Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor-acceptor interactions.
García de la Concepción, Juan; Ávalos, Martín; Cintas, Pedro; Jiménez, José L; Light, Mark E.; Organic & biomolecular chemistry 16 (2018) 3438–3452; doi:10.1039/c8ob00683k

data_7156196
_publ_section_title
;
 Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic
 thioisom\"unchnones with alkenes. A computational rationale focused on
 donor-acceptor interactions.
;
_journal_issue                   18
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3438
_journal_page_last               3452
_journal_paper_doi               10.1039/c8ob00683k
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H17 N O5 S2'
_chemical_formula_sum            'C17 H17 N O5 S2'
_chemical_formula_weight         379.43
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-10-22
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.10.16 svn.r3037 for OlexSys, GUI svn.r4914)
;
_audit_update_record
;
2018-03-19 deposited with the CCDC.
2018-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.84070(10)
_cell_length_b                   14.9477(4)
_cell_length_c                   19.3104(6)
_cell_measurement_reflns_used    13829
_cell_measurement_temperature    120
_cell_measurement_theta_max      30.5
_cell_measurement_theta_min      1.4
_cell_volume                     1685.90(7)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.0 r13 (Rigaku, 2011)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r13 (Rigaku, 2011)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.0 r13 (Rigaku, 2011)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
scan:
    Number of images: 36
               Slice: 20.0000 - 200.0000
         Image width: 5.0000
            Exp time: 780.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 54.0000
                 Phi: 270.0000
                 XTD: 127.4000
              2theta: -0.0449
scan:
    Number of images: 27
               Slice: 53.0000 - 188.0000
         Image width: 5.0000
            Exp time: 780.0000
       Rotation axis: Omega
               Omega: 0.0000
               Kappa: 0.0000
                 Phi: 0.0000
                 XTD: 127.4000
              2theta: -0.0449
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS Spider'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support Mitegen
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.166520
_diffrn_orient_matrix_UB_12      0.009944
_diffrn_orient_matrix_UB_13      0.038548
_diffrn_orient_matrix_UB_21      -0.004212
_diffrn_orient_matrix_UB_22      -0.057958
_diffrn_orient_matrix_UB_23      0.033147
_diffrn_orient_matrix_UB_31      0.011591
_diffrn_orient_matrix_UB_32      -0.025689
_diffrn_orient_matrix_UB_33      -0.043445
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            21760
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.695
_diffrn_reflns_theta_min         2.923
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.345
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
Jacobson, R. (1998). REQAB. Private communication to the 
Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.495
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.62
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 1806 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.030(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         4321
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0228
_refine_ls_R_factor_gt           0.0226
_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^)+(0.0322P)^2^+0.1987P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0601
_refine_ls_wR_factor_ref         0.0602
_reflns_Friedel_coverage         0.737
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                4287
_reflns_number_total             4321
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob00683k2.cif
_cod_data_source_block           2014acc0005
_cod_depositor_comments
'Adding full bibliography for 7156195--7156203.cif.'
_cod_database_code               7156196
_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 Ternary CH refined with riding coordinates:
 C6(H6), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C13(H13), C16(H16), C14(H14), C15(H15)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              27346
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'