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_1572929
_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         'C86 H88 O4 P5 Pd6, 2(C4 H8 O)'
_chemical_formula_sum            'C94 H104 O6 P5 Pd6'
_chemical_formula_weight         2123.02
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-26
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-26 deposited with the CCDC.	2024-10-15 downloaded from the CCDC.
;
_cell_angle_alpha                75.5537(14)
_cell_angle_beta                 85.6199(13)
_cell_angle_gamma                84.3876(13)
_cell_formula_units_Z            4
_cell_length_a                   15.4929(2)
_cell_length_b                   20.2644(3)
_cell_length_c                   32.5025(5)
_cell_measurement_reflns_used    41723
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      71.1130
_cell_measurement_theta_min      3.7820
_cell_volume                     9820.0(3)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  30.00   1.00    3.50    --    0.00 -77.00-180.00   51
  2  \w    -21.00  69.00   1.00    3.50    --    0.00  57.00 -30.00   90
  3  \w     33.00 123.00   1.00   14.00    --   54.00  57.00 150.00   90
  4  \w    -15.00  75.00   1.00   14.00    --   54.00 -57.00-180.00   90
  5  \w     10.00 127.00   1.00   14.00    --   54.00  19.00  90.00  117
  6  \w     27.00 111.00   1.00   14.00    --   54.00-125.00 120.00   84
  7  \w    -15.00  75.00   1.00   14.00    --   54.00 -57.00 -90.00   90
  8  \w     36.00 178.00   1.00   14.00    --  108.00  12.00 -90.00  142
  9  \w     40.00 130.00   1.00   14.00    --  108.00 -63.00-180.00   90
 10  \w     36.00 134.00   1.00   14.00    --  108.00 -38.00   0.00   98
 11  \w     36.00 109.00   1.00   14.00    --  108.00-111.00 -60.00   73
 12  \w     36.00 109.00   1.00   14.00    --  108.00-111.00  60.00   73
 13  \w     40.00 130.00   1.00   14.00    --  108.00 -63.00 -60.00   90
 14  \w    103.00 178.00   1.00   14.00    --  108.00  77.00 -60.00   75
 15  \w     35.00 142.00   1.00   14.00    --  108.00 -25.00-120.00  107
 16  \w     36.00 109.00   1.00   14.00    --  108.00-111.00-150.00   73
 17  \w     38.00 130.00   1.00   14.00    --  108.00 -50.00 150.00   92
 18  \w     61.00 146.00   1.00   14.00    --  108.00 178.00-120.00   85
 19  \w     36.00 109.00   1.00   14.00    --  108.00-111.00 120.00   73
 20  \w    -21.00  30.00   1.00    3.50    --    0.00 -77.00 120.00   51
 21  \w    -73.00  44.00   1.00    3.50    --    0.00 -19.00-180.00  117
 22  \w     33.00 123.00   1.00   14.00    --   54.00  57.00 -60.00   90
 23  \w     27.00 123.00   1.00   14.00    --   54.00  71.00 -27.00   96
 24  \w     33.00 123.00   1.00   14.00    --   54.00  57.00  90.00   90
 25  \w     33.00 123.00   1.00   14.00    --   54.00  57.00-150.00   90
 26  \w     33.00 123.00   1.00   14.00    --   54.00  57.00-120.00   90
;
_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      0.0708422000
_diffrn_orient_matrix_UB_12      -0.0582039000
_diffrn_orient_matrix_UB_13      -0.0019528000
_diffrn_orient_matrix_UB_21      -0.0409241000
_diffrn_orient_matrix_UB_22      -0.0124146000
_diffrn_orient_matrix_UB_23      -0.0388673000
_diffrn_orient_matrix_UB_31      0.0576093000
_diffrn_orient_matrix_UB_32      0.0515996000
_diffrn_orient_matrix_UB_33      -0.0298017000
_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  0.0570
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            95656
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.505
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.814
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.174
_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 greenish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       plate
_exptl_crystal_F_000             4268
_exptl_crystal_recrystallization_method
'Crystallisation from tetrahydrofuran and water'
_exptl_crystal_size_max          0.232
_exptl_crystal_size_mid          0.179
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.910
_refine_diff_density_min         -1.577
_refine_diff_density_rms         0.172
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2019
_refine_ls_number_reflns         34970
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0750
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0825P)^2^+95.9278P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1806
_refine_ls_wR_factor_ref         0.1890
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28842
_reflns_number_total             34970
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05346j3.cif
_cod_data_source_block           ijsf21006a
_cod_depositor_comments
'Adding full bibliography for 1572926--1572929.cif.'
