Coordination complexes of P<sup>III</sup>-doped heterobuckybowls and their applications in catalysis.
Feng, Lijun; Hua, Xinqiang; Shang, Jihai; Shao, Xiangfeng; Organic & biomolecular chemistry 23 (2025) 665–672; doi:10.1039/d4ob01737d

data_7160257
_publ_section_title
;
 Coordination complexes of P<sup>III</sup>-doped heterobuckybowls and
 their applications in catalysis.
;
_journal_issue                   3
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              665
_journal_page_last               672
_journal_paper_doi               10.1039/d4ob01737d
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety
'0.5(C96 H118 Cl4 O12 P2 Pd2 S4), C50 H62 Cl2 N O6 P Pd S2'
_chemical_formula_sum            'C98 H121 Cl4 N O12 P2 Pd2 S4'
_chemical_formula_weight         2049.73
_chemical_name_common            4-PdCl2
_chemical_name_systematic        4-PdCl2
_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     iterative
_audit_creation_date             2023-08-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-05-15 deposited with the CCDC.	2024-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                100.1680(10)
_cell_angle_beta                 103.3670(10)
_cell_angle_gamma                95.8090(10)
_cell_formula_units_Z            4
_cell_length_a                   16.9381(2)
_cell_length_b                   20.3995(2)
_cell_length_c                   29.6262(3)
_cell_measurement_reflns_used    54939
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.9490
_cell_measurement_theta_min      2.4530
_cell_volume                     9694.55(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.944
_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     36.00 120.00   0.50    0.08    --   47.45  50.00 -99.00  168
  2  \w     95.00 161.00   0.50    0.23    --  107.75  57.00-180.00  132
  3  \w    133.00 175.00   0.50    0.23    --  107.75  50.00 -99.00   84
  4  \w     94.00 129.00   0.50    0.23    --  107.75  50.00 -99.00   70
  5  \w     99.00 125.00   0.50    0.23    --  107.75  37.00 -60.00   52
  6  \w    128.00 168.00   0.50    0.23    --  107.75  37.00 -60.00   80
  7  \w     72.00 107.00   0.50    0.08    --   47.45  37.00  90.00   70
  8  \w     31.00  61.00   0.50    0.08    --   47.45 -57.00 150.00   60
  9  \w     18.00  45.00   0.50    0.08    --   47.45 -50.00 114.00   54
 10  \w    -23.00  25.00   0.50    0.08    --   47.45 -57.00 150.00   96
 11  \w    -26.00  23.00   0.50    0.08    --   47.45 -19.00 -30.00   98
 12  \w    -27.00  23.00   0.50    0.08    --   47.45 -19.00 -90.00  100
 13  \w    -20.00  21.00   0.50    0.08    --   47.45 -19.00-180.00   82
 14  \w     45.00 110.00   0.50    0.23    --  107.75-125.00 -60.00  130
 15  \w     35.00 106.00   0.50    0.23    --  107.75 -99.00  30.00  142
 16  \w     35.00  83.00   0.50    0.23    --  107.75 -99.00  90.00   96
 17  \w     87.00 112.00   0.50    0.23    --  107.75-125.00 150.00   50
 18  \w     37.00  71.00   0.50    0.23    --  107.75 -99.00 120.00   68
 19  \w     42.00  69.00   0.50    0.23    --  107.75 -99.00  60.00   54
 20  \w     75.00 100.00   0.50    0.23    --  107.75 -99.00   0.00   50
 21  \w     36.00  61.00   0.50    0.23    --  107.75 -57.00 -90.00   50
 22  \w     74.00 100.00   0.50    0.23    --  107.75 -77.00-120.00   52
 23  \w     59.00  84.00   0.50    0.23    --  107.75 -77.00 120.00   50
 24  \w   -116.00 -71.00   0.50    0.23    -- -100.00 131.00 -50.56   90
 25  \w   -112.00 -52.00   0.50    0.23    -- -100.00 125.00-150.00  120
 26  \w   -112.00 -29.00   0.50    0.23    -- -100.00 125.00-180.00  166
 27  \w    -94.00 -24.00   0.50    0.08    --  -47.45 125.00  30.00  140
 28  \w   -112.00 -53.00   0.50    0.23    -- -100.00 125.00 150.00  118
