The ubiquitous P(<i>o</i>-tol)<sub>3</sub> ligand promotes formation of catalytically-active higher order palladacyclic clusters.
Husbands, David R.; Tanner, Theo; Whitwood, Adrian C.; Hodnett, Neil S.; Wheelhouse, Katherine M. P.; Fairlamb, Ian J. S.; Chemical science 15 (2024) 18627–18633; doi:10.1039/d4sc05346j

data_1572926
_publ_section_title
;
 The ubiquitous P(<i>o</i>-tol)<sub>3</sub> ligand promotes formation of
 catalytically-active higher order palladacyclic clusters.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              18627
_journal_page_last               18633
_journal_paper_doi               10.1039/d4sc05346j
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C84 H82 O3 P4 Pd4'
_chemical_formula_sum            'C84 H82 O3 P4 Pd4'
_chemical_formula_weight         1688.97
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-25 deposited with the CCDC.	2024-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                98.300(2)
_cell_angle_beta                 93.130(2)
_cell_angle_gamma                116.152(3)
_cell_formula_units_Z            2
_cell_length_a                   13.6277(4)
_cell_length_b                   14.8406(4)
_cell_length_c                   20.3507(5)
_cell_measurement_reflns_used    14589
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      71.0130
_cell_measurement_theta_min      3.6760
_cell_volume                     3623.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -21.00   5.00   1.00    5.50    --    0.00 -77.00  90.00   26
  2  \w    -21.00  14.00   1.00    5.50    --    0.00 -77.00-150.00   35
  3  \w    -36.00  -8.00   1.00    5.50    --    0.00 -57.00 -30.00   28
  4  \w    -69.00 -39.00   1.00    5.50    --    0.00 -57.00 -30.00   30
  5  \w    -10.00  27.00   1.00    5.50    --    0.00 -77.00  60.00   37
  6  \w    -14.00  28.00   1.00    5.50    --    0.00 -77.00   0.00   42
  7  \w     46.00 109.00   1.00   22.00    --   54.00-125.00-150.00   63
  8  \w      1.00  78.00   1.00   22.00    --   54.00 -38.00 120.00   77
  9  \w     32.00 125.00   1.00   22.00    --   54.00  38.00  60.00   93
 10  \w     28.00  80.00   1.00   22.00    --   54.00-125.00 120.00   52
 11  \w     97.00 123.00   1.00   22.00    --   54.00  57.00 -60.00   26
 12  \w     18.00  71.00   1.00   22.00    --   54.00 -57.00 -90.00   53
 13  \w    -15.00  15.00   1.00   22.00    --   54.00 -57.00 120.00   30
 14  \w     37.00 123.00   1.00   22.00    --   54.00  57.00 -90.00   86
 15  \w    116.00 144.00   1.00   22.00    --  108.00 111.00-120.00   28
 16  \w     54.00 130.00   1.00   22.00    --  108.00 -63.00  60.00   76
 17  \w    107.00 133.00   1.00   22.00    --  108.00  77.00 -90.00   26
 18  \w     37.00  67.00   1.00   22.00    --  108.00 -91.00 -60.00   30
 19  \w    105.00 148.00   1.00   22.00    --  108.00 111.00  90.00   43
 20  \w    109.00 168.00   1.00   22.00    --  108.00  63.00  60.00   59
 21  \w     47.00 108.00   1.00   22.00    --  108.00-111.00-180.00   61
 22  \w    133.00 169.00   1.00   22.00    --  108.00  77.00  30.00   36
 23  \w     37.00 108.00   1.00   22.00    --  108.00-111.00-120.00   71
 24  \w    103.00 128.00   1.00   22.00    --  108.00  77.00  30.00   25
 25  \w     88.00 161.00   1.00   22.00    --  108.00  63.00-180.00   73
 26  \w     54.00 109.00   1.00   22.00    --  108.00-111.00 -60.00   55
 27  \w     48.00 129.00   1.00   22.00    --  108.00 -50.00 -30.00   81
 28  \w    143.00 177.00   1.00   22.00    --  108.00  77.00 120.00   34
 29  \w     48.00 104.00   1.00   22.00    --  108.00 -91.00 -30.00   56
 30  \w     60.00 109.00   1.00   22.00    --  108.00-108.00  82.00   49
 31  \w    103.00 129.00   1.00   22.00    --  108.00  77.00 120.00   26
 32  \w    109.00 165.00   1.00   22.00    --  108.00 111.00   0.00   56
 33  \w     87.00 174.00   1.00   22.00    --  108.00  38.00 150.00   87
;
_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      0.1070219000
_diffrn_orient_matrix_UB_12      0.0363033000
_diffrn_orient_matrix_UB_13      0.0480578000
_diffrn_orient_matrix_UB_21      0.0682450000
_diffrn_orient_matrix_UB_22      0.0332767000
_diffrn_orient_matrix_UB_23      -0.0577728000
_diffrn_orient_matrix_UB_31      0.0059579000
_diffrn_orient_matrix_UB_32      0.1069495000
_diffrn_orient_matrix_UB_33      0.0176311000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_av_unetI/netI     0.0404
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            25088
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         3.378
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.099
_exptl_absorpt_correction_T_max  0.947
_exptl_absorpt_correction_T_min  0.705
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1708
_exptl_crystal_recrystallization_method
'crystallisation from dichloromethane and pentane'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.055
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     870
_refine_ls_number_reflns         12912
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0308
_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^)+(0.0341P)^2^+3.6378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0777
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11265
_reflns_number_total             12912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05346j3.cif
_cod_data_source_block           ijsf21009
_cod_depositor_comments
'Adding full bibliography for 1572926--1572929.cif.'
_cod_original_cell_volume        3623.25(19)
_cod_database_code               1572926
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C84 H82 O3 P4 Pd4'
_chemical_oxdiff_usercomment     'David Husbands DRH-01-131'
_shelx_estimated_absorpt_t_max   0.712
_shelx_estimated_absorpt_t_min   0.384
_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, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O3-H3A = O1-H1
 0.87 with sigma of 0.001
 Pd4-H3A = H3A-Pd3
 2.57 with sigma of 0.01
 Pd1-H1 = H1-Pd2
 2.57 with sigma of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C22(H22A,H22B), C43(H43A,H43B), C64(H64A,H64B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C16(H16), C17(H17), C18(H18), C19(H19), C24(H24), C25(H25), C26(H26), C27(H27),
  C30(H30), C31(H31), C32(H32), C33(H33), C37(H37), C38(H38), C39(H39),
 C40(H40), C45(H45), C46(H46), C47(H47), C48(H48), C51(H51), C52(H52), C53(H53),
  C54(H54), C58(H58), C59(H59), C60(H60), C61(H61), C66(H66), C67(H67),
 C68(H68), C69(H69), C72(H72), C73(H73), C74(H74), C75(H75), C79(H79), C80(H80),
  C81(H81), C82(H82)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C35(H35A,H35B,H35C), C42(H42A,H42B,
 H42C), C56(H56A,H56B,H56C), C63(H63A,H63B,H63C), C77(H77A,H77B,H77C), C84(H84A,
 H84B,H84C)
;
_shelx_res_checksum              53811
_olex2_date_sample_data_collection 2021-01-28
_olex2_date_sample_submission    2021-01-25
_olex2_exptl_crystal_mounting_method 'oil on 75 micrometre micromount'
_olex2_submission_original_sample_id DRH-01-131
_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 2.275
_oxdiff_exptl_absorpt_empirical_full_min 0.603