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_1572927
_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 H80 Cl2 O P4 Pd4, 1.435(C H2 Cl2), 0.295(C5 H12)'
_chemical_formula_sum            'C86.91 H86.4 Cl4.87 O P4 Pd4'
_chemical_formula_weight         1869.00
_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             2024-09-25
_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                82.3154(14)
_cell_angle_beta                 83.1540(13)
_cell_angle_gamma                82.3315(13)
_cell_formula_units_Z            2
_cell_length_a                   13.9903(2)
_cell_length_b                   15.1118(2)
_cell_length_c                   19.6632(3)
_cell_measurement_reflns_used    29947
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.6730
_cell_measurement_theta_min      3.9330
_cell_volume                     4061.19(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.70a 64-bit (release 22-09-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_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    -84.00 -21.00   0.50    5.15    --  -48.95 130.00-124.00  126
  2  \w   -119.00 -94.00   0.50    5.15    --  -48.95-130.00 163.00   50
  3  \w   -108.00 -65.00   0.50    5.15    --  -48.95-139.00 -10.00   86
  4  \w    -96.00 -70.00   0.50    5.15    --  -48.95 139.00  49.00   52
  5  \w     38.00  98.00   0.50    5.15    --   48.95-130.00 163.00  120
  6  \w     42.00 100.00   0.50    5.15    --   48.95-139.00 -10.00  116
  7  \w    128.00 160.00   0.50   20.60    --  107.75 139.00  49.00   64
  8  \w     76.00 102.00   0.50   20.60    --  107.75-130.00 163.00   52
  9  \w    119.00 145.00   0.50   20.60    --  107.75 130.00-124.00   52
 10  \w     83.00 113.00   0.50   20.60    --  107.75-139.00 -10.00   60
 11  \w    -61.00 -35.00   0.50    5.15    --  -48.95  37.00-180.00   52
 12  \w   -116.00 -26.00   0.50    5.15    --  -48.95 -77.00-150.00  180
 13  \w   -101.00 -76.00   0.50    5.15    --  -48.95 -77.00  90.00   50
 14  \w   -119.00 -74.00   0.50    5.15    --  -48.95-125.00-150.00   90
 15  \w   -118.00 -87.00   0.50    5.15    --  -48.95-125.00-180.00   62
 16  \w    -28.00  24.00   0.50    5.15    --  -48.95  37.00-180.00  104
 17  \w   -116.00 -83.00   0.50    5.15    --  -48.95-125.00  30.00   66
 18  \w    -20.00  58.00   0.50    5.15    --   48.95 -57.00 150.00  156
 19  \w     37.00 122.00   0.50   20.60    --  107.75 -57.00 -60.00  170
 20  \w     80.00 130.00   0.50   20.60    --  107.75 -77.00 150.00  100
 21  \w     38.00 106.00   0.50   20.60    --  107.75 -99.00 150.00  136
 22  \w    114.00 174.00   0.50   20.60    --  107.75 125.00-180.00  120
 23  \w     38.00  66.00   0.50   20.60    --  107.75-125.00   0.00   56
 24  \w     80.00 112.00   0.50   20.60    --  107.75-125.00   0.00   64
 25  \w     40.00 119.00   0.50   20.60    --  107.75 -37.00 120.00  158
 26  \w     35.00  61.00   0.50   20.60    --  107.75 -77.00 150.00   52
 27  \w     71.00 106.00   0.50   20.60    --  107.75 -99.00-150.00   70
 28  \w    102.00 177.00   0.50   20.60    --  107.75  37.00-120.00  150
 29  \w     40.00 105.00   0.50   20.60    --  107.75 -99.00  90.00  130
 30  \w     98.00 178.00   0.50   20.60    --  107.75  37.00 -90.00  160
 31  \w     33.00 119.00   0.50   20.60    --  107.75 -19.00  90.00  172
 32  \w     37.00 101.00   0.50   20.60    --  107.75 -99.00 -30.00  128
 33  \w     91.00 126.00   0.50   20.60    --  107.75-144.00  94.56   70
 34  \w    130.00 178.00   0.50   20.60    --  107.75  19.00 -60.00   96
 35  \w     41.00 110.00   0.50   20.60    --  107.75 -37.00 -60.00  138
 36  \w    113.00 139.00   0.50   20.60    --  107.75 125.00  90.00   52
 37  \w    125.00 167.00   0.50   20.60    --  107.75  19.00   0.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0219357000
