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_4033926
_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         'C26 H17 Cl3 N2 O4 Pd, C2 H3 N'
_chemical_formula_sum            'C28 H20 Cl3 N3 O4 Pd'
_chemical_formula_weight         675.22
_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     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                 92.1608(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.7195(3)
_cell_length_b                   15.3316(2)
_cell_length_c                   10.94788(19)
_cell_measurement_reflns_used    17343
_cell_measurement_temperature    100(3)
_cell_measurement_theta_max      31.2530
_cell_measurement_theta_min      3.4010
_cell_volume                     2636.62(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      100(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.904
_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     27.00  69.00   1.00   60.00    --   16.06  38.00  30.00   42
  2  \w    -19.00  27.00   1.00   60.00    --  -14.18 -99.00 120.00   46
  3  \w   -103.00 -78.00   1.00   60.00    --  -14.18-178.00 -30.00   25
  4  \w    -56.00  38.00   1.00   60.00    --   16.06 -57.00-150.00   94
  5  \w   -101.00 -76.00   1.00   60.00    --  -14.18 178.00-180.00   25
  6  \w    -43.00   6.00   1.00   60.00    --  -14.18  92.00 139.00   49
  7  \w     -2.00  88.00   1.00   60.00    --   16.06  38.00 -30.00   90
  8  \w     14.00  75.00   1.00   60.00    --   16.06  77.00  60.00   61
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0445544000
_diffrn_orient_matrix_UB_12      -0.0049887000
_diffrn_orient_matrix_UB_13      -0.0054342000
_diffrn_orient_matrix_UB_21      -0.0066101000
_diffrn_orient_matrix_UB_22      -0.0422021000
_diffrn_orient_matrix_UB_23      -0.0251560000
_diffrn_orient_matrix_UB_31      -0.0031032000
_diffrn_orient_matrix_UB_32      0.0182756000
_diffrn_orient_matrix_UB_33      -0.0595230000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0404
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.904
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            32677
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.526
_diffrn_reflns_theta_min         3.245
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.049
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63172
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.701
_exptl_crystal_description       plate
_exptl_crystal_F_000             1352
_exptl_crystal_size_max          0.436
_exptl_crystal_size_mid          0.352
_exptl_crystal_size_min          0.183
_refine_diff_density_max         0.676
_refine_diff_density_min         -1.146
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.209
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     393
_refine_ls_number_reflns         7960
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.210
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0336
_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^)+(0.0130P)^2^+4.3274P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0722
_refine_ls_wR_factor_ref         0.0755
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7116
_reflns_number_total             7960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00115_si_004.cif
_cod_data_source_block           cat-10-236
_cod_original_cell_volume        2636.61(8)
_cod_database_code               4033926
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Pd1 C26 O4 N2 Cl3'
_shelx_estimated_absorpt_t_max   0.831
_shelx_estimated_absorpt_t_min   0.658
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.64
_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. Uiso/Uaniso restraints and constraints
Uanis(C26B) \\sim Ueq, Uanis(C26A) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.008
3. Others
 Sof(O3B)=Sof(O4B)=Sof(C25B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(O3A)=Sof(O4A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C9(H9), C10(H10), C13(H13), C14(H14),
 C18(H18), C19(H19), C21(H21)
4.b Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C26A(H26A,H26B,H26C), C26B(H26D,H26E,H26F), C27(H27A,
 H27B,H27C)
;
_shelx_res_checksum              32556
_shelx_hkl_checksum              37265
_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 1.474
_oxdiff_exptl_absorpt_empirical_full_min 0.660