TEMPO Radical-Functionalized Supramolecular Coordination Complexes with Controllable Spin-Spin Interactions.
Jiang, Wei-Ling; Peng, Zhiyong; Huang, Bin; Zhao, Xiao-Li; Sun, Di; Shi, Xueliang; Yang, Hai-Bo; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c11738

data_4135432
_publ_section_title
;
 TEMPO Radical-Functionalized Supramolecular Coordination Complexes with
 Controllable Spin-Spin Interactions.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c11738
_journal_year                    2020
_chemical_formula_moiety         '3(B F4), C124 H120 N12 O16 Pd2'
_chemical_formula_sum            'C124 H120 B3 F12 N12 O16 Pd2'
_chemical_formula_weight         2507.54
_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             2020-09-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                92.012(5)
_cell_angle_beta                 115.044(8)
_cell_angle_gamma                91.519(5)
_cell_formula_units_Z            2
_cell_length_a                   19.4785(15)
_cell_length_b                   19.5995(7)
_cell_length_c                   20.0531(19)
_cell_measurement_reflns_used    7189
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      59.7690
_cell_measurement_theta_min      3.4660
_cell_volume                     6924.4(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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    -30.00   8.00   1.00    5.00    --    0.00 -19.00 -30.00   38
  2  \w    -35.00  32.00   1.00    5.00    --    0.00 -82.00-120.00   67
  3  \w    -89.00  29.00   1.00    5.00    --    0.00 -77.00 150.00  118
  4  \w     16.00  77.00   1.00    5.00    --    0.00  57.00-120.00   61
  5  \w    -16.00  11.00   1.00    5.00    --    0.00  57.00-120.00   27
  6  \w    -76.00 -23.00   1.00    5.00    --    0.00 -38.00 -90.00   53
  7  \w     59.00  84.00   1.00    5.00    --    0.00  38.00-180.00   25
  8  \w     39.00 118.00   1.00    5.00    --   95.80 -61.00 120.00   79
  9  \w      9.00 126.00   1.00    5.00    --   95.80 -82.00 -90.00  117
 10  \w     33.00 112.00   1.00    5.00    --   95.80 -30.00 120.00   79
 11  \w     48.00 126.00   1.00    5.00    --   95.80 -82.00 120.00   78
 12  \w     16.00 119.00   1.00    5.00    --   95.80 -61.00 -90.00  103
 13  \w     34.00 107.00   1.00    5.00    --   95.80 -15.00 120.00   73
 14  \w     78.00 184.00   1.00    5.00    --   95.80  30.00 150.00  106
 15  \w     87.00 112.00   1.00    5.00    --   95.80 -45.00 -30.00   25
 16  \w     84.00 115.00   1.00    5.00    --   95.80 -82.00  30.00   31
 17  \w     78.00 184.00   1.00    5.00    --   95.80  30.00 120.00  106
 18  \w     21.00  49.00   1.00    5.00    --   95.80 -45.00 -30.00   28
 19  \w     86.00 121.00   1.00    5.00    --   95.80 -82.00 -30.00   35
 20  \w     83.00 109.00   1.00    5.00    --   95.80 -61.00-180.00   26
 21  \w     68.00 105.00   1.00    5.00    --   95.80 -82.00-150.00   37
 22  \w      7.00 100.00   1.00    5.00    --   95.80 -61.00  30.00   93
 23  \w    108.00 154.00   1.00    5.00    --   95.80  61.00  60.00   46
 24  \w     17.00  75.00   1.00    5.00    --   95.80 -82.00  30.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0311275000
_diffrn_orient_matrix_UB_12      -0.0714417000
_diffrn_orient_matrix_UB_13      0.0061189000
_diffrn_orient_matrix_UB_21      -0.0168847000
_diffrn_orient_matrix_UB_22      0.0277428000
_diffrn_orient_matrix_UB_23      0.0640807000
_diffrn_orient_matrix_UB_31      -0.0798929000
_diffrn_orient_matrix_UB_32      0.0180362000
_diffrn_orient_matrix_UB_33      -0.0553675000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1251
_diffrn_reflns_av_unetI/netI     0.1537
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            71123
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.236
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.734
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51523
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.203
_exptl_crystal_description       block
_exptl_crystal_F_000             2582
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         4.281
_refine_diff_density_min         -1.181
_refine_diff_density_rms         0.210
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1527
_refine_ls_number_reflns         24567
_refine_ls_number_restraints     531
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.2495
_refine_ls_R_factor_gt           0.1898
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1800P)^2^+170.3579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4383
_refine_ls_wR_factor_ref         0.4764
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13028
_reflns_number_total             24567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11738_si_005.cif
_cod_data_source_block           exp_1358
_cod_database_code               4135432
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.639
_shelx_estimated_absorpt_t_min   0.537
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2. Restrained distances
 C103-C104
 1.52 with sigma of 0.01
 O5-C103
 1.4 with sigma of 0.01
 C92-O11
 1.42 with sigma of 0.01
 C110-C108
 1.52 with sigma of 0.01
 C112-C113
 2.3 with sigma of 0.02
 C107-C112
 1.52 with sigma of 0.01
3. Rigid bond restraints
 C107, N9, C108, C109, C105, C106
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C97, N12, C96, C95, C94, C98
