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_4033925
_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         'C34 H35 Cl N2 O4 Pd, C H4 O'
_chemical_formula_sum            'C35 H39 Cl N2 O5 Pd'
_chemical_formula_weight         709.53
_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                 98.9993(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.83330(13)
_cell_length_b                   33.6758(3)
_cell_length_c                   7.13456(7)
_cell_measurement_reflns_used    16932
_cell_measurement_temperature    200(3)
_cell_measurement_theta_max      72.7460
_cell_measurement_theta_min      2.6080
_cell_volume                     3520.01(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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_environment      N~2~
_diffrn_ambient_temperature      200(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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    -57.00   1.00   0.50    3.20    --  -38.95  99.00   4.00  116
  2  \w    -19.00  27.00   0.50    3.20    --   38.95 -99.00-101.00   92
  3  \w     93.00 131.00   0.50   12.80    --  104.92  99.00   4.00   76
  4  \w     37.00 110.00   0.50   12.80    --  104.92 -99.00-101.00  146
  5  \w    -16.00  20.00   0.50    3.20    --  -38.95  65.00 -60.00   72
  6  \w    -56.00 -26.00   0.50    3.20    --  -38.95 -43.00 -90.00   60
  7  \w    -57.00  12.00   0.50    3.20    --  -38.95  77.00 -30.00  138
  8  \w    -57.00 -18.00   0.50    3.20    --  -38.95 -65.00  90.00   78
  9  \w   -105.00 -68.00   0.50    3.20    --  -38.95 -43.00 -90.00   74
 10  \w    -97.00 -68.00   0.50    3.20    --  -38.95 -65.00  90.00   58
 11  \w    -46.00  27.00   0.50    3.20    --  -38.95  32.00 -30.00  146
 12  \w    -64.00 -39.00   0.50    3.20    --  -38.95  77.00  90.00   50
 13  \w    -10.00  27.00   0.50    3.20    --  -38.95  77.00  90.00   74
 14  \w    -53.00 -26.00   0.50    3.20    --  -38.95  65.00 -60.00   54
 15  \w    -26.00  12.00   0.50    3.20    --   38.95 -43.00  60.00   76
 16  \w     23.00  98.00   0.50    3.20    --   38.95  43.00  30.00  150
 17  \w     67.00  93.00   0.50    3.20    --   38.95  65.00  30.00   52
 18  \w     48.00  73.00   0.50    3.20    --   38.95 -99.00-101.00   50
 19  \w     25.00  50.00   0.50    3.20    --   38.95  65.00  30.00   50
 20  \w     31.00  56.00   0.50    3.20    --   38.95 -43.00  60.00   50
 21  \w    -25.00  47.00   0.50    3.20    --   38.95 -54.00  60.00  144
 22  \w     96.00 154.00   0.50   12.80    --  104.92  30.00 150.00  116
 23  \w     31.00  56.00   0.50   12.80    --  104.92 -93.00 -60.00   50
 24  \w     91.00 148.00   0.50   12.80    --  104.92  61.00  90.00  114
 25  \w     82.00 155.00   0.50   12.80    --  104.92  93.00  30.00  146
 26  \w    128.00 153.00   0.50   12.80    --  104.92  45.00 120.00   50
 27  \w     76.00 118.00   0.50   12.80    --  104.92 -45.00-180.00   84
 28  \w     40.00  65.00   0.50   12.80    --  104.92 -45.00-180.00   50
 29  \w     93.00 150.00   0.50   12.80    --  104.92  53.00-150.00  114
 30  \w     50.00 127.00   0.50   12.80    --  104.92 -77.00 -90.00  154
 31  \w     61.00 125.00   0.50   12.80    --  104.92 -53.00-120.00  128
 32  \w     93.00 122.00   0.50   12.80    --  104.92 -45.00 -90.00   58
 33  \w     89.00 114.00   0.50   12.80    --  104.92 -93.00 -60.00   50
 34  \w     34.00 115.00   0.50   12.80    --  104.92 -22.00-120.00  162
 35  \w    131.00 157.00   0.50   12.80    --  104.92  30.00 -30.00   52
 36  \w     41.00  72.00   0.50   12.80    --  104.92 -45.00 -90.00   62
 37  \w     87.00 151.00   0.50   12.80    --  104.92  77.00  60.00  128
 38  \w     90.00 115.00   0.50   12.80    --  104.92  45.00 120.00   50
 39  \w    -52.00 -27.00   0.50    3.20    --  -38.95  99.00   4.00   50
 40  \w   -102.00 -62.00   0.50    3.20    --  -38.95 -54.00-180.00   80
 41  \w    -91.00 -40.00   0.50    3.20    --  -38.95 -54.00  60.00  102
 42  \w    -56.00 -25.00   0.50    3.20    --  -38.95 -43.00-120.00   62
 43  \w     67.00 105.00   0.50    3.20    --   38.95  32.00-180.00   76
 44  \w     70.00  99.00   0.50    3.20    --   38.95  43.00 120.00   58
 45  \w     53.00  79.00   0.50    3.20    --   38.95  32.00 -60.00   52
 46  \w     36.00  86.00   0.50    3.20    --   38.95-138.00-120.00  100
 47  \w     22.00  65.00   0.50    3.20    --   38.95  43.00 120.00   86
 48  \w     90.00 117.00   0.50   12.80    --  104.92  77.00   0.00   54
 49  \w    100.00 125.00   0.50   12.80    --  104.92-133.00  30.00   50
 50  \w     74.00 116.00   0.50   12.80    --  104.92-133.00 -90.00   84
 51  \w     51.00 106.00   0.50   12.80    --  104.92-133.00  90.00  110
 52  \w     62.00 123.00   0.50   12.80    --  104.92 -61.00  90.00  122
 53  \w     52.00 115.00   0.50   12.80    --  104.92 -30.00  90.00  126
 54  \w     43.00 119.00   0.50   12.80    --  104.92 -30.00   0.00  152
