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_7160258
_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(C95 H118 Cl2 O13 P2 Pt S4), 0.5(C96 H117 Cl2 O12 P2 Pt S4), 0.5(C2 H3 N)'
_chemical_formula_sum            'C96.5 H119 Cl2 N0.5 O12.5 P2 Pt S4'
_chemical_formula_weight         1942.08
_chemical_name_common            4-PtCl2
_chemical_name_systematic        4-PtCl2
_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             2023-08-17
_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                89.5107(13)
_cell_angle_beta                 79.0226(14)
_cell_angle_gamma                86.6647(15)
_cell_formula_units_Z            4
_cell_length_a                   17.4708(3)
_cell_length_b                   22.2672(4)
_cell_length_c                   24.0276(4)
_cell_measurement_reflns_used    42680
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.2940
_cell_measurement_theta_min      1.8430
_cell_volume                     9160.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 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 0.940
_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     29.00  66.00   0.50    0.20    --   44.32  26.00-115.00   74
  2  \w     89.00 136.00   0.50    0.30    --  109.62  77.00 -60.00   94
  3  \w    106.00 157.00   0.50    0.30    --  109.62  45.00 -30.00  102
  4  \w    107.00 168.00   0.50    0.30    --  109.62  26.00-115.00  122
  5  \w    134.00 169.00   0.50    0.30    --  109.62  15.00-180.00   70
  6  \w     87.00 112.00   0.50    0.30    --  109.62  15.00-180.00   50
  7  \w   -120.00 -52.00   0.50    0.20    --  -44.32 179.00-120.00  136
  8  \w   -126.00 -81.00   0.50    0.30    -- -100.00 144.00-126.59   90
  9  \w   -121.00 -52.00   0.50    0.30    -- -100.00 138.00-160.92  138
 10  \w    -66.00 -38.00   0.50    0.30    -- -100.00 144.00-126.59   56
 11  \w    -62.00 -27.00   0.50    0.30    -- -100.00 125.00 -90.00   70
 12  \w    -97.00 -36.00   0.50    0.30    -- -100.00 125.00-120.00  122
 13  \w   -110.00 -84.00   0.50    0.30    -- -100.00 125.00 -90.00   52
 14  \w    -79.00 -28.00   0.50    0.30    -- -100.00 125.00   0.00  102
 15  \w   -111.00 -85.00   0.50    0.30    -- -100.00 125.00   0.00   52
 16  \w    -86.00 -60.00   0.50    0.30    -- -100.00 125.00 -60.00   52
 17  \w    -65.00 -39.00   0.50    0.30    -- -100.00 125.00-180.00   52
 18  \w   -112.00 -60.00   0.50    0.30    -- -100.00 125.00  30.00  104
 19  \w    -86.00 -26.00   0.50    0.30    -- -100.00 125.00  60.00  120
 20  \w   -126.00 -50.00   0.50    0.30    -- -100.00 144.00 130.72  152
 21  \w    -60.00 -26.00   0.50    0.30    -- -100.00  61.00  90.00   68
 22  \w    -53.00 -25.00   0.50    0.30    -- -100.00  45.00  90.00   56
 23  \w    -53.00 -28.00   0.50    0.30    -- -100.00  45.00  60.00   50
 24  \w    -51.00 -25.00   0.50    0.30    -- -100.00  45.00  30.00   52
 25  \w    -54.00 -28.00   0.50    0.30    -- -100.00  45.00 -60.00   52
 26  \w    -54.00 -26.00   0.50    0.30    -- -100.00  45.00 -90.00   56
 27  \w    -53.00 -26.00   0.50    0.30    -- -100.00  45.00-120.00   54