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C84, C83, C87, C86, N11, C85
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C2, C1, C3, C4, C5, N6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C16, C17, C18, C19, N4, C20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C33, C28, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C76, C80
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C108, C111
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O11, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C64, C65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C58, C59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C59, C60
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C55, C54
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C66, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C76, C77
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C75, C76
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C96, C101, C102
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C61, C62, C63, C64, C65, N2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O5, C103
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O6, C104
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C41, B1, F3, F4, F1, F2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.01
 F5, B3, F8, F6, F7
 with sigma for 1-2 distances of 1 and sigma for 1-3 distances of 1
 C12, C13, C8, C9, C10, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C74, C75
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C23, C24, C22, C25, N5, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C23, C22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C49, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C110, C108
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C68, C67, C66
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
O5 \\sim C103: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O6 \\sim C104: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
B1 \\sim F3 \\sim F2 \\sim F1 \\sim F4: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.08
B3 \\sim F8 \\sim F5 \\sim F6 \\sim F7: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.08
C12 \\sim C13 \\sim C8 \\sim C9 \\sim C10 \\sim C11: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.08
C24 \\sim C25 \\sim N5 \\sim C21 \\sim C22 \\sim C23: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C49 \\sim C50: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C110 \\sim C108: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C68 \\sim C67 \\sim C66: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C104) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(N6) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(C112) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C113) \\sim Ueq: with sigma
of 0.002 and sigma for terminal atoms of 0.004
Uanis(C104) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C1)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(O11) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C91)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(B3) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(B2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C120) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C69) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(F5)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C81) \\sim Ueq: with sigma of 0.002 and
sigma for terminal atoms of 0.004
Uanis(C79) \\sim Ueq, Uanis(C90) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(O5) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C111) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C57) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C110) \\sim Ueq, Uanis(F10) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
5.a Ternary CH refined with riding coordinates:
 C83(H83), C94(H94), C105(H105), C114(H114)
5.b Secondary CH2 refined with riding coordinates:
 C034(H03A,H03B), C81(H81A,H81B), C84(H84A,H84B), C87(H87A,H87B), C92(H92A,
 H92B), C98(H98A,H98B), C103(H10J,H10K), C106(H10L,H10M), C109(H10N,H10O),
 C115(H11M,H11N), C118(H11O,H11P)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C1(H1), C5(H5), C3(H3), C9(H9), C10(H10), C11(H11), C17(H17),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C29(H29),
  C30(H30), C31(H31), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
 C42(H42), C43(H43), C45(H45), C49(H49), C50(H50), C51(H51), C57(H57), C58(H58),
  C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C65(H65), C69(H69),
 C70(H70), C71(H71), C77(H77), C78(H78), C79(H79), C80(H80), C95(H95)
5.d Fitted hexagon refined as free rotating group:
 C2(C1,N6,C5,C4,C3)
5.e Idealised Me refined as rotating group:
 C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,
 H91C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C), C101(H10D,H10E,H10F),
 C102(H10G,H10H,H10I), C110(H11A,H11B,H11C), C111(H11D,H11E,H11F), C112(H11G,
 H11H,H11I), C113(H11J,H11K,H11L), C119(H11Q,H11R,H11S), C120(H12A,H12B,H12C),
 C121(H12D,H12E,H12F), C122(H12G,H12H,H12I)
5.f Idealised tetrahedral OH refined as rotating group:
 O7(H7)
;
_shelx_res_checksum              72698
_shelx_hkl_checksum              82426
_shelx_fab_checksum              27284
_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 2.597
_oxdiff_exptl_absorpt_empirical_full_min 0.492