Stabilizing the Naphthalenediimide Radical within a Tetracationic Cyclophane.
Jiao, Tianyu; Cai, Kang; Nelson, Jordan N.; Jiao, Yang; Qiu, Yunyan; Wu, Guangcheng; Zhou, Jiawang; Cheng, Chuyang; Shen, Dengke; Feng, Yuanning; Liu, Zhichang; Wasielewski, Michael R.; Stoddart, J. Fraser; Li, Hao; Journal of the American Chemical Society 141 (2019) 16915–16922; doi:10.1021/jacs.9b08926

data_4127940
_publ_section_title
;
 Stabilizing the Naphthalenediimide Radical within a Tetracationic
 Cyclophane.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16915
_journal_page_last               16922
_journal_paper_doi               10.1021/jacs.9b08926
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C48 H40 N4, C36 H40 N2 O12, 4(F6 P)'
_chemical_formula_sum            'C84 H80 F24 N6 O12 P4'
_chemical_formula_weight         1945.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.317(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   44.908(2)
_cell_length_b                   17.6979(8)
_cell_length_c                   27.6580(12)
_cell_measurement_reflns_used    9406
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      62.47
_cell_measurement_theta_min      2.717
_cell_volume                     20186.7(16)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.880
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0674
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_Laue_measured_fraction_full 0.880
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -51
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            79617
_diffrn_reflns_point_group_measured_fraction_full 0.880
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         62.531
_diffrn_reflns_theta_min         2.143
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.576
_exptl_absorpt_correction_T_max  0.7522
_exptl_absorpt_correction_T_min  0.4771
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1316 before and 0.0519 after correction. The Ratio of minimum to maximum transmission is 0.6422. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       pate
_exptl_crystal_F_000             7984
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.579
_exptl_crystal_size_mid          0.511
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.461
_refine_diff_density_min         -0.746
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1336
_refine_ls_number_reflns         16052
_refine_ls_number_restraints     343
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0962
_refine_ls_R_factor_gt           0.0810
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1621P)^2^+48.8785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2379
_refine_ls_wR_factor_ref         0.2575
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12483
_reflns_number_total             16052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08926_si_003.cif
_cod_data_source_block           cx1118
_cod_original_cell_volume        20186.8(16)
_cod_database_code               4127940
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.462
_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
2. Restrained distances
 C73A-C75A
 2.5 with sigma of 0.02
 F20A-F23A \\sim F20A-F21A \\sim F20A-F24A \\sim F20A-F22A \\sim F23A-F19A
\\sim F23A-F24A \\sim F23A-
 F22A \\sim F19A-F21A \\sim F19A-F24A \\sim F19A-F22A \\sim F21A-F24A \\sim
F21A-F22A
 with sigma of 0.02
 P4-F20A \\sim P4-F23A \\sim P4-F19A \\sim P4-F21A \\sim P4-F24A \\sim P4-F22A
 with sigma of 0.01
 F18-F17 \\sim F18-F15 \\sim F18-F13 \\sim F17-F14 \\sim F17-F16 \\sim F17-F13
\\sim F14-F16 \\sim F15-F16
 \\sim F15-F13 \\sim F16-F13
 with sigma of 0.04
 P3-F18 \\sim P3-F17 \\sim P3-F14 \\sim P3-F15 \\sim P3-F16 \\sim P3-F13
 with sigma of 0.02
 F18A-F17A \\sim F18A-F15A \\sim F18A-F13A \\sim F17A-F14A \\sim F17A-F16A
\\sim F17A-F13A \\sim F14A-
 F16A \\sim F15A-F16A \\sim F15A-F13A \\sim F16A-F13A
 with sigma of 0.04
 P3A-F18A \\sim P3A-F17A \\sim P3A-F14A \\sim P3A-F15A \\sim P3A-F16A \\sim
P3A-F13A
 with sigma of 0.02
 C76A-C75A \\sim C76-C75 \\sim C72A-C71 \\sim C72-C71
 with sigma of 0.01
 C73A-C72A \\sim C73-C72 \\sim C75A-C74A \\sim C75-C74
 with sigma of 0.01
 C74A-C73A \\sim C74-C73
 with sigma of 0.01
3. Rigid bond restraints
 C72A, C72, C73A, C73, C74, C74A, C75A, C75, C76, C76A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C72A \\sim C72 \\sim C73A \\sim C73 \\sim C74 \\sim C74A \\sim C75A \\sim C75
\\sim C76 \\sim C76A: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
5. Others
 Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(1)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=FVAR(1)
 Sof(P3A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(2)
 Sof(P3)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(2)
 Sof(H71C)=Sof(H71D)=Sof(C72A)=Sof(C73A)=Sof(C74A)=Sof(C75A)=Sof(C76A)=
 Sof(H76C)=Sof(H76D)=1-FVAR(3)
 Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(C73)=Sof(C74)=Sof(C75)=Sof(C76)=Sof(H76A)=
 Sof(H76B)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C25(H25A,H25B), C32(H32A,H32B), C63(H63A,H63B),
 C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B),
  C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B), C71(H71C,H71D), C76(H76A,
 H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B),
 C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C76A(H76C,H76D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24),
  C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C34(H34), C36(H36),
 C37(H37), C39(H39), C40(H40), C42(H42), C43(H43), C45(H45), C46(H46), C47(H47),
  C48(H48), C51(H51), C52(H52), C57(H57), C58(H58)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 4365.2 Ang^3^ [21.6%]
Total electron count / cell = 1238.6
;
_shelx_res_checksum              43754
_shelx_hkl_checksum              53010
_shelx_fab_checksum              30831
_olex2_date_sample_data_collection 2017-11-21
_olex2_date_sample_submission    2017-11-21
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a glass fibre in Paratone oil'
_olex2_submission_original_sample_id cx1118
_olex2_submission_special_instructions 'No special instructions were received'