Formation of a low-symmetry Pd<sub>8</sub> molecular barrel employing a hetero donor tetradentate ligand, and its use in the binding and extraction of C<sub>70</sub>.
Prajapati, Dharmraj; Clegg, Jack K.; Mukherjee, Partha Sarathi; Chemical science 15 (2024) 12502–12510; doi:10.1039/d4sc01332h

data_1572001
_publ_section_title
;
 Formation of a low-symmetry Pd<sub>8</sub> molecular barrel employing a
 hetero donor tetradentate ligand, and its use in the binding and
 extraction of C<sub>70</sub>.
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              12502
_journal_page_last               12510
_journal_paper_doi               10.1039/d4sc01332h
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '2(C78 H101 N22 Pd4), 16[NO3H2OH2O]'
_chemical_formula_sum            'C156 H266 N60 O80 Pd8'
_chemical_formula_weight         5113.47
_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             2023-12-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-12-17 deposited with the CCDC.	2024-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                87.8618(14)
_cell_angle_beta                 77.0258(15)
_cell_angle_gamma                82.1629(14)
_cell_formula_units_Z            2
_cell_length_a                   21.8333(4)
_cell_length_b                   21.8629(3)
_cell_length_c                   30.2029(6)
_cell_measurement_reflns_used    60434
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.2120
_cell_measurement_theta_min      1.8440
_cell_volume                     13917.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.78a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.78a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.78a (Rigaku OD, 2022)'
_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      150(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_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    -45.00 -12.00   0.50  180.00    --   -4.80 124.00 162.00   66
  2  \w    -71.00 -32.00   0.50  180.00    --   -4.80 147.00 -33.00   78
  3  \w     51.00  77.00   0.50  180.00    --    3.16  57.00-120.00   52
  4  \w    -18.00  40.00   0.50  180.00    --    3.16  57.00-120.00  116
  5  \w     41.00  74.00   0.50  180.00    --    3.16  57.00 -30.00   66
  6  \w     -1.00  37.00   0.50  180.00    --    3.16 -99.00 120.00   76
  7  \w    -17.00  39.00   0.50  180.00    --    3.16  57.00 -30.00  112
  8  \w    -66.00  29.00   0.50  180.00    --    3.16 -77.00 150.00  190
  9  \w      1.00  39.00   0.50  180.00    --    3.16 -99.00 -60.00   76
 10  \w    -25.00  31.00   0.50  180.00    --    3.16  19.00 -60.00  112
 11  \w     60.00  85.00   0.50  180.00    --    3.16  19.00 -60.00   50
 12  \w     17.00  43.00   0.50  180.00    --    3.16 -99.00   0.00   52
 13  \w    -53.00  33.00   0.50  180.00    --    3.16 -77.00 -90.00  172
 14  \w    -72.00   3.00   0.50  180.00    --    3.16 -57.00  30.00  150
 15  \w     -5.00  20.00   0.50  180.00    --   -4.80  57.00 120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0256708000
_diffrn_orient_matrix_UB_12      0.0143115000
_diffrn_orient_matrix_UB_13      -0.0128072000
_diffrn_orient_matrix_UB_21      0.0094364000
_diffrn_orient_matrix_UB_22      0.0056717000
_diffrn_orient_matrix_UB_23      0.0203002000
_diffrn_orient_matrix_UB_31      0.0195687000
_diffrn_orient_matrix_UB_32      -0.0289061000
_diffrn_orient_matrix_UB_33      -0.0021684000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0876
_diffrn_reflns_av_unetI/netI     0.0591
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            269222
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.123
_diffrn_reflns_theta_max         25.123
_diffrn_reflns_theta_min         1.901
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.584
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95483
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.78a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.220
_exptl_crystal_description       block
_exptl_crystal_F_000             5260
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.647
_refine_diff_density_min         -1.339
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1903
_refine_ls_number_reflns         49608
_refine_ls_number_restraints     1253
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.1302
_refine_ls_R_factor_gt           0.0979
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1768P)^2^+62.9791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2843
_refine_ls_wR_factor_ref         0.3153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                31518
_reflns_number_total             49608
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01332h2.cif
_cod_data_source_block           spm23jc04
_cod_depositor_comments          'Adding full bibliography for 1572001.cif.'
