Effects of thionation and fluorination on cis-trans isomerization in tertiary amides: an investigation of N-alkylglycine (peptoid) rotamers.
Engel-Andreasen, Jens; Wich, Kathrine; Laursen, Jonas S.; Harris, Pernille; Olsen, Christian A.; The Journal of organic chemistry 80 (2015) 5415–5427; doi:10.1021/acs.joc.5b00048

data_4030995
_publ_section_title
;
 Effects of thionation and fluorination on cis-trans isomerization in
 tertiary amides: an investigation of N-alkylglycine (peptoid) rotamers.
;
_journal_issue                   11
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5415
_journal_page_last               5427
_journal_paper_doi               10.1021/acs.joc.5b00048
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H20 F2 N2 O2'
_chemical_formula_sum            'C18 H20 F2 N2 O2'
_chemical_formula_weight         334.36
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                72.375(5)
_cell_angle_beta                 78.013(5)
_cell_angle_gamma                74.229(5)
_cell_formula_units_Z            2
_cell_length_a                   7.3111(4)
_cell_length_b                   8.9012(5)
_cell_length_c                   14.1362(8)
_cell_measurement_reflns_used    6979
_cell_measurement_temperature    120.3(5)
_cell_measurement_theta_max      28.4610
_cell_measurement_theta_min      3.3670
_cell_volume                     835.84(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_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      120.3(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3073
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.887
_diffrn_measurement_details
;
  1 omega   -3.00   84.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161   38.0000  -60.0000 87

  2 omega   50.00   80.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161   38.0000  -30.0000 30

  3 omega  -13.00   85.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161   38.0000 -150.0000 98

  4 omega  -20.00   52.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161  -99.0000  -90.0000 72

  5 omega  -17.00   52.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161  -99.0000   30.0000 69

  6 omega  -52.00   39.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161  -57.0000  150.0000 91

  7 omega  -21.00   84.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -       10.7161   77.0000   60.0000 105

  8 omega  -84.00  -40.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -      -11.5754  150.0000  -41.0385 44

  9 omega  -80.00  -53.00   1.0000   12.3200
omega____ theta____ kappa____ phi______ frames
    -      -11.5754  145.0000   32.4748 27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0770943000
_diffrn_orient_matrix_UB_12      -0.0408277000
_diffrn_orient_matrix_UB_13      0.0282143000
_diffrn_orient_matrix_UB_21      -0.0554078000
_diffrn_orient_matrix_UB_22      -0.0553892000
_diffrn_orient_matrix_UB_23      0.0309835000
_diffrn_orient_matrix_UB_31      0.0366464000
_diffrn_orient_matrix_UB_32      -0.0512399000
_diffrn_orient_matrix_UB_33      -0.0326876000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.887
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14006
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.830
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.518
_diffrn_reflns_theta_min         2.923
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87983
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       irregular
_exptl_crystal_F_000             352
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 2728 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.0(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     439
_refine_ls_number_reflns         7733
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0522
_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^)+(0.1000P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1508
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.772
_reflns_number_gt                6603
_reflns_number_total             7733
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00048_si_002.cif
_cod_data_source_block           compound_13
_cod_depositor_comments
'Adding full bibliography for 4030982--4030996.cif.'
_cod_database_code               4030995
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C20 H20 N2 F2 S Cl3'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C1B(H), C1A(H1A), C7A(H7A), C7B(HE)
2.b Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C3B(HF,HG)
2.c Aromatic/amide H refined with riding coordinates:
 C16A(H16A), C10A(H10A), C15B(HD), C11A(H11A), C15A(H15A), C14A(H14A),
 C17A(H17A), C12A(H12A), C10B(HH), C16B(HI), C12B(HJ), C17B(HQ), C11B(HR),
 C14B(HS)
2.d Idealised Me refined as rotating group:
 C6A(H6AA,H6AB,H6AC), C5B(HA,HB,HC), C8A(H8AA,H8AB,H8AC), C5A(H5AA,H5AB,H5AC),
 C6B(HK,HL,HM), C8B(HN,HO,HP)
;
_shelx_res_checksum              58979
_shelx_hkl_checksum              13726
_olex2_submission_special_instructions 'No special instructions were received'