Redox Active [Pd2L4]4+ Cages Constructed from Rotationally Flexible 1,1′-Disubstituted Ferrocene Ligands
Vasdev, Roan A. S.; Findlay, James A.; Garden, Anna L.; Crowley, James D.; Chemical Communications  (2019) –; doi:10.1039/C9CC03321A

data_7123584
_publ_section_title
;
 Redox Active [Pd2L4]4+ Cages Constructed from Rotationally Flexible
 1,1&#x2032;-Disubstituted Ferrocene Ligands
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03321A
_journal_year                    2019
_chemical_formula_moiety         '2(C48 H32 Fe2 N4 Pd), 4(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C100 H70 B4 F16 Fe4 N10 Pd2'
_chemical_formula_weight         2195.10
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-03-07 deposited with the CCDC.    2019-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                78.150(5)
_cell_angle_beta                 89.339(4)
_cell_angle_gamma                85.522(6)
_cell_formula_units_Z            2
_cell_length_a                   14.7833(9)
_cell_length_b                   15.2557(13)
_cell_length_c                   21.7631(10)
_cell_measurement_reflns_used    8456
_cell_measurement_temperature    99.97(11)
_cell_measurement_theta_max      72.6530
_cell_measurement_theta_min      4.1360
_cell_volume                     4788.9(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1725
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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   -114.00 -13.00   1.00    4.50    --  -40.79 -57.00  60.00  101
  2  \w    -69.00  32.00   1.00    4.50    --  -40.79  57.00-150.00  101
  3  \w   -128.00 -34.00   1.00    4.50    --  -40.79 178.00-180.00   94
  4  \w      8.00 117.00   1.00    4.50    --   40.79  77.00 -30.00  109
  5  \w     57.00 130.00   1.00    4.50    --   40.79 178.00-180.00   73
  6  \w     32.00 133.00   1.00   18.00    --  104.32 -61.00  30.00  101
  7  \w     78.00 177.00   1.00   18.00    --  104.32  45.00  30.00   99
  8  \w     28.00 137.00   1.00   18.00    --  104.32 -77.00 150.00  109
  9  \w     31.00 117.00   1.00   18.00    --  104.32-125.00 -90.00   86
 10  \w     31.00 130.00   1.00   18.00    --  104.32 -45.00-180.00   99
 11  \w     78.00 177.00   1.00   18.00    --  104.32  45.00-180.00   99
 12  \w     31.00 117.00   1.00   18.00    --  104.32-125.00 -30.00   86
 13  \w     31.00 117.00   1.00   18.00    --  104.32-125.00 150.00   86
 14  \w     75.00 177.00   1.00   18.00    --  104.32  61.00 -30.00  102
 15  \w     22.00 109.00   1.00   18.00    --  104.32 -95.00   0.00   87
 16  \w     31.00 130.00   1.00   18.00    --  104.32 -45.00   0.00   99
 17  \w     94.00 178.00   1.00   18.00    --  104.32 125.00  30.00   84
 18  \w     52.00 178.00   1.00   18.00    --  104.32  15.00 120.00  126
 19  \w   -115.00 -16.00   1.00    4.50    --  -40.79 -38.00-120.00   99
 20  \w   -117.00  -8.00   1.00    4.50    --  -40.79 -77.00  30.00  109
 21  \w   -117.00  -8.00   1.00    4.50    --  -40.79 -77.00-180.00  109
 22  \w   -114.00 -13.00   1.00    4.50    --  -40.79 -57.00-150.00  101
 23  \w   -117.00  -8.00   1.00    4.50    --  -40.79 -77.00 -60.00  109
 24  \w      1.00  82.00   1.00    4.50    --   40.79 -99.00   0.00   81
 25  \w     76.00 178.00   1.00   18.00    --  104.32  30.00 -90.00  102
 26  \w     72.00 178.00   1.00   18.00    --  104.32  77.00 120.00  106
;
_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      0.0459069000
_diffrn_orient_matrix_UB_12      0.0803912000
_diffrn_orient_matrix_UB_13      0.0151006000
_diffrn_orient_matrix_UB_21      0.0838607000
_diffrn_orient_matrix_UB_22      -0.0627912000
_diffrn_orient_matrix_UB_23      0.0254200000
_diffrn_orient_matrix_UB_31      0.0422669000
_diffrn_orient_matrix_UB_32      0.0174668000
_diffrn_orient_matrix_UB_33      -0.0660107000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1666
_diffrn_reflns_av_unetI/netI     0.1185
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            45798
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        49.087
_diffrn_reflns_theta_max         49.087
_diffrn_reflns_theta_min         3.655
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.407
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69937
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_description       plate
_exptl_crystal_F_000             2200
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.041
_refine_diff_density_max         1.099
_refine_diff_density_min         -0.758
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1227
_refine_ls_number_reflns         9376
_refine_ls_number_restraints     2766
_refine_ls_restrained_S_all      0.880
_refine_ls_R_factor_all          0.1231
_refine_ls_R_factor_gt           0.0822
_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^)+(0.1082P)^2^+20.1684P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1908
_refine_ls_wR_factor_ref         0.2200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6203
_reflns_number_total             9376
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03321a3.cif
_cod_data_source_block           rav-555
_cod_database_code               7123584
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C96 H64 B4 F16 Fe4 N4 Pd2'
_chemical_oxdiff_usercomment     L761
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 3.5A with sigma of 0.15 and sigma
for terminal atoms of 0.35
Uanis(F16) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F14)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F3) \\sim Ueq,
Uanis(F2) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F7) \\sim
Ueq, Uanis(F5) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F4)
\\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(C94) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C95) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(N10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
3.a Aromatic/amide H refined with riding coordinates:
 C97(H97), C20(H20), C24(H24), C16(H16), C33(H33), C1(H1), C93(H93), C9(H9),
 C48(H48), C10(H10), C95(H95), C13(H13), C47(H47), C60(H60), C38(H38), C25(H25),
  C14(H14), C39(H39), C68(H68), C44(H44), C85(H85), C52(H52), C46(H46),
 C57(H57), C74(H74), C22(H22), C34(H34), C82(H82), C2(H2), C88(H88), C61(H61),
 C11(H11), C36(H36), C12(H12), C37(H37), C72(H72), C89(H89), C23(H23), C70(H70),
  C15(H15), C49(H49), C35(H35), C64(H64), C96(H96), C28(H28), C3(H3), C71(H71),
 C75(H75), C84(H84), C87(H87), C59(H59), C77(H77), C76(H76), C50(H50), C58(H58),
  C51(H51), C40(H40), C62(H62), C26(H26), C27(H27), C86(H86), C63(H63), C4(H4),
 C83(H83)
3.b Idealised Me refined as rotating group:
 C98(H98A,H98B,H98C), C100(H10A,H10B,H10C)
;
_shelx_res_checksum              96144
_shelx_fab_checksum              79535
_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 1.443
_oxdiff_exptl_absorpt_empirical_full_min 0.674