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_4130525
_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         '5(