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_7248009
_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         'C24 H23 Cl N2 O5 S'
_chemical_formula_sum            'C24 H23 Cl N2 O5 S'
_chemical_formula_weight         486.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-23
_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                90
_cell_angle_beta                 108.353(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.5028(18)
_cell_length_b                   9.2793(6)
_cell_length_c                   24.775(2)
_cell_measurement_reflns_used    2010
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.6660
_cell_measurement_theta_min      3.5850
_cell_volume                     4691.9(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (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 (Sheldrick, 2015)'
_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    -83.00   1.00   0.60   75.00    --  -15.48 -57.00 -30.00  140
  2  \w    -24.00  12.60   0.60   75.00    --  -15.48 -99.00-120.00   61
  3  \w    -85.00  -3.40   0.60   75.00    --  -15.48 -38.00-120.00  136
  4  \w    -83.00 -57.80   0.60   75.00    --  -15.48 -19.00  30.00   42
;
_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      -0.0011481000
_diffrn_orient_matrix_UB_12      0.0064638000
_diffrn_orient_matrix_UB_13      0.0282054000
_diffrn_orient_matrix_UB_21      -0.0346676000
_diffrn_orient_matrix_UB_22      0.0047344000
_diffrn_orient_matrix_UB_23      -0.0105286000
_diffrn_orient_matrix_UB_31      -0.0022526000
_diffrn_orient_matrix_UB_32      -0.0759860000
_diffrn_orient_matrix_UB_33      0.0017556000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_av_unetI/netI     0.0672
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            10760
_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         3.027
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.290
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69625
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.691
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         4793
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1341
_refine_ls_R_factor_gt           0.0881
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0884P)^2^+21.3276P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2256
_refine_ls_wR_factor_ref         0.2551
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2939
_reflns_number_total             4793
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc04425d2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7248007--7248009.cif.'
_cod_database_code               7248009
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         c12h12n2o3
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.905
_reflns_odcompleteness_completeness 99.75
_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 Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C11(H11), C12(H12), C14(H14), C15(H15), C20(H20), C21(H21), C22(H22),
 C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              28458
_shelx_hkl_checksum              12423
_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 1.302
_oxdiff_exptl_absorpt_empirical_full_min 0.644