 29  \w   -112.00 -28.00   0.50    0.23    -- -100.00 125.00  90.00  168
 30  \w   -108.00 -30.00   0.50    0.23    -- -100.00 111.00  39.59  156
 31  \w    -85.00 -27.00   0.50    0.23    -- -100.00  77.00   0.00  116
 32  \w    -68.00 -28.00   0.50    0.23    -- -100.00  57.00  60.00   80
 33  \w    -62.00 -27.00   0.50    0.23    -- -100.00  57.00   0.00   70
 34  \w    -60.00 -34.00   0.50    0.23    -- -100.00  57.00 -30.00   52
 35  \w    -65.00 -40.00   0.50    0.23    -- -100.00  57.00 -90.00   50
 36  \w    -57.00 -27.00   0.50    0.23    -- -100.00  50.00 -99.00   60
 37  \w    -69.00 -35.00   0.50    0.23    -- -100.00  57.00-150.00   68
 38  \w    -42.00 -17.00   0.50    0.08    --  -47.45  50.00 -99.00   50
 39  \w    -82.00 -35.00   0.50    0.23    -- -100.00   0.00 -30.00   94
 40  \w   -171.00 -99.00   0.50    0.23    -- -100.00   0.00 -30.00  144
 41  \w   -170.00-116.00   0.50    0.23    -- -100.00 -99.00  30.00  108
 42  \w   -171.00 -89.00   0.50    0.23    -- -100.00 -50.00 114.00  164
 43  \w   -172.00-103.00   0.50    0.23    -- -100.00 -57.00  60.00  138
 44  \w   -116.00 -35.00   0.50    0.08    --  -47.45 -50.00 114.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0314247000
_diffrn_orient_matrix_UB_12      0.0468920000
_diffrn_orient_matrix_UB_13      -0.0334343000
_diffrn_orient_matrix_UB_21      0.0878568000
_diffrn_orient_matrix_UB_22      0.0190079000
_diffrn_orient_matrix_UB_23      -0.0044228000
_diffrn_orient_matrix_UB_31      -0.0151544000
_diffrn_orient_matrix_UB_32      -0.0588127000
_diffrn_orient_matrix_UB_33      -0.0429718000
_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  0.0596
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            140699
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.503
_diffrn_reflns_theta_min         2.225
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.599
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       block
_exptl_crystal_F_000             4264
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.498
_refine_diff_density_min         -1.082
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2344
_refine_ls_number_reflns         38957
_refine_ls_number_restraints     170
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.1086
_refine_ls_R_factor_gt           0.0969
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0238P)^2^+172.2322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2363
_refine_ls_wR_factor_ref         0.2413
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32526
_reflns_number_total             38957
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01737d2.cif
_cod_data_source_block           4-PdCl2
_cod_depositor_comments
'Adding full bibliography for 7160252--7160260.cif.'
_cod_database_code               7160257
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.80
_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 C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C13-C14
 1.5 with sigma of 0.01
 C14-C15
 1.5 with sigma of 0.01
 C17-C18
 1.5 with sigma of 0.01
 C13-C15
 2.3 with sigma of 0.01
 C05H-C06H \\sim C05H-C5
 with sigma of 0.02
 C04C-C060 \\sim C04C-C0
 with sigma of 0.02
 C05I-C060 \\sim C05I-C0
 with sigma of 0.02
 C05I-C06O \\sim C05I-C8
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C06H) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C6)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C0) \\sim Ueq, Uanis(C060) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C8) \\sim Ueq, Uanis(C06O) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C11)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C20) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C28) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C06A) \\sim Ueq, Uanis(C064) \\sim Ueq, Uanis(C067) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C066) \\sim Ueq, Uanis(C06L) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C12) \\sim Ueq, Uanis(C06B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: H04l(0.3) H04m(0.3) H04n(0.7) H04o(0.7) H04t(0.5) H04u(0.5)
