Dialkylamino and trialkylammonium groups in close proximity: intra- and intermolecular ways of formation, structural consequences, and properties. A case of metal-free directed ortho alkylation
Kolupaeva, Ekaterina V.; Ozeryanskii, Valery A.; New Journal of Chemistry 46 (2022) 17140–17144; doi:10.1039/D2NJ02653H

data_7061956
_publ_section_title
;
 Dialkylamino and trialkylammonium groups in close proximity: intra- and
 intermolecular ways of formation, structural consequences, and
 properties. A case of metal-free directed ortho alkylation
;
_journal_issue                   36
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              17140
_journal_page_last               17144
_journal_paper_doi               10.1039/D2NJ02653H
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         'Br, C18 H23 N2'
_chemical_formula_sum            'C18 H23 Br N2'
_chemical_formula_weight         347.29
_chemical_temperature_decomposition 442.1(10)
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-12-13 deposited with the CCDC.	2022-08-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.6140(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.79650(10)
_cell_length_b                   18.2667(2)
_cell_length_c                   11.37140(10)
_cell_measurement_reflns_used    21438
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.9300
_cell_measurement_theta_min      3.7870
_cell_volume                     1618.83(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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 -26.00   0.50    0.15    --  -47.20  50.00-105.00   54
  2  \w    -82.00 -56.00   0.50    0.50    -- -106.00 125.00  30.00   52
  3  \w    -67.00 -37.00   0.50    0.50    -- -106.00 109.00  85.63   60
  4  \w    -71.00 -46.00   0.50    0.50    -- -106.00  61.00 -30.00   50
  5  \w    -60.00 -34.00   0.50    0.50    -- -106.00 111.00-121.06   52
  6  \w    -66.00 -33.00   0.50    0.50    -- -106.00 142.00 -83.60   66
  7  \w    -86.00 -33.00   0.50    0.50    -- -106.00  77.00-120.00  106
  8  \w   -108.00 -83.00   0.50    0.50    -- -106.00 111.00-121.06   50
  9  \w   -124.00 -89.00   0.50    0.50    -- -106.00 142.00 -83.60   70
 10  \w   -111.00 -85.00   0.50    0.50    -- -106.00 125.00  30.00   52
 11  \w   -108.00 -71.00   0.50    0.50    -- -106.00 109.00  85.63   74
 12  \w    -95.00 -55.00   0.50    0.50    -- -106.00 114.00  68.56   80
 13  \w   -103.00 -73.00   0.50    0.50    -- -106.00  77.00  60.00   60
 14  \w   -104.00 -34.00   0.50    0.50    -- -106.00  77.00  90.00  140
 15  \w   -111.00 -34.00   0.50    0.50    -- -106.00 125.00 120.00  154
 16  \w   -129.00 -97.00   0.50    0.50    -- -106.00 -15.00  30.00   64
 17  \w   -118.00 -86.00   0.50    0.50    -- -106.00 -77.00  60.00   64
 18  \w   -113.00 -35.00   0.50    0.15    --  -47.20 -50.00 107.00  156
 19  \w    -11.00  57.00   0.50    0.15    --   47.20 -50.00 107.00  136
 20  \w     64.00  94.00   0.50    0.15    --   47.20-125.00  90.00   60
 21  \w     34.00  92.00   0.50    0.15    --   47.20-125.00 -30.00  116
 22  \w     80.00 110.00   0.50    0.50    --  107.75-125.00  30.00   60
 23  \w     70.00 112.00   0.50    0.50    --  107.75-125.00  90.00   84
 24  \w     46.00  71.00   0.50    0.50    --  107.75 -61.00   0.00   50
 25  \w     38.00  71.00   0.50    0.50    --  107.75 -61.00 -60.00   66
 26  \w     55.00 105.00   0.50    0.50    --  107.75 -94.00 -90.00  100
 27  \w     70.00 112.00   0.50    0.50    --  107.75-125.00-150.00   84
 28  \w     75.00 105.00   0.50    0.50    --  107.75 -94.00-180.00   60
 29  \w     40.00 112.00   0.50    0.50    --  107.75-125.00-180.00  144
 30  \w     37.00  94.00   0.50    0.50    --  107.75 -77.00 -90.00  114
 31  \w     41.00  74.00   0.50    0.50    --  107.75-125.00  30.00   66
 32  \w     35.00 105.00   0.50    0.50    --  107.75 -94.00  90.00  140
 33  \w    148.00 177.00   0.50    0.50    --  107.75  15.00 120.00   58
 34  \w     96.00 174.00   0.50    0.50    --  107.75  61.00   0.00  156
 35  \w    105.00 176.00   0.50    0.50    --  107.75  45.00  30.00  142
 36  \w    100.00 178.00   0.50    0.50    --  107.75  50.00-105.00  156
 37  \w    101.00 150.00   0.50    0.50    --  107.75  77.00 -90.00   98
 38  \w     74.00  99.00   0.50    0.15    --   47.20 125.00 -90.00   50