_diffrn_orient_matrix_UB_12      -0.0003585000
_diffrn_orient_matrix_UB_13      -0.0748955000
_diffrn_orient_matrix_UB_21      0.0909737000
_diffrn_orient_matrix_UB_22      0.0467263000
_diffrn_orient_matrix_UB_23      -0.0264972000
_diffrn_orient_matrix_UB_31      0.0609991000
_diffrn_orient_matrix_UB_32      -0.0924744000
_diffrn_orient_matrix_UB_33      -0.0024361000
_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  0.0414
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            50180
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         3.523
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.597
_exptl_absorpt_correction_T_max  0.956
_exptl_absorpt_correction_T_min  0.506
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
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_density_diffrn    1.528
_exptl_crystal_description       sphere
_exptl_crystal_F_000             1885
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_exptl_crystal_size_rad          0.024
_refine_diff_density_max         1.120
_refine_diff_density_min         -0.813
_refine_diff_density_rms         0.092
_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     952
_refine_ls_number_reflns         14483
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0326
_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^)+(0.0537P)^2^+1.8381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0847
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12849
_reflns_number_total             14483
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05346j3.cif
_cod_data_source_block           ijsf22044
_cod_depositor_comments
'Adding full bibliography for 1572926--1572929.cif.'
_cod_original_cell_volume        4061.19(11)
_cod_original_formula_sum        'C86.91 H86.40 Cl4.87 O P4 Pd4'
_cod_database_code               1572927
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C87.5 H87 Cl5.2 O1 P4 Pd4'
_chemical_oxdiff_usercomment     'David Husbands DRH-03-75'
_shelx_estimated_absorpt_t_max   0.762
_shelx_estimated_absorpt_t_min   0.327
_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
 C91-C90 = C90-C89 = C88-C89 = C88-C87
 1.53 with sigma of 0.02
 C21A-C20A
 1.54 with sigma of 0.02
 C88-C90 = C89-C91
 2.48 with sigma of 0.04
 C87-C89
 2.48 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C90) \\sim Ueq, Uanis(C91) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C18) = Uanis(C18A)
Uanis(C19) = Uanis(C19A)
Uanis(C61) = Uanis(C20) = Uanis(C20A)
Uanis(C17A) = Uanis(C17)
Uanis(C21) = Uanis(C21A)
Uanis(C16A) = Uanis(C16)
Uanis(Cl6) = Uanis(C89)
Uanis(C86) = Uanis(C88)
Uanis(Cl5) = Uanis(C87)
Uanis(C89) = Uanis(Cl6)
4. Others
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=
 Sof(H19A)=Sof(C20A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=
 Sof(C20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(Cl5)=Sof(Cl6)=FVAR(2)
 Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(C89)=
 Sof(H89A)=Sof(H89B)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(C91)=Sof(H91A)=Sof(H91B)=
 Sof(H91C)=FVAR(3)
 Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(Cl3)=Sof(Cl4)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C22(H22A,H22B), C43(H43A,H43B), C64(H64A,H64B), C86(H86A,H86B),
 C85(H85A,H85B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), 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)
5.c Fitted hexagon refined as free rotating group:
 C15(C16A,C17A,C18A,C19A,C20A)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F), C35(H35A,H35B,
 H35C), C42(H42A,H42B,H42C), C56(H56A,H56B,H56C), C63(H63A,H63B,H63C), C77(H77A,
 H77B,H77C), C84(H84A,H84B,H84C), C87(H87A,H87B,H87C), C91(H91A,H91B,H91C)
;
_shelx_res_checksum              9265
_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 1.273
_oxdiff_exptl_absorpt_empirical_full_min 0.769