Mechanistic interrogation of the asymmetric lithiation-trapping of N-thiopivaloyl azetidine and pyrrolidine.
Rayner, Peter J.; Smith, Joshua C.; Denneval, Charline; O'Brien, Peter; Clarke, Paul A.; Horan, Richard A. J.; Chemical communications (Cambridge, England) 52 (2016) 1354–1357; doi:10.1039/c5cc08690f

data_7118444
_publ_section_title
;
 Mechanistic interrogation of the asymmetric lithiation-trapping of
 N-thiopivaloyl azetidine and pyrrolidine.
;
_journal_issue                   7
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1354
_journal_page_last               1357
_journal_paper_doi               10.1039/c5cc08690f
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C15 H21 N O S'
_chemical_formula_sum            'C15 H21 N O S'
_chemical_formula_weight         263.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-12-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_audit_update_record
;
2015-08-05 deposited with the CCDC.
2015-11-24 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 100.4273(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.24752(10)
_cell_length_b                   12.75550(14)
_cell_length_c                   13.60131(17)
_cell_measurement_reflns_used    9517
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      29.9654
_cell_measurement_theta_min      2.9701
_cell_volume                     1407.24(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9960
_diffrn_measured_fraction_theta_max 0.9884
_diffrn_measurement_details
;
  1 omega  -97.00   31.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740    0.0000  -30.0000 128

  2 omega  -60.00   19.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740   97.0000  -44.0000 79

  3 omega   64.00  102.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3240  178.0000  150.0000 38

  4 omega  -94.00   -4.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740  -57.0000  150.0000 90

  5 omega -102.00  -34.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740  178.0000   30.0000 68

  6 omega  -95.00  -70.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740  -77.0000   30.0000 25

  7 omega  -95.00    5.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740  -77.0000  -90.0000 100
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0138358000
_diffrn_orient_matrix_UB_12      -0.0540225000
_diffrn_orient_matrix_UB_13      -0.0077575000
_diffrn_orient_matrix_UB_21      -0.0460594000
_diffrn_orient_matrix_UB_22      0.0038465000
_diffrn_orient_matrix_UB_23      -0.0492253000
_diffrn_orient_matrix_UB_31      0.0730132000
_diffrn_orient_matrix_UB_32      0.0126909000
_diffrn_orient_matrix_UB_33      -0.0180961000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15785
_diffrn_reflns_theta_full        29.97
_diffrn_reflns_theta_max         30.03
_diffrn_reflns_theta_min         2.98
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.969
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.243
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             568
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform/pentane'
_exptl_crystal_size_max          0.1998
_exptl_crystal_size_mid          0.1883
_exptl_crystal_size_min          0.1512
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     170
_refine_ls_number_reflns         4109
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0377
_refine_ls_R_factor_gt           0.0330
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0386P)^2^+0.5714P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0841
_refine_ls_wR_factor_ref         0.0879
_reflns_number_gt                3647
_reflns_number_total             4109
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5cc08690f2.cif
_cod_data_source_block           pac1201
_cod_database_code               7118444
_chemical_oxdiff_formula         'C15 H21 N1 O1 S1'
_chemical_oxdiff_usercomment     'Joshua jcs-1-25-1'
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H9 of C9, H8 of C8, H7 of C7, H3 of C3, H4 of C4, {H2A,H2B} of C2, H6 of C6,
   H10 of C10, {H1A,H1B} of C1
 At 1.5 times of:
  {H15A,H15B,H15C} of C15, {H14A,H14B,H14C} of C14, {H13A,H13B,H13C} of C13
2.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C1(H1A,H1B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C10(H10), C9(H9), C7(H7), C8(H8)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C13(H13A,H13B,H13C)
;