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_7132814
_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         'C19 H22 Cl N O'
_chemical_formula_sum            'C19 H22 Cl N O'
_chemical_formula_weight         315.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-11-13 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.509(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7373(9)
_cell_length_b                   6.1891(2)
_cell_length_c                   18.0916(11)
_cell_measurement_reflns_used    12633
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      77.1450
_cell_measurement_theta_min      4.4180
_cell_volume                     1755.30(17)
_computing_cell_refinement       'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.930
_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    -82.00  -1.00   0.50    2.00    --  -48.75 -24.00  99.00  162
  2  \w   -117.00 -91.00   0.50    2.00    --  -48.75 -24.00  99.00   52
  3  \w    -21.00   5.00   0.50    2.00    --  -48.75  24.00 -95.00   52
  4  \w      6.00  34.00   0.50    2.00    --  -48.75  24.00 -95.00   56
  5  \w    -71.00 -45.00   0.50    2.00    --  -92.21 -24.00  99.00   52
  6  \w     98.00 152.00   0.50    2.00    --   96.68  24.00 -95.00  108
  7  \w     47.00  96.00   0.50    2.00    --   48.00  38.00 -60.00   98
  8  \w     43.00  68.00   0.50    2.00    --   48.00  24.00 -95.00   50
  9  \w    -25.00  34.00   0.50    2.00    --  -48.75  19.00   0.00  118
 10  \w   -126.00 -28.00   0.50    2.00    --  -48.75 -57.00  30.00  196
 11  \w     17.00  42.00   0.50    2.00    --   54.00  87.00  -7.61   50
 12  \w     17.00  42.00   0.50    2.00    --   54.00  88.00   6.56   50
 13  \w     17.00  42.00   0.50    2.00    --   54.00  88.00  50.90   50
 14  \w    -83.00 -55.00   0.50    2.00    --  -78.00 -67.00  27.38   56
 15  \w    -80.00 -51.00   0.50    2.00    --  -82.00 -77.00 -17.10   58
 16  \w    -76.00 -51.00   0.50    2.00    --  -82.00 -76.00 -45.79   50
 17  \w    -82.00 -56.00   0.50    2.00    --  -86.00 -76.00   6.40   52
 18  \w   -152.00 -94.00   0.50    2.00    --  -86.00 -77.00  -1.03  116
 19  \w    -90.00 -55.00   0.50    2.00    --  -86.00 -77.00  -1.03   70
 20  \w   -161.00 -60.00   0.50    2.00    --  -90.00 -77.00 -16.27  202
 21  \w    -88.00 -60.00   0.50    2.00    --  -90.00 -74.00  13.50   56
 22  \w   -122.00 -97.00   0.50    2.00    --  -90.00 -74.00  13.50   50
 23  \w   -103.00 -62.00   0.50    2.00    --  -90.00 -75.00 -46.06   82
 24  \w    -62.00 -21.00   0.50    2.00    --  -92.21 125.00 120.00   82
 25  \w    -92.00 -66.00   0.50    2.00    --  -92.21 125.00 120.00   52
 26  \w    -51.00 -16.00   0.50    2.00    --  -92.21  45.00 -30.00   70
 27  \w    -68.00 -23.00   0.50    2.00    --  -92.21  61.00  60.00   90
 28  \w    -93.00 -67.00   0.50    2.00    --  -92.21 -77.00  60.00   52
 29  \w    -35.00 -10.00   0.50    2.00    --  -92.21  30.00 -60.00   50
 30  \w   -168.00 -70.00   0.50    2.00    --  -92.21 -61.00  60.00  196
 31  \w    -35.00 -10.00   0.50    2.00    --  -92.21  30.00  90.00   50
 32  \w    -87.00 -62.00   0.50    2.00    --  -92.21 -77.00 -30.00   50
 33  \w    -89.00 -61.00   0.50    2.00    --  -92.21 -77.00  30.00   56
 34  \w    -70.00 -15.00   0.50    2.00    --  -92.21  61.00   0.00  110
 35  \w     19.00  50.00   0.50    2.00    --   96.68 -45.00 -30.00   62
 36  \w   -154.00 -69.00   0.50    2.00    --  -99.00 -75.00 -41.16  170
 37  \w     34.00  59.00   0.50    2.00    --  108.19 -61.00-180.00   50
 38  \w     35.00  60.00   0.50    2.00    --  108.19 -61.00  30.00   50
 39  \w     34.00  60.00   0.50    2.00    --  108.19 -61.00 120.00   52
 40  \w     61.00  87.00   0.50    2.00    --  108.19-125.00  60.00   52
 41  \w     39.00 105.00   0.50    2.00    --  108.19 -95.00 -60.00  132
 42  \w     31.00  57.00   0.50    2.00    --  108.19-125.00  60.00   52
 43  \w    148.00 174.00   0.50    2.00    --  108.19  77.00   0.00   52
 44  \w     81.00 123.00   0.50    2.00    --  108.19  77.00   0.00   84
 45  \w    119.00 144.00   0.50    2.00    --  108.19  24.00 -95.00   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      -0.0918998000
_diffrn_orient_matrix_UB_12      0.0783270000
_diffrn_orient_matrix_UB_13      -0.0438903000
_diffrn_orient_matrix_UB_21      -0.0168383000
_diffrn_orient_matrix_UB_22      0.0019995000
_diffrn_orient_matrix_UB_23      0.0784042000
_diffrn_orient_matrix_UB_31      0.0306426000
_diffrn_orient_matrix_UB_32      0.2362214000
_diffrn_orient_matrix_UB_33      0.0138874000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            20357
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.948
_diffrn_reflns_theta_min         4.463
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.923
_exptl_absorpt_correction_T_max  0.936
_exptl_absorpt_correction_T_min  0.787
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.60a (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    1.195
_exptl_crystal_description       prism
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.437
_refine_diff_density_rms         0.049
_refine_ls_extinction_coef       0.0020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.148
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     233
_refine_ls_number_reflns         3493
_refine_ls_number_restraints     234
_refine_ls_restrained_S_all      1.180
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0611P)^2^+0.8242P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3016
_reflns_number_total             3493
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00268g3.cif
_cod_data_source_block           rja220003_fa
_cod_depositor_comments
'Adding full bibliography for 7132810--7132818.cif.'
_cod_database_code               7132814
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H22 Cl1 N1 O1'
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.635
_reflns_odcompleteness_completeness 99.91
_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) groups
2. Restrained distances
 C19B-C16 \\sim C19A-C16 \\sim C18B-C16 \\sim C18A-C16 \\sim C17B-C16 \\sim
C17A-C16
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C17A \\sim C18A \\sim C19A \\sim C17B \\sim C18B \\sim C19B: 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: C17A(0.71929) H17A(0.71929) H17B(0.71929) H17C(0.71929)
 C18A(0.71929) H18A(0.71929) H18B(0.71929) H18C(0.71929) C19A(0.71929)
 H19A(0.71929) H19B(0.71929) H19C(0.71929) C17B(0.28071) H17D(0.28071)
 H17E(0.28071) H17F(0.28071) C18B(0.28071) H18D(0.28071) H18E(0.28071)
 H18F(0.28071) C19B(0.28071) H19D(0.28071) H19E(0.28071) H19F(0.28071)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14), C15(H15)
6.c Idealised Me refined as rotating group:
 C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C17B(H17D,
 H17E,H17F), C18B(H18D,H18E,H18F), C19B(H19D,H19E,H19F)
;
_shelx_res_checksum              51376
_shelx_hkl_checksum              23169
_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 1.995
_oxdiff_exptl_absorpt_empirical_full_min 0.505