Stereodefined synthesis of cyclic amidines by domino 1,7-H shift and 6π electrocyclisation.
Martin, Matthew L.; Wilson, Claire; Boyer, Alistair; Chemical communications (Cambridge, England) 59 (2023) 4899–4902; doi:10.1039/d3cc01127e

data_7131518
_publ_section_title
;
 Stereodefined synthesis of cyclic amidines by domino 1,7-H shift and
 6&#x3c0; electrocyclisation.
;
_journal_issue                   33
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4899
_journal_page_last               4902
_journal_paper_doi               10.1039/d3cc01127e
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'C15 H19 N3 O4 S'
_chemical_formula_sum            'C15 H19 N3 O4 S'
_chemical_formula_weight         337.39
_chemical_name_systematic
N-(4-nitrobenzenesulfonyl)-trans-1-ethyl-5,6-dimethyl-5,6-dihydropyridin-2-imine
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-11-04 deposited with the CCDC.	2023-03-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.592(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.4133(13)
_cell_length_b                   26.128(5)
_cell_length_c                   8.6554(16)
_cell_measurement_reflns_used    4441
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.958
_cell_measurement_theta_min      2.543
_cell_volume                     1629.6(5)
_computing_cell_refinement       'SAINT V8.37A (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'charge integrating pixel array detector'
_diffrn_detector_area_resol_mean 7.4074
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'multilayer mirror optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            14811
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.353
_diffrn_reflns_theta_min         2.543
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'INCOATEC I\ms 3.0'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.222
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5836
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1305 before and 0.0737 after correction. The Ratio of minimum to maximum transmission is 0.7826. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.375
_exptl_crystal_description       plate
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         4057
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.1077
_refine_ls_R_factor_gt           0.0738
_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^)+(0.0513P)^2^+1.5911P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1548
_refine_ls_wR_factor_ref         0.1685
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2841
_reflns_number_total             4057
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc01127e2.cif
_cod_data_source_block           mo_2019gu0023_150k_0m
_cod_depositor_comments          'Adding full bibliography for 7131518.cif.'
_cod_original_cell_volume        1629.5(5)
_cod_database_code               7131518
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.916
_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. Restrained distances
 C2A-C10 = C3-C11A = C2-C11 = C3A-C10A = C9A-C8A = C9-C8 = C4-C3A = C3A-C2A
 1.51 with sigma of 0.01
3. Others
 Fixed Sof: N1(0.8) C2(0.8) H2(0.8) C3(0.8) H3(0.8) H4A(0.8) H4B(0.2) H5A(0.8)
 H5B(0.2) C6(0.8) C8(0.8) H8A(0.8) H8B(0.8) C9(0.8) H9A(0.8) H9B(0.8) H9C(0.8)
 C10(0.2) H10A(0.2) H10B(0.2) H10C(0.2) C11(0.8) H11A(0.8) H11B(0.8) H11C(0.8)
 N1A(0.2) C2A(0.2) H2A(0.2) C3A(0.2) H3A(0.2) C6A(0.2) C8A(0.2) H8AA(0.2)
 H8AB(0.2) C9A(0.2) H9AA(0.2) H9AB(0.2) H9AC(0.2) C10A(0.2) H10D(0.2) H10E(0.2)
 H10F(0.2) C11A(0.8) H11D(0.8) H11E(0.8) H11F(0.8)
4.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C2A(H2A), C3A(H3A)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C8A(H8AA,H8AB)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4A), C4(H4B), C5(H5A), C5(H5B), C13(H13), C14(H14), C16(H16), C17(H17)
4.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C9A(H9AA,H9AB,
 H9AC), C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F)
;
_shelx_res_checksum              61629
_shelx_hkl_checksum              57039
_olex2_submission_special_instructions 'No special instructions were received'