 39  \w     40.00 119.00   0.50    0.15    --   47.20  50.00-105.00  158
 40  \w     35.00  61.00   0.50    0.50    --  107.75 -61.00-180.00   52
 41  \w     35.00 106.00   0.50    0.50    --  107.75 -94.00-120.00  142
 42  \w     -6.00  26.00   0.50    0.15    --   47.20 -19.00   0.00   64
 43  \w    -24.00  25.00   0.50    0.15    --   47.20 -19.00 -30.00   98
 44  \w     97.00 134.00   0.50    0.50    --  107.75  15.00 120.00   74
 45  \w   -116.00 -91.00   0.50    0.15    --  -47.20-125.00  60.00   50
 46  \w   -164.00-122.00   0.50    0.50    -- -106.00 -50.00 107.00   84
 47  \w   -168.00-142.00   0.50    0.50    -- -106.00 -77.00  60.00   52
 48  \w   -169.00-144.00   0.50    0.50    -- -106.00 -15.00  30.00   50
 49  \w   -153.00 -88.00   0.50    0.50    -- -106.00 -77.00-150.00  130
 50  \w   -132.00 -94.00   0.50    0.50    -- -106.00 -94.00-180.00   76
 51  \w   -131.00 -92.00   0.50    0.50    -- -106.00 -61.00-180.00   78
 52  \w   -161.00-136.00   0.50    0.50    -- -106.00 -94.00-180.00   50
 53  \w    -22.00  17.00   0.50    0.15    --   47.20 -50.00 107.00   78
 54  \w     -9.00  21.00   0.50    0.15    --   14.00  85.00 141.33   60
 55  \w    -14.00  11.00   0.50    0.15    --   18.00  96.00  61.62   50
 56  \w     -1.00  24.00   0.50    0.15    --   30.00  95.00-129.19   50
 57  \w      8.00  33.00   0.50    0.15    --   38.00  93.00 -95.21   50
 58  \w     16.00  41.00   0.50    0.15    --   42.00  84.00  28.45   50
 59  \w     17.00  42.00   0.50    0.15    --   46.00  90.00-134.71   50
 60  \w     17.00  42.00   0.50    0.15    --   46.00  90.00 -65.36   50
 61  \w    -72.00 -35.00   0.50    0.15    --  -47.20 -37.00   0.00   74
 62  \w     26.00  61.00   0.50    0.15    --   47.20  77.00 120.00   70
 63  \w     33.00  58.00   0.50    0.15    --   54.00  72.00  76.33   50
 64  \w     31.00  66.00   0.50    0.15    --   54.00  78.00 145.30   70
 65  \w     32.00  58.00   0.50    0.15    --   54.00  78.00-103.81   52
 66  \w     33.00  58.00   0.50    0.15    --   54.00  72.00  -2.83   50
 67  \w     35.00  75.00   0.50    0.15    --   58.00  78.00 172.68   80
 68  \w     35.00  61.00   0.50    0.15    --   58.00  79.00 -58.78   52
 69  \w     39.00  65.00   0.50    0.15    --   62.00  77.00 -15.71   52
 70  \w     39.00  65.00   0.50    0.15    --   62.00  78.00  24.27   52
 71  \w     43.00  69.00   0.50    0.15    --   62.00  72.00-103.35   52
 72  \w     39.00  65.00   0.50    0.15    --   62.00  77.00   9.94   52
 73  \w     40.00  65.00   0.50    0.15    --   62.00  75.00 105.10   50
 74  \w     41.00  67.00   0.50    0.15    --   62.00  74.00 159.79   52
 75  \w     39.00  85.00   0.50    0.15    --   62.00  77.00  51.99   92
 76  \w     39.00  67.00   0.50    0.15    --   62.00  77.00-156.42   56
 77  \w    110.00 135.00   0.50    0.15    --   62.00  78.00  24.27   50
 78  \w     43.00  68.00   0.50    0.15    --   66.00  78.00 177.75   50
 79  \w     43.00  68.00   0.50    0.15    --   66.00  78.00  59.56   50
 80  \w    -73.00 -47.00   0.50    0.15    --  -70.00 -77.00 127.99   52
 81  \w    -74.00 -48.00   0.50    0.15    --  -70.00 -80.00 -79.79   52
 82  \w     47.00  73.00   0.50    0.15    --   70.00  77.00 112.93   52
 83  \w     49.00  75.00   0.50    0.15    --   70.00  76.00 -55.94   52
 84  \w     47.00  72.00   0.50    0.15    --   70.00  78.00 -98.28   50
 85  \w    105.00 137.00   0.50    0.15    --   70.00  78.00 -98.28   64
 86  \w     49.00  75.00   0.50    0.15    --   70.00  76.00  65.91   52
 87  \w     92.00 143.00   0.50    0.15    --   70.00  76.00  65.91  102
 88  \w    -90.00 -56.00   0.50    0.15    --  -74.00 -65.00  -0.44   68
 89  \w    -77.00 -51.00   0.50    0.15    --  -74.00 -77.00-153.77   52
 90  \w    -77.00 -51.00   0.50    0.15    --  -74.00 -76.00-179.25   52
 91  \w    -80.00 -54.00   0.50    0.15    --  -74.00 -69.00-157.56   52
 92  \w     51.00  77.00   0.50    0.15    --   74.00  77.00 -13.15   52
 93  \w    -88.00 -55.00   0.50    0.50    --  -78.00 -76.00  50.55   66
 94  \w    -82.00 -56.00   0.50    0.50    --  -78.00 -74.00 -18.06   52
 95  \w    -87.00 -62.00   0.50    0.50    --  -82.00 -73.00   6.93   50
 96  \w    -88.00 -62.00   0.50    0.50    --  -82.00 -73.00 172.35   52
 97  \w    -86.00 -60.00   0.50    0.50    --  -82.00 -74.00 157.31   52
 98  \w    -87.00 -61.00   0.50    0.50    --  -82.00 -74.00 -52.22   52