 H04v(0.5) H04w(0.5) Hy(0.6) Hz(0.6) H18(0.4) H53(0.4) H05r(0.6) H05s(0.6)
 H05t(0.4) H05u(0.4) H05v(0.3) H05w(0.3) H05x(0.7) H05y(0.7) H72(0.5) H73(0.5)
 H21(0.5) H74(0.5) C060(0.3) H06a(0.3) H06b(0.3) H06m(0.5) H06n(0.5) H06o(0.5)
 H06p(0.5) C06F(0.5) H06y(0.5) H85(0.5) C06H(0.6) H06(0.6) H88(0.6) C06O(0.5)
 H7(0.5) H93(0.5) H94(0.5) C5(0.4) H5a(0.4) H5b(0.4) C6(0.6) H6a(0.6) H6b(0.6)
 C7(0.4) H7a(0.4) H7b(0.4) C0(0.7) H0a(0.7) H0b(0.7) C8(0.5) H8a(0.5) H8b(0.5)
 H8c(0.5) C10(0.6) H10a(0.6) H10b(0.6) C11(0.8) H11a(0.8) H11b(0.8) H11c(0.8)
 C9(0.4) H9a(0.4) H9b(0.4) C46(0.2) H46a(0.2) H46b(0.2) H46c(0.2) C20(0.5)
 H20c(0.5) H20d(0.5) H20e(0.5) C28(0.5) H28a(0.5) H28b(0.5) H28c(0.5) C35(0.5)
 H35a(0.5) H35b(0.5) H35c(0.5) C14(0.5) H14a(0.5) H14b(0.5) C15(0.5) H13a(0.5)
 H13b(0.5) H13c(0.5) H13d(0.5) C205(0.5) H20a(0.5) H20b(0.5) C16(0.5) H16a(0.5)
 H16b(0.5) H16c(0.5) C18(0.5) C17(0.5) H17a(0.5) H17b(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C036(H03a,H03b), C03D(H03h,H03j), C03P(H03d,H03e), C03R(H03f,H03g), C03V(H03l,
 H03m), C03X(H03n,H03o), C041(H04a,H04b), C043(H04f,H04g), C044(H29,H),
 C045(H30,Ha), C046(H31,Hb), C047(H04h,H04i), C048(H8,Hc), C04A(H9,Hd),
 C04B(H04j,H04k), C04C(H04l,H04m), C04C(H04n,H04o), C04D(H04p,H04q), C04F(H32,
 He), C04H(H33,Hf), C04I(H34,Hg), C04M(H04t,H04u), C04M(H04v,H04w), C04N(H12,
 Hh), C04O(H36,Hi), C04P(H04x,H04y), C04Q(H04z,Hj), C04R(H13,Hk), C04T(H04,Hl),
 C04U(H1,Hm), C04V(H2,Hn), C04Z(H39,Hs), C050(H05a,H05b), C051(H40,Ht),
 C052(H41,Hu), C055(H05c,H05d), C056(H16,Hv), C057(H05e,H05f), C059(H05g,H05h),
 C05A(H05i,H05j), C05C(H05n,H05o), C05D(H42,Hw), C05E(H17,Hx), C05F(Hy,Hz),
 C05F(H18,H53), C05G(H05p,H05q), C05H(H05r,H05s), C05H(H05t,H05u), C05I(H05v,
 H05w), C05I(H05x,H05y), C05K(H44,H54), C05N(H05,H59), C05O(H19,H60), C05P(H3,
 H61), C05Q(H46,H62), C05S(H20,H65), C05U(H48,H68), C05V(H5,H69), C05X(H72,H73),
  C05X(H21,H74), C05Y(H49,H75), C05Z(H22,H76), C060(H06a,H06b), C063(H23,H79),
 C064(H06f,H06g), C066(H24,H80), C067(H06k,H06l), C068(H06m,H06n), C068(H06o,
 H06p), C06A(H06q,H06r), C06F(H06y,H85), C06H(H06,H88), C06I(H52,H89), C12(H12a,
 H12b), C06L(H26,H90), C5(H5a,H5b), C6(H6a,H6b), C7(H7a,H7b), C0(H0a,H0b),
 C10(H10a,H10b), C9(H9a,H9b), C14(H14a,H14b), C13(H13a,H13b), C13(H13c,H13d),
 C205(H20a,H20b), C17(H17a,H17b)
5.b Aromatic/amide H refined with riding coordinates:
 C02T(H02T), C02U(H02U), C033(H033), C034(H034), C039(H039), C03B(H03c),
 C03I(H03I), C03K(H03K), C03Q(H03Q), C03W(H03W), C049(H049), C04E(H04r),
 C04G(H10), C04J(H04s), C04K(H35), C04L(H11), C04S(H14), C04Y(H38), C058(H058),
 C05J(H43)
5.c Idealised Me refined as rotating group:
 C042(H04c,H04d,H04e), C04W(H37,Ho,Hp), C04X(H15,Hq,Hr), C05B(H05k,H05l,H05m),
 C05L(H45,H55,H56), C05M(H05z,H57,H58), C05R(H47,H63,H64), C05T(H4,H66,H67),
 C05W(H6,H70,H71), C061(H06c,H06d,H06e), C062(H50,H77,H78), C065(H06h,H06i,
 H06j), C069(H25,H81,H82), C06B(H06s,H06t,H06u), C06D(H06v,H06w,H06x), C06E(H51,
 H83,H84), C06G(H06z,H86,H87), C06N(H27,H91,H92), C06O(H7,H93,H94), C06P(H28,
 H95,H96), C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C8(H8a,H8b,H8c), C11(H11a,H11b,
 H11c), C46(H46a,H46b,H46c), C20(H20c,H20d,H20e), C28(H28a,H28b,H28c), C35(H35a,
 H35b,H35c), C15(H15a,H15b,H15c), C16(H16a,H16b,H16c)
;
_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 2.033
_oxdiff_exptl_absorpt_empirical_full_min 0.661