_cod_database_code               1572929
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C104 H92 O8.5 P5 Pd6'
_chemical_oxdiff_usercomment     'David Husbands DRH-01-123'
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.209
_reflns_odcompleteness_completeness 99.72
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C198) \\sim Ueq: with sigma of 0.025 and sigma for terminal atoms of 0.05
Uanis(C160) \\sim Ueq, Uanis(C167) \\sim Ueq, Uanis(C168) \\sim Ueq,
Uanis(C169) \\sim Ueq: with sigma of 0.025 and sigma for terminal atoms of 0.05
Uanis(C200) \\sim Ueq, Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq,
Uanis(C203) \\sim Ueq, Uanis(C204) \\sim Ueq: with sigma of 0.025 and sigma for
terminal atoms of 0.05
3.a Ternary CH refined with riding coordinates:
 O1(H1), O4(H4A), O5(H5A), O8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C24(H24A,H24B), C45(H45A,H45B), C66(H66A,H66B), C87(H87A,H87B),
 C117(H11D,H11E), C131(H13D,H13E), C152(H15D,H15E), C197(H19A,H19B), C198(H19C,
 H19D), C199(H19E,H19F), C200(H20A,H20B), C173(H17D,H17E), C174(H17F,H17G),
 C175(H17H,H17I), C176(H17J,H17K), C177(H17L,H17M), C178(H17N,H17O), C179(H17P,
 H17Q), C180(H18A,H18B), C201(H20C,H20D), C202(H20E,H20F), C203(H20G,H20H),
 C204(H20I,H20J)
3.c 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), C26(H26), C27(H27), C28(H28), C29(H29),
  C32(H32), C33(H33), C34(H34), C35(H35), C39(H39), C40(H40), C41(H41),
 C42(H42), C47(H47), C48(H48), C49(H49), C50(H50), C53(H53), C54(H54), C55(H55),
  C56(H56), C60(H60), C61(H61), C62(H62), C63(H63), C68(H68), C69(H69),
 C70(H70), C71(H71), C74(H74), C75(H75), C76(H76), C77(H77), C81(H81), C82(H82),
  C83(H83), C84(H84), C89(H89), C90(H90), C91(H91), C92(H92), C95(H95),
 C96(H96), C97(H97), C98(H98), C102(H102), C103(H103), C104(H104), C105(H105),
 C111(H111), C112(H112), C113(H113), C114(H114), C119(H119), C120(H120),
 C121(H121), C122(H122), C125(H125), C126(H126), C127(H127), C128(H128),
 C133(H133), C134(H134), C135(H135), C136(H136), C139(H139), C140(H140),
 C141(H141), C142(H142), C146(H146), C147(H147), C148(H148), C149(H149),
 C154(H154), C155(H155), C156(H156), C157(H157), C160(H160), C161(H161),
 C162(H162), C163(H163), C167(H167), C168(H168), C169(H169), C170(H170)
3.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C37(H37A,H37B,H37C), C44(H44A,H44B,H44C), C58(H58A,H58B,H58C), C65(H65A,
 H65B,H65C), C79(H79A,H79B,H79C), C86(H86A,H86B,H86C), C100(H10A,H10B,H10C),
 C107(H10D,H10E,H10F), C108(H10G,H10H,H10I), C109(H10J,H10K,H10L), C116(H11A,
 H11B,H11C), C130(H13A,H13B,H13C), C144(H14D,H14E,H14F), C151(H15A,H15B,H15C),
 C165(H16A,H16B,H16C), C172(H17A,H17B,H17C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              12669
_shelx_fab_checksum              91108
_olex2_date_sample_data_collection 2021-01-19
_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 2.751
_oxdiff_exptl_absorpt_empirical_full_min 0.705