Synthesis, structure and stereodynamics of atropisomeric <i>N</i>-chloroamides.
Campbell, Aaron D. G.; Roper, Natalie J.; Waddell, Paul G.; Wills, Corinne; Dixon, Casey M.; Denton, Ross M.; Ermanis, Kristaps; Armstrong, Roly J.; Chemical communications (Cambridge, England) 60 (2024) 3818–3821; doi:10.1039/d4cc00268g

data_7132811
_publ_section_title
;
 Synthesis, structure and stereodynamics of atropisomeric
 <i>N</i>-chloroamides.
;
_journal_issue                   28
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3818
_journal_page_last               3821
_journal_paper_doi               10.1039/d4cc00268g
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C18 H17 Cl F2.998 N O'
_chemical_formula_sum            'C18 H17 Cl F3 N O'
_chemical_formula_weight         355.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-21
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2023-11-13 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.551(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.21560(10)
_cell_length_b                   11.1571(3)
_cell_length_c                   24.7517(6)
_cell_measurement_reflns_used    9858
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      77.9080
_cell_measurement_theta_min      3.5570
_cell_volume                     1714.78(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.944
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -26.00  28.00   0.50    0.37    --  -49.76  19.00 120.00  108
  2  \w    -22.00  29.00   0.50    0.37    --  -49.76  19.00   0.00  102
  3  \w   -105.00 -45.00   0.50    0.37    --  -92.01  77.00 -30.00  120
  4  \w    -71.00 -17.00   0.50    0.37    --  -92.01  61.00-150.00  108
  5  \w    -51.00 -26.00   0.50    0.37    --  -92.01  45.00-180.00   50
  6  \w    -26.00  23.00   0.50    0.37    --  -49.76  19.00-150.00   98
  7  \w    -24.00  28.00   0.50    0.37    --  -49.76  19.00 -60.00  104
  8  \w   -108.00 -66.00   0.50    0.37    --  -92.01 109.00  -4.00   84
  9  \w   -110.00 -20.00   0.50    0.37    --  -92.01 125.00  30.00  180
 10  \w    -31.00  -1.00   0.50    0.37    --  -49.76 109.00  -4.00   60
 11  \w   -118.00 -37.00   0.50    0.37    --  -99.00 133.00 151.67  162
 12  \w   -171.00 -79.00   0.50    0.37    --  -92.01 -30.00  90.00  184
 13  \w   -103.00 -65.00   0.50    0.37    --  -92.01 -77.00 -60.00   76
 14  \w    -93.00 -68.00   0.50    0.37    --  -94.00 -75.00 -52.10   50
 15  \w   -104.00 -65.00   0.50    0.37    --  -92.01 -77.00-180.00   78
 16  \w   -160.00-122.00   0.50    0.37    --  -92.01 -77.00-180.00   76
 17  \w   -149.00 -82.00   0.50    0.37    --  -92.01-109.00-100.00  134
 18  \w   -122.00 -81.00   0.50    0.37    --  -49.76-125.00 -30.00   82
 19  \w     44.00  69.00   0.50    0.37    --  108.00 -77.00 -90.00   50
 20  \w     71.00  97.00   0.50    0.37    --  108.00 -77.00 -90.00   52
 21  \w     47.00 100.00   0.50    0.37    --  108.00 -77.00   0.00  106
 22  \w     41.00  91.00   0.50    0.37    --  108.00 -77.00  90.00  100
 23  \w     22.00  48.00   0.50    0.37    --   96.11 -45.00 120.00   52
 24  \w     20.00  51.00   0.50    0.37    --   96.11 -45.00  90.00   62
 25  \w     19.00  44.00   0.50    0.37    --   96.11 -45.00  30.00   50
 26  \w     19.00  50.00   0.50    0.37    --   96.11 -45.00 -30.00   62
 27  \w     19.00  51.00   0.50    0.37    --   96.11 -45.00 -90.00   64
 28  \w     25.00  50.00   0.50    0.37    --   96.11 -45.00-120.00   50
 29  \w     -8.00  25.00   0.50    0.37    --   48.76 -19.00 -90.00   66
 30  \w      1.00  69.00   0.50    0.37    --   48.76-109.00-100.00  136
 31  \w     79.00 106.00   0.50    0.37    --   96.11-109.00-100.00   54
 32  \w     49.00  74.00   0.50    0.37    --  108.00-109.00-100.00   50
 33  \w     37.00  71.00   0.50    0.37    --   96.11-109.00-100.00   68
 34  \w    136.00 177.00   0.50    0.37    --  108.00  45.00 150.00   82
 35  \w    101.00 126.00   0.50    0.37    --   96.11 109.00  -4.00   50
 36  \w     88.00 113.00   0.50    0.37    --  108.00 109.00  -4.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0669536000
_diffrn_orient_matrix_UB_12      0.0806550000
_diffrn_orient_matrix_UB_13      -0.0483839000
_diffrn_orient_matrix_UB_21      0.0214130000
_diffrn_orient_matrix_UB_22      -0.1073038000
_diffrn_orient_matrix_UB_23      -0.0385430000
_diffrn_orient_matrix_UB_31      -0.2380109000
_diffrn_orient_matrix_UB_32      -0.0323477000
_diffrn_orient_matrix_UB_33      0.0072576000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            18811
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.919
_diffrn_reflns_theta_min         3.575
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.295
_exptl_absorpt_correction_T_max  0.911
_exptl_absorpt_correction_T_min  0.735
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
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)
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    1.378
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.0011(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/1 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3491
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0361
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0471P)^2^+0.6771P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0986
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3099
_reflns_number_total             3491
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00268g3.cif
_cod_data_source_block           rja230010_fa
_cod_depositor_comments
'Adding full bibliography for 7132810--7132818.cif.'
_cod_database_code               7132811
_chemical_oxdiff_formula         'C18 H17 Cl1 F3 N1 O1'
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.620
_diffrn_oxdiff_digest_frames
;
01d3d39685bfae4f1fb6df4b80f1963ad10306085ac
;
_diffrn_oxdiff_digest_hkl
;
01cfcc104836c0b903f9c8f773220fe9051da0
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1C-C8 \\sim F1B-C8 \\sim F1A-C8 \\sim F3C-C8 \\sim F3A-C8 \\sim F3B-C8 \\sim
F2C-C8 \\sim F2B-C8 \\sim F2A-C8
 with sigma of 0.02
 F1A-F2A \\sim F1A-F3A \\sim F2A-F3A \\sim F1B-F2B \\sim F1B-F3B \\sim F2B-F3B
\\sim F1C-F2C \\sim F1C-F3C
 \\sim F2C-F3C
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1A \\sim F2A \\sim F3A \\sim F1B \\sim F2B \\sim F3B \\sim F1C \\sim F2C \\sim
F3C: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F1A(0.37372) F2A(0.37372) F3A(0.37372) F1B(0.49655) F2B(0.49655)
 F3B(0.49655) F1C(0.12892) F2C(0.12892) F3C(0.12892)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14)
6.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              30211
_shelx_hkl_checksum              46214
_shelx_shelxl_version_number     2019/1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.331
_oxdiff_exptl_absorpt_empirical_full_min 0.624