Axially chiral dimethylaminobenzimidazoles and their preliminary evaluation as acyl-transfer reagents.
Toman, Daniel; Nemec, Ivan; Kurka, Ondřej; Přibylka, Adam; Cankař, Petr; Organic & biomolecular chemistry 23 (2025) 2672–2682; doi:10.1039/d4ob02052a

data_7160366
_publ_section_title
;
 Axially chiral dimethylaminobenzimidazoles and their preliminary
 evaluation as acyl-transfer reagents.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2672
_journal_page_last               2682
_journal_paper_doi               10.1039/d4ob02052a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C23 H24 N4, C2 H6 O'
_chemical_formula_sum            'C25 H30 N4 O'
_chemical_formula_weight         402.53
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2024-12-02 deposited with the CCDC.	2025-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.455(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.4550(2)
_cell_length_b                   13.9094(2)
_cell_length_c                   10.4634(2)
_cell_measurement_reflns_used    13763
_cell_measurement_temperature    89.9(4)
_cell_measurement_theta_max      68.2460
_cell_measurement_theta_min      4.2150
_cell_volume                     1083.03(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.115a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.57a 64-bit (release 20-05-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.115a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      89.9(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -53.00 -24.00   0.50    2.00    --  -42.75 136.00 -45.00   58
  2  \w    -91.00 -57.00   0.50    2.00    --  -42.75 136.00 -45.00   68
  3  \w    -64.00 -24.00   0.50    2.00    --  -42.75 133.00 136.00   80
  4  \w     34.00  99.00   0.50    2.00    --   44.32-136.00-110.00  130
  5  \w     31.00  58.00   0.50    2.00    --   44.32-133.00  67.00   54
  6  \w    -99.00 -74.00   0.50    6.20    --  -93.31 136.00 -45.00   50
  7  \w   -130.00-105.00   0.50    6.20    --  -93.31-136.00-110.00   50
  8  \w    -94.00 -67.00   0.50    6.20    --  -93.31 133.00 136.00   54
  9  \w     74.00 108.00   0.50    6.20    --   94.87-133.00  67.00   68
 10  \w     94.00 121.00   0.50    6.20    --   94.87 136.00 -45.00   54
 11  \w     90.00 115.00   0.50    6.20    --   94.87 133.00 136.00   50
 12  \w     66.00 120.00   0.50    6.20    --   94.87-136.00-110.00  108
 13  \w    -55.00 -16.00   0.50    2.00    --   -4.00 129.00  56.70   78
 14  \w    -35.00 -10.00   0.50    2.00    --    8.00 118.00-127.58   50
 15  \w    -12.00  14.00   0.50    2.00    --   20.00 100.00  62.69   52
 16  \w     -9.00  16.00   0.50    2.00    --   24.00 101.00-126.93   50
 17  \w      4.00  29.00   0.50    2.00    --   36.00  96.00  82.18   50
 18  \w      5.00  30.00   0.50    2.00    --   36.00  94.00  32.07   50
 19  \w      4.00  30.00   0.50    2.00    --   36.00  96.00-162.82   52
 20  \w      4.00  29.00   0.50    2.00    --   36.00  95.00 134.90   50
 21  \w      4.00  29.00   0.50    2.00    --   36.00  96.00 -18.87   50
 22  \w     12.00  39.00   0.50    2.00    --   40.00  89.00 169.33   54
 23  \w     12.00  37.00   0.50    2.00    --   40.00  85.00   3.07   50
 24  \w     11.00  36.00   0.50    2.00    --   40.00  89.00 -99.97   50
 25  \w     11.00  36.00   0.50    2.00    --   40.00  87.00 141.78   50
 26  \w     10.00  35.00   0.50    2.00    --   40.00  90.00 -57.31   50
 27  \w     11.00  36.00   0.50    2.00    --   40.00  89.00 -78.98   50
 28  \w      9.00  34.00   0.50    2.00    --   40.00  93.00-147.87   50
