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_4127943
_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
'C36 H40 N2 O12, C48 H40 N4, 3(F6 P), C2 H3 N'
_chemical_formula_sum            'C86 H83 F18 N7 O12 P3'
_chemical_formula_weight         1841.50
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.895(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.5470(13)
_cell_length_b                   27.825(3)
_cell_length_c                   18.3914(14)
_cell_measurement_reflns_used    8735
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      54.161
_cell_measurement_theta_min      2.925
_cell_volume                     8786.7(13)
_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      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.658
_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  0.0765
_diffrn_reflns_av_unetI/netI     0.1277
_diffrn_reflns_Laue_measured_fraction_full 0.658
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20915
_diffrn_reflns_point_group_measured_fraction_full 0.658
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         54.297
_diffrn_reflns_theta_min         2.924
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.514
_exptl_absorpt_correction_T_max  0.7507
_exptl_absorpt_correction_T_min  0.5453
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1202 before and 0.0829 after correction. The Ratio of minimum to maximum transmission is 0.7264. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       needle
_exptl_crystal_F_000             3804
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.466
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.691
_refine_diff_density_min         -0.642
_refine_diff_density_rms         0.202
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.475
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1192
_refine_ls_number_reflns         10467
_refine_ls_number_restraints     1084
_refine_ls_restrained_S_all      1.448
_refine_ls_R_factor_all          0.1952
_refine_ls_R_factor_gt           0.1616
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3917
_refine_ls_wR_factor_ref         0.4184
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6977
_reflns_number_total             10467
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08926_si_005.cif
_cod_data_source_block           cx1147b
_cod_original_cell_volume        8786.6(12)
_cod_database_code               4127943
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.539
_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
 C82A-C81A \\sim C82-C81
 with sigma of 0.01
 O11-C81 \\sim O11-C81A \\sim O12-C82A \\sim O12-C82
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F4A)=Sof(F6A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F4)=Sof(F6)=FVAR(1)
 Sof(C81A)=Sof(H81C)=Sof(H81D)=Sof(C82A)=Sof(H82C)=Sof(H82D)=1-FVAR(2)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 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),
 C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B),
  C81(H81A,H81B), C81A(H81C,H81D), C82(H82A,H82B), C82A(H82C,H82D), C83(H83A,
 H83B), C84(H84A,H84B), C1(H1A,H1B), C18(H18A,H18B), C25(H25A,H25B), C42(H42A,
 H42B)
5.b Aromatic/amide H refined with riding coordinates:
 C51(H51), C52(H52), C57(H57), C58(H58), C2(H2), C3(H3), C5(H5), C6(H6),
 C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17),
 C20(H20), C21(H21), C23(H23), C24(H24), 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)
5.c Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C)
;
_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 = 917.4 Ang^3^ [10.4%]
Total electron count / cell = 258.5
;
_shelx_res_checksum              98800
_shelx_hkl_checksum              68083
_shelx_fab_checksum              35644
_olex2_date_sample_data_collection 2017-12-21
_olex2_date_sample_submission    2017-12-13
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder'
_olex2_submission_original_sample_id cx1147b
_olex2_submission_special_instructions 'No special instructions were received'