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_7118445
_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_absolute_configuration syn
_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      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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.12 svn.r3133 for OlexSys, GUI svn.r4987)
;
_audit_update_record
;
2015-08-05 deposited with the CCDC.
2015-11-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.0524(3)
_cell_length_b                   17.7693(8)
_cell_length_c                   22.6194(7)
_cell_measurement_reflns_used    4278
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      30.2129
_cell_measurement_theta_min      2.9097
_cell_volume                     2834.6(2)
_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    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.885
_diffrn_measurement_details
;
  1 omega  -88.00  -60.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.6164 -178.0000   90.0000 28

  2 omega  -22.00   91.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       21.8664   19.0000   90.0000 113

  3 omega  -51.00    5.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.6164   77.0000    0.0000 56
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0758696000
_diffrn_orient_matrix_UB_12      0.0105519000
_diffrn_orient_matrix_UB_13      -0.0188535000
_diffrn_orient_matrix_UB_21      0.0154775000
_diffrn_orient_matrix_UB_22      0.0383395000
_diffrn_orient_matrix_UB_23      0.0072291000
_diffrn_orient_matrix_UB_31      0.0642945000
_diffrn_orient_matrix_UB_32      0.0032479000
_diffrn_orient_matrix_UB_33      -0.0239833000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0431
_diffrn_reflns_av_unetI/netI     0.0701
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.885
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            12242
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.801
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.280
_diffrn_reflns_theta_min         2.916
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.217
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.997
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform/pentane'
_exptl_crystal_size_max          0.2128
_exptl_crystal_size_mid          0.1273
_exptl_crystal_size_min          0.0856
_refine_diff_density_max         2.116
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details
;
 Flack x determined using 1951 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.05(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         6773
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0820
_refine_ls_R_factor_gt           0.0691
_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^)+(0.1072P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1650
_refine_ls_wR_factor_ref         0.1787
_reflns_Friedel_coverage         0.611
_reflns_Friedel_fraction_full    0.882
_reflns_Friedel_fraction_max     0.694
_reflns_number_gt                5679
_reflns_number_total             6773
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08690f2.cif
_cod_data_source_block           pac1202
_cod_original_cell_volume        2834.56(19)
_cod_database_code               7118445
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C15 H21 N1 O1 S1'
_chemical_oxdiff_usercomment     'Joshua jcs-1-25-2'
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_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:
 C7(H7), C8(H8), C22(H22), C23(H23)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C24(H24A,H24B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_olex2_date_sample_data_collection 2012-12-19
_olex2_date_sample_submission    11/12/2012
_olex2_exptl_crystal_mounting_method 'oil on loop'
_olex2_submission_special_instructions 'No special instructions were received'