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_1569526
_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, 2(B F4), C H3 O3 S, 3(C2 H3 N), 1[B2F8C2H6C2N2]'
_chemical_formula_sum            'C83 H82 B4 F16 N29 O3 Pd Pt S'
_chemical_formula_weight         2214.600
_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                79.615(2)
_cell_angle_beta                 75.366(2)
_cell_angle_gamma                89.377(2)
_cell_formula_units_Z            2
_cell_length_a                   13.8621(2)
_cell_length_b                   14.0385(3)
_cell_length_c                   27.2264(6)
_cell_measurement_reflns_used    31815
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.0890
_cell_measurement_theta_min      3.8930
_cell_volume                     5039.14(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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 (Sheldrick, 2015)'
_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 0.9969
_diffrn_measured_fraction_theta_max 0.9661
_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   -115.00 -14.00   1.00   13.50    --  -42.17 -57.00-120.00  101
  2  \w   -116.00 -18.00   1.00   13.50    --  -42.17 -38.00 120.00   98
  3  \w      9.00  42.00   1.00   13.50    --   42.17  78.00-135.48   33
  4  \w    -21.00  75.00   1.00   13.50    --   42.17 -77.00   0.00   96
  5  \w      9.00  42.00   1.00   13.50    --   42.17  79.00 138.33   33
  6  \w     30.00 106.00   1.00   54.00    --  112.00 -95.00  30.00   76
  7  \w     86.00 178.00   1.00   54.00    --  112.00  45.00  60.00   92
  8  \w     30.00 106.00   1.00   54.00    --  112.00 -95.00 -60.00   76
  9  \w     30.00 106.00   1.00   54.00    --  112.00 -95.00-120.00   76
 10  \w     84.00 178.00   1.00   54.00    --  112.00  30.00 150.00   94
 11  \w     83.00 178.00   1.00   54.00    --  112.00  63.00-158.89   95
 12  \w     83.00 178.00   1.00   54.00    --  112.00  61.00-120.00   95
 13  \w    103.00 178.00   1.00   54.00    --  112.00  77.00  90.00   75
 14  \w     40.00 141.00   1.00   54.00    --  112.00 -61.00  60.00  101
 15  \w     32.00 108.00   1.00   54.00    --  112.00-102.00 140.12   76
 16  \w    -67.00  32.00   1.00   13.50    --  -42.17  38.00 150.00   99
 17  \w   -115.00 -14.00   1.00   13.50    --  -42.17 -57.00   0.00  101
 18  \w    -87.00  -6.00   1.00   13.50    --  -42.17 125.00 150.00   81
 19  \w      9.00  42.00   1.00   13.50    --   42.17  81.00  11.37   33
 20  \w     85.00 178.00   1.00   54.00    --  112.00  49.00   9.26   93
 21  \w     83.00 178.00   1.00   54.00    --  112.00  61.00  90.00   95
 22  \w     59.00 178.00   1.00   54.00    --  112.00  15.00   0.00  119
 23  \w     82.00 132.00   1.00   54.00    --  112.00  64.00 167.61   50
;
_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      0.0511411000
_diffrn_orient_matrix_UB_12      -0.0962189000
_diffrn_orient_matrix_UB_13      0.0121016000
_diffrn_orient_matrix_UB_21      -0.0194905000
_diffrn_orient_matrix_UB_22      0.0111559000
_diffrn_orient_matrix_UB_23      0.0569228000
_diffrn_orient_matrix_UB_31      -0.1010705000
_diffrn_orient_matrix_UB_32      -0.0554702000
_diffrn_orient_matrix_UB_33      0.0124138000
_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  0.0423
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.9969
_diffrn_reflns_Laue_measured_fraction_max 0.9661
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            55561
_diffrn_reflns_point_group_measured_fraction_full 0.9969
_diffrn_reflns_point_group_measured_fraction_max 0.9661
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.58
_diffrn_reflns_theta_min         3.90
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.967
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70319
