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_7160365
_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_absolute_configuration ad
_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                 93.5230(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.46170(10)
_cell_length_b                   13.90680(10)
_cell_length_c                   10.46010(10)
_cell_measurement_reflns_used    18399
_cell_measurement_temperature    89.9(4)
_cell_measurement_theta_max      69.7260
_cell_measurement_theta_min      4.2230
_cell_volume                     1083.376(19)
_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 0.995
_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    -46.00  -2.00   0.50    0.40    --  -42.75 110.00 116.00   88
  2  \w    -82.00 -55.00   0.50    0.40    --  -42.75 110.00 116.00   54
  3  \w    -98.00 -67.00   0.50    1.50    --  -95.95 110.00 116.00   62
  4  \w   -146.00-121.00   0.50    1.50    --  -95.95-110.00  21.00   50
  5  \w     82.00 113.00   0.50    1.50    --   97.51 110.00 116.00   62
  6  \w     46.00  88.00   0.50    1.50    --   97.51-110.00  21.00   84
  7  \w    -27.00   0.00   0.50    0.40    --   10.00 106.00  45.08   54
  8  \w    -22.00   7.00   0.50    0.40    --   14.00 103.00-138.68   58
  9  \w    -13.00  12.00   0.50    0.40    --   22.00 102.00  99.71   50
 10  \w     -3.00  27.00   0.50    0.40    --   26.00  97.00-151.13   60
 11  \w     -2.00  23.00   0.50    0.40    --   30.00  97.00-105.53   50
 12  \w      2.00  27.00   0.50    0.40    --   34.00  95.00 -47.19   50
 13  \w     10.00  35.00   0.50    0.40    --   38.00  85.00-173.61   50
 14  \w    -34.00  -7.00   0.50    0.40    --  -38.00 -94.00  60.66   54
 15  \w    -34.00  -8.00   0.50    0.40    --  -38.00 -91.00 104.91   52
 16  \w      8.00  33.00   0.50    0.40    --   38.00  92.00  58.11   50
 17  \w      7.00  32.00   0.50    0.40    --   38.00  94.00  82.67   50
 18  \w    -35.00  -9.00   0.50    0.40    --  -38.00 -90.00 -56.52   52
 19  \w     12.00  41.00   0.50    0.40    --   42.00  92.00-147.98   58
 20  \w    -41.00 -15.00   0.50    0.40    --  -42.00 -82.00 106.03   52
 21  \w     12.00  37.00   0.50    0.40    --   42.00  90.00   5.83   50
 22  \w    -95.00 -19.00   0.50    0.40    --  -42.75 138.00-150.00  152
 23  \w    -99.00 -59.00   0.50    0.40    --  -42.75 138.00 -30.00   80
 24  \w    -90.00 -20.00   0.50    0.40    --  -42.75 138.00 150.00  140
 25  \w     49.00  75.00   0.50    0.40    --   44.32-110.00  21.00   52
 26  \w     16.00  41.00   0.50    0.40    --   44.32  86.00  10.69   50
 27  \w     17.00  42.00   0.50    0.40    --   46.00  88.00 -28.67   50
 28  \w     16.00  41.00   0.50    0.40    --   46.00  91.00 -55.33   50
 29  \w     16.00  41.00   0.50    0.40    --   46.00  90.00-108.09   50
 30  \w    -41.00 -16.00   0.50    0.40    --  -46.00 -92.00 167.57   50
 31  \w     26.00  51.00   0.50    0.40    --   50.00  77.00  42.88   50
 32  \w    -86.00 -37.00   0.50    0.40    --  -54.00 -62.00  86.62   98
 33  \w    -61.00 -29.00   0.50    0.40    --  -54.00 -77.00 134.29   64
 34  \w    -71.00 -34.00   0.50    0.40    --  -58.00 -73.00   8.28   74
 35  \w   -119.00 -94.00   0.50    0.40    --  -58.00 -73.00   8.28   50
 36  \w    -59.00 -33.00   0.50    0.40    --  -58.00 -76.00-168.44   52
 37  \w    -69.00 -33.00   0.50    0.40    --  -58.00 -76.00-128.88   72
 38  \w    -59.00 -34.00   0.50    0.40    --  -58.00 -73.00 -97.31   50
 39  \w     33.00  59.00   0.50    0.40    --   58.00  77.00 -12.75   52
 40  \w    -61.00 -33.00   0.50    0.40    --  -58.00 -77.00 -30.12   56
 41  \w   -124.00 -85.00   0.50    0.40    --  -58.00 -77.00 -30.12   78
 42  \w   -122.00 -96.00   0.50    0.40    --  -58.00 -73.00 -97.31   52
 43  \w   -117.00 -91.00   0.50    0.40    --  -58.00 -76.00-168.44   52
 44  \w    -62.00 -37.00   0.50    0.40    --  -62.00 -75.00  96.17   50
 45  \w    -70.00 -40.00   0.50    0.40    --  -62.00 -69.00  68.39   60
 46  \w    -70.00 -39.00   0.50    0.40    --  -62.00 -70.00  37.32   62
 47  \w    -65.00 -39.00   0.50    0.40    --  -62.00 -70.00 151.10   52
 48  \w    -89.00 -41.00   0.50    0.40    --  -62.00 -67.00  55.11   96
