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_4030987
_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_formula_moiety         'C19 H22 N2 O S'
_chemical_formula_sum            'C19 H22 N2 O S'
_chemical_formula_weight         326.44
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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     direct
_audit_creation_date             2014-09-24
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4866)
;
_cell_angle_alpha                78.273(3)
_cell_angle_beta                 86.460(3)
_cell_angle_gamma                78.272(3)
_cell_formula_units_Z            2
_cell_length_a                   8.6606(3)
_cell_length_b                   8.8909(2)
_cell_length_c                   11.7871(4)
_cell_measurement_reflns_used    10387
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      73.7910
_cell_measurement_theta_min      3.8190
_cell_volume                     869.92(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3073
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
  1 omega  -40.00  -13.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554  -57.0000  -60.0000 27

  2 omega  -56.00  -23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554  -38.0000    0.0000 33

  3 omega  -50.00   28.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554   38.0000  120.0000 78

  4 omega  -16.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0554  -77.0000    0.0000 58

  5 omega   30.00   97.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0554 -125.0000 -120.0000 67

  6 omega   39.00   96.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310  -45.0000    0.0000 57

  7 omega   40.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310  -95.0000    0.0000 67

  8 omega   87.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310 -121.0000   -4.0000 31

  9 omega   44.00  139.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310  -77.0000  150.0000 95

 10 omega   47.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310 -125.0000  150.0000 71

 11 omega   33.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310 -121.0000   -4.0000 51

 12 omega  115.00  143.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   60.0000   31.2198 28

 13 omega  123.00  174.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   76.0000   19.3171 51

 14 omega  124.00  150.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000  -60.0000 26

 15 omega  112.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000  -90.0000 65

 16 omega  102.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   76.0000  -78.0893 26

 17 omega   83.00  138.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   76.0000  -14.6076 55

 18 omega  104.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000   60.0000 72

 19 omega  145.00  171.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000  150.0000 26

 20 omega  114.00  148.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000   90.0000 34

 21 omega   89.00  126.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000  109.8675 37

 22 omega   79.00  112.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   61.0000   60.0000 33

 23 omega   79.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000   90.0000 31

 24 omega   79.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   61.0000   90.0000 26

 25 omega   74.00  100.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000   30.0000 26

 26 omega   78.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   61.0000    0.0000 99

 27 omega   78.00  171.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   61.0000  -30.0000 93

 28 omega   74.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000  -60.0000 29

 29 omega   77.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000  -90.0000 28

 30 omega   74.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000 -120.0000 73

 31 omega   75.00  133.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000 -180.0000 58

 32 omega   74.00  140.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000 -150.0000 66

 33 omega   57.00   88.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       86.0000   72.0000  -66.5393 31

 34 omega   42.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   75.0000  -57.5794 28

 35 omega   30.00   57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   76.0000  -14.6076 27

 36 omega   41.00   73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   60.0000   31.2198 32

 37 omega   66.00   92.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   76.0000   19.3171 26

 38 omega   74.00  100.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000   60.0000 26

 39 omega   68.00  161.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   71.0000  135.7158 93

 40 omega   77.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6310   77.0000  150.0000 38

 41 omega   43.00   72.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   71.0000  143.2849 29

 42 omega   40.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   65.0000  111.0559 25

 43 omega   26.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000  109.8675 58

 44 omega   21.00   46.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   78.0000   46.4123 25

 45 omega   11.00   36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   84.0000  112.9472 25

 46 omega   16.00   41.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   81.0000   88.8855 25

 47 omega    7.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   84.0000  122.2130 26

 48 omega    9.00   34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   81.0000   23.1961 25

 49 omega   20.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   81.0000  -38.1713 25

 50 omega   34.00   59.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   76.0000  -78.0893 25

 51 omega   34.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   75.0000 -113.4248 29

 52 omega   53.00   79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000   64.0000 -157.8636 26

 53 omega   54.00   80.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000   57.0000 -176.0734 26

 54 omega   26.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000 -175.4040 27

 55 omega   20.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   81.0000 -141.5597 25

 56 omega    0.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.0000   93.0000  -81.3435 25

 57 omega -105.00  -47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554  -57.0000  -60.0000 58

 58 omega -112.00  -70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554  -38.0000    0.0000 42

 59 omega -106.00  -79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554  -38.0000  150.0000 27

 60 omega  -68.00  -24.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0554  -38.0000  150.0000 44
;
_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      -0.0149331000
_diffrn_orient_matrix_UB_12      0.0784909000
_diffrn_orient_matrix_UB_13      0.1063289000
_diffrn_orient_matrix_UB_21      0.0449056000
_diffrn_orient_matrix_UB_22      -0.1620495000
_diffrn_orient_matrix_UB_23      0.0794848000
_diffrn_orient_matrix_UB_31      0.1754453000
_diffrn_orient_matrix_UB_32      0.0116864000
_diffrn_orient_matrix_UB_33      -0.0142424000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_laue_measured_fraction_full 0.995
_diffrn_reflns_laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13664
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.953
_diffrn_reflns_theta_min         3.831
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.688
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69366
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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    1.246
_exptl_crystal_description       block
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.275
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         3444
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0424P)^2^+0.7801P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1060
_refine_ls_wR_factor_ref         0.1072
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3274
_reflns_number_total             3444
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00048_si_002.cif
_cod_data_source_block           compound_5c
_cod_depositor_comments
'Adding full bibliography for 4030982--4030996.cif.'
_cod_database_code               4030987
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C19 H22 N2 O1 S1'
_reflns_odcompleteness_completeness 99.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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,H,H,H) groups
2. Others
 Fixed Sof: H6A(0.5) H6B(0.5) H6C(0.5) H6D(0.5) H6E(0.5) H6F(0.5) H2A(0.5)
 H2B(0.5) H2C(0.5) H2D(0.5) H2E(0.5) H2F(0.5) H1A(0.5) H1B(0.5) H1C(0.5)
 H1D(0.5) H1E(0.5) H1F(0.5)
3.a Ternary CH refined with riding coordinates:
 C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
3.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C9(H9), C17(H17), C15(H15), C19(H19), C18(H18), C16(H16), C12(H12),
 C10(H10), C11(H11)
3.d Disordered Me refined as rotating group:
 C6(H6A,H6B,H6C,H6D,H6E,H6F), C2(H2A,H2B,H2C,H2D,H2E,H2F), C1(H1A,H1B,H1C,H1D,
 H1E,H1F)
;
_shelx_res_checksum              81200
_shelx_hkl_checksum              956
_olex2_submission_special_instructions 'No special instructions were received'