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_4130524
_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
'C36 H32 N4, C22 H28 N3, 1.5(C2 H3 N), 4(F6 P)'
_chemical_formula_sum            'C61 H64.5 F24 N8.5 P4'
_chemical_formula_weight         1496.59
_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             2014-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                87.962(4)
_cell_angle_beta                 83.733(4)
_cell_angle_gamma                75.084(4)
_cell_formula_units_Z            4
_cell_length_a                   13.8924(9)
_cell_length_b                   19.3041(11)
_cell_length_c                   28.5592(17)
_cell_measurement_reflns_used    2026
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      50.495
_cell_measurement_theta_min      3.114
_cell_volume                     7356.5(8)
_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  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.962
_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_unetI/netI     0.1201
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            14372
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        50.555
_diffrn_reflns_theta_max         50.557
_diffrn_reflns_theta_min         1.556
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.874
_exptl_absorpt_correction_T_max  0.749957
_exptl_absorpt_correction_T_min  0.449872
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1079 before and 0.0369 after correction.
 The Ratio of minimum to maximum transmission is 0.61.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1150 before and 0.0361 after correction.
 The Ratio of minimum to maximum transmission is 0.61.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 24866 reflections, Rint = 0.0779
 (4917 with I > 3sig(I), Rint = 0.0583)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       block
_exptl_crystal_F_000             3064
_exptl_crystal_size_max          0.387
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.016
_refine_diff_density_max         0.967
_refine_diff_density_min         -0.547
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1737
_refine_ls_number_reflns         14372
_refine_ls_number_restraints     2425
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.1754
_refine_ls_R_factor_gt           0.1187
_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          0.3038
_refine_ls_wR_factor_ref         0.3391
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8042
_reflns_number_total             14372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04343_si_006.cif
_cod_data_source_block           n3261_sq_s
_cod_original_formula_sum        'C61 H64.50 F24 N8.50 P4'
_cod_database_code               4130524
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.531
_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
 F43-F46 \\sim F43-F44 \\sim F43-F48 \\sim F43-F47 \\sim F46-F48 \\sim F46-F45
\\sim F46-F47 \\sim F44-F48
 \\sim F44-F45 \\sim F44-F47 \\sim F48-F45 \\sim F45-F47
 with sigma of 0.04
 P8-F43 \\sim P8-F46 \\sim P8-F44 \\sim P8-F48 \\sim P8-F45 \\sim P8-F47
 with sigma of 0.02
 F43A-F46A \\sim F43A-F44A \\sim F43A-F48A \\sim F43A-F47A \\sim F46A-F48A
\\sim F46A-F45A \\sim F46A-
 F47A \\sim F44A-F48A \\sim F44A-F45A \\sim F44A-F47A \\sim F48A-F45A \\sim
F45A-F47A
 with sigma of 0.04
 P8A-F43A \\sim P8A-F46A \\sim P8A-F44A \\sim P8A-F48A \\sim P8A-F45A \\sim
P8A-F47A
 with sigma of 0.02
 F31-F34 \\sim F31-F35 \\sim F31-F32 \\sim F31-F36 \\sim F34-F33 \\sim F34-F35
\\sim F34-F36 \\sim F33-F35
 \\sim F33-F32 \\sim F33-F36 \\sim F35-F32 \\sim F32-F36
 with sigma of 0.04
 P6-F31 \\sim P6-F34 \\sim P6-F33 \\sim P6-F35 \\sim P6-F32 \\sim P6-F36
 with sigma of 0.02
 F31A-F34A \\sim F31A-F35A \\sim F31A-F32A \\sim F31A-F36A \\sim F34A-F33A
\\sim F34A-F35A \\sim F34A-
 F36A \\sim F33A-F35A \\sim F33A-F32A \\sim F33A-F36A \\sim F35A-F32A \\sim
F32A-F36A
 with sigma of 0.04
 P6A-F31A \\sim P6A-F34A \\sim P6A-F33A \\sim P6A-F35A \\sim P6A-F32A \\sim
P6A-F36A
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C53A) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C49A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(P8) = Uanis(F43) = Uanis(F46) = Uanis(F44) = Uanis(F48) = Uanis(F45) =
Uanis(F47) = Uanis(P8A) = Uanis(F43A) = Uanis(F46A) = Uanis(F44A) = Uanis(F48A)
= Uanis(F45A) = Uanis(F47A)
Uanis(P6) = Uanis(F31) = Uanis(F34) = Uanis(F33) = Uanis(F35) = Uanis(F32) =
Uanis(F36) = Uanis(F31A) = Uanis(P6A) = Uanis(F34A) = Uanis(F35A) = Uanis(F33A)
= Uanis(F32A) = Uanis(F36A)
5. Others
 Sof(P8A)=Sof(F43A)=Sof(F44A)=Sof(F45A)=Sof(F46A)=Sof(F47A)=Sof(F48A)=1-FVAR(1)
 Sof(P8)=Sof(F43)=Sof(F44)=Sof(F45)=Sof(F46)=Sof(F47)=Sof(F48)=FVAR(1)
 Sof(P6A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(F34A)=Sof(F35A)=Sof(F36A)=1-FVAR(2)
 Sof(P6)=Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=Sof(F36)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C18(H18A,H18B), C29(H29A,H29B), C36(H36A,H36B), C11A(H11C,
 H11D), C18A(H18C,H18D), C29A(H29C,H29D), C36A(H36C,H36D), C44(H44A,H44B),
 C45(H45A,H45B), C56(H56A,H56B), C57(H57A,H57B), C44A(H44C,H44D), C45A(H45C,
 H45D), C56A(H56C,H56D), C57A(H57C,H57D)
6.b Me refined with riding coordinates:
 C43A(H43D,H43E,H43F)
6.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),
 C1A(H1A), C2A(H2A), C4A(H4A), C5A(H5A), C7A(H7A), C8A(H8A), C9A(H9A),
 C10A(H10A), C13A(H13A), C14A(H14A), C16A(H16A), C17A(H17A), C19A(H19A),
 C20A(H20A), C22A(H22A), C23A(H23A), C25A(H25A), C26A(H26A), C27A(H27A),
 C28A(H28A), C31A(H31A), C32A(H32A), C34A(H34A), C35A(H35A), C37(H37), C39(H39),
  C41(H41), C46(H46), C47(H47), C49(H49), C50(H50), C52(H52), C53(H53),
 C54(H54), C55(H55), C37A(H37A), C39A(H39A), C41A(H41A), C46A(H46A), C47A(H47A),
  C49A(H49A), C50A(H50A), C52A(H52A), C53A(H53A), C54A(H54A), C55A(H55A)
6.d Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C58(H58A,H58B,H58C), C42A(H42D,H42E,
 H42F), C58A(H58D,H58E,H58F), C6S(H6SA,H6SB,H6SC), C2S(H2SA,H2SB,H2SC),
 C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              92215
_shelx_hkl_checksum              55035
_shelx_fab_checksum              99601