 49  \w   -127.00-102.00   0.50    0.40    --  -62.00 -67.00  55.11   50
 50  \w    -71.00 -45.00   0.50    0.40    --  -62.00 -57.00 100.84   52
 51  \w    -86.00 -41.00   0.50    0.40    --  -66.00 -76.00-123.49   90
 52  \w   -128.00 -97.00   0.50    0.40    --  -66.00 -76.00-123.49   62
 53  \w    -70.00 -45.00   0.50    1.50    --  -70.00 -76.00  69.58   50
 54  \w    -70.00 -45.00   0.50    1.50    --  -70.00 -75.00 -39.36   50
 55  \w   -128.00-103.00   0.50    1.50    --  -70.00 -75.00 -39.36   50
 56  \w     45.00  71.00   0.50    0.40    --   70.00  77.00  59.64   52
 57  \w    109.00 136.00   0.50    0.40    --   70.00  77.00  59.64   54
 58  \w    -82.00 -49.00   0.50    1.50    --  -74.00 -77.00 107.26   66
 59  \w   -128.00-103.00   0.50    1.50    --  -74.00 -77.00 107.26   50
 60  \w     52.00  78.00   0.50    1.50    --   74.00  75.00 117.20   52
 61  \w    -88.00 -49.00   0.50    1.50    --  -74.00 -77.00 -54.31   78
 62  \w   -138.00 -96.00   0.50    1.50    --  -74.00 -77.00 -54.31   84
 63  \w    -85.00 -55.00   0.50    1.50    --  -78.00 -74.00 -81.71   60
 64  \w    -78.00 -53.00   0.50    1.50    --  -78.00 -75.00 129.33   50
 65  \w    -82.00 -54.00   0.50    1.50    --  -78.00 -75.00 155.78   56
 66  \w   -145.00-120.00   0.50    1.50    --  -78.00 -76.00 103.39   50
 67  \w    -82.00 -53.00   0.50    1.50    --  -78.00 -75.00   9.36   58
 68  \w   -138.00-112.00   0.50    1.50    --  -78.00 -75.00   9.36   52
 69  \w   -108.00 -53.00   0.50    1.50    --  -78.00 -76.00 103.39  110
 70  \w    -88.00 -58.00   0.50    1.50    --  -78.00 -67.00-141.76   60
 71  \w   -109.00 -60.00   0.50    1.50    --  -82.00 -77.00 173.70   98
 72  \w    -84.00 -58.00   0.50    1.50    --  -82.00 -74.00 -96.92   52
 73  \w   -118.00 -58.00   0.50    1.50    --  -82.00 -74.00  57.39  120
 74  \w    -90.00 -59.00   0.50    1.50    --  -82.00 -71.00-158.47   62
 75  \w   -148.00-122.00   0.50    1.50    --  -82.00 -71.00-158.47   52
 76  \w    -83.00 -58.00   0.50    1.50    --  -82.00 -73.00  -4.99   50
 77  \w    -85.00 -59.00   0.50    1.50    --  -82.00 -75.00-113.22   52
 78  \w   -106.00 -61.00   0.50    1.50    --  -86.00 -75.00 -30.39   90
 79  \w    -87.00 -61.00   0.50    1.50    --  -86.00 -76.00-128.76   52
 80  \w   -150.00-102.00   0.50    1.50    --  -86.00 -76.00-128.76   96
 81  \w    -94.00 -61.00   0.50    1.50    --  -86.00 -75.00  46.76   66
 82  \w    -98.00 -63.00   0.50    1.50    --  -86.00 -76.00  -3.66   70
 83  \w    -89.00 -63.00   0.50    1.50    --  -86.00 -74.00 -89.29   52
 84  \w   -147.00 -97.00   0.50    1.50    --  -86.00 -74.00 -89.29  100
 85  \w   -129.00 -99.00   0.50    1.50    --  -86.00 -75.00  46.76   60
 86  \w    -88.00 -63.00   0.50    1.50    --  -86.00 -73.00 140.49   50
 87  \w    -91.00 -63.00   0.50    1.50    --  -86.00 -69.00-172.65   56
 88  \w   -133.00 -66.00   0.50    1.50    --  -90.00 -76.00 137.33  134
 89  \w   -136.00 -88.00   0.50    1.50    --  -94.00 -60.00 179.03   96
 90  \w   -160.00-130.00   0.50    1.50    --  -95.95 -76.00 117.88   60
 91  \w   -126.00 -75.00   0.50    1.50    --  -95.95 -68.00 -60.00  102
 92  \w   -162.00 -79.00   0.50    1.50    --  -95.95 -68.00-150.00  166
 93  \w   -105.00 -33.00   0.50    1.50    --  -95.95  77.00 120.00  144
 94  \w    -81.00 -40.00   0.50    1.50    --  -95.95  68.00  60.00   82
 95  \w   -164.00 -75.00   0.50    1.50    --  -95.95 -77.00   0.00  178
 96  \w   -143.00 -90.00   0.50    1.50    --  -95.95 -33.00   0.00  106
 97  \w    -99.00 -74.00   0.50    1.50    --  -95.95 -68.00  90.00   50
 98  \w   -132.00-106.00   0.50    1.50    --  -95.95 -68.00  90.00   52
 99  \w    -98.00 -71.00   0.50    1.50    --  -95.95 -77.00-180.00   54
100  \w    -74.00 -33.00   0.50    1.50    --  -95.95  68.00 -30.00   82
101  \w   -107.00 -71.00   0.50    1.50    --  -95.95 -76.00 117.88   72
102  \w   -162.00 -99.00   0.50    1.50    --  -95.95 -59.00-120.00  126
103  \w   -165.00 -84.00   0.50    1.50    --  -95.95 -96.00 -60.00  162
104  \w   -161.00 -77.00   0.50    1.50    --  -95.95 -77.00 -90.00  168
105  \w   -159.00 -76.00   0.50    1.50    --  -95.95 -77.00 -30.00  166
106  \w    -68.00 -30.00   0.50    1.50    --  -95.95 145.00 150.00   76