 28  \w    -51.00 -25.00   0.50    0.30    -- -100.00  45.00-180.00   52
 29  \w     -3.00  33.00   0.50    0.20    --  -44.32  26.00-115.00   72
 30  \w    -19.00  12.00   0.50    0.20    --  -44.32  19.00  30.00   62
 31  \w   -123.00 -31.00   0.50    0.20    --  -44.32 -26.00  81.00  184
 32  \w   -177.00 -79.00   0.50    0.30    -- -100.00 -26.00  81.00  196
 33  \w   -165.00 -79.00   0.50    0.30    -- -100.00 -45.00 150.00  172
 34  \w   -119.00 -58.00   0.50    0.20    --  -44.32-179.00   0.00  122
 35  \w   -173.00 -94.00   0.50    0.30    -- -100.00 -61.00-120.00  158
 36  \w    -13.00  13.00   0.50    0.20    --   44.32 -19.00 -90.00   52
 37  \w    -28.00  52.00   0.50    0.20    --   44.32 -57.00-150.00  160
 38  \w     37.00  62.00   0.50    0.30    --  109.62 -61.00 -30.00   50
 39  \w    -32.00  19.00   0.50    0.20    --   44.32 -26.00  81.00  102
 40  \w    -27.00  38.00   0.50    0.20    --   44.32 -37.00 120.00  130
 41  \w     48.00 102.00   0.50    0.30    --  109.62 -94.00  90.00  108
 42  \w     37.00  93.00   0.50    0.30    --  109.62 -94.00 120.00  112
 43  \w     41.00 106.00   0.50    0.30    --  109.62 -94.00 150.00  130
 44  \w     36.00  91.00   0.50    0.30    --  109.62 -94.00   0.00  110
 45  \w     46.00 106.00   0.50    0.30    --  109.62 -94.00 -60.00  120
 46  \w     48.00  87.00   0.50    0.30    --  109.62 -94.00-150.00   78
;
_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      0.0802526000
_diffrn_orient_matrix_UB_12      0.0258466000
_diffrn_orient_matrix_UB_13      -0.0211914000
_diffrn_orient_matrix_UB_21      0.0403404000
_diffrn_orient_matrix_UB_22      -0.0623527000
_diffrn_orient_matrix_UB_23      0.0065115000
_diffrn_orient_matrix_UB_31      -0.0052090000
_diffrn_orient_matrix_UB_32      -0.0157155000
_diffrn_orient_matrix_UB_33      -0.0614339000
_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  0.0775
_diffrn_reflns_av_unetI/netI     0.0636
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            121966
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.603
_diffrn_reflns_theta_min         1.873
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.072
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12256
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       needle
_exptl_crystal_F_000             4030
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.831
_refine_diff_density_min         -1.859
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2224
_refine_ls_number_reflns         36241
_refine_ls_number_restraints     2026
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0575
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0880P)^2^+10.1742P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1414
_refine_ls_wR_factor_ref         0.1514
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28271
_reflns_number_total             36241
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01737d2.cif
_cod_data_source_block           4-PtCl2
_cod_depositor_comments
'Adding full bibliography for 7160252--7160260.cif.'
_cod_original_cell_volume        9160.8(3)