 99  \w    -86.00 -58.00   0.50    0.50    --  -82.00 -79.00  81.17   56
100  \w    -92.00 -66.00   0.50    0.50    --  -86.00 -73.00  50.67   52
101  \w    -90.00 -64.00   0.50    0.50    --  -86.00 -74.00 107.29   52
102  \w    -94.00 -68.00   0.50    0.50    --  -86.00 -65.00 -82.42   52
103  \w    -87.00 -62.00   0.50    0.50    --  -86.00 -79.00  44.89   50
104  \w    -89.00 -63.00   0.50    0.50    --  -86.00 -76.00-123.41   52
105  \w    -91.00 -65.00   0.50    0.50    --  -86.00 -72.00 -42.10   52
106  \w    -93.00 -68.00   0.50    0.50    --  -86.00 -65.00-108.21   50
107  \w    -93.00 -68.00   0.50    0.50    --  -86.00 -65.00 -36.86   50
108  \w   -128.00-102.00   0.50    0.50    --  -86.00 -65.00 -36.86   52
109  \w   -153.00-127.00   0.50    0.50    --  -90.00 -75.00 -49.66   52
110  \w    -97.00 -72.00   0.50    0.50    --  -90.00 -64.00 -23.32   50
111  \w    -94.00 -69.00   0.50    0.50    --  -90.00 -72.00 133.93   50
112  \w   -126.00-100.00   0.50    0.50    --  -90.00 -72.00 133.93   52
113  \w     73.00  99.00   0.50    0.50    --   90.00  65.00 -74.36   52
114  \w    -94.00 -69.00   0.50    0.50    --  -90.00 -72.00 122.05   50
115  \w    -97.00 -72.00   0.50    0.50    --  -90.00 -64.00-149.91   50
116  \w    -92.00 -67.00   0.50    0.50    --  -90.00 -76.00 162.62   50
117  \w    -96.00 -70.00   0.50    0.50    --  -90.00 -71.00  -0.14   52
118  \w    -93.00 -68.00   0.50    0.50    --  -90.00 -75.00 -49.66   50
119  \w   -134.00 -79.50   0.50    0.50    --  -94.00 -67.00 -74.46  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0519858000
_diffrn_orient_matrix_UB_12      -0.0803002000
_diffrn_orient_matrix_UB_13      0.0222579000
_diffrn_orient_matrix_UB_21      -0.0144917500
_diffrn_orient_matrix_UB_22      -0.0153293500
_diffrn_orient_matrix_UB_23      -0.1331056000
_diffrn_orient_matrix_UB_31      0.1901900500
_diffrn_orient_matrix_UB_32      0.0207218500
_diffrn_orient_matrix_UB_33      -0.0123269000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0280
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            22273
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.974
_diffrn_reflns_theta_min         4.842
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.405
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86013
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       prism
_exptl_crystal_F_000             720
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Diethyl ether/dichloromethane'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.132
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1415 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.060(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2966
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0139
_refine_ls_R_factor_gt           0.0139
_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^)+(0.0196P)^2^+0.5885P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0359
_refine_ls_wR_factor_ref         0.0360
_reflns_Friedel_coverage         0.926
_reflns_Friedel_fraction_full    0.951
_reflns_Friedel_fraction_max     0.933
_reflns_number_gt                2960
_reflns_number_total             2966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj02653h2.cif
_cod_data_source_block           Structure-5
_cod_depositor_comments
;
The following automatic conversions were performed:

data name '_chemical_melting_point' was changed to
'_chemical_temperature_decomposition' since the value had been given
as '168-170 deg.C (decomp.)'. The value was changed to '442.1(10)' --
it was converted from degrees Celsius (C) to kelvins (K), the average
value was taken and precision was estimated.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               7061956
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H27 N2 Br1'
_shelx_estimated_absorpt_t_max   0.772
_shelx_estimated_absorpt_t_min   0.647
_diffrn_oxdiff_digest_frames
;
01a0f70d4208699a307e68d303486e2bb8000488986
;
_diffrn_oxdiff_digest_hkl
;
0166a51585206b56f341db87c6751e3a3e0745
;
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B), C16(H16A,
 H16B), C17(H17A,H17B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              60111
_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 1.433
_oxdiff_exptl_absorpt_empirical_full_min 0.832