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_4135433
_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         'C122 H187 N6 O8 P8 Pt4, 4(F6 P), 2(C3 H6 O)'
_chemical_formula_sum            'C128 H199 F24 N6 O10 P12 Pt4'
_chemical_formula_weight         3589.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.6120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.2240(2)
_cell_length_b                   19.75010(10)
_cell_length_c                   27.1586(2)
_cell_measurement_reflns_used    110968
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.0010
_cell_measurement_theta_min      3.0800
_cell_volume                     16194.86(18)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_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     40.00  89.00   1.00    1.00    --    0.00  57.00-180.00   49
  2  \w    -22.00  24.00   1.00    1.00    --    0.00  57.00-120.00   46
  3  \w     53.00  89.00   1.00    1.00    --    0.00  38.00-120.00   36
  4  \w    -88.00 -23.00   1.00    1.00    --    0.00 -38.00 -60.00   65
  5  \w     -4.00  59.00   1.00    1.00    --    0.00  57.00 -60.00   63
  6  \w     30.00  76.00   1.00    1.00    --    0.00  57.00-120.00   46
  7  \w     -7.00  19.00   1.00    1.00    --    0.00 -38.00 -60.00   26
  8  \w    -24.00  44.00   1.00    1.00    --    0.00  19.00 150.00   68
  9  \w    -18.00  28.00   1.00    1.00    --    0.00  38.00-120.00   46
 10  \w     43.00  69.00   1.00    1.00    --    0.00  77.00 -30.00   26
 11  \w     -3.00  23.00   1.00    1.00    --    0.00  77.00 -30.00   26
 12  \w     58.00  86.00   1.00    1.00    --    0.00  57.00  30.00   28
 13  \w     43.00  78.00   1.00    1.00    --    0.00  38.00   0.00   35
 14  \w    -18.00  32.00   1.00    1.00    --    0.00  38.00   0.00   50
 15  \w    -23.00  47.00   1.00    1.00    --    0.00  57.00  30.00   70
 16  \w    -23.00  23.00   1.00    1.00    --    0.00  57.00-180.00   46
 17  \w    -71.00   7.00   1.00    1.00    --    0.00 -57.00-180.00   78
 18  \w     60.00  89.00   1.00    1.00    --    0.00  19.00 150.00   29
 19  \w     65.00 185.00   1.00    1.00    --   95.80  77.00 165.00  120
 20  \w    155.00 181.00   1.00    1.00    --   95.80  72.00   3.11   26
 21  \w     75.00 177.00   1.00    1.00    --   95.80  43.00  67.37  102
 22  \w     67.00  93.00   1.00    1.00    --   95.80  72.00   3.11   26
 23  \w     55.00 126.00   1.00    1.00    --   95.80 -77.00 120.00   71
 24  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -95.54   26
 25  \w     68.00 119.00   1.00    1.00    --   95.80 -61.00 -90.00   51
 26  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 27  \w     83.00 128.00   1.00    1.00    --   95.80 -82.00 -30.00   45
 28  \w     71.00 167.00   1.00    1.00    --   95.80  61.00  30.00   96
 29  \w      6.00 105.00   1.00    1.00    --   95.80 -82.00  60.00   99
 30  \w     37.00 127.00   1.00    1.00    --   95.80 -82.00 -90.00   90
 31  \w     63.00  88.00   1.00    1.00    --   95.80  81.00 126.28   25
 32  \w     74.00 185.00   1.00    1.00    --   95.80  50.00 -81.53  111
 33  \w    123.00 162.00   1.00    1.00    --   95.80  68.00 117.79   39
 34  \w     64.00 103.00   1.00    1.00    --   95.80  80.00-175.94   39
 35  \w     64.00  90.00   1.00    1.00    --   95.80  79.00 140.00   26
 36  \w     68.00  94.00   1.00    1.00    --   95.80  68.00   2.91   26
 37  \w     97.00 179.00   1.00    1.00    --   95.80  82.00  74.24   82
 38  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 39  \w    134.00 184.00   1.00    1.00    --   95.80  82.00 -90.00   50
 40  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  74.24   25
 41  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 42  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-180.00   25
 43  \w     63.00  88.00   1.00    1.00    --   95.80  82.00   0.00   25
 44  \w     69.00  94.00   1.00    1.00    --   95.80  66.00-111.68   25
 45  \w     71.00 183.00   1.00    1.00    --   95.80  60.00-110.60  112
 46  \w     34.00 128.00   1.00    1.00    --   95.80 -82.00  90.00   94
 47  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  30.00   26