_cod_original_formula_sum        'C96.50 H119 Cl2 N0.50 O12.50 P2 Pt S4'
_cod_database_code               7160258
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H78a,H78b} of C78, {H83a,H83b} of C83, {H81a,H81b} of C81,
   {H58a,H58b} of C58, {H12l,H12m} of C127, {H11m,H11n} of C115, {H11i,H11j} of
  C113, {H11g,H11h} of C110, {H96a,H96b} of C96, {H11k,H11l} of C114, {H89a,
  H89b} of C89, {H12n,H12o} of C129, {H93a,H93b} of C93, {H10n,H10o} of C104,
  {H13e,H13f} of C131, {H10p,H10q} of C108, {H88a,H88b} of C88, {H92a,H92b} of
  C92, {H84a,H84b} of C84, {H12f,H12g} of C120, {H12j,H12k} of C125, {H12h,
  H12i} of C123, {H15n,H15o} of C152, {H14n,H14o} of C145, {H15p,H15q} of C153,
  {H14t,H14u} of C149, {H13g,H13h} of C132, {H13k,H13l} of C137, {H14i,H14j} of
  C140, {H13i,H13j} of C133, {H14p,H14q} of C146, {H14r,H14s} of C147, {H16t,
  H16u} of C163, {H16v,H16w} of C167, {H17z,H} of C177, {H70a,H70b} of C70,
  {H10g,H10h} of C102, {H11a,H11b} of C111, {H87a,H87b} of C87, {H98a,H98b} of
  C98, {H94a,H94b} of C94, {H75a,H75b} of C75, {H86a,H86b} of C86, {H10e,H10f}
  of C101, {H10i,H10j} of C106, {H18o,H18p} of C181, {H19u,H19v} of C199, {H19p,
  H19q} of C197, {H20a,H20b} of C200, {H19i,H19j} of C194, {H19n,H19o} of C196,
  {H14a,H14b} of C141, {H11e,H11f} of C119, {H15a,H15b} of C151, {H12d,H12e} of
  C128, {H15i,H15j} of C159, {H15e,H15f} of C157, {H15g,H15h} of C158, {H15c,
  H15d} of C155, {H14c,H14d} of C142, {H13c,H13d} of C138, {H11c,H11d} of C117,
  {H13a,H13b} of C136, {H17f,H17g} of C173, {H17d,H17e} of C172, {H18k,H18l} of
  C187, {H19c,H19d} of C191, {H19e,H19f} of C192, {H19a,H19b} of C190, {H16p,
  H16q} of C168, {H16n,H16o} of C166, {H18c,H18d} of C182, {H16r,H16s} of C169,
  {H18a,H18b} of C180, {H19g,H19h} of C193, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H18m,H18n} of C189, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C143-C193 = C193-C192
 1.54 with sigma of 0.02
 C143-C194
 1.54 with sigma of 0.02
 C193-C192 = C192-C174
 1.54 with sigma of 0.02
 C100-C159 = C159-C190
 1.54 with sigma of 0.02
 C159-C190 = C190-C195
 1.54 with sigma of 0.02
 C159-C190 = C190-C187
 1.54 with sigma of 0.02
 C193-C174
 2.515 with sigma of 0.04
 C194-C174
 2.515 with sigma of 0.04
 C143-C192
 2.515 with sigma of 0.04
 C159-C195
 2.515 with sigma of 0.04
 C159-C187
 2.515 with sigma of 0.04
 C100-C190
 2.515 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C187) \\sim Ueq, Uanis(C195) \\sim Ueq, Uanis(C185) \\sim Ueq,
Uanis(C193) \\sim Ueq, Uanis(C194) \\sim Ueq, Uanis(C192) \\sim Ueq,
Uanis(C142) \\sim Ueq, Uanis(C169) \\sim Ueq, Uanis(C189) \\sim Ueq,
Uanis(C158) \\sim Ueq, Uanis(C172) \\sim Ueq, Uanis(C186) \\sim Ueq,
Uanis(C196) \\sim Ueq, Uanis(C182) \\sim Ueq, Uanis(C191) \\sim Ueq,
Uanis(C197) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
4. Rigid body (RIGU) restrains
 C100, C159, C190, C187, C195
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C143, C194, C193, C192, C174
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Fixed Sof: H10a(0.5) H10b(0.5) H10c(0.5) H10d(0.5) H14e(0.5) H14f(0.5)
