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_7061958
_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         'C19 H25 N2, B F4'
_chemical_formula_sum            'C19 H25 B F4 N2'
_chemical_formula_weight         368.22
_chemical_melting_point          488.1(10)
_chemical_name_common
'1,1'-(2-Methylnaphthalene-1,8-diyl)dipyrrolidine hydrogen tetrafluoroborate'
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2022-04-26 deposited with the CCDC.	2022-08-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.1060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.78120(10)
_cell_length_b                   10.34370(10)
_cell_length_c                   17.7597(2)
_cell_measurement_reflns_used    11644
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.9480
_cell_measurement_theta_min      4.5840
_cell_volume                     1789.69(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2529
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -66.00  33.00   1.00    1.00    --  -41.60  37.00  -5.00   99
  2  \w   -116.00 -17.00   1.00    1.00    --  -41.60 -37.00-161.00   99
  3  \w    -33.00  66.00   1.00    1.00    --   41.60 -37.00-161.00   99
  4  \w     17.00 116.00   1.00    1.00    --   41.60  37.00  -5.00   99
  5  \w     38.00 136.00   1.00    2.30    --  112.00 -37.00-161.00   98
  6  \w     88.00 178.00   1.00    2.30    --  112.00  37.00  -5.00   90
  7  \w     23.00  98.00   1.00    1.00    --   41.60-125.00  30.00   75
  8  \w     23.00  98.00   1.00    1.00    --   41.60-125.00-150.00   75
  9  \w     36.00 113.00   1.00    2.30    --  112.00-111.00  30.00   77
 10  \w     36.00 113.00   1.00    2.30    --  112.00-111.00-150.00   77
 11  \w     57.00 150.00   1.00    2.30    --  112.00 178.00-150.00   93
 12  \w     59.00 178.00   1.00    2.30    --  112.00  15.00 -30.00  119
 13  \w     59.00 178.00   1.00    2.30    --  112.00  15.00  90.00  119
 14  \w    100.00 178.00   1.00    2.30    --  112.00 111.00 -30.00   78
 15  \w    100.00 178.00   1.00    2.30    --  112.00 111.00   0.00   78
 16  \w     30.00 110.00   1.00    2.30    --  112.00 -95.00 120.00   80
 17  \w     79.00 140.00   1.00    2.30    --  112.00  77.00  30.00   61
 18  \w     38.00 102.00   1.00    2.30    --  112.00-111.00   0.00   64
 19  \w     78.00 104.00   1.00    2.30    --  112.00-111.00  90.00   26
 20  \w    135.00 161.00   1.00    2.30    --  112.00 111.00  30.00   26
 21  \w     36.00  63.00   1.00    2.30    --  112.00-111.00 -60.00   27
 22  \w     81.00 106.00   1.00    2.30    --  112.00-111.00  60.00   25
 23  \w     58.00 110.00   1.00    2.30    --  112.00 -95.00-120.00   52
 24  \w    137.00 163.00   1.00    2.30    --  112.00 111.00 150.00   26
 25  \w     46.00  87.00   1.00    2.30    --  112.00-111.00-180.00   41
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0335733000
_diffrn_orient_matrix_UB_12      0.0082489000
_diffrn_orient_matrix_UB_13      0.0829765000
_diffrn_orient_matrix_UB_21      -0.1373002000
_diffrn_orient_matrix_UB_22      -0.0697789000
_diffrn_orient_matrix_UB_23      -0.0208037000
_diffrn_orient_matrix_UB_31      0.0708617000
_diffrn_orient_matrix_UB_32      -0.1313613000
_diffrn_orient_matrix_UB_33      0.0162666000
_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  0.0263
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            18984
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.282
_diffrn_reflns_theta_min         4.953
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.917
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.556
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             776
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Dichloromethane'
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.147
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.0002(2)
_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   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         3735
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0511P)^2^+0.8206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1044
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3472
_reflns_number_total             3735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj02653h2.cif
_cod_data_source_block           Structure-18b
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '214-216 deg.C' was changed
to '488.1(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               7061958
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H25 B F4 N2'
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.809
_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. Uiso/Uaniso restraints and constraints
Uanis(F4) = Uanis(F4A)
Uanis(F1) = Uanis(F1A)
Uanis(F3A) = Uanis(F3)
3. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=1-FVAR(1)
 Sof(F3)=Sof(F4)=Sof(F1)=Sof(F2)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C12(H12A,H12B), C19(H19A,H19B), C13(H13A,
 H13B), C17(H17A,H17B), C18(H18A,H18B), C14(H14A,H14B)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C2(H2), C6(H6), C3(H3)
4.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
;
_shelx_res_checksum              3569
_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 1.534
_oxdiff_exptl_absorpt_empirical_full_min 0.770