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_7118447
_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 ad
_chemical_formula_moiety         'C9 H15 N O2 S'
_chemical_formula_sum            'C9 H15 N O2 S'
_chemical_formula_weight         201.28
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-05-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2015-08-05 deposited with the CCDC.
2015-11-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.266(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6985(3)
_cell_length_b                   6.50545(16)
_cell_length_c                   17.1860(5)
_cell_measurement_reflns_used    3995
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      31.8520
_cell_measurement_theta_min      3.5710
_cell_volume                     1081.31(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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_environment      N~2~
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0326108000
_diffrn_orient_matrix_UB_12      -0.0095958000
_diffrn_orient_matrix_UB_13      -0.0354321000
_diffrn_orient_matrix_UB_21      -0.0655598000
_diffrn_orient_matrix_UB_22      -0.0113799000
_diffrn_orient_matrix_UB_23      -0.0207067000
_diffrn_orient_matrix_UB_31      -0.0038697000
_diffrn_orient_matrix_UB_32      0.1080384000
_diffrn_orient_matrix_UB_33      -0.0053068000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0447
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10292
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         29.992
_diffrn_reflns_theta_min         3.053
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.270
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.950
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.236
_exptl_crystal_description       plank
_exptl_crystal_F_000             432
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethyl acetate/pentane'
_exptl_crystal_size_max          0.2111
_exptl_crystal_size_mid          0.1102
_exptl_crystal_size_min          0.0427
_refine_diff_density_max         0.532
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2296 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         6093
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0556P)^2^+0.0836P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1047
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.923
_reflns_number_gt                5582
_reflns_number_total             6093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc08690f2.cif
_cod_data_source_block           pac1403
_cod_database_code               7118447
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C9 H15 N1 O2 S1'
_chemical_oxdiff_usercomment     'Joshua Smith 3-69-1-F'
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_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, All O(H) groups
2.a Riding coordinates:
 O2(H2A)
2.b Ternary CH refined with riding coordinates:
 C2(H2), C11(H11)
2.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C12(H12A,H12B), C13(H13A,H13B)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              17090