 48  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 49  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -60.00   25
 50  \w     12.00  62.00   1.00    1.00    --   95.80 -61.00 -90.00   50
 51  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -90.00   25
 52  \w     65.00 180.00   1.00    1.00    --   95.80  77.00 -30.00  115
 53  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 54  \w     65.00  96.00   1.00    1.00    --   95.80  77.00 150.00   31
 55  \w     71.00 166.00   1.00    1.00    --   95.80  61.00 150.00   95
 56  \w     65.00  90.00   1.00    1.00    --   95.80  78.00 -71.08   25
 57  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-120.00   25
 58  \w     71.00 114.00   1.00    1.00    --   95.80  61.00 -60.00   43
 59  \w     60.00 124.00   1.00    1.00    --   95.80 -82.00-180.00   64
 60  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 61  \w     65.00 181.00   1.00    1.00    --   95.80  78.00 -46.36  116
 62  \w     73.00 167.00   1.00    1.00    --   95.80  56.00 140.62   94
 63  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-150.00   25
 64  \w     63.00  94.00   1.00    1.00    --   95.80  82.00  90.00   31
 65  \w     72.00 166.00   1.00    1.00    --   95.80  55.00-133.97   94
 66  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   26
 67  \w     71.00  97.00   1.00    1.00    --   95.80  61.00  90.00   26
 68  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 69  \w     68.00  93.00   1.00    1.00    --   95.80  70.00 -91.52   25
 70  \w     68.00  94.00   1.00    1.00    --   95.80  68.00-138.18   26
 71  \w     74.00 163.00   1.00    1.00    --   95.80  48.00  20.39   89
 72  \w     68.00  94.00   1.00    1.00    --   95.80  68.00 117.79   26
 73  \w     70.00 124.00   1.00    1.00    --   95.80  63.00  62.59   54
;
_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      0.0301837000
_diffrn_orient_matrix_UB_12      -0.0028529000
_diffrn_orient_matrix_UB_13      0.0472247000
_diffrn_orient_matrix_UB_21      0.0398052000
_diffrn_orient_matrix_UB_22      -0.0176816000
_diffrn_orient_matrix_UB_23      -0.0310389000
_diffrn_orient_matrix_UB_31      0.0104094000
_diffrn_orient_matrix_UB_32      0.0759280000
_diffrn_orient_matrix_UB_33      -0.0054703000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0895
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            411147
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         3.165
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.097
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17128
_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    1.472
_exptl_crystal_description       block
_exptl_crystal_F_000             7188
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_refine_diff_density_max         3.165
_refine_diff_density_min         -4.170
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1620
_refine_ls_number_reflns         28716
_refine_ls_number_restraints     170
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0804
_refine_ls_R_factor_gt           0.0736
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0718P)^2^+203.4191P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1754
_refine_ls_wR_factor_ref         0.1804
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25602
_reflns_number_total             28716
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11738_si_002.cif
_cod_data_source_block           exp_1239
_cod_database_code               4135433
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.269
_shelx_estimated_absorpt_t_min   0.181
_reflns_odcompleteness_completeness 99.97
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C78-C77
 1.52 with sigma of 0.01
 C84-C83
 1.52 with sigma of 0.01
 C81-C82
 1.52 with sigma of 0.01
 C108-C106
 1.52 with sigma of 0.01
 C107-C106
 1.52 with sigma of 0.01
 O8-C108 = O8-C107
 1.4 with sigma of 0.01
 C107-O8
 1.4 with sigma of 0.01
 C108-O8
 1.4 with sigma of 0.01
 C110-C109
 1.52 with sigma of 0.01
 C110-C111
 1.52 with sigma of 0.01
 C109-C113
 1.52 with sigma of 0.01
 C112-C114
 1.52 with sigma of 0.01
 C111-C112
 1.52 with sigma of 0.01
 C114-C112
 1.52 with sigma of 0.01
3. Rigid bond restraints
 C85, C86
