Exploiting reduced-symmetry ligands with pyridyl and imidazole donors to construct a second-generation stimuli-responsive heterobimetallic [PdPtL<sub>4</sub>]<sup>4+</sup> cage.
Pearcy, Aston C.; Lisboa, Lynn S.; Preston, Dan; Page, Nick B.; Lawrence, Tristan; Wright, L. James; Hartinger, Christian G.; Crowley, James D.; Chemical science 14 (2023) 8615–8623; doi:10.1039/d3sc01354e

data_1569525
_publ_section_title
;
 Exploiting reduced-symmetry ligands with pyridyl and imidazole donors to
 construct a second-generation stimuli-responsive heterobimetallic
 [PdPtL<sub>4</sub>]<sup>4+</sup> cage.
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              8615
_journal_page_last               8623
_journal_paper_doi               10.1039/d3sc01354e
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
'C72 H64 N24 Pd Pt, 3(B F4), 2(C H3 N O2), 1[CH3NO2BF4]'
_chemical_formula_sum            'C75 H73 B4 F16 N27 O6 Pd Pt'
_chemical_formula_weight         2097.358
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-22 deposited with the CCDC.	2023-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                102.420(4)
_cell_angle_beta                 99.049(3)
_cell_angle_gamma                100.243(4)
_cell_formula_units_Z            2
_cell_length_a                   11.6471(5)
_cell_length_b                   15.8160(7)
_cell_length_c                   25.1824(10)
_cell_measurement_reflns_used    9397
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.3490
_cell_measurement_theta_min      3.8700
_cell_volume                     4364.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3449
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9980
_diffrn_measured_fraction_theta_max 0.9688
_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    -67.00  32.00   1.00    7.00    --  -42.04  38.00  60.00   99
  2  \w   -116.00 -18.00   1.00    7.00    --  -42.04 -38.00-120.00   98
  3  \w    -75.00  34.00   1.00    7.00    --  -42.04  77.00 150.00  109
  4  \w      9.00  42.00   1.00    7.00    --   42.04  80.00-108.97   33
  5  \w     86.00 178.00   1.00   28.00    --  112.00  45.00-180.00   92
  6  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00 150.00   76
  7  \w     40.00 141.00   1.00   28.00    --  112.00 -61.00 -60.00  101
  8  \w     39.00 138.00   1.00   28.00    --  112.00 -45.00-180.00   99
  9  \w     84.00 178.00   1.00   28.00    --  112.00  30.00   0.00   94
 10  \w     39.00 112.00   1.00   28.00    --  112.00-125.00   0.00   73
 11  \w     39.00 112.00   1.00   28.00    --  112.00-125.00 120.00   73
 12  \w     30.00 106.00   1.00   28.00    --  112.00 -95.00-150.00   76
 13  \w     40.00 141.00   1.00   28.00    --  112.00 -61.00  60.00  101
 14  \w     59.00 178.00   1.00   28.00    --  112.00  15.00 120.00  119
 15  \w   -116.00 -17.00   1.00    7.00    --  -42.04 -42.00  40.00   99
 16  \w      8.00  42.00   1.00    7.00    --   42.04  82.00  52.41   34
 17  \w     10.00  36.00   1.00    7.00    --   42.04  75.00   9.21   26
 18  \w      9.00  42.00   1.00    7.00    --   42.04  81.00 149.52   33
 19  \w     83.00 155.00   1.00   28.00    --  112.00  61.00 -60.00   72
 20  \w     84.00 178.00   1.00   28.00    --  112.00  30.00 -90.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0496315000
_diffrn_orient_matrix_UB_12      0.0869963000
_diffrn_orient_matrix_UB_13      -0.0148424000
_diffrn_orient_matrix_UB_21      0.1258477000
_diffrn_orient_matrix_UB_22      0.0001251000
_diffrn_orient_matrix_UB_23      0.0301526000
_diffrn_orient_matrix_UB_31      0.0233457000
_diffrn_orient_matrix_UB_32      -0.0536909000
_diffrn_orient_matrix_UB_33      -0.0544459000
_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  0.0765
_diffrn_reflns_av_unetI/netI     0.0933