 29  \w     17.00  42.00   0.50    2.00    --   44.00  83.00-148.67   50
 30  \w     15.00  40.00   0.50    2.00    --   44.00  89.00-134.86   50
 31  \w     15.00  40.00   0.50    2.00    --   44.00  88.00 -96.06   50
 32  \w     14.00  39.00   0.50    2.00    --   44.00  92.00 139.30   50
 33  \w     17.00  42.00   0.50    2.00    --   44.00  83.00 -47.86   50
 34  \w     14.00  39.00   0.50    2.00    --   44.32  92.00  71.29   50
 35  \w     16.00  41.00   0.50    2.00    --   44.32  87.00   2.61   50
 36  \w     83.00 108.00   0.50    2.00    --   44.32  77.00  60.00   50
 37  \w     21.00  52.00   0.50    2.00    --   44.32  77.00  60.00   62
 38  \w     23.00  50.00   0.50    2.00    --   48.00  76.00 -79.87   54
 39  \w    -49.00 -24.00   0.50    2.00    --  -48.00 -72.00  50.87   50
 40  \w     90.00 120.00   0.50    2.00    --   52.00  77.00 -56.07   60
 41  \w    -54.00 -28.00   0.50    2.00    --  -52.00 -73.00-176.65   52
 42  \w    -55.00 -28.00   0.50    2.00    --  -52.00 -73.00 102.57   54
 43  \w     28.00  53.00   0.50    2.00    --   52.00  77.00 -56.07   50
 44  \w   -117.00 -92.00   0.50    2.00    --  -52.00 -73.00-176.65   50
 45  \w   -105.00 -77.00   0.50    2.00    --  -52.00 -73.00 102.57   56
 46  \w    -58.00 -29.00   0.50    2.00    --  -52.00 -70.00 -57.03   58
 47  \w   -121.00 -90.00   0.50    2.00    --  -56.00 -58.00  14.80   62
 48  \w   -121.00 -81.00   0.50    2.00    --  -56.00 -70.00-153.55   80
 49  \w     33.00  83.00   0.50    2.00    --   56.00  76.00 145.95  100
 50  \w    -87.00 -37.00   0.50    2.00    --  -56.00 -58.00  14.80  100
 51  \w    -58.00 -33.00   0.50    2.00    --  -56.00 -70.00-153.55   50
 52  \w   -121.00 -84.00   0.50    2.00    --  -60.00 -76.00 -68.59   74
 53  \w     35.00  62.00   0.50    2.00    --   60.00  77.00 179.02   54
 54  \w    -61.00 -35.00   0.50    2.00    --  -60.00 -76.00 -68.59   52
 55  \w    -75.00 -39.00   0.50    2.00    --  -64.00 -75.00 -76.03   72
 56  \w    -71.00 -41.00   0.50    2.00    --  -64.00 -69.00 -10.36   60
 57  \w    -67.00 -41.00   0.50    2.00    --  -64.00 -70.00 -25.82   52
 58  \w    -67.00 -42.00   0.50    2.00    --  -64.00 -68.00  58.45   50
 59  \w   -129.00-102.00   0.50    2.00    --  -64.00 -68.00  58.45   54
 60  \w    -64.00 -39.00   0.50    2.00    --  -64.00 -77.00 107.44   50
 61  \w    -70.00 -45.00   0.50    2.00    --  -68.00 -73.00  84.28   50
 62  \w   -123.00 -93.00   0.50    2.00    --  -68.00 -73.00  84.28   60
 63  \w    -68.00 -43.00   0.50    2.00    --  -68.00 -76.00 -23.89   50
 64  \w    -69.00 -44.00   0.50    2.00    --  -68.00 -72.00  32.01   50
 65  \w   -123.00 -96.00   0.50    2.00    --  -68.00 -72.00  32.01   54
 66  \w   -134.00 -81.00   0.50    6.20    --  -72.00 -76.00-125.62  106
 67  \w    -75.00 -48.00   0.50    6.20    --  -72.00 -76.00-144.20   54
 68  \w    -73.00 -47.00   0.50    6.20    --  -72.00 -76.00-125.62   52
 69  \w    -74.00 -47.00   0.50    6.20    --  -72.00 -76.00-169.18   54
 70  \w     51.00  80.00   0.50    6.20    --   72.00  76.00  59.95   58
 71  \w    -74.00 -47.00   0.50    6.20    --  -72.00 -76.00 168.48   54
 72  \w    -88.00 -61.00   0.50    6.20    --  -72.00 -66.00  71.70   54
 73  \w    -76.00 -51.00   0.50    6.20    --  -76.00 -77.00-154.44   50
 74  \w   -143.00-118.00   0.50    6.20    --  -76.00 -77.00-154.44   50
 75  \w    -87.00 -51.00   0.50    6.20    --  -76.00 -76.00 156.48   72
 76  \w   -141.00 -94.00   0.50    6.20    --  -76.00 -76.00 156.48   94
 77  \w    -91.00 -52.00   0.50    6.20    --  -76.00 -73.00 -92.06   78
