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_7061957
_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         'C17 H23 N2, I'
_chemical_formula_sum            'C17 H23 I N2'
_chemical_formula_weight         382.27
_chemical_temperature_decomposition 408.1(10)
_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             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                 93.0630(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.96030(10)
_cell_length_b                   9.88890(10)
_cell_length_c                   27.9480(2)
_cell_measurement_reflns_used    15276
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.2900
_cell_measurement_theta_min      3.1540
_cell_volume                     3300.81(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_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                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_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   -100.00 -74.00   0.50    0.30    --  -38.82 154.00 141.00   52
  2  \w    -80.00 -54.00   0.50    0.30    --  -38.82 120.00 -16.00   52
  3  \w     44.00  74.00   0.50    0.30    --   38.82-154.00 101.00   60
  4  \w     17.00  51.00   0.50    0.30    --   38.82-120.00-100.00   68
  5  \w     33.00  98.00   0.50    1.20    --  100.00-120.00-100.00  130
  6  \w     84.00 109.00   0.50    1.20    --  100.00 154.00 141.00   50
  7  \w     67.00 126.00   0.50    1.20    --  100.00-154.00 101.00  118
  8  \w     91.00 119.00   0.50    1.20    --  100.00 120.00 -16.00   56
  9  \w   -104.00 -70.00   0.50    0.30    --  -38.82 -65.00  90.00   68
 10  \w    -73.00 -10.00   0.50    0.30    --  -38.82 104.00-180.00  126
 11  \w    -57.00  28.00   0.50    0.30    --  -38.82  77.00  30.00  170
 12  \w    -65.00 -20.00   0.50    0.30    --  -38.82 -65.00  90.00   90
 13  \w   -111.00 -21.00   0.50    0.30    --  -38.82 -21.00-150.00  180
 14  \w    -74.00 -22.00   0.50    0.30    --  -38.82 -43.00  30.00  104
 15  \w     38.00  71.00   0.50    0.30    --   38.82 -11.00  90.00   66
 16  \w     -4.00  66.00   0.50    0.30    --   38.82 -77.00 -90.00  140
 17  \w    -25.00   2.00   0.50    0.30    --   38.82 -11.00  90.00   54
 18  \w    -19.00   9.00   0.50    0.30    --   38.82 -54.00  90.00   56
 19  \w     23.00  49.00   0.50    0.30    --   38.82 -54.00  90.00   52
 20  \w     36.00 108.00   0.50    1.20    --  100.00-111.00 -90.00  144
 21  \w     87.00 113.00   0.50    1.20    --  100.00  30.00 150.00   52
 22  \w     81.00 109.00   0.50    1.20    --  100.00  22.00  60.00   56
 23  \w     36.00 120.00   0.50    1.20    --  100.00 -53.00-120.00  168
 24  \w     83.00 127.00   0.50    1.20    --  100.00 -77.00   0.00   88
 25  \w     45.00  71.00   0.50    1.20    --  100.00 -77.00   0.00   52
 26  \w    122.00 157.00   0.50    1.20    --  100.00  22.00  90.00   70
 27  \w     85.00 118.00   0.50    1.20    --  100.00-133.00  30.00   66
 28  \w     49.00  75.00   0.50    1.20    --  100.00-133.00  30.00   52
 29  \w    114.00 156.00   0.50    1.20    --  100.00  77.00 -60.00   84
 30  \w     81.00 129.00   0.50    1.20    --  100.00  22.00 -60.00   96
 31  \w     80.00 105.00   0.50    1.20    --  100.00 -93.00  30.00   50
 32  \w     42.00  68.00   0.50    1.20    --  100.00-111.00-180.00   52
 33  \w     52.00  78.00   0.50    1.20    --  100.00 -93.00 -90.00   52
 34  \w    126.00 156.00   0.50    1.20    --  100.00  45.00  30.00   60
 35  \w     59.00 115.00   0.50    1.20    --  100.00 -22.00-150.00  112
 36  \w     53.00 113.00   0.50    1.20    --  100.00 -86.00-120.00  120
 37  \w     52.00  96.00   0.50    1.20    --  100.00-111.00  60.00   88
 38  \w    129.00 155.00   0.50    1.20    --  100.00  22.00  60.00   52
 39  \w     83.00 109.00   0.50    1.20    --  100.00  45.00  30.00   52
 40  \w     50.00 104.00   0.50    1.20    --  100.00 -77.00-120.00  108
 41  \w     37.00  90.00   0.50    1.20    --  100.00 -15.00  30.00  106
 42  \w    107.00 132.00   0.50    1.20    --  100.00  30.00-120.00   50
 43  \w     97.00 157.00   0.50    1.20    --  100.00  77.00 -30.00  120
 44  \w    102.00 128.00   0.50    1.20    --  100.00 -86.00  60.00   52
 45  \w     86.00 111.00   0.50    1.20    --  100.00 -45.00 150.00   50
 46  \w     57.00 110.00   0.50    1.20    --  100.00 -30.00-150.00  106
 47  \w     65.00  91.00   0.50    0.30    --   38.82  65.00 -90.00   52
 48  \w    -62.00 -33.00   0.50    0.30    --  -38.82 -32.00 150.00   58
 49  \w    -78.00 -52.00   0.50    0.30    --  -38.82 -43.00 -30.00   52
 50  \w   -107.00 -19.00   0.50    0.30    --  -38.82 -21.00 120.00  176
 51  \w    -50.00 -24.00   0.50    0.30    --  -38.82 -43.00 -30.00   52
 52  \w    -18.00  38.00   0.50    0.30    --   38.82 -77.00  90.00  112
 53  \w     41.00  65.50   0.50    0.30    --   38.82-138.00 150.00   49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0899471000
_diffrn_orient_matrix_UB_12      0.0814494000
_diffrn_orient_matrix_UB_13      -0.0249884000
_diffrn_orient_matrix_UB_21      0.0646385000
_diffrn_orient_matrix_UB_22      -0.1315467000
_diffrn_orient_matrix_UB_23      -0.0088347000
_diffrn_orient_matrix_UB_31      -0.0660912000
_diffrn_orient_matrix_UB_32      -0.0180350000
_diffrn_orient_matrix_UB_33      -0.0484341000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            24250
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.993
_diffrn_reflns_theta_min         3.167
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.169
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78791
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_description       prism
_exptl_crystal_F_000             1536
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Diethyl ether/dichloromethane'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.230
_refine_diff_density_min         -1.789
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     367
_refine_ls_number_reflns         6246
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0445P)^2^+14.3800P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0978
_refine_ls_wR_factor_ref         0.0993
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5881
_reflns_number_total             6246
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj02653h2.cif
_cod_data_source_block           Structure-14
_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 '134-136 deg.C (decomp.)'. The value was changed to '408.1(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               7061957
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C17 H23 N2 I1'
_shelx_estimated_absorpt_t_max   0.377
_shelx_estimated_absorpt_t_min   0.263
_reflns_odcompleteness_completeness 98.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     70.93
_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:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C1'(H1'A,H1'B), C2'(H2'A,
 H2'B), C3'(H3'A,H3'B), C4'(H4'A,H4'B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C9'(H9'),
 C10'(H10'), C11'(H11'), C13'(H13'), C14'(H14'), C15'(H15')
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C5'(H5'A,H5'B,H5'C),
 C6'(H6'A,H6'B,H6'C), C7'(H7'A,H7'B,H7'C)
;
_shelx_res_checksum              39557
_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 1.443
_oxdiff_exptl_absorpt_empirical_full_min 0.794