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_7248007
_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         'C17 H16 Cl N3 O3 S'
_chemical_formula_sum            'C17 H16 Cl N3 O3 S'
_chemical_formula_weight         377.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-11-17
_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                 103.775(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4261(5)
_cell_length_b                   9.6846(4)
_cell_length_c                   16.4306(7)
_cell_measurement_reflns_used    2263
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.1390
_cell_measurement_theta_min      3.4560
_cell_volume                     1765.87(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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
;
  1 omega  -30.00   42.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773   57.0000   30.0000 72

  2 omega  -25.00    1.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773   57.0000   90.0000 26

  3 omega  -21.00   15.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773  -99.0000  150.0000 36

  4 omega  -82.00  -56.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773 -178.0000   60.0000 26

  5 omega  -84.00    3.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773  -38.0000 -150.0000 87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0630673000
_diffrn_orient_matrix_UB_12      0.0093021000
_diffrn_orient_matrix_UB_13      0.0146557000
_diffrn_orient_matrix_UB_21      0.0084185000
_diffrn_orient_matrix_UB_22      -0.0725541000
_diffrn_orient_matrix_UB_23      -0.0000215000
_diffrn_orient_matrix_UB_31      0.0059548000
_diffrn_orient_matrix_UB_32      0.0032924000
_diffrn_orient_matrix_UB_33      -0.0419722000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0385
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8593
_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         3.247
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.356
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89385
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3599
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0605
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0467P)^2^+0.6078P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1036
_refine_ls_wR_factor_ref         0.1133
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2841
_reflns_number_total             3599
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc04425d2.cif
_cod_data_source_block           201117_s4_sws_1
_cod_depositor_comments
'Adding full bibliography for 7248007--7248009.cif.'
_cod_original_cell_volume        1765.86(13)
_cod_database_code               7248007
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c12h12n2o3cl1
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.886
_reflns_odcompleteness_completeness 99.71
_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:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C12(H12), C13(H13), C15(H15), C16(H16)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              25736
_shelx_hkl_checksum              3197
_olex2_submission_special_instructions 'No special instructions were received'