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.460
_exptl_crystal_description       plate
_exptl_crystal_F_000             2223.315
_exptl_crystal_preparation
'Slow diffusion of diethyl ether into acetonitrile in the fridge'
_exptl_crystal_recrystallization_method
'Slow diffusion of diethyl ether into a concentrated acetonitrile solution of the host guest adduct at 277 K'
_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.098
_refine_diff_density_max         2.8811
_refine_diff_density_min         -2.0988
_refine_diff_density_rms         0.2156
_refine_ls_d_res_high            0.7926
_refine_ls_d_res_low             11.3449
_refine_ls_goodness_of_fit_ref   1.0290
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    136
_refine_ls_number_parameters     1130
_refine_ls_number_reflns         20488
_refine_ls_number_restraints     35
_refine_ls_restrained_S_all      1.0280
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0710
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0462P)^2^+65.7314P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1775
_refine_ls_wR_factor_ref         0.1804
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              17
_reflns_limit_h_min              -16
_reflns_limit_k_max              17
_reflns_limit_k_min              -17
_reflns_limit_l_max              34
_reflns_limit_l_min              0
_reflns_number_gt                19096
_reflns_number_total             20488
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3sc01354e2.cif
_cod_data_source_block           exp_3876
_cod_depositor_comments
'Adding full bibliography for 1569522--1569526.cif.'
_cod_original_formula_sum        'C83 H82 B4 F16 N29 O3 Pd1 Pt1 S1'
_cod_database_code               1569526
_chemical_oxdiff_usercomment     M710
_reflns_odcompleteness_completeness 99.52
_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. Restrained distances
 O6-S01Q
 1.7 with sigma of 0.02
 O15-C038
 3 with sigma of 0.04
 O6-C038
 3 with sigma of 0.04
 O3-C038
 3 with sigma of 0.04
 O18-C038
 3 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O6 \\sim O3 \\sim O15 \\sim O18: within 1.7A with sigma of 0.0004 and sigma for
terminal atoms of 0.0008 within 1.7A
Uanis(O18) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O15)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C01C) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Fixed Sof: F031(0.5) F03G(0.5) F03I(0.5) O18(0.75) O15(0.75) F11(0.5)
 O3(0.75) O6(0.75)
5.a Secondary CH2 refined with riding coordinates:
 C01O(H01a,H01b), C01S(H01h,H01i), C01Y(H01j,H01m), C02D(H02d,H02e), C02F(H02g,
 H02h), C02T(H02u,H02v), C02Y(H02w,H02y), C02Z(H02z,Hb)
5.b Aromatic/amide H refined with riding coordinates:
 C00O(H00O), C00P(H00P), C00W(H00W), C00X(H00X), C00Z(H00Z), C010(H010),
 C011(H011), C014(H014), C015(H015), C017(H017), C018(H018), C019(H019),
 C01C(H01C), C01D(H01D), C01E(H01E), C01F(H01F), C01G(H01G), C01K(H01K),
 C01L(H01L), C01N(H01N), C01R(H01R), C01Z(H01Z), C020(H020), C021(H021),
 C022(H022), C023(H023), C024(H024), C025(H025), C027(H027), C028(H028),
 C029(H029), C02A(H02A), C02B(H02B), C02C(H02C), C02E(H02f), C02G(H02i),
 C02H(H02j), C02I(H02k), C02J(H02l), C02K(H02m), C02L(H02n), C02M(H02o),
 C02N(H02p), C02P(H02q), C02Q(H02r), C02R(H02s), C02S(H02t), C02X(H02X)
5.c Idealised Me refined as rotating group:
 C02W(H02,H,Ha), C033(H03g,H03h,H03i), C038(H03a,H03b,H03c), C03H(H03d,H03e,
 H03f)
6. A solvent mask was applied to resolve diffuse electron density, where a void consisting of 122 electrons was measured in the asymmetric unit, this was attributed to two tetrafluoroborate anions and two molecules of acetonitrile.
;
_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 1.544
_oxdiff_exptl_absorpt_empirical_full_min 0.371