Influence of Constitution and Charge on Radical Pairing Interactions in Tris-radical Tricationic Complexes.
Cheng, Chuyang; Cheng, Tao; Xiao, Hai; Krzyaniak, Matthew D.; Wang, Yuping; McGonigal, Paul R.; Frasconi, Marco; Barnes, Jonathan C.; Fahrenbach, Albert C.; Wasielewski, Michael R.; Goddard, 3rd, William A; Stoddart, J. Fraser; Journal of the American Chemical Society 138 (2016) 8288–8300; doi:10.1021/jacs.6b04343

data_4130521
_publ_section_title
;
 Influence of Constitution and Charge on Radical Pairing Interactions in
 Tris-radical Tricationic Complexes.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8288
_journal_page_last               8300
_journal_paper_doi               10.1021/jacs.6b04343
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         '4(F6 P), C36 H32 N4, C23 H30 N3'
_chemical_formula_sum            'C59 H62 F24 N7 P4'
_chemical_formula_weight         1449.03
_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             2014-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                75.037(13)
_cell_angle_beta                 70.814(13)
_cell_angle_gamma                62.956(14)
_cell_formula_units_Z            2
_cell_length_a                   16.640(4)
_cell_length_b                   16.710(3)
_cell_length_c                   17.160(4)
_cell_measurement_reflns_used    2199
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      51.678
_cell_measurement_theta_min      3.311
_cell_volume                     3980.0(16)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_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    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.02
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.598
_diffrn_measured_fraction_theta_max 0.888
_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  0.0596
_diffrn_reflns_av_unetI/netI     0.1371
_diffrn_reflns_Laue_measured_fraction_full 0.598
_diffrn_reflns_Laue_measured_fraction_max 0.888
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12511
_diffrn_reflns_point_group_measured_fraction_full 0.598
_diffrn_reflns_point_group_measured_fraction_max 0.888
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         54.161
_diffrn_reflns_theta_min         2.749
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    1.710
_exptl_absorpt_correction_T_max  0.7507
_exptl_absorpt_correction_T_min  0.6063
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1261 before and 0.0414 after correction.
The Ratio of minimum to maximum transmission is 0.8076.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             1482
_exptl_crystal_size_max          0.125
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.543
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.929
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     877
_refine_ls_number_reflns         8609
_refine_ls_number_restraints     1263
_refine_ls_restrained_S_all      0.920
_refine_ls_R_factor_all          0.1916
_refine_ls_R_factor_gt           0.1078
_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^)+(0.1813P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2756
_refine_ls_wR_factor_ref         0.3129
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3641
_reflns_number_total             8609
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04343_si_007.cif
_cod_data_source_block           n3735
_cod_original_cell_volume        3979.9(16)
_cod_database_code               4130521
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.815
_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
 N7-C57A \\sim N7-C57
 with sigma of 0.02
 C58A-C57A \\sim C58-C57 \\sim C59A-C58A \\sim C59-C58
 with sigma of 0.02
3. Rigid bond restraints
 C34, N1, C1, C5, C36, C2, C4, C33, C3, C32, C6, C31, C35, C7, C10, C30, C8,
 C9, C29, N2, N4, C11, C26, C27, C12, C25, C28, C13, C17, C24, C14, C16, C21,
 C15, C20, C22, C18, C19, C23, N3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C57A, C57, C58A, C58, C59A, C59
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C34 \\sim N1 \\sim C1 \\sim C5 \\sim C36 \\sim C2 \\sim C4 \\sim C33 \\sim C3
\\sim C32 \\sim C6 \\sim C31 \\sim C35 \\sim C7 \\sim C10 \\sim C30 \\sim C8
\\sim C9 \\sim C29 \\sim N2 \\sim N4 \\sim C11 \\sim C26 \\sim C27 \\sim C12
\\sim C25 \\sim C28 \\sim C13 \\sim C17 \\sim C24 \\sim C14 \\sim C16 \\sim C21
\\sim C15 \\sim C20 \\sim C22 \\sim C18 \\sim C19 \\sim C23 \\sim N3: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
C57A \\sim C57 \\sim C58A \\sim C58 \\sim C59A \\sim C59: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C3) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. 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
6. Others
 Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=Sof(H58C)=Sof(H58D)=Sof(C59A)=
 Sof(H59D)=Sof(H59E)=Sof(H59F)=1-FVAR(1)
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(H59A)=
 Sof(H59B)=Sof(H59C)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C18(H18A,H18B), C29(H29A,H29B), C36(H36A,H36B), C44(H44A,
 H44B), C45(H45A,H45B), C46(H46A,H46B), C57(H57A,H57B), C58(H58A,H58B),
 C57A(H57C,H57D), C58A(H58C,H58D)
7.b Me refined with riding coordinates:
 C59(H59A,H59B,H59C), C59A(H59D,H59E,H59F)
7.c 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), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25),
  C26(H26), C27(H27), C28(H28), C31(H31), C32(H32), C34(H34), C35(H35),
 C37(H37), C39(H39), C41(H41), C47(H47), C48(H48), C50(H50), C51(H51), C53(H53),
  C54(H54), C55(H55), C56(H56)
7.d Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C)
;
_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 = 1117.1 Ang^3^ [28.1%]
Total electron count / cell = 151.4
;
_shelx_res_checksum              2740
_shelx_hkl_checksum              46349
_olex2_submission_original_sample_id ccy_7_29
_olex2_submission_special_instructions 'No special instructions were received'