Isoxazole Strategy for the Synthesis of 2,2'-Bipyridine Ligands: Symmetrical and Unsymmetrical 6,6'-Binicotinates, 2,2'-Bipyridine-5-carboxylates, and Their Metal Complexes.
Galenko, Ekaterina E.; Novikov, Mikhail S.; Shakirova, Firuza M.; Shakirova, Julia R.; Kornyakov, Ilya V.; Bodunov, Vladimir A.; Khlebnikov, Alexander F.; The Journal of organic chemistry 84 (2019) 3524–3536; doi:10.1021/acs.joc.9b00115

data_4033927
_publ_section_title
;
 Isoxazole Strategy for the Synthesis of 2,2'-Bipyridine Ligands:
 Symmetrical and Unsymmetrical 6,6'-Binicotinates,
 2,2'-Bipyridine-5-carboxylates, and Their Metal Complexes.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3524
_journal_page_last               3536
_journal_paper_doi               10.1021/acs.joc.9b00115
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C22 H16 N2 O4 S2'
_chemical_formula_sum            'C22 H16 N2 O4 S2'
_chemical_formula_weight         436.49
_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             2018-12-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.902(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.6496(3)
_cell_length_b                   8.8096(2)
_cell_length_c                   16.5349(3)
_cell_measurement_reflns_used    5397
_cell_measurement_temperature    100(3)
_cell_measurement_theta_max      30.8240
_cell_measurement_theta_min      3.2800
_cell_volume                     1979.93(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_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      100(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2096
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.887
_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      6.00  43.00   1.00    5.00    --  -22.58  38.00   0.00   37
  2  \w    -47.00  47.00   1.00    5.00    --   23.52 -77.00 120.00   94
  3  \w     39.00  66.00   1.00    5.00    --   23.52 178.00   0.00   27
  4  \w      4.00  92.00   1.00    5.00    --   23.52  57.00-120.00   88
  5  \w    -99.00 -74.00   1.00    5.00    --  -22.58 178.00  60.00   25
  6  \w      2.00  32.00   1.00    5.00    --   23.52  57.00 -30.00   30
;
_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      -0.0021083000
_diffrn_orient_matrix_UB_12      0.0711498000
_diffrn_orient_matrix_UB_13      0.0192926000
_diffrn_orient_matrix_UB_21      0.0267206000
_diffrn_orient_matrix_UB_22      -0.0307369000
_diffrn_orient_matrix_UB_23      0.0418344000
_diffrn_orient_matrix_UB_31      0.0447808000
_diffrn_orient_matrix_UB_32      0.0217645000
_diffrn_orient_matrix_UB_33      -0.0039487000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0172
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.887
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13023
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.887
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.933
_diffrn_reflns_theta_min         2.755
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.302
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97224
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.464
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.635
_exptl_crystal_size_mid          0.459
_exptl_crystal_size_min          0.455
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.498
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         5563
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0497P)^2^+1.2802P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0952
_refine_ls_wR_factor_ref         0.1011
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4792
_reflns_number_total             5563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00115_si_002.cif
_cod_data_source_block           cat-10-179
_cod_original_cell_volume        1979.92(7)
_cod_database_code               4033927
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'S2 C22 N2 O4'
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.831
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.51
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C2, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C9(H9), C10(H10), C13(H13), C14(H14), C20(H20),
 C21(H21), C22(H22)
3.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              78062
_shelx_hkl_checksum              24446
_olex2_date_sample_data_collection 2018-11-07
_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 1.102
_oxdiff_exptl_absorpt_empirical_full_min 0.946