The Anancomeric Character of the Pharmacophore 1,3,4-Thiadiazoline Framework in Chiral Spiro-Cyclohexyl Derivatives: Effects on Stereochemistry and Spiro-Junction Lability. Thermodynamic Aspects.
Menta, Sergio; Carradori, Simone; Secci, Daniela; Faggi, Cristina; Mannina, Luisa; Cirilli, Roberto; Pierini, Marco; The Journal of organic chemistry 80 (2015) 11932–11940; doi:10.1021/acs.joc.5b01635

data_4031756
_publ_section_title
;
 The Anancomeric Character of the Pharmacophore 1,3,4-Thiadiazoline
 Framework in Chiral Spiro-Cyclohexyl Derivatives: Effects on
 Stereochemistry and Spiro-Junction Lability. Thermodynamic Aspects.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11932
_journal_page_last               11940
_journal_paper_doi               10.1021/acs.joc.5b01635
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H25 N3 O2 S'
_chemical_formula_sum            'C15 H25 N3 O2 S'
_chemical_formula_weight         311.44
_chemical_name_systematic
;
(5S,6S)-(+)-N-(6-tert-butyl-1-formyl-4-thia-1,2-
diazaspiro[4.5]dec-2-en-3-yl)acetamide
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date
;
'Wed May 09 22:13:55 2012'
;
_audit_creation_method
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.6020(10)
_cell_length_b                   11.7940(10)
_cell_length_c                   15.0170(10)
_cell_measurement_reflns_used    5521
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.9999
_cell_measurement_theta_min      4.6014
_cell_volume                     1700.6(3)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_data_reduction
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
;
_computing_molecular_graphics    Ortep3
_computing_publication_material  Ciftab
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR2004 J.Appl.Cryst.38,381-388'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 8.1241
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details
;
  1 omega   44.00  113.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       46.4074   37.0000 -180.0000 69

  2 omega  -24.00   61.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       46.4074  -37.0000    0.0000 85

  3 omega  -63.00  -29.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000   45.0000 -180.0000 34

  4 omega   40.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -77.0000  -90.0000 75

  5 omega   79.00  118.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000  -60.0000 39

  6 omega   87.00  167.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000  -30.0000 80

  7 omega   32.00   76.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -45.0000  -30.0000 44

  8 omega   77.00  169.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000   30.0000 92

  9 omega   31.00   57.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -45.0000 -180.0000 26

 10 omega   16.00  118.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       46.4074   77.0000  -90.0000 102

 11 omega   16.00  118.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       46.4074   77.0000   60.0000 102

 12 omega   21.00   59.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -90.0000  107.0000 38
;
_diffrn_measurement_device_type  'Xcalibur, Onyx'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_sigmaI/netI    0.0320
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            9397
_diffrn_reflns_theta_full        72.15
_diffrn_reflns_theta_max         72.15
_diffrn_reflns_theta_min         4.77
_diffrn_source                   'Enhance (Cu) X-ray Source'
_diffrn_standards_decay_%        50
_diffrn_standards_interval_count 200
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    1.755
_exptl_absorpt_correction_T_max  0.9322
_exptl_absorpt_correction_T_min  0.8690
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET)
(compiled Oct 25 2010,18:11:34)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             672
_exptl_crystal_recrystallization_method acetone-water
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.03(2)
_refine_ls_extinction_coef       0.0063(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     195
_refine_ls_number_reflns         3220
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0387
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0609P)^2^+0.3742P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1133
_reflns_number_gt                2681
_reflns_number_total             3220
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5b01635_si_002.cif
_cod_data_source_block           exp_713
_cod_depositor_comments
'Adding full bibliography for 4031753--4031756.cif.'
_cod_database_code               4031756