_diffrn_reflns_Laue_measured_fraction_full 0.9980
_diffrn_reflns_Laue_measured_fraction_max 0.9688
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            43070
_diffrn_reflns_point_group_measured_fraction_full 0.9980
_diffrn_reflns_point_group_measured_fraction_max 0.9688
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.57
_diffrn_reflns_theta_min         3.67
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.499
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91408
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.596
_exptl_crystal_description       plate
_exptl_crystal_F_000             2096.503
_exptl_crystal_recrystallization_method
'Vapour diffusion of diethyl ether into a concentrated nitromethane solution of the cage'
_exptl_crystal_size_max          0.094
_exptl_crystal_size_mid          0.064
_exptl_crystal_size_min          0.027
_refine_diff_density_max         4.1032
_refine_diff_density_min         -4.8608
_refine_diff_density_rms         0.1850
_refine_ls_d_res_high            0.7926
_refine_ls_d_res_low             12.0393
_refine_ls_goodness_of_fit_ref   1.0423
_refine_ls_matrix_type           full
_refine_ls_number_constraints    134
_refine_ls_number_parameters     1173
_refine_ls_number_reflns         17771
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.0421
_refine_ls_R_factor_all          0.1027
_refine_ls_R_factor_gt           0.0694
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0540P)^2^+18.7819P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1616
_refine_ls_wR_factor_ref         0.1861
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              19
_reflns_limit_k_min              -19
_reflns_limit_l_max              31
_reflns_limit_l_min              0
_reflns_number_gt                12417
_reflns_number_total             17771
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3sc01354e2.cif
_cod_data_source_block           ACP_082
_cod_depositor_comments
'Adding full bibliography for 1569522--1569526.cif.'
_cod_original_formula_sum        'C75 H73 B4 F16 N27 O6 Pd1 Pt1'
_cod_database_code               1569525
_chemical_oxdiff_formula         'C72 H64 N24 Pt Pd B4 F16'
_chemical_oxdiff_usercomment     M555
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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. Uiso/Uaniso restraints and constraints
Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: F15(0.5) F13(0.5) F14(0.5) F10(0.5) N21(0.5) F11(0.5) N20(0.5)
 C59(0.5) C60(0.5) H60(0.5) C58(0.5) H58(0.5) C62(0.5) H62(0.5) F12(0.5)
 C56(0.5) H56(0.5) C63(0.5) N22(0.5) N23(0.5) C61(0.5) H61(0.5) C57(0.5)
 H57(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C15(H15a,H15b), C33(H33a,H33b), C8(H8a,H8b), C73(H73a,H73b), C51(H51a,H51b),
 C26(H26a,H26b), C44(H44a,H44b), C66(H66a,H66b)
4.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C18(H18), C17(H17), C28(H28), C35(H35), C34(H34), C25(H25),
 C76(H76), C13(H13), C74(H74), C12(H12), C11(H11), C20(H20), C19(H19), C54(H54),
  C7(H7), C36(H36), C48(H48), C29(H29), C65(H65), C49(H49), C10(H10), C1(H1),
 C55(H55), C75(H75), C47(H47), C53(H53), C52(H52), C21(H21), C31(H31), C71(H71),
  C4(H4), C70(H70), C38(H38), C46(H46), C2(H2), C22(H22), C69(H69), C43(H43),
 C30(H30), C37(H37), C3(H3), C39(H39), C40(H40), C68(H68), C60(H60), C58(H58),
 C62(H62), C56(H56), C61(H61), C57(H57)
4.c Idealised Me refined as rotating group:
 C77(H77a,H77b,H77c), C78(H78a,H78b,H78c)
5. A solvent mask was applied to resolve diffuse electron density, where a void consisting
 of 58 electrons was measured in the asymmetric unit, this was attributed to a molecule of nitromethane and a tetrafluoroborate anion.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.879