 H14g(0.5) H14h(0.5) C159(0.5) H15i(0.5) H15j(0.5) H16i(0.5) H16j(0.5)
 H16g(0.5) H16h(0.5) H17k(0.5) H17l(0.5) H17m(0.5) H17h(0.5) H17i(0.5)
 H17j(0.5) C182(0.5) H18c(0.5) H18d(0.5) C187(0.5) H18k(0.5) H18l(0.5)
 C190(0.5) H19a(0.5) H19b(0.5) C191(0.5) H19c(0.5) H19d(0.5) C192(0.5)
 H19e(0.5) H19f(0.5) C193(0.5) H19g(0.5) H19h(0.5) C194(0.5) H19i(0.5)
 H19j(0.5) C195(0.5) H19k(0.5) H19l(0.5) H19m(0.5) C196(0.5) H19n(0.5)
 H19o(0.5) C197(0.5) H19p(0.5) H19q(0.5) H17n(0.5) H17o(0.5) H17p(0.5)
 H17q(0.5) H17r(0.5) H17s(0.5) C198(0.5) H19r(0.5) H19s(0.5) H19t(0.5)
 C199(0.5) H19u(0.5) H19v(0.5) C200(0.5) H20a(0.5) H20b(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C58(H58a,H58b), C78(H78a,H78b), C81(H81a,H81b), C83(H83a,H83b), C84(H84a,
 H84b), C88(H88a,H88b), C89(H89a,H89b), C92(H92a,H92b), C93(H93a,H93b),
 C96(H96a,H96b), C104(H10n,H10o), C108(H10p,H10q), C110(H11g,H11h), C113(H11i,
 H11j), C114(H11k,H11l), C115(H11m,H11n), C120(H12f,H12g), C123(H12h,H12i),
 C125(H12j,H12k), C127(H12l,H12m), C129(H12n,H12o), C131(H13e,H13f), C132(H13g,
 H13h), C133(H13i,H13j), C137(H13k,H13l), C140(H14i,H14j), C145(H14n,H14o),
 C146(H14p,H14q), C147(H14r,H14s), C149(H14t,H14u), C152(H15n,H15o), C153(H15p,
 H15q), C163(H16t,H16u), C167(H16v,H16w), C177(H17z,H), C181(H18o,H18p),
 C70(H70a,H70b), C75(H75a,H75b), C86(H86a,H86b), C87(H87a,H87b), C94(H94a,H94b),
  C98(H98a,H98b), C100(H10a,H10b), C100(H10c,H10d), C101(H10e,H10f), C102(H10g,
 H10h), C106(H10i,H10j), C111(H11a,H11b), C117(H11c,H11d), C119(H11e,H11f),
 C128(H12d,H12e), C136(H13a,H13b), C138(H13c,H13d), C141(H14a,H14b), C142(H14c,
 H14d), C143(H14e,H14f), C143(H14g,H14h), C151(H15a,H15b), C155(H15c,H15d),
 C157(H15e,H15f), C158(H15g,H15h), C159(H15i,H15j), C164(H16i,H16j), C164(H16g,
 H16h), C166(H16n,H16o), C168(H16p,H16q), C169(H16r,H16s), C172(H17d,H17e),
 C173(H17f,H17g), C180(H18a,H18b), C182(H18c,H18d), C187(H18k,H18l), C190(H19a,
 H19b), C191(H19c,H19d), C192(H19e,H19f), C193(H19g,H19h), C194(H19i,H19j),
 C196(H19n,H19o), C197(H19p,H19q), C199(H19u,H19v), C200(H20a,H20b)
6.b Me refined with riding coordinates:
 C175(H17k,H17l,H17m), C175(H17h,H17i,H17j), C195(H19k,H19l,H19m), C174(H17n,
 H17o,H17p), C174(H17q,H17r,H17s), C198(H19r,H19s,H19t)
6.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C56(H56), C65(H65), C79(H79), C103(H103), C105(H105), C112(H112),
 C116(H116), C118(H118), C130(H130), C85(H85), C90(H90), C97(H97), C99(H99),
 C109(H109), C121(H121), C122(H122), C124(H124), C134(H134), C135(H135)
6.d Idealised Me refined as rotating group:
 C139(H13m,H13n,H13o), C144(H14k,H14l,H14m), C150(H15k,H15l,H15m), C154(H15r,
 H15s,H15t), C156(H15u,H15v,H15w), C170(H17t,H17u,H17v), C176(H17w,H17x,H17y),
 C178(H17,Ha,Hb), C179(H1,Hc,Hd), C184(H18q,H18r,H18s), C185(H18t,H18u,H18v),
 C188(H18w,H18x,H18y), C107(H10k,H10l,H10m), C126(H12a,H12b,H12c), C161(H16a,
 H16b,H16c), C162(H16d,H16e,H16f), C165(H16k,H16l,H16m), C171(H17a,H17b,H17c),
 C183(H18e,H18f,H18g), C186(H18h,H18i,H18j), C160(H16x,H16y,He)
;
_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 5.335
_oxdiff_exptl_absorpt_empirical_full_min 0.438