Quaternary N-(2-Pyridyl)-DABCO Salts: One-Pot in Situ Formation from Pyridine-N-oxides and Reactions with Nucleophiles: A Mild and Selective Route to Substituted N-(2-Pyridyl)-N'-ethylpiperazines.
Bugaenko, Dmitry I.; Yurovskaya, Marina A.; Karchava, Alexander V.; The Journal of organic chemistry 82 (2017) 2136–2149; doi:10.1021/acs.joc.6b02952

data_4032270
_publ_section_title
;
 Quaternary N-(2-Pyridyl)-DABCO Salts: One-Pot in Situ Formation from
 Pyridine-N-oxides and Reactions with Nucleophiles: A Mild and Selective
 Route to Substituted N-(2-Pyridyl)-N'-ethylpiperazines.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2136
_journal_page_last               2149
_journal_paper_doi               10.1021/acs.joc.6b02952
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C21 H29 Br N5, C N S'
_chemical_formula_sum            'C22 H29 Br N6 S'
_chemical_formula_weight         489.48
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-10-21
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.80(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.826(8)
_cell_length_b                   7.652(9)
_cell_length_c                   20.88(3)
_cell_measurement_reflns_used    680
_cell_measurement_temperature    120
_cell_measurement_theta_max      25.875
_cell_measurement_theta_min      2.836
_cell_volume                     1089(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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_temperature      120
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1663
_diffrn_reflns_av_unetI/netI     0.2825
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            6543
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.010
_diffrn_reflns_theta_min         1.953
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.005
_exptl_absorpt_correction_T_max  0.0932
_exptl_absorpt_correction_T_min  0.0440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2008/2 (Bruker,2010) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1354 before and 0.0749 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1539 before and 0.0776 after correction.
 The Ratio of minimum to maximum transmission is 0.39.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 9111 reflections, Rint = 0.2277
 (2295 with I > 3sig(I), Rint = 0.1331)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.493
_exptl_crystal_description       plate
_exptl_crystal_F_000             508
_exptl_crystal_recrystallization_method 'crystallized from CH2CL2'
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.206
_refine_diff_density_min         -1.251
_refine_diff_density_rms         0.141
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.980
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3933
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      0.968
_refine_ls_R_factor_all          0.2198
_refine_ls_R_factor_gt           0.0994
_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^)+(0.0767P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1970
_refine_ls_wR_factor_ref         0.2507
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1756
_reflns_number_total             3933
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02952_si_002.cif
_cod_data_source_block           a
_cod_database_code               4032270
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95(5) 0.05(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Uiso/Uaniso restraints and constraints
S1S \\sim C1S \\sim N1S: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.01
N11 \\sim H8 \\sim C2 \\sim C16 \\sim H16A \\sim H16B \\sim C3 \\sim H3 \\sim
C12 \\sim H12A \\sim H12B \\sim C13 \\sim H13A \\sim H15B \\sim C10 \\sim C4
\\sim H4 \\sim C15 \\sim N1 \\sim C9 \\sim C8: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C20(H20A,H20B), C24(H24A,H24B), C16(H16A,H16B), C12(H12A,
 H12B), C13(H13A,H13B), C18(H18A,H18B), C17(H17A,H17B), C15(H15A,H15B),
 C26(H26A,H26B), C23(H23A,H23B), C21(H21A,H21B)
4.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C3(H3), C4(H4), C5(H5)
;
_shelx_res_checksum              178
_shelx_hkl_checksum              34572
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'mounted on aneedle'
_olex2_submission_special_instructions 'No special instructions were received'