The ubiquitous cross-coupling catalyst system ‘Pd(OAc)2’/2PPh3 forms a unique dinuclear PdI complex: an important entry point into catalytically competent cyclic Pd3 clusters
Scott, Neil W. J.; Ford, Mark J.; Schotes, Christoph; Parker, Rachel R.; Whitwood, Adrian C.; Fairlamb, Ian J. S.; Chemical Science  (2019) –; doi:10.1039/C9SC01847F

data_1552101
_publ_section_title
;
 The ubiquitous cross-coupling catalyst system
 &#x2018;Pd(OAc)2&#x2019;/2PPh3 forms a unique dinuclear PdI complex: an
 important entry point into catalytically competent cyclic Pd3 clusters
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01847F
_journal_year                    2019
_chemical_formula_moiety         'C50 H43 O2 P3 Pd2, C4 H8 O'
_chemical_formula_sum            'C54 H51 O3 P3 Pd2'
_chemical_formula_weight         1053.66
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-31 deposited with the CCDC.    2019-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.7289(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8269(2)
_cell_length_b                   29.4867(5)
_cell_length_c                   14.1794(2)
_cell_measurement_reflns_used    7773
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      71.0530
_cell_measurement_theta_min      3.5840
_cell_volume                     4683.03(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -20.00  18.00   1.00    1.00    --    0.00  57.00-180.00   38
  2  \w     24.00  51.00   1.00    1.00    --    0.00  57.00-180.00   27
  3  \w    -16.00  55.00   1.00    1.00    --    0.00  57.00  90.00   71
  4  \w    -15.00  50.00   1.00    3.00    --   54.00 -57.00-150.00   65
  5  \w    -12.00  69.00   1.00    3.00    --   54.00 -57.00 120.00   81
  6  \w     71.00 123.00   1.00    3.00    --   54.00  57.00 -90.00   52
  7  \w     48.00  83.00   1.00    3.00    --   54.00 -99.00-180.00   35
  8  \w     21.00  81.00   1.00    3.00    --   54.00 -77.00 -90.00   60
  9  \w    118.00 172.00   1.00    3.00    --  108.00 111.00-120.00   54
 10  \w    109.00 134.00   1.00    3.00    --  108.00 -37.00 120.00   25
 11  \w     49.00  78.00   1.00    3.00    --  108.00 -37.00 120.00   29
 12  \w     38.00 122.00   1.00    3.00    --  108.00 -50.00 120.00   84
 13  \w     40.00 126.00   1.00    3.00    --  108.00 -37.00 -60.00   86
 14  \w     44.00  79.00   1.00    3.00    --  108.00-111.00 -30.00   35
 15  \w     89.00 176.00   1.00    3.00    --  108.00  63.00 -90.00   87
 16  \w     65.00 132.00   1.00    3.00    --  108.00 -77.00 -60.00   67
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1252616000
_diffrn_orient_matrix_UB_12      0.0167507000
_diffrn_orient_matrix_UB_13      0.0619243000
_diffrn_orient_matrix_UB_21      0.0328977000
_diffrn_orient_matrix_UB_22      0.0055497000
_diffrn_orient_matrix_UB_23      -0.0960565000
_diffrn_orient_matrix_UB_31      -0.0463042000
_diffrn_orient_matrix_UB_32      0.0491710000
_diffrn_orient_matrix_UB_33      -0.0102082000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            17077
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.617
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.503
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.319
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_description       plate
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.603
_refine_diff_density_rms         0.075
_refine_ls_extinction_coef       0.000044(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     561
_refine_ls_number_reflns         8345
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0301P)^2^+2.0234P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0646
_refine_ls_wR_factor_ref         0.0684
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7242
_reflns_number_total             8345
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01847f2.cif
_cod_data_source_block           ijsf1817
_cod_original_cell_volume        4683.01(14)
_cod_database_code               1552101
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H51 O3 P3 Pd2'
_chemical_oxdiff_usercomment     'Neil Scott NWJS-3-246-crystal1'
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.248
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 O3A-C54A \\sim O3A-C51A
 with sigma of 0.02
 C53A-C54A \\sim C51A-C52A
 with sigma of 0.02
 O3A-C52A \\sim O3A-C53A
 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C51A(H51A,H51B), C52A(H52A,H52B), C53A(H53A,H53B), C54A(H54A,H54B)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22),
  C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30),
 C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40),
  C41(H41), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48),
 C49(H49), C50(H50)
3.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C)
;
_shelx_res_checksum              1524
_olex2_date_sample_data_collection 2018-07-18
_olex2_date_sample_submission    2018-07-16
_olex2_exptl_crystal_mounting_method 'oil on 100 micrometre micromount'
_olex2_submission_original_sample_id NWJS-3-246-crystal1
_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 1.281
_oxdiff_exptl_absorpt_empirical_full_min 0.811