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_1552721
_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         '0.5(C34 H30 N4 S), 2(F6 P), 0.5(C2 H3 N)'
_chemical_formula_sum            'C18 H16.5 F12 N2.5 P2 S0.5'
_chemical_formula_weight         573.81
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-28
_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                101.314(6)
_cell_angle_beta                 111.832(6)
_cell_angle_gamma                107.987(6)
_cell_formula_units_Z            4
_cell_length_a                   13.6030(13)
_cell_length_b                   13.8062(13)
_cell_length_c                   16.0216(16)
_cell_measurement_reflns_used    9978
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.024
_cell_measurement_theta_min      2.529
_cell_volume                     2486.3(5)
_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      100.02
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'QuazarTM optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0787
_diffrn_reflns_av_unetI/netI     0.1146
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33847
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.521
_diffrn_reflns_theta_min         1.463
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    0.317
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5600
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0999 before and 0.0748 after correction. The Ratio of minimum to maximum transmission is 0.7513. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.533
_exptl_crystal_description       block
_exptl_crystal_F_000             1152
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.058
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.945
_refine_diff_density_min         -0.554
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.299
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         10194
_refine_ls_number_restraints     411
_refine_ls_restrained_S_all      1.300
_refine_ls_R_factor_all          0.2373
_refine_ls_R_factor_gt           0.1355
_refine_ls_shift/su_max          0.003
_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          0.3849
_refine_ls_wR_factor_ref         0.4408
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4014
_reflns_number_total             10194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04860j2.cif
_cod_data_source_block           cx1121
_cod_depositor_comments
;Adding full bibliography for 1552713--1552722.cif.

 Adding full bibliography for 1552713--1552722.cif.
;
_cod_original_cell_volume        2486.3(4)
_cod_original_formula_sum        'C18 H16.50 F12 N2.50 P2 S0.50'
_cod_database_code               1552721
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.982
_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
 S2-C34 \\sim S2-C31 \\sim S1_$1-C12_$1 \\sim S1_$1-C15_$1
 with sigma of 0.01
 C17-C16 \\sim C17-C12 \\sim C13-C12 \\sim C14-C13 \\sim C15-C14 \\sim C16-C15
\\sim C33_$2-C32_$2 ~
 C34_$2-C33_$2 \\sim C35_$2-C34_$2 \\sim C36_$2-C35_$2 \\sim C36_$2-C31_$2
\\sim C32_$2-C31_$2
 with sigma of 0.01
 S1-C12 \\sim S1-C15 \\sim S2_$2-C31_$2 \\sim S2_$2-C34_$2
 with sigma of 0.01
 S2-C35 \\sim S1_$3-C14_$3 \\sim S1_$3-C13_$3 \\sim S2-C36
 with sigma of 0.001
 F18-F16 \\sim F18-F21 \\sim F18-F19 \\sim F18-F17 \\sim F16-F20 \\sim F16-F21
\\sim F16-F19 \\sim F20-F21
 \\sim F20-F19 \\sim F20-F17 \\sim F21-F17 \\sim F19-F17
 with sigma of 0.04
 P4-F18 \\sim P4-F16 \\sim P4-F20 \\sim P4-F21 \\sim P4-F19 \\sim P4-F17
 with sigma of 0.02
 F18A-F16A \\sim F18A-F21A \\sim F18A-F19A \\sim F18A-F17A \\sim F16A-F20A
\\sim F16A-F21A \\sim F16A-
 F19A \\sim F20A-F21A \\sim F20A-F19A \\sim F20A-F17A \\sim F21A-F17A \\sim
F19A-F17A
 with sigma of 0.04
 P4A-F18A \\sim P4A-F16A \\sim P4A-F20A \\sim P4A-F21A \\sim P4A-F19A \\sim
P4A-F17A
 with sigma of 0.02
3. Rigid bond restraints
 C31, C32, C33, C34A, C35A, C36A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S2, C31, C34, C35, C36
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1, C12, C13, C14, C15, C16, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C31 \\sim C32 \\sim C33 \\sim C34A \\sim C35A \\sim C36A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
S2 \\sim C31 \\sim C34 \\sim C35 \\sim C36: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
S1 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(P4A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(1)
 Sof(P4)=Sof(F16)=Sof(F17)=Sof(F18)=Sof(F19)=Sof(F20)=Sof(F21)=FVAR(1)
 Fixed Sof: S1(0.5) C16(0.5) H16(0.5) C17(0.5) H17(0.5) S2(0.5) H19C(0.5)
 H19D(0.5) H19A(0.5) H19B(0.5) C32(0.5) H32(0.5) C33(0.5) H33(0.5) C34A(0.5)
 C35A(0.5) H35A(0.5) C36A(0.5) H36A(0.5) C34(0.5) C35(0.5) H35(0.5) C36(0.5)
 H36(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C18(H18A,H18B), C19(H19C,H19D), C19(H19A,H19B), C30(H30A,H30B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C13(H13),
 C14(H14), C16(H16), C17(H17), C20(H20), C21(H21), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C32(H32), C33(H33), C35A(H35A), C36A(H36A),
 C35(H35), C36(H36)
6.c Fitted hexagon refined as free rotating group:
 C31(C32,C33,C34A,C35A,C36A)
6.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C)
;
_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 = 348.6 Ang^3^ [14.5%]
Total electron count / cell = 80.0
;
_shelx_res_checksum              51587
_shelx_fab_checksum              36796
_olex2_date_sample_data_collection 2017-11-27
_olex2_date_sample_submission    2017-11-22
_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 cx1121
_olex2_submission_special_instructions 'No special instructions were received'