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_7156197
_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         'C24 H22 N2 O3 S2'
_chemical_formula_sum            'C24 H22 N2 O3 S2'
_chemical_formula_weight         450.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-11-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.11.07 svn.r3078 for OlexSys, GUI svn.r4941)
;
_audit_update_record
;
2018-03-19 deposited with the CCDC.
2018-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.3263(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3941(2)
_cell_length_b                   6.92520(11)
_cell_length_c                   21.6163(4)
_cell_measurement_reflns_used    24195
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.9040
_cell_measurement_theta_min      2.4270
_cell_volume                     2148.62(6)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_collection       'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_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      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.917
_diffrn_measurement_details
;
  1 omega -112.00   68.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0000    0.0000    0.0000 180

  2 omega  -45.00   57.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0000   72.0000  -90.0000 102

  3 omega  -84.00  -21.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0000  -54.0000  120.0000 63

  4 omega -112.00   -1.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0000    0.0000   30.0000 111
;
_diffrn_measurement_device       'four-circle \k diffractometer'
_diffrn_measurement_device_type  'Rigaku AFC12 FRE-HF'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMesh'
_diffrn_orient_matrix_UB_11      0.0269260000
_diffrn_orient_matrix_UB_12      0.0011782000
_diffrn_orient_matrix_UB_13      -0.0261620000
_diffrn_orient_matrix_UB_21      -0.0285449000
_diffrn_orient_matrix_UB_22      0.0747530000
_diffrn_orient_matrix_UB_23      -0.0134024000
_diffrn_orient_matrix_UB_31      0.0300804000
_diffrn_orient_matrix_UB_32      0.0699844000
_diffrn_orient_matrix_UB_33      0.0147656000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'Confocal mirrors, HF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0179
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.917
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            26689
_diffrn_reflns_point_group_measured_fraction_full 0.779
_diffrn_reflns_point_group_measured_fraction_max 0.654
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.054
_diffrn_reflns_theta_min         2.276
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.277
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95569
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) 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    1.393
_exptl_crystal_description       rod
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.183
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 2347 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     563
_refine_ls_number_reflns         9824
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0264
_refine_ls_R_factor_gt           0.0253
_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^)+(0.0402P)^2^+0.3568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0651
_refine_ls_wR_factor_ref         0.0657
_reflns_Friedel_coverage         0.331
_reflns_Friedel_fraction_full    0.516
_reflns_Friedel_fraction_max     0.351
_reflns_number_gt                9566
_reflns_number_total             9824
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob00683k2.cif
_cod_data_source_block           2014acc0007
_cod_depositor_comments
'Adding full bibliography for 7156195--7156203.cif.'
_cod_database_code               7156197
_diffrn_measurement_device_type2 'Rigaku AFC12 (Right)'
_reflns_odcompleteness_completeness 91.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.98
_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:
 C101(H101), C104(H104), C107(H107), C108(H108), C201(H201), C204(H204),
 C207(H207), C208(H208)
2.b Secondary CH2 refined with riding coordinates:
 C105(H10G,H10H), C205(H20G,H20H)
2.c Aromatic/amide H refined with riding coordinates:
 C114(H114), C115(H115), C116(H116), C117(H117), C118(H118), C120(H120),
 C121(H121), C122(H122), C123(H123), C124(H124), C214(H214), C215(H215),
 C216(H216), C217(H217), C218(H218), C220(H220), C221(H221), C222(H222),
 C223(H223), C224(H224)
2.d Idealised Me refined as rotating group:
 C102(H10A,H10B,H10C), C103(H10D,H10E,H10F), C202(H20A,H20B,H20C), C203(H20D,
 H20E,H20F)
;
_shelx_res_checksum              47559
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_submission    08/11/2014
_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_original_sample_id caqnphrfalto
_olex2_submission_special_instructions 'No special instructions were received'