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_4135431
_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         'C134 H192 N6 O8 P8 Pt4, 4(F6 P)'
_chemical_formula_sum            'C134 H192 F24 N6 O8 P12 Pt4'
_chemical_formula_weight         3622.92
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                84.6870(10)
_cell_angle_beta                 81.2170(10)
_cell_angle_gamma                88.5680(10)
_cell_formula_units_Z            1
_cell_length_a                   9.4316(2)
_cell_length_b                   21.0748(3)
_cell_length_c                   21.3237(3)
_cell_measurement_reflns_used    31666
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.0960
_cell_measurement_theta_min      3.1350
_cell_volume                     4170.54(12)
_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 0.993
_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    -23.00  67.00   1.00    1.00    --    0.00  57.00 -30.00   90
  2  \w    -25.00   4.00   1.00    1.00    --    0.00  77.00  90.00   29
  3  \w    -23.00  11.00   1.00    1.00    --    0.00  57.00-180.00   34
  4  \w     50.00  77.00   1.00    1.00    --    0.00  77.00  60.00   27
  5  \w    -23.00   3.00   1.00    1.00    --    0.00  19.00 120.00   26
  6  \w     51.00  87.00   1.00    1.00    --    0.00  82.00 -90.00   36
  7  \w    -24.00  48.00   1.00    1.00    --    0.00  19.00 -30.00   72
  8  \w     36.00  63.00   1.00    1.00    --    0.00  57.00-180.00   27
  9  \w    -16.00  43.00   1.00    1.00    --    0.00  82.00 -90.00   59
 10  \w    -88.00 -44.00   1.00    1.00    --    0.00 -38.00-180.00   44
 11  \w     53.00  78.00   1.00    1.00    --    0.00  19.00 120.00   25
 12  \w    -27.00   9.00   1.00    1.00    --    0.00  77.00  60.00   36
 13  \w     28.00  87.00   1.00    1.00    --    0.00  57.00 150.00   59
 14  \w     63.00  88.00   1.00    1.00    --    0.00  77.00-120.00   25
 15  \w     10.00  50.00   1.00    1.00    --    0.00  19.00 120.00   40
 16  \w    -22.00   4.00   1.00    1.00    --    0.00  57.00 150.00   26
 17  \w    -26.00  15.00   1.00    1.00    --    0.00 -38.00-180.00   41
 18  \w    -30.00  44.00   1.00    1.00    --    0.00  77.00-120.00   74
 19  \w     45.00  83.00   1.00    1.00    --    0.00  77.00  90.00   38
 20  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-106.59   26
 21  \w    113.00 185.00   1.00    1.00    --   95.80  74.00  16.02   72
 22  \w    111.00 137.00   1.00    1.00    --   95.80  55.00 112.13   26
 23  \w    121.00 151.00   1.00    1.00    --   95.80  77.00 120.00   30
 24  \w     66.00 102.00   1.00    1.00    --   95.80  74.00  16.02   36
 25  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 26  \w      8.00  55.00   1.00    1.00    --   95.80 -82.00-180.00   47
 27  \w     57.00 127.00   1.00    1.00    --   95.80 -82.00-180.00   70
 28  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 29  \w     93.00 127.00   1.00    1.00    --   95.80 -82.00 -30.00   34
 30  \w     63.00  89.00   1.00    1.00    --   95.80  81.00-169.22   26
 31  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 32  \w     68.00 106.00   1.00    1.00    --   95.80  69.00   0.62   38
 33  \w     72.00  98.00   1.00    1.00    --   95.80  55.00 112.13   26
 34  \w     75.00 184.00   1.00    1.00    --   95.80  46.00 -85.77  109
 35  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 36  \w      6.00 119.00   1.00    1.00    --   95.80 -82.00 -90.00  113
 37  \w     66.00  92.00   1.00    1.00    --   95.80  75.00 145.38   26
 38  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 39  \w      6.00 127.00   1.00    1.00    --   95.80 -82.00  74.49  121
 40  \w     76.00 165.00   1.00    1.00    --   95.80  45.00 150.00   89
 41  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-150.00   26
 42  \w     65.00  94.00   1.00    1.00    --   95.80  77.00 -60.00   29
 43  \w     72.00  97.00   1.00    1.00    --   95.80  61.00 -90.00   25
 44  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-180.00   26
 45  \w     65.00  91.00   1.00    1.00    --   95.80  78.00 -38.41   26
 46  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 47  \w    159.00 185.00   1.00    1.00    --   95.80  75.00 -70.99   26
 48  \w     72.00 175.00   1.00    1.00    --   95.80  55.00 -69.69  103
 49  \w      7.00 127.00   1.00    1.00    --   95.80 -82.00  30.00  120
