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_4135430
_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         'C67 H97 N3 O4 P4 Pt2, 2(C3 H6 O), 1.5(F6 P)'
_chemical_formula_sum            'C73 H109 F9 N3 O6 P5.5 Pt2'
_chemical_formula_weight         1856.14
_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             2020-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90.302(3)
_cell_angle_beta                 103.428(4)
_cell_angle_gamma                97.512(3)
_cell_formula_units_Z            2
_cell_length_a                   13.8359(5)
_cell_length_b                   14.2602(4)
_cell_length_c                   24.8906(10)
_cell_measurement_reflns_used    11463
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      59.7020
_cell_measurement_theta_min      3.6010
_cell_volume                     4732.5(3)
_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 0.990
_diffrn_measured_fraction_theta_max 0.963
_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    -17.00  30.00   1.00    2.00    --    0.00  38.00 -30.00   47
  2  \w    -24.00  73.00   1.00    2.00    --    0.00  19.00-120.00   97
  3  \w    -76.00 -34.00   1.00    2.00    --    0.00 -57.00  60.00   42
  4  \w     43.00  75.00   1.00    2.00    --    0.00  19.00  90.00   32
  5  \w     25.00  72.00   1.00    2.00    --    0.00  77.00-120.00   47
  6  \w    -30.00  18.00   1.00    2.00    --    0.00  77.00-120.00   48
  7  \w     14.00  86.00   1.00    2.00    --    0.00  38.00-120.00   72
  8  \w    -24.00  23.00   1.00    2.00    --    0.00 -57.00  60.00   47
  9  \w    -22.00  19.00   1.00    2.00    --    0.00  57.00 120.00   41
 10  \w    -16.00  41.00   1.00    2.00    --    0.00  38.00  90.00   57
 11  \w     33.00  66.00   1.00    2.00    --    0.00  57.00 120.00   33
 12  \w     49.00  88.00   1.00    2.00    --    0.00  38.00  90.00   39
 13  \w     45.00  70.00   1.00    2.00    --    0.00  38.00 -30.00   25
 14  \w    -86.00  17.00   1.00    2.00    --    0.00 -77.00 -60.00  103
 15  \w    -24.00  35.00   1.00    2.00    --    0.00  19.00  90.00   59
 16  \w     68.00  94.00   1.00    2.00    --   95.80  68.00  59.95   26
 17  \w     67.00 185.00   1.00    2.00    --   95.80  73.00 142.00  118
 18  \w     68.00  96.00   1.00    2.00    --   95.80  69.00  66.73   28
 19  \w     68.00  95.00   1.00    2.00    --   95.80  69.00 150.84   27
 20  \w     68.00  95.00   1.00    2.00    --   95.80  68.00-177.32   27
 21  \w     68.00 183.00   1.00    2.00    --   95.80  70.00  75.65  115
 22  \w     71.00 115.00   1.00    2.00    --   95.80  60.00  34.99   44
 23  \w     67.00  93.00   1.00    2.00    --   95.80  73.00-154.23   26
 24  \w    140.00 167.00   1.00    2.00    --   95.80  73.00-154.23   27
 25  \w     21.00  46.00   1.00    2.00    --   95.80 -82.00-180.00   25
 26  \w     60.00 128.00   1.00    2.00    --   95.80 -82.00-180.00   68
 27  \w     74.00 101.00   1.00    2.00    --   95.80  61.00 -30.00   27
 28  \w    134.00 185.00   1.00    2.00    --   95.80  61.00 -30.00   51
 29  \w      7.00  50.00   1.00    2.00    --   95.80 -82.00 120.00   43
 30  \w     64.00 128.00   1.00    2.00    --   95.80 -82.00 120.00   64
 31  \w    142.00 167.00   1.00    2.00    --   95.80  78.00  97.69   25
 32  \w     65.00  92.00   1.00    2.00    --   95.80  78.00  97.69   27
 33  \w    131.00 175.00   1.00    2.00    --   95.80  71.00  -0.63   44
 34  \w     67.00 125.00   1.00    2.00    --   95.80  73.00 119.01   58
 35  \w     67.00  93.00   1.00    2.00    --   95.80  73.00 -93.49   26
 36  \w     67.00 115.00   1.00    2.00    --   95.80  71.00  -0.63   48
 37  \w     72.00 176.00   1.00    2.00    --   95.80  55.00 -67.37  104
 38  \w     64.00  91.00   1.00    2.00    --   95.80  82.00-150.00   27
 39  \w    107.00 185.00   1.00    2.00    --   95.80  82.00-150.00   78
 40  \w     63.00  92.00   1.00    2.00    --   95.80  82.00-120.00   29
 41  \w     65.00  91.00   1.00    2.00    --   95.80  77.00   0.00   26
 42  \w     63.00  90.00   1.00    2.00    --   95.80  82.00 120.00   27
 43  \w     63.00  90.00   1.00    2.00    --   95.80  82.00 -90.00   27
