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_7156195
_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         'C30 H29 N3 O5 S2'
_chemical_formula_sum            'C30 H29 N3 O5 S2'
_chemical_formula_weight         575.68
_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     dual
_audit_creation_date             2017-03-15
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-03-15 deposited with the CCDC.
2018-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.4730(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.60010(10)
_cell_length_b                   17.1655(2)
_cell_length_c                   9.58080(10)
_cell_measurement_reflns_used    11186
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.4890
_cell_measurement_theta_min      4.0660
_cell_volume                     1410.06(3)
_computing_cell_refinement
;
CrysAlisPro 1.171.39.9g (Rigaku OD, 2015) 
;
_computing_data_collection
;
CrysAlisPro 1.171.39.9g (Rigaku OD, 2015) 
;
_computing_data_reduction
;
CrysAlisPro 1.171.39.9g (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_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 0.995
_diffrn_measured_fraction_theta_max 0.997
_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   -100.00  15.00   1.00    4.00    --  -19.10 -57.00  60.00  115
  2  \w   -104.00  17.00   1.00    4.00    --  -19.10 -72.00 -60.00  121
  3  \w    -43.00  17.00   1.00    4.00    --  -19.10 -72.00 120.00   60
  4  \w    -42.00  -2.00   1.00    4.00    --  -19.10  38.00 -90.00   40
  5  \w      9.00  64.00   1.00    4.00    --  -19.10  38.00 -90.00   55
  6  \w    -54.00  61.00   1.00    4.00    --  -19.10  57.00  30.00  115
;
_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_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0374620000
_diffrn_orient_matrix_UB_12      -0.0367879000
_diffrn_orient_matrix_UB_13      0.0053835000
_diffrn_orient_matrix_UB_21      -0.0734586000
_diffrn_orient_matrix_UB_22      -0.0185191000
_diffrn_orient_matrix_UB_23      0.0026351000
_diffrn_orient_matrix_UB_31      -0.0063782000
_diffrn_orient_matrix_UB_32      -0.0033583000
_diffrn_orient_matrix_UB_33      -0.0740350000
_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_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0259
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            17745
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.694
_diffrn_reflns_theta_min         3.879
_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    0.234
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       prism
_exptl_crystal_F_000             604
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.163
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 3183 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     363
_refine_ls_number_reflns         7251
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0310
_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^)+(0.0308P)^2^+0.2549P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0697
_refine_ls_wR_factor_ref         0.0704
_reflns_Friedel_coverage         0.936
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                7054
_reflns_number_total             7251
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob00683k2.cif
_cod_data_source_block           2017acc0012_k1_100k
_cod_depositor_comments
'Adding full bibliography for 7156195--7156203.cif.'
_cod_database_code               7156195
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C35 H35 N23 O3 S1'
_chemical_oxdiff_usercomment     'Caffeine Hydrate recollection'
_diffrn_measurement_device_type2 'Rigaku AFC12 (Right)'
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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:
 C1(H1), C4(H4), C8(H8), C23(H23)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30)
2.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder silicon oil'
_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 1.646
_oxdiff_exptl_absorpt_empirical_full_min 0.685