 50  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  60.00   26
 51  \w    160.00 185.00   1.00    1.00    --   95.80  77.00-137.48   25
 52  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  90.00   26
 53  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -90.00   26
 54  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -30.00   26
 55  \w     72.00  97.00   1.00    1.00    --   95.80  61.00 120.00   25
 56  \w     71.00 136.00   1.00    1.00    --   95.80  61.00 150.00   65
 57  \w     75.00 170.00   1.00    1.00    --   95.80  45.00   0.00   95
 58  \w     75.00 137.00   1.00    1.00    --   95.80  45.00  60.00   62
 59  \w    113.00 185.00   1.00    1.00    --   95.80  82.00 -30.00   72
 60  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -30.00   26
 61  \w     65.00  92.00   1.00    1.00    --   95.80  77.00  60.00   27
 62  \w     65.00 119.00   1.00    1.00    --   95.80  77.00-137.48   54
 63  \w     66.00  92.00   1.00    1.00    --   95.80  75.00 -70.99   26
 64  \w     64.00  89.00   1.00    1.00    --   95.80  82.00  90.00   25
 65  \w    121.00 147.00   1.00    1.00    --   95.80  77.00-120.00   26
 66  \w     67.00 185.00   1.00    1.00    --   95.80  73.00-178.75  118
 67  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 68  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 69  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  30.00   26
 70  \w    140.00 166.00   1.00    1.00    --   95.80  82.00-106.59   26
 71  \w     69.00 117.00   1.00    1.00    --   95.80  67.00  69.12   48
 72  \w      7.00 107.00   1.00    1.00    --   95.80 -61.00 -90.00  100
 73  \w     69.00  95.00   1.00    1.00    --   95.80  67.00  61.74   26
 74  \w     65.00 173.00   1.00    1.00    --   95.80  77.00 164.76  108
 75  \w     21.00  62.00   1.00    1.00    --   95.80 -82.00 120.00   41
 76  \w     94.00 123.00   1.00    1.00    --   95.80 -82.00 120.00   29
 77  \w     74.00 185.00   1.00    1.00    --   95.80  50.00 106.99  111
;
_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      0.0248752000
_diffrn_orient_matrix_UB_12      0.0445575000
_diffrn_orient_matrix_UB_13      -0.0620442000
_diffrn_orient_matrix_UB_21      -0.0558232000
_diffrn_orient_matrix_UB_22      0.0569717000
_diffrn_orient_matrix_UB_23      0.0374279000
_diffrn_orient_matrix_UB_31      0.1535754000
_diffrn_orient_matrix_UB_32      0.0126210000
_diffrn_orient_matrix_UB_33      0.0117186000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0834
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            103392
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         4.213
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.859
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22249
_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    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             1810
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.28
_refine_diff_density_max         6.564
_refine_diff_density_min         -1.788
_refine_diff_density_rms         0.260
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     934
_refine_ls_number_reflns         14633
_refine_ls_number_restraints     320
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1100
_refine_ls_R_factor_gt           0.0954
_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^)+(0.1783P)^2^+22.5735P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2544
_refine_ls_wR_factor_ref         0.2719
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11387
_reflns_number_total             14633
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11738_si_007.cif
_cod_data_source_block           exp_1243
_cod_database_code               4135431
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.217
_shelx_estimated_absorpt_t_min   0.154
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C46-C45
 1.52 with sigma of 0.01
 C40-C39
 1.52 with sigma of 0.01
 C53-C54
 1.52 with sigma of 0.01
 C51-C52
 1.52 with sigma of 0.01
 C55-C56
 1.52 with sigma of 0.01
 C45-C46
 1.52 with sigma of 0.01
 C49-C50
 1.52 with sigma of 0.01
 C47-C48
 1.52 with sigma of 0.01
 C38-C37
 1.52 with sigma of 0.01
 C35-C36
 1.52 with sigma of 0.01
 C33-C34
 1.52 with sigma of 0.01
 C41-C42
 1.52 with sigma of 0.01
 C43-C44
 1.52 with sigma of 0.01
 N4-C60
 1.4 with sigma of 0.02
 C68-C64
 1.55 with sigma of 0.02
 C50-C49
 1.55 with sigma of 0.02
 P3-C45