_cod_database_code               1572001
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 N12 H30 Pd O6'
_chemical_oxdiff_usercomment     'DRP 235 NO3'
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.944
_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
 C15-C21
 2.5 with sigma of 0.02
 H7B-H26B
 1.6 with sigma of 0.02
 N192-C7
 1.43 with sigma of 0.02
 N192-C26
 1.58 with sigma of 0.02
 N192-C31
 1.58 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.02 and sigma
for terminal atoms of 0.04
4.a Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C179(H17D,H17E), C180(H18A,H18B), C45(H45A,H45B), C163(H16G,
 H16H), C164(H16L,H16M), C160(H16Q,H16R), C197(H19D,H19E), C2(H2A,H2B),
 C14(H14A,H14B), C3(H3A,H3B), C1(H1A,H1B), C7(H7A,H7B), C28(H28A,H28B),
 C23(H23A,H23B), C102(H10D,H10E)
4.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C)
4.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C90(H90), C62(H62), C125(H125), C86(H86), C84(H84), C107(H107),
 C109(H109), C147(H147), C94(H94), C75(H75), C70(H70), C56(H56), C63(H63),
 C12(H12), C99(H99), C33(H33), C60(H60), C103(H103), C17(H17), C146(H146),
 C10(H10), C106(H106), C19(H19), C110(H110), C92(H92), C143(H143), C81(H81),
 C73(H73), C132(H132), C27(H27), C112(H112), C38(H38), C104(H104), C115(H115),
 C141(H141), C41(H41), C97(H97), C52(H52), C121(H121), C24(H24), C58(H58),
 C127(H127), C50(H50), C78(H78), C113(H113), C67(H67), C124(H124), C82(H82),
 C72(H72), C32(H32), C116(H116), C39(H39), C65(H65), C64(H64), C30(H30),
 C29(H29), C25(H25), C130(H130), C119(H119), C136(H136), C144(H144), C68(H68),
 C42(H42), C96(H96), C138(H138), C150(H150), C128(H128), C149(H149), C36(H36),
 C79(H79), C134(H134), C139(H139), C35(H35)
4.d Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C168(H16A,H16B,H16C), C152(H15A,
 H15B,H15C), C202(H20A,H20B,H20C), C167(H16D,H16E,H16F), C159(H15D,H15E,H15F),
 C171(H17A,H17B,H17C), C185(H18C,H18D,H18E), C161(H16I,H16J,H16K), C184(H18F,
 H18G,H18H), C183(H18I,H18J,H18K), C153(H15G,H15H,H15I), C195(H19A,H19B,H19C),
 C169(H16N,H16O,H16P), C182(H18L,H18M,H18N), C196(H19F,H19G,H19H), C166(H16S,
 H16T,H16U), C8(H8A,H8B,H8C), C5(H5A,H5B,H5C), C15(H15J,H15K,H15L), C54(H54A,
 H54B,H54C), C43(H43A,H43B,H43C), C21(H21A,H21B,H21C), C31(H31A,H31B,H31C),
 C66(H66A,H66B,H66C), C69(H69A,H69B,H69C), C40(H40A,H40B,H40C), C100(H10A,H10B,
 H10C), C26(H26A,H26B,H26C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1905 electrons were 
found per unit cell. 
This was included in the formula as
16NO3 anions and 32 H2O solvent molecules per Asymmetric Unit.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              64645
_shelx_hkl_checksum              41849
_shelx_fab_checksum              56311
_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 1.121
_oxdiff_exptl_absorpt_empirical_full_min 0.879