 78  \w    -76.00 -51.00   0.50    6.20    --  -76.00 -75.00 129.24   50
 79  \w   -140.00-113.00   0.50    6.20    --  -76.00 -75.00 129.24   54
 80  \w    -88.00 -58.00   0.50    6.20    --  -80.00 -76.00 151.33   60
 81  \w    -87.00 -60.00   0.50    6.20    --  -80.00 -62.00 -12.97   54
 82  \w    -92.00 -55.00   0.50    6.20    --  -80.00 -75.00 -98.30   74
 83  \w   -136.00-109.00   0.50    6.20    --  -80.00 -75.00 -98.30   54
 84  \w    -87.00 -61.00   0.50    6.20    --  -84.00 -71.00 -64.57   52
 85  \w   -143.00-116.00   0.50    6.20    --  -84.00 -71.00 -64.57   54
 86  \w    -91.00 -59.00   0.50    6.20    --  -84.00 -75.00  48.20   64
 87  \w   -106.00 -62.00   0.50    6.20    --  -84.00 -67.00-148.56   88
 88  \w   -147.00 -94.00   0.50    6.20    --  -84.00 -75.00 117.07  106
 89  \w     61.00  96.00   0.50    6.20    --   84.00  72.00 110.38   70
 90  \w   -117.00 -61.00   0.50    6.20    --  -84.00 -69.00 -23.68  112
 91  \w    -88.00 -61.00   0.50    6.20    --  -84.00 -75.00 117.07   54
 92  \w   -141.00 -65.00   0.50    6.20    --  -88.00 -69.00-178.02  152
 93  \w    -96.00 -63.00   0.50    6.20    --  -88.00 -76.00-114.41   66
 94  \w   -146.00 -63.00   0.50    6.20    --  -88.00 -77.00 -26.97  166
 95  \w   -157.00 -99.00   0.50    6.20    --  -93.31-117.00 -90.00  116
 96  \w    -94.00 -68.00   0.50    6.20    --  -93.31 -77.00 115.03   52
 97  \w   -138.00 -71.00   0.50    6.20    --  -93.31 -72.00 -43.77  134
 98  \w   -122.00 -68.00   0.50    6.20    --  -93.31 -77.00  30.00  108
 99  \w    -54.00 -23.00   0.50    6.20    --  -93.31  96.00 120.00   62
100  \w   -100.00 -70.00   0.50    6.20    --  -93.31 -72.00  18.73   60
101  \w   -104.00 -55.00   0.50    6.20    --  -93.31  96.00 120.00   98
102  \w   -148.00-113.00   0.50    6.20    --  -93.31 -72.00  18.73   70
103  \w   -151.00-115.00   0.50    6.20    --  -93.31 -77.00 115.03   72
104  \w    -90.00 -24.00   0.50    6.20    --  -93.31  96.00 150.00  132
105  \w   -160.00 -70.00   0.50    6.20    --  -93.31 -72.00  79.60  180
106  \w   -104.00 -25.00   0.50    6.20    --  -93.31  96.00 -30.00  158
107  \w   -148.00-121.00   0.50    6.20    --  -93.31 -77.00-150.00   54
108  \w   -123.00 -68.00   0.50    6.20    --  -93.31 -77.00 150.00  110
109  \w    -80.00 -55.00   0.50    6.20    --  -93.31  68.00  90.00   50
110  \w   -159.00-129.00   0.50    6.20    --  -93.31 -77.00 150.00   60
111  \w   -137.00-112.00   0.50    6.20    --  -93.31-133.00  67.00   50
112  \w    -93.00 -68.00   0.50    6.20    --  -93.31 -77.00 -69.15   50
113  \w   -157.00 -68.00   0.50    6.20    --  -93.31 -77.00  60.00  178
114  \w   -146.00 -68.00   0.50    6.20    --  -93.31 -77.00   0.00  156
115  \w   -111.00 -71.00   0.50    6.20    --  -93.31 -77.00-150.00   80
116  \w    -82.00 -34.00   0.50    6.20    --  -93.31  77.00 -60.00   96
117  \w   -139.00-112.00   0.50    6.20    --  -93.31 -77.00 -69.15   54
118  \w     97.00 124.00   0.50    6.20    --   94.87  77.00 -30.00   54
119  \w     71.00 157.00   0.50    6.20    --   94.87  77.00-120.00  172
120  \w    111.00 136.00   0.50    6.20    --   94.87  59.00 -60.00   50
121  \w     80.00 106.00   0.50    6.20    --   94.87  59.00 -60.00   52
122  \w     72.00 159.00   0.50    6.20    --   94.87  77.00  90.00  174
123  \w     70.00  96.00   0.50    6.20    --   94.87  77.00-180.00   52
124  \w     74.00 159.00   0.50    6.20    --   94.87  77.00 -90.00  170
125  \w     91.00 162.00   0.50    6.20    --   94.87  59.00-180.00  142
126  \w     29.00  56.00   0.50    6.20    --   94.87 -50.00 -60.00   54