 55  \w     45.00  75.00   0.50   12.80    --  104.92-133.00-180.00   60
 56  \w     88.00 137.00   0.50   12.80    --  104.92  45.00 -30.00   98
 57  \w    100.00 143.00   0.50   12.80    --  104.92  -7.00 -90.00   86
 58  \w     36.00  82.00   0.50   12.80    --  104.92  -7.00 -90.00   92
 59  \w     98.00 124.00   0.50   12.80    --  104.92-133.00-180.00   52
 60  \w     47.00  73.00   0.50   12.80    --  104.92-133.00 -60.00   52
 61  \w     46.00  72.00   0.50   12.80    --  104.92-133.00  30.00   52
 62  \w    132.00 157.00   0.50   12.80    --  104.92  77.00   0.00   50
 63  \w     41.00 125.00   0.50   12.80    --  104.92-133.00 120.00  168
 64  \w     48.00 132.00   0.50   12.80    --  104.92 -93.00  90.00  168
 65  \w     92.00 152.00   0.50   12.80    --  104.92  30.00 -60.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0792418000
_diffrn_orient_matrix_UB_12      -0.0283977000
_diffrn_orient_matrix_UB_13      -0.0206540000
_diffrn_orient_matrix_UB_21      0.0454614000
_diffrn_orient_matrix_UB_22      0.0327366000
_diffrn_orient_matrix_UB_23      -0.1036831000
_diffrn_orient_matrix_UB_31      0.0520265000
_diffrn_orient_matrix_UB_32      0.0146535000
_diffrn_orient_matrix_UB_33      0.1914271000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            33252
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.788
_diffrn_reflns_theta_min         2.624
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.282
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74094
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.339
_exptl_crystal_description       plate
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.057
_refine_diff_density_min         -1.424
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         6984
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0533
_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^)+(0.0563P)^2^+12.0002P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1424
_refine_ls_wR_factor_ref         0.1446
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6410
_reflns_number_total             6984
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00115_si_003.cif
_cod_data_source_block           cat-10-214
_cod_original_cell_volume        3520.00(6)
_cod_database_code               4033925
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Pd1 C34 Cl1 N2 O4'
_shelx_estimated_absorpt_t_max   0.709
_shelx_estimated_absorpt_t_min   0.174
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     70.93
_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, All O(H) groups
2. Restrained distances
 C29A-C27A
 1.5 with sigma of 0.05
 C28A-C27A
 1.5 with sigma of 0.05
 C27A-C30A
 1.5 with sigma of 0.05
 C32A-C31A
 1.5 with sigma of 0.05
 C34A-C31A
 1.5 with sigma of 0.05
 C33A-C31A
 1.5 with sigma of 0.05
 C31B-C33B
 1.5 with sigma of 0.05
 C31B-C34B
 1.5 with sigma of 0.05
 C31B-C32B
 1.5 with sigma of 0.05
 C28B-C27B
 1.5 with sigma of 0.05
 C30B-C27B
 1.5 with sigma of 0.05
 C29B-C27B
 1.5 with sigma of 0.05
3. Uiso/Uaniso restraints and constraints
Uanis(C28A) \\sim Ueq, Uanis(C28B) \\sim Ueq: with sigma of 0 and sigma for
terminal atoms of 0.02
Uanis(C30B) \\sim Ueq, Uanis(C30A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C29B) \\sim Ueq, Uanis(C29A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C32A) \\sim Ueq, Uanis(C32B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C33B) \\sim Ueq, Uanis(C33A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C34A) \\sim Ueq, Uanis(C34B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C31A) \\sim Ueq, Uanis(C31B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C27A) \\sim Ueq, Uanis(C27B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C35) = Uanis(O5)
4. Others
 Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33A)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=1-FVAR(1)
 Sof(C31B)=Sof(C32B)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33B)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=FVAR(1)
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(2)
 Sof(C27B)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29B)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C11(H11), C12(H12), C15(H15), C16(H16),
 C22(H22), C23(H23), C25(H25)
5.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C19(H19A,H19B,H19C), C28A(H28A,H28B,H28C), C28B(H28D,
 H28E,H28F), C29A(H29A,H29B,H29C), C29B(H29D,H29E,H29F), C30A(H30A,H30B,H30C),
 C30B(H30D,H30E,H30F), C32A(H32A,H32B,H32C), C32B(H32D,H32E,H32F), C33A(H33D,
 H33E,H33F), C33B(H33A,H33B,H33C), C34A(H34A,H34B,H34C), C34B(H34D,H34E,H34F),
 C35(H35A,H35B,H35C)
5.c Idealised tetrahedral OH refined as rotating group:
 O5(H5A)
;
_shelx_res_checksum              4028
_shelx_hkl_checksum              69784
_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 1.651
_oxdiff_exptl_absorpt_empirical_full_min 0.537