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_4127941
_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
'2(C24 H20 N2), 0.8(O6 C15 N1 H19), 3.2(F6 P), 2.8(C2 H3 N)'
_chemical_formula_sum            'C65.6 H63.6 F19.2 N7.6 O4.8 P3.2'
_chemical_formula_weight         1499.14
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                94.246(4)
_cell_angle_beta                 90.646(4)
_cell_angle_gamma                92.596(4)
_cell_formula_units_Z            2
_cell_length_a                   10.9442(7)
_cell_length_b                   16.0723(12)
_cell_length_c                   19.1059(13)
_cell_measurement_reflns_used    9960
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      63.634
_cell_measurement_theta_min      2.760
_cell_volume                     3347.7(4)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.893
_diffrn_measured_fraction_theta_max 0.973
_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  0.0307
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.893
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            23296
_diffrn_reflns_point_group_measured_fraction_full 0.893
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         64.051
_diffrn_reflns_theta_min         2.760
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.834
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.6281
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0909 before and 0.0428 after correction. The Ratio of minimum to maximum transmission is 0.8348. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_description       block
_exptl_crystal_F_000             1539
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.071
_refine_diff_density_max         1.146
_refine_diff_density_min         -0.700
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1092
_refine_ls_number_reflns         10819
_refine_ls_number_restraints     428
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0912
_refine_ls_R_factor_gt           0.0829
_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^)+(0.1416P)^2^+6.8159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2339
_refine_ls_wR_factor_ref         0.2433
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9301
_reflns_number_total             10819
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08926_si_006.cif
_cod_data_source_block           cx1152
_cod_original_formula_sum        'C65.60 H63.60 F19.20 N7.60 O4.80 P3.20'
_cod_database_code               4127941
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.881
_shelx_estimated_absorpt_t_min   0.643
_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
 F17-F16 \\sim F17-F13 \\sim F17-F14 \\sim F16-F13 \\sim F16-F14 \\sim F16-F15
\\sim F18-F13 \\sim F18-F14
 \\sim F18-F15 \\sim F13-F15 \\sim F14-F15
 with sigma of 0.02
 P3-F17 \\sim P3-F16 \\sim P3-F18 \\sim P3-F13 \\sim P3-F14 \\sim P3-F15
 with sigma of 0.01
 F18A-F15A \\sim F18A-F13A \\sim F18A-F14A \\sim F15A-F14A \\sim F15A-F16A
\\sim F13A-F16A \\sim F13A-
 F17A \\sim F14A-F16A \\sim F14A-F17A \\sim F16A-F17A
 with sigma of 0.02
 P3-F18A \\sim P3-F15A \\sim P3-F13A \\sim P3-F14A \\sim P3-F16A \\sim P3-F17A
 with sigma of 0.01
 F20-F22 \\sim F20-F21 \\sim F20-F23 \\sim F20-F24 \\sim F22-F21 \\sim F22-F23
\\sim F22-F19 \\sim F21-F24
 \\sim F21-F19 \\sim F23-F24
 with sigma of 0.02
 P5-F20 \\sim P5-F22 \\sim P5-F21 \\sim P5-F23 \\sim P5-F24 \\sim P5-F19
 with sigma of 0.01
 O6A-C63A \\sim O6-C63 \\sim O5-C62A \\sim O5-C62 \\sim O5-C61
 with sigma of 0.01
3. Rigid bond restraints
 F13, F13A, F14, F14A, F15, F15A, F16, F16A, F17, F17A, F18, F18A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 P5, F19, F20, F21, F22, F23, F24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N7, C66, C67
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O6, O6A, C62, C62A, C63, C63A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F13 \\sim F13A \\sim F14 \\sim F14A \\sim F15 \\sim F15A \\sim F16 \\sim F16A
\\sim F17 \\sim F17A \\sim F18 \\sim F18A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
P5 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
N7 \\sim C66 \\sim C67: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O6 \\sim O6A \\sim C62 \\sim C62A \\sim C63 \\sim C63A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
5. Others
 Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(1)
 Sof(O6A)=Sof(H6A)=Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C63A)=Sof(H63C)=Sof(H63D)=
 0.8*(1-FVAR(3))
 Sof(O6)=Sof(H6)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=0.8*
 FVAR(3)
 Fixed Sof: O1(0.8) O2(0.8) O3(0.8) O4(0.8) O5(0.8) N5(0.8) C49(0.8) C50(0.8)
 C51(0.8) H51(0.8) C52(0.8) H52(0.8) C53(0.8) C54(0.8) C55(0.8) C56(0.8)
 H56A(0.8) H56B(0.8) C57(0.8) H57A(0.8) H57B(0.8) C58(0.8) H58A(0.8) H58B(0.8)
 C59(0.8) H59A(0.8) H59B(0.8) C60(0.8) H60A(0.8) H60B(0.8) C61(0.8) H61A(0.8)
 H61B(0.8) P5(0.2) F19(0.2) F20(0.2) F21(0.2) F22(0.2) F23(0.2) F24(0.2)
 N7(0.8) C66(0.8) C67(0.8) H67A(0.8) H67B(0.8) H67C(0.8)
6.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57(H57A,H57B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,
 H61B), C62(H62A,H62B), C62A(H62C,H62D), C63(H63A,H63B), C63A(H63C,H63D),
 C25(H25A,H25B), C42(H42A,H42B), C1(H1A,H1B), C8(H8A,H8B)
6.b Aromatic/amide H refined with riding coordinates:
 C51(H51), C52(H52), C26(H26), C27(H27), C29(H29), C30(H30), C32(H32),
 C33(H33), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C44(H44),
  C45(H45), C47(H47), C48(H48), C3(H3), C4(H4), C6(H6B), 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)
6.c Tetrahedral OH refined with riding coordinates:
 O6(H6), O6A(H6A)
6.d Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              47897
_shelx_hkl_checksum              20729
_olex2_date_sample_data_collection 2018-01-04
_olex2_date_sample_submission    2017-12-19
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1152
_olex2_submission_special_instructions 'No special instructions were received'