127  \w     29.00  80.00   0.50    6.20    --   94.87 -68.00 -90.00  102
128  \w     30.00  57.00   0.50    6.20    --   94.87 -68.00-120.00   54
129  \w     96.00 157.00   0.50    6.20    --   94.87  77.00-150.00  122
130  \w     29.00  56.00   0.50    6.20    --   94.87 -50.00  90.00   54
131  \w     29.00  56.00   0.50    6.20    --   94.87 -50.00  60.00   54
132  \w     31.00  56.00   0.50    6.20    --   94.87 -50.00  30.00   50
133  \w     44.00  91.00   0.50    6.20    --   94.87 -77.00   0.00   94
134  \w     71.00 118.00   0.50    6.20    --   94.87  77.00  60.00   94
135  \w    125.00 158.00   0.50    6.20    --   94.87  68.00 120.00   66
136  \w     73.00 106.00   0.50    6.20    --   94.87  68.00 120.00   66
137  \w     40.00  80.00   0.50    6.20    --   94.87 -68.00  60.00   80
138  \w     42.00  67.00   0.50    6.20    --   94.87 -59.00-180.00   50
139  \w    119.00 146.00   0.50    6.20    --   94.87  42.00 150.00   54
140  \w     77.00 104.00   0.50    6.20    --   94.87-117.00 -90.00   54
141  \w    120.00 156.00   0.50    6.20    --   94.87  68.00  60.00   72
142  \w    134.00 159.00   0.50    6.20    --   94.87  68.00  30.00   50
143  \w     40.00  74.00   0.50    6.20    --   94.87-117.00 -90.00   68
144  \w     73.00 100.00   0.50    6.20    --   94.87  68.00  60.00   54
145  \w     76.00 103.00   0.50    6.20    --   94.87  68.00  30.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0057336000
_diffrn_orient_matrix_UB_12      -0.0230787000
_diffrn_orient_matrix_UB_13      -0.1437092000
_diffrn_orient_matrix_UB_21      0.0019713000
_diffrn_orient_matrix_UB_22      0.1083184000
_diffrn_orient_matrix_UB_23      -0.0306487000
_diffrn_orient_matrix_UB_31      0.2069078000
_diffrn_orient_matrix_UB_32      -0.0004975000
_diffrn_orient_matrix_UB_33      0.0131615000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            23167
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.642
_diffrn_reflns_theta_min         4.233
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.603
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78183
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.115a (Rigaku Oxford Diffraction, 2024)
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    1.234
_exptl_crystal_description       prism
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.179
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 1698 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.17(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3941
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0382
_refine_ls_R_factor_gt           0.0366
_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^)+(0.0609P)^2^+0.1170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0942
_refine_ls_wR_factor_ref         0.0952
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                3766
_reflns_number_total             3941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob02052a2.cif
_cod_data_source_block           Sa5f
_cod_depositor_comments
'Adding full bibliography for 7160364--7160367.cif.'
_cod_database_code               7160366
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O '
_chemical_oxdiff_usercomment     'DT B'
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.874
_reflns_odcompleteness_completeness 99.95
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13), C15(H15),
 C16(H16), C17(H17)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              31612
_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 1.429
_oxdiff_exptl_absorpt_empirical_full_min 0.661