Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes.
Cai, Kang; Shi, Yi; Cao, Changsu; Vemuri, Suneal; Cui, Binbin; Shen, Dengke; Wu, Huang; Zhang, Long; Qiu, Yunyan; Chen, Hongliang; Jiao, Yang; Stern, Charlotte L.; Alsubaie, Fehaid M.; Xiao, Hai; Li, Jun; Stoddart, J. Fraser; Chemical science 11 (2020) 107–112; doi:10.1039/c9sc04860j

data_1552714
_publ_section_title
;
 Tuning radical interactions in trisradical tricationic complexes by
 varying host-cavity sizes.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              107
_journal_page_last               112
_journal_paper_doi               10.1039/c9sc04860j
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         '2(C36 H32 N4), 5(F6 P), 3(C2 H3 N)'
_chemical_formula_sum            'C78 H73 F30 N11 P5'
_chemical_formula_weight         1889.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-09-24 deposited with the CCDC.	2019-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.886(4)
_cell_length_b                   20.698(4)
_cell_length_c                   20.515(4)
_cell_measurement_reflns_used    9913
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      62.064
_cell_measurement_theta_min      3.083
_cell_volume                     8444(3)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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  0.0421
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            31740
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.528
_diffrn_reflns_theta_max         66.528
_diffrn_reflns_theta_min         3.082
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    2.051
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6744
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0827 before and 0.0513 after correction. The Ratio of minimum to maximum transmission is 0.8959. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       block
_exptl_crystal_F_000             3852
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.083
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.232
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.40(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         7349
_refine_ls_number_restraints     325
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0876
_refine_ls_R_factor_gt           0.0542
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0874P)^2^+2.9460P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1341
_refine_ls_wR_factor_ref         0.1579
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                5011
_reflns_number_total             7349
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04860j2.cif
_cod_data_source_block           cx1163
_cod_depositor_comments
;Adding full bibliography for 1552713--1552722.cif.

 Adding full bibliography for 1552713--1552722.cif.
;
_cod_database_code               1552714
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.848
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60(4)
 0.40(4)
2. 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
3. Restrained distances
 F6-F10 \\sim F6-F9 \\sim F6-F8 \\sim F6-F7 \\sim F5-F10 \\sim F5-F9 \\sim
F5-F8 \\sim F5-F7 \\sim F10-F9 ~
 F10-F7 \\sim F9-F8
 with sigma of 0.02
 P2-F6 \\sim P2-F5 \\sim P2-F10 \\sim P2-F9 \\sim P2-F8 \\sim P2-F7
 with sigma of 0.01
 F16-F12 \\sim F16-F15 \\sim F16-F11 \\sim F16-F13 \\sim F12-F15 \\sim F12-F13
\\sim F12-F14 \\sim F15-F11
 \\sim F15-F14
 with sigma of 0.02
 P3-F16 \\sim P3-F12 \\sim P3-F15 \\sim P3-F11 \\sim P3-F13 \\sim P3-F14
 with sigma of 0.01
 F5-F7 \\sim F5-F8 \\sim F5-F9 \\sim F5-F10 \\sim F6-F7 \\sim F6-F8 \\sim F6-F9
\\sim F6-F10 \\sim F7-F8 \\sim F7-
 F10 \\sim F8-F9 \\sim F9-F10
 with sigma of 0.02
 P2-F5 \\sim P2-F6 \\sim P2-F7 \\sim P2-F8 \\sim P2-F9 \\sim P2-F10
 with sigma of 0.01
 F5A-F7A \\sim F5A-F8A \\sim F5A-F9A \\sim F5A-F10A \\sim F6A-F7A \\sim F6A-F8A
\\sim F6A-F9A \\sim F6A-
 F10A \\sim F7A-F8A \\sim F7A-F10A \\sim F8A-F9A \\sim F9A-F10A
 with sigma of 0.02
 P2A-F5A \\sim P2A-F6A \\sim P2A-F7A \\sim P2A-F8A \\sim P2A-F9A \\sim P2A-F10A
 with sigma of 0.01
 F11-F13 \\sim F11-F14 \\sim F11-F15 \\sim F11-F16 \\sim F12-F13 \\sim F12-F14
\\sim F12-F15 \\sim F12-F16
 \\sim F13-F14 \\sim F13-F16 \\sim F14-F15 \\sim F15-F16
 with sigma of 0.02
 P3-F11 \\sim P3-F12 \\sim P3-F13 \\sim P3-F14 \\sim P3-F15 \\sim P3-F16
 with sigma of 0.01
 F11A-F13A \\sim F11A-F14A \\sim F11A-F15A \\sim F11A-F16A \\sim F12A-F13A
\\sim F12A-F14A \\sim F12A-
 F15A \\sim F12A-F16A \\sim F13A-F14A \\sim F13A-F16A \\sim F14A-F15A \\sim
F15A-F16A
 with sigma of 0.02
 P3A-F11A \\sim P3A-F12A \\sim P3A-F13A \\sim P3A-F14A \\sim P3A-F15A \\sim
P3A-F16A
 with sigma of 0.01
4. Rigid body (RIGU) restrains
 F5A, F6A, F7A, F8A, F9A, F10A, F5, F6, F7, F8, F9, F10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F13A, F16A, F11A, F12A, F14A, F15A, F11, F12, F13, F14, F15, F16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(P2A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=1-FVAR(1)
 Sof(P2)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=FVAR(1)
 Sof(P3A)=Sof(F11A)=Sof(F12A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=1-FVAR(2)
 Sof(P3)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=FVAR(2)
 Fixed Sof: H21A(0.5) H21B(0.5) H21C(0.5) H23A(0.5) H23B(0.5) H23C(0.5)
 H25A(0.5) H25B(0.5) H25C(0.5)
6.a Everything fixed:
 H23A, H23B, H23C
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C15(H15A,H15B), C4A(H4AA,H4AB), C15A(H15C,H15D)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C17(H17), C18(H18), C19(H19), C1A(H1A), C3A(H3A), C5A(H5A), C6A(H6A),
  C8A(H8A), C9A(H9A), C11A(H11A), C12A(H12A), C13A(H13A), C14A(H14A),
 C17A(H17A), C18A(H18A), C19A(H19A)
6.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C25(H25A,H25B,H25C)
;
_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 = 366.3 Ang^3^ [4.3%]
Total electron count / cell = 107.8
;
_shelx_res_checksum              28831
_shelx_fab_checksum              7397
_olex2_date_sample_data_collection 2018-01-11
_olex2_date_sample_submission    2018-01-08
_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 cx1163
_olex2_submission_special_instructions 'No special instructions were received'