 1.7 with sigma of 0.02
3. Rigid bond restraints
 C39, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C45, C46
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C55, C56
 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
 C53, C54
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C47, C48
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C41, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C37, C38
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C43, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F1, P5
 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
 F5, P5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F3, P5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F4, P5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F2, P5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F11, P6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F10, P6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F9, P6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F7, P6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F12, P6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F8, P6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C72 \\sim C73 \\sim C74 \\sim O3 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim
C65 \\sim N4 \\sim O9 \\sim C32/ \\sim C64 \\sim C66 \\sim C67 \\sim C68 \\sim
C70 \\sim C71 \\sim N3 \\sim O69: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008
C72 \\sim C73 \\sim C74 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C65 \\sim
N4 \\sim O9 \\sim C32/: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C39 \\sim C40: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C45 \\sim C46: 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
C55 \\sim C56: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C47 \\sim C48: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C41 \\sim C42: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C33 \\sim C34: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C37 \\sim C38: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F1 \\sim P5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F6 \\sim P5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F5 \\sim P5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F4 \\sim P5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F2 \\sim P5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F12 \\sim P6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F11 \\sim P6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F10 \\sim P6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F9 \\sim P6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F8 \\sim P6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
F7 \\sim P6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim N1: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: H72A(0.5) H72B(0.5) H74C(0.5) H74D(0.5) H74A(0.5) H74B(0.5)
 C60(0.5) C61(0.5) H61A(0.5) H61B(0.5) H61C(0.5) C62(0.5) H62A(0.5) H62B(0.5)
 H62C(0.5) C63(0.5) H63A(0.5) H63B(0.5) H63C(0.5) C65(0.5) H65A(0.5) H65B(0.5)
 H65C(0.5) N4(0.5) O9(0.5) C32/(0.5) C64(0.5) C66(0.5) C67(0.5) H67A(0.5)
 H67B(0.5) H67C(0.5) C68(0.5) H68A(0.5) H68B(0.5) H68C(0.5) C70(0.5) H70A(0.5)
 H70B(0.5) H70C(0.5) C71(0.5) H71A(0.5) H71B(0.5) H71C(0.5) N3(0.5) O69(0.5)
6.a Riding coordinates:
 C40(H40A,H40B,H40C), C62(H62A,H62B,H62C), C65(H65A,H65B,H65C), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C)
6.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C35(H35A,H35B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,
 H41B), C43(H43A,H43B), C45(H45A,H45B), C47(H47A,H47B), C49(H49A,H49B),
 C51(H51A,H51B), C53(H53A,H53B), C55(H55A,H55B), C57(H57A,H57B), C72(H72A,H72B),
  C74(H74C,H74D), C74(H74A,H74B)
6.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), C21(H21), C23(H23), C25(H25), C29(H29), C30(H30),
  C31(H31), C32(H32)
6.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C42(H42A,H42B,
 H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C50(H50A,
 H50B,H50C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C),
 C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C67(H67A,H67B,H67C), C68(H68A,H68B,
 H68C)
;
_shelx_res_checksum              52945
_shelx_hkl_checksum              58655
_shelx_fab_checksum              42594
_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 3.287
_oxdiff_exptl_absorpt_empirical_full_min 0.527