 44  \w    117.00 185.00   1.00    2.00    --   95.80  82.00 -90.00   68
 45  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 150.00   26
 46  \w     65.00  91.00   1.00    2.00    --   95.80  77.00-180.00   26
 47  \w    100.00 133.00   1.00    2.00    --   95.80  77.00-180.00   33
 48  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  90.00   26
 49  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -60.00   26
 50  \w    141.00 168.00   1.00    2.00    --   95.80  82.00 -60.00   27
 51  \w     75.00 105.00   1.00    2.00    --   95.80  45.00 -30.00   30
 52  \w     63.00  90.00   1.00    2.00    --   95.80  82.00   0.00   27
 53  \w     63.00  89.00   1.00    2.00    --   95.80  82.00  30.00   26
 54  \w     75.00 184.00   1.00    2.00    --   95.80  45.00   0.00  109
 55  \w     65.00  92.00   1.00    2.00    --   95.80  77.00-150.00   27
 56  \w     34.00 118.00   1.00    2.00    --   95.80 -82.00   0.00   84
 57  \w     71.00 156.00   1.00    2.00    --   95.80  61.00-120.00   85
 58  \w     71.00 145.00   1.00    2.00    --   95.80  61.00-150.00   74
 59  \w     65.00  91.00   1.00    2.00    --   95.80  77.00-120.00   26
 60  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -30.00   26
 61  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -60.00   26
 62  \w    135.00 160.00   1.00    2.00    --   95.80  69.00  -2.05   25
 63  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -30.00   26
 64  \w     56.00 127.00   1.00    2.00    --   95.80 -82.00 -90.00   71
 65  \w     68.00  95.00   1.00    2.00    --   95.80  69.00  -2.05   27
 66  \w    132.00 178.00   1.00    2.00    --   95.80  76.00-126.45   46
 67  \w      6.00 121.00   1.00    2.00    --   95.80 -82.00  60.00  115
 68  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 150.00   26
 69  \w    160.00 185.00   1.00    2.00    --   95.80  73.00  81.65   25
 70  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  30.00   26
 71  \w     71.00 183.00   1.00    2.00    --   95.80  61.00  60.00  112
 72  \w    157.00 184.00   1.00    2.00    --   95.80  61.00 -60.00   27
 73  \w     71.00  98.00   1.00    2.00    --   95.80  61.00-180.00   27
 74  \w     72.00 173.00   1.00    2.00    --   95.80  56.00 127.01  101
 75  \w     73.00 100.00   1.00    2.00    --   95.80  61.00 -60.00   27
 76  \w     67.00  94.00   1.00    2.00    --   95.80  73.00  81.65   27
 77  \w     42.00  73.00   1.00    2.00    --   95.80 -82.00-150.00   31
 78  \w     75.00 119.00   1.00    2.00    --   95.80 -82.00-150.00   44
 79  \w     65.00  91.00   1.00    2.00    --   95.80  76.00-126.45   26
 80  \w    140.00 167.00   1.00    2.00    --   95.80  60.00  34.99   27
 81  \w    115.00 182.00   1.00    2.00    --   95.80  68.00  33.95   67
 82  \w     68.00  94.00   1.00    2.00    --   95.80  68.00  33.95   26
;
_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      -0.0942927000
_diffrn_orient_matrix_UB_12      -0.0172403000
_diffrn_orient_matrix_UB_13      0.0234231000
_diffrn_orient_matrix_UB_21      0.0642632000
_diffrn_orient_matrix_UB_22      -0.0280479000
_diffrn_orient_matrix_UB_23      0.0552613000
_diffrn_orient_matrix_UB_31      0.0181449000
_diffrn_orient_matrix_UB_32      0.1039535000
_diffrn_orient_matrix_UB_33      0.0212628000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1637
_diffrn_reflns_av_unetI/netI     0.1015
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            124925
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.441
_diffrn_reflns_theta_min         3.388
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17171
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       block
_exptl_crystal_F_000             1871
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         5.341
_refine_diff_density_min         -1.126
_refine_diff_density_rms         0.206
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     909
_refine_ls_number_reflns         18895
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1431
_refine_ls_R_factor_gt           0.1086
_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^)+(0.1301P)^2^+41.3109P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2530
