
_cell_measurement_reflns_used    3463
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.8340
_cell_measurement_theta_min      3.2650
_cell_volume                     1096.13(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.847
_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    -79.00  11.00   1.00    1.00    --  -11.59 -57.00 150.00   90
  2  \w    -40.00  59.00   1.00    1.00    --  -11.59  57.00 -60.00   99
  3  \w    -12.00  77.00   1.00    1.00    --   11.74  77.00  60.00   89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0016145000
_diffrn_orient_matrix_UB_12      0.0815348000
_diffrn_orient_matrix_UB_13      -0.0340413000
_diffrn_orient_matrix_UB_21      0.0108384000
_diffrn_orient_matrix_UB_22      -0.0574611000
_diffrn_orient_matrix_UB_23      -0.0466528000
_diffrn_orient_matrix_UB_31      -0.0542196000
_diffrn_orient_matrix_UB_32      -0.0090306000
_diffrn_orient_matrix_UB_33      -0.0108579000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0452
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.847
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            7903
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.847
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.631
_diffrn_reflns_theta_min         3.175
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.252
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48601
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.238
_exptl_crystal_description       block
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.296
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         2619
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0512P)^2^+0.2366P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1006
_refine_ls_wR_factor_ref         0.1086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2201
_reflns_number_total             2619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01370a2.cif
_cod_data_source_block           hlj1027
_cod_depositor_comments          'Adding full bibliography for 7156971.cif.'
_cod_database_code               7156971
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.92
_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:
 C11(H11A,H11B), C9(H9A,H9B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C6(H6), C5(H5)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_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 2.140
_oxdiff_exptl_absorpt_empirical_full_min 0.668