Selective synthesis of gem-dihalopiperidines and 4-halo-1,2,3,6-tetrahydropyridines from halogen substituted homoallylic benzenesulfonamides and aldehydes
Bora, Surjya Kumar; Saikia, Anil K.; RSC Advances 15 (2025) 21257–21268; doi:10.1039/D5RA03630E

data_7250582
_publ_section_title
;
 Selective synthesis of gem-dihalopiperidines and
 4-halo-1,2,3,6-tetrahydropyridines from halogen substituted homoallylic
 benzenesulfonamides and aldehydes
;
_journal_issue                   27
_journal_name_full               'RSC Advances'
_journal_page_first              21257
_journal_page_last               21268
_journal_paper_doi               10.1039/D5RA03630E
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C19 H21 Br Cl N O2 S'
_chemical_formula_sum            'C19 H21 Br Cl N O2 S'
_chemical_formula_weight         442.79
_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
_audit_creation_date             2025-03-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-03-16 deposited with the CCDC.	2025-06-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.424(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.319(4)
_cell_length_b                   10.440(2)
_cell_length_c                   9.3782(19)
_cell_measurement_reflns_used    9958
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      24.42
_cell_measurement_theta_min      2.20
_cell_volume                     1956.6(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      295.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0692
_diffrn_reflns_av_unetI/netI     0.0578
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            19480
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.433
_diffrn_reflns_theta_min         2.201
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.356
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5548
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1778 before and 0.1191 after correction.
The Ratio of minimum to maximum transmission is 0.7443.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.503
_exptl_crystal_description       needle
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.583
_refine_diff_density_min         -0.563
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.150(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3954
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0630
_refine_ls_R_factor_gt           0.0515
_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^)+(0.0958P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1331
_refine_ls_wR_factor_ref         0.1418
_reflns_Friedel_coverage         0.980
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                3317
_reflns_number_total             3954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra03630e3.cif
_cod_data_source_block           skbclbr1_0m_a
_cod_database_code               7250582
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.850(18)
 0.150(18)
2. 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
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B)
3.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C17(H17), C18(H18)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              47478
_olex2_submission_special_instructions 'No special instructions were received'