_refine_ls_wR_factor_ref         0.2740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13175
_reflns_number_total             18895
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11738_si_004.cif
_cod_data_source_block           exp_1305
_cod_original_formula_sum        'C73 H109 F9 N3 O6 P5.50 Pt2'
_cod_database_code               4135430
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.373
_shelx_estimated_absorpt_t_min   0.219
_reflns_odcompleteness_completeness 99.62
_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
2. Restrained distances
 C60-C61
 1.52 with sigma of 0.01
 C56-C57
 1.52 with sigma of 0.01
 C58-C59
 1.52 with sigma of 0.01
 C62-C63
 1.52 with sigma of 0.01
 C67-C66
 1.52 with sigma of 0.01
 C64-C65
 1.52 with sigma of 0.01
 C51-C50
 1.52 with sigma of 0.01
 C47-C46
 1.52 with sigma of 0.01
 C48-C49
 1.52 with sigma of 0.01
 C45-C44
 1.52 with sigma of 0.01
 C55-C54
 1.52 with sigma of 0.01
 C50-C51
 1.52 with sigma of 0.01
 C53-C52
 1.52 with sigma of 0.01
 C71-C72
 1.52 with sigma of 0.01
 C72-C73
 1.52 with sigma of 0.01
3. Rigid bond restraints
 C61, C60
 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
 C57, C56
 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
 C66, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C62, C63
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C46, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C44, C45
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C48, C49
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C54, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C52, C53
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C50, C51
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C71, C72, C73
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 P5, F3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 P5, F2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 P5, F5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 P5, F4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F6, P5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 P3, C58
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C62 \\sim C63: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C64 \\sim C65: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C66 \\sim C67: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C61 \\sim C60: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C58 \\sim C59: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C56 \\sim C57: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C55 \\sim C54: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C52 \\sim C53: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C50 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C48 \\sim C49: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C46 \\sim C47: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C44 \\sim C45: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C71 \\sim C72 \\sim C73: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
P3 \\sim C58: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C72) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
5.a Ternary CH refined with riding coordinates:
 C35(H35)
5.b Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C39(H39A,H39B), C44(H44A,H44B), C46(H46A,H46B), C48(H48A,
 H48B), C50(H50A,H50B), C52(H52A,H52B), C54(H54A,H54B), C56(H56A,H56B),
 C58(H58A,H58B), C60(H60A,H60B), C62(H62A,H62B), C64(H64A,H64B), C66(H66A,H66B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C23(H23), C24(H24), C25(H25), C29(H29), C30(H30),
  C31(H31), C32(H32), C33(H33)
5.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C51(H51A,
 H51B,H51C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C),
 C59(H59A,H59B,H59C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C65(H65A,H65B,
 H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C71(H71A,
 H71B,H71C), C73(H73A,H73B,H73C)
;
_shelx_res_checksum              45827
_shelx_hkl_checksum              25929
_shelx_fab_checksum              23965
_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 5.200
_oxdiff_exptl_absorpt_empirical_full_min 0.443