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C81, C82
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C93, C94
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C107, O7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C127, C126
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C128, C129
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C124, C1A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 P6, C126
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C79, C80
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 P6, C124
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C100, C101
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C82, C81
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C85 \\sim C86: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C82 \\sim C81: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C93 \\sim C94: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C126 \\sim C127: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C128 \\sim C129: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C1A \\sim C124: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
P6 \\sim C126: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C79 \\sim C80: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
P6 \\sim C124: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C100 \\sim C101: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C81 \\sim C82: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(N6) \\sim Ueq, Uanis(C116)
\\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(O9) \\sim Ueq:
with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C111) \\sim Ueq, Uanis(C109) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C113) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C112) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C107) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O7) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C108) \\sim Ueq, Uanis(O6) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C116) = Uanis(C117) = Uanis(C113) = Uanis(C99) = Uanis(C104) = Uanis(C105)
Uanis(O9) = Uanis(N6) = Uanis(N5) = Uanis(O5)
Uanis(C111) = Uanis(C115) = Uanis(C114) = Uanis(C100) = Uanis(C102) =
Uanis(C103)
Uanis(C109) = Uanis(C98)
Uanis(C81) = Uanis(C79)
5. Others
 Fixed Sof: H10A(0.5) H10B(0.5) H10C(0.5) H10D(0.5) C107(0.5) O7(0.5)
 C108(0.5) O6(0.5)
6.a Ternary CH refined with riding coordinates:
 C97(H97)
6.b Secondary CH2 refined with riding coordinates:
 C106(H10A,H10B), C106(H10C,H10D), C53(H53A,H53B), C55(H55A,H55B), C57(H57A,
 H57B), C59(H59A,H59B), C61(H61A,H61B), C63(H63A,H63B), C65(H65A,H65B),
 C67(H67A,H67B), C69(H69A,H69B), C71(H71A,H71B), C73(H73A,H73B), C75(H75A,H75B),
  C77(H77A,H77B), C79(H79A,H79B), C81(H81A,H81B), C83(H83A,H83B), C85(H85A,
 H85B), C87(H87A,H87B), C89(H89A,H89B), C91(H91A,H91B), C93(H93A,H93B),
 C95(H95A,H95B), C98(H98A,H98B), C101(H10E,H10F), C109(H10S,H10T), C111(H11A,
 H11B), C124(H12A,H12B), C126(H12C,H12D), C128(H12H,H12I)
6.c Me refined with riding coordinates:
 C114(H11C,H11D,H11E)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), 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), C42(H42),
 C43(H43), C45(H45), C46(H46), C48(H48), C49(H49), C51(H51), C52(H52)
6.e Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C60(H60A,H60B,
 H60C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C68(H68A,
 H68B,H68C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C),
 C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C82(H82A,H82B,
 H82C), C84(H84A,H84B,H84C), C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C90(H90A,
 H90B,H90C), C92(H92A,H92B,H92C), C94(H94A,H94B,H94C), C102(H10G,H10H,H10I),
 C103(H10J,H10K,H10L), C104(H10M,H10N,H10O), C105(H10P,H10Q,H10R), C115(H11F,
 H11G,H11H), C116(H11I,H11J,H11K), C117(H11L,H11M,H11N), C118(H11O,H11P,H11Q),
 C120(H12M,H12N,H12O), C121(H12P,H12Q,H12R), C123(H12S,H12T,H12U), C1A(H1AA,
 H1AB,H1AC), C127(H12E,H12F,H12G), C129(H12J,H12K,H12L)
;
_shelx_res_checksum              2743
_shelx_hkl_checksum              75973
_shelx_fab_checksum              5600
_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 3.186
_oxdiff_exptl_absorpt_empirical_full_min 0.511