107  \w   -127.00 -88.00   0.50    1.50    --  -95.95 145.00 150.00   78
108  \w    -64.00 -38.00   0.50    1.50    --  -95.95 110.00 116.00   52
109  \w   -100.00 -74.00   0.50    1.50    --  -95.95 -77.00  30.00   52
110  \w   -148.00-119.00   0.50    1.50    --  -95.95 -77.00  30.00   58
111  \w     73.00 154.00   0.50    1.50    --   97.51  77.00  90.00  162
112  \w     74.00 126.00   0.50    1.50    --   97.51  77.00 -60.00  104
113  \w    129.00 155.00   0.50    1.50    --   97.51  68.00 -90.00   52
114  \w     31.00  56.00   0.50    1.50    --   97.51 -50.00 150.00   50
115  \w     43.00  68.00   0.50    1.50    --   97.51 -59.00  60.00   50
116  \w     76.00 102.00   0.50    1.50    --   97.51  68.00 -90.00   52
117  \w    137.00 162.00   0.50    1.50    --   97.51  68.00-120.00   50
118  \w     79.00 105.00   0.50    1.50    --   97.51  68.00-120.00   52
119  \w    117.00 162.00   0.50    1.50    --   97.51 117.00   0.00   90
120  \w     73.00 160.00   0.50    1.50    --   97.51  77.00  60.00  174
121  \w     73.00 144.00   0.50    1.50    --   97.51  77.00  30.00  142
122  \w     75.00 163.00   0.50    1.50    --   97.51  68.00 120.00  176
123  \w     33.00  67.00   0.50    1.50    --   97.51 -59.00-120.00   68
124  \w     38.00 107.00   0.50    1.50    --   97.51 -96.00 -90.00  138
125  \w     31.00  56.00   0.50    1.50    --   97.51 -50.00 -30.00   50
126  \w     78.00 109.00   0.50    1.50    --   97.51-117.00   0.00   62
127  \w     40.00  74.00   0.50    1.50    --   97.51-117.00   0.00   68
128  \w     31.00  56.00   0.50    1.50    --   97.51 -59.00   0.00   50
129  \w     80.00 162.00   0.50    1.50    --   97.51 117.00 -30.00  164
130  \w     31.00  56.00   0.50    1.50    --   97.51 -50.00 -90.00   50
131  \w     76.00 102.00   0.50    1.50    --   97.51  68.00  90.00   52
132  \w     37.00 101.00   0.50    1.50    --   97.51-117.00-150.00  128
;
_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      -0.0263931000
_diffrn_orient_matrix_UB_12      -0.0394180000
_diffrn_orient_matrix_UB_13      -0.1375397000
_diffrn_orient_matrix_UB_21      -0.0348130000
_diffrn_orient_matrix_UB_22      -0.1010501000
_diffrn_orient_matrix_UB_23      0.0535251000
_diffrn_orient_matrix_UB_31      -0.2021699000
_diffrn_orient_matrix_UB_32      0.0224572000
_diffrn_orient_matrix_UB_33      -0.0005856000
_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  0.0362
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_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            23039
_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         69.603
_diffrn_reflns_theta_min         4.235
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.602
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71201
_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          0.34
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.133
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 1834 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.09(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         4030
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0286
_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^)+(0.0396P)^2^+0.1274P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0711
_refine_ls_wR_factor_ref         0.0717
_reflns_Friedel_coverage         0.903
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                3922
_reflns_number_total             4030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob02052a2.cif
_cod_data_source_block           Ra5f
_cod_depositor_comments
'Adding full bibliography for 7160364--7160367.cif.'
_cod_database_code               7160365
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O '
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.821
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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:
 C24(H24A,H24B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B)
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:
 C25(H25A,H25B,H25C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              69904
_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 1.370
_oxdiff_exptl_absorpt_empirical_full_min 0.744