Pyrazole based palladacycles for the synthesis of β-aminoketones by redox coupling of allyl alcohols and anilines.
Samser, Shaikh; Biswal, Priyabrata; Mamidala, Ramesh; Meher, Sushanta Kumar; Venkatasubbaiah, Krishnan; Organic & biomolecular chemistry 22 (2024) 8488–8492; doi:10.1039/d4ob01232a

data_7160151
_publ_section_title
;
 Pyrazole based palladacycles for the synthesis of &#x3b2;-aminoketones by
 redox coupling of allyl alcohols and anilines.
;
_journal_issue                   42
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8488
_journal_page_last               8492
_journal_paper_doi               10.1039/d4ob01232a
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C86 H50 F12 N4 O8 P2 Pd2, C4 H10 O2'
_chemical_formula_sum            'C90 H60 F12 N4 O10 P2 Pd2'
_chemical_formula_weight         1860.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2024-07-24 deposited with the CCDC.	2024-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.902(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.2159(5)
_cell_length_b                   19.6780(4)
_cell_length_c                   15.4208(5)
_cell_measurement_reflns_used    27749
_cell_measurement_temperature    112.2(4)
_cell_measurement_theta_max      75.0170
_cell_measurement_theta_min      3.8200
_cell_volume                     3880.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      112.2(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.964
_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   -102.00 -31.00   0.50    1.50    --  -38.50 -51.00 -38.00  142
  2  \w    -45.00  25.00   0.50    1.50    --  -38.50  51.00 106.00  140
  3  \w    -15.00  56.00   0.50    1.50    --   48.56 -51.00 -38.00  142
  4  \w     42.00 112.00   0.50    1.50    --   48.56  51.00 106.00  140
  5  \w     96.00 166.00   0.50    6.00    --  102.63  51.00 106.00  140
  6  \w     39.00 110.00   0.50    6.00    --  102.63 -51.00 -38.00  142
  7  \w    -42.00  28.00   0.50    1.50    --  -38.50  37.00-120.00  140
  8  \w   -105.00 -35.00   0.50    1.50    --  -38.50 -37.00  60.00  140
  9  \w    -50.00  24.00   0.50    1.50    --  -38.50  57.00 -30.00  148
 10  \w     25.00 113.00   0.50    1.50    --   48.56  77.00 -90.00  176
 11  \w     45.00 115.00   0.50    1.50    --   48.56  37.00-180.00  140
 12  \w     25.00 113.00   0.50    1.50    --   48.56  77.00-150.00  176
 13  \w     45.00 115.00   0.50    1.50    --   48.56  37.00 -30.00  140
 14  \w     43.00 117.00   0.50    1.50    --   48.56  19.00  90.00  148
 15  \w     25.00 113.00   0.50    1.50    --   48.56  77.00-180.00  176
 16  \w     38.00 126.00   0.50    6.00    --  102.63 -77.00 -30.00  176
 17  \w     80.00 167.00   0.50    6.00    --  102.63  77.00 150.00  174
 18  \w     90.00 165.00   0.50    6.00    --  102.63  61.00-180.00  150
 19  \w     80.00 108.00   0.50    6.00    --  102.63  77.00-180.00   56
 20  \w     39.00 103.00   0.50    6.00    --  102.63 -45.00-120.00  128
 21  \w     43.00 112.00   0.50    6.00    --  102.63 -61.00  60.00  138
 22  \w     80.00 108.00   0.50    6.00    --  102.63  77.00-150.00   56
 23  \w     88.00 117.00   0.50    6.00    --  102.63  64.00-176.28   58
 24  \w     78.00 105.00   0.50    6.00    --  102.63 -94.00  90.00   54
 25  \w     90.00 118.00   0.50    6.00    --  102.63  61.00-150.00   56
 26  \w     98.00 161.00   0.50    6.00    --  102.63  45.00-120.00  126
 27  \w     80.00 165.00   0.50    6.00    --  102.63  77.00-120.00  170
 28  \w    129.00 158.00   0.50    6.00    --  102.63  77.00-150.00   58
 29  \w    117.00 157.00   0.50    6.00    --  102.63  30.00 -30.00   80
 30  \w     38.00  87.00   0.50    6.00    --  102.63 -45.00 150.00   98
 31  \w    107.00 139.00   0.50    6.00    --  102.63  45.00  30.00   64
 32  \w     76.00 107.00   0.50    6.00    --  102.63 -94.00 -60.00   62
 33  \w     89.00 117.00   0.50    6.00    --  102.63  62.00-125.49   56
 34  \w    115.00 167.00   0.50    6.00    --  102.63  45.00 120.00  104
 35  \w    103.00 165.00   0.50    6.00    --  102.63  45.00 -90.00  124
 36  \w     99.00 138.00   0.50    6.00    --  102.63  45.00-150.00   78
 37  \w     90.00 117.00   0.50    6.00    --  102.63  61.00 150.00   54
 38  \w     35.00  70.00   0.50    6.00    --  102.63 -94.00 -60.00   70
 39  \w     90.00 128.00   0.50    6.00    --  102.63  61.00-120.00   76
 40  \w     38.00 109.00   0.50    6.00    --  102.63 -77.00  60.00  142
 41  \w    104.00 154.00   0.50    6.00    --  102.63  45.00-180.00  100
 42  \w     93.00 120.00   0.50    6.00    --  102.63  55.00 144.70   54
 43  \w    131.00 164.00   0.50    6.00    --  102.63  55.00 144.70   66
 44  \w    134.00 166.00   0.50    6.00    --  102.63  77.00-180.00   64
 45  \w     54.00  84.00   0.50    6.00    --  102.63 -45.00-180.00   60
 46  \w    106.00 155.00   0.50    6.00    --  102.63 125.00   0.00   98
 47  \w    100.00 162.00   0.50    6.00    --  102.63  15.00-150.00  124
 48  \w     36.00 106.00   0.50    6.00    --  102.63 -30.00 120.00  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0945357000
_diffrn_orient_matrix_UB_12      0.0407365000
_diffrn_orient_matrix_UB_13      -0.0045056000
_diffrn_orient_matrix_UB_21      -0.0196972000
_diffrn_orient_matrix_UB_22      0.0274094000
_diffrn_orient_matrix_UB_23      -0.1000723000
_diffrn_orient_matrix_UB_31      -0.0721854000
_diffrn_orient_matrix_UB_32      -0.0609352000
_diffrn_orient_matrix_UB_33      -0.0480501000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0986
_diffrn_reflns_av_unetI/netI     0.0708
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            52529
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.759
_diffrn_reflns_theta_min         3.456
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.948
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28735
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_description       block
_exptl_crystal_F_000             1876
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         5.306
_refine_diff_density_min         -1.681
_refine_diff_density_rms         0.190
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.025(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1084
_refine_ls_number_reflns         15378
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1108
_refine_ls_R_factor_gt           0.0922
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1063P)^2^+53.6460P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2250
_refine_ls_wR_factor_ref         0.2359
_reflns_Friedel_coverage         0.942
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                14099
_reflns_number_total             15378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01232a2.cif
_cod_data_source_block           kv-sam-35cf-bnl-dme
_cod_depositor_comments
'Adding full bibliography for 7160150--7160151.cif.'
_cod_database_code               7160151
_chemical_oxdiff_formula         'C148 H136 F26 N42 O14 P4 Pd4 '
_diffrn_oxdiff_ac3_digest_frames
;
016c97a3a7a1ae2ef26d8e1f95fa7927ac053443706
;
_diffrn_oxdiff_ac3_digest_hkl
;
01a3a54d8643ac3278718d3d490ce612512a9b
;
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.025(15) -0.025(15)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C88(H88A,H88B), C87(H87A,H87B)
3.b Aromatic/amide H refined with riding coordinates:
 C40(H40), C54(H54), C6(H6), C31(H31), C8(H8), C42(H42), C79(H79), C44(H44),
 C21(H21), C85(H85), C2(H2), C61(H61), C69(H69), C59(H59), C15(H15), C64(H64),
 C30(H30), C60(H60), C73(H73), C7(H7), C80(H80), C84(H84), C74(H74), C35(H35),
 C25(H25), C19(H19), C37(H37), C36(H36), C72(H72), C17(H17), C53(H53), C48(H48),
  C28(H28), C11(H11), C5(H5), C29(H29), C14(H14), C71(H71), C49(H49), C65(H65),
 C62(H62), C51(H51), C81(H81), C68(H68), C52(H52), C34(H34), C38(H38), C12(H12),
  C82(H82), C13(H13)
3.c Idealised Me refined as rotating group:
 C89(H89A,H89B,H89C), C90(H90A,H90B,H90C)
;
_shelx_res_checksum              50043
_shelx_shelxl_version_number     2014/7
_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 3.208
_oxdiff_exptl_absorpt_empirical_full_min 0.208