An electron-donor–acceptor complex between two intermediates enables a N–N bond cleavage cascade process to access 2,3-difunctionalized pyridines
Liu, Ya-Zhou; Chen, Yu; Wang, Amu; Shen, Zhongke; Zhou, Xueting; Zhang, Jichao; Jian, Yinxiang; Ma, Xiaofeng; Green Chemistry 26 (2024) 2280–2289; doi:10.1039/D3GC04425D

data_7248008
_publ_section_title
;
 An electron-donor--acceptor complex between two intermediates enables a
 N--N bond cleavage cascade process to access 2,3-difunctionalized
 pyridines
;
_journal_issue                   4
_journal_name_full               'Green Chemistry'
_journal_page_first              2280
_journal_page_last               2289
_journal_paper_doi               10.1039/D3GC04425D
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C21 H19 Br N2 O4 S2, C3 H6 O'
_chemical_formula_sum            'C24 H25 Br N2 O5 S2'
_chemical_formula_weight         565.49
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-10-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-11-27 deposited with the CCDC.	2024-01-10 downloaded from the CCDC.
;
_cell_angle_alpha                92.802(6)
_cell_angle_beta                 98.268(7)
_cell_angle_gamma                103.730(7)
_cell_formula_units_Z            2
_cell_length_a                   8.1423(8)
_cell_length_b                   12.2839(8)
_cell_length_c                   12.9853(9)
_cell_measurement_reflns_used    1959
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.2890
_cell_measurement_theta_min      3.3200
_cell_volume                     1243.89(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0874
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_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     -2.00  49.00   1.00    2.25    --  -15.48  57.00 -60.00   51
  2  \w    -42.00  52.00   1.00    2.25    --  -15.48  77.00 150.00   94
  3  \w    -17.00  19.00   1.00    2.25    --  -15.48 -99.00 -60.00   36
  4  \w    -19.00  39.00   1.00    2.25    --  -15.48  57.00-150.00   58
  5  \w      3.00  79.00   1.00    2.25    --   17.66  57.00 -60.00   76
  6  \w     -8.00  85.00   1.00    2.25    --   17.66  77.00  60.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0208346000
_diffrn_orient_matrix_UB_12      -0.0573454000
_diffrn_orient_matrix_UB_13      0.0105406000
_diffrn_orient_matrix_UB_21      0.0129889000
_diffrn_orient_matrix_UB_22      0.0164513000
_diffrn_orient_matrix_UB_23      0.0542679000
_diffrn_orient_matrix_UB_31      -0.0874683000
_diffrn_orient_matrix_UB_32      0.0007814000
_diffrn_orient_matrix_UB_33      -0.0036688000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0724
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            10277
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         3.182
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.858
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79581
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.510
_exptl_crystal_description       block
_exptl_crystal_F_000             580
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         5093
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1004
_refine_ls_R_factor_gt           0.0543
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0578P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1130
_refine_ls_wR_factor_ref         0.1347
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3207
_reflns_number_total             5093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc04425d2.cif
_cod_data_source_block           221011_s4_lyz
_cod_depositor_comments
'Adding full bibliography for 7248007--7248009.cif.'
_cod_database_code               7248008
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         c12h12n2o3
_shelx_estimated_absorpt_t_max   0.654
_shelx_estimated_absorpt_t_min   0.562
_diffrn_oxdiff_digest_frames
;
0127f5b8d7120ecf6fefb0bdba1d1d016000029311c
;
_diffrn_oxdiff_digest_hkl
;
01e62c10eb1c671a073b62e8949411a15be98b
;
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Ternary CH refined with riding coordinates:
 C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13), C16(H16), C17(H17),
 C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C)
;
_shelx_res_checksum              25083
_shelx_hkl_checksum              34787
_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 1.225
_oxdiff_exptl_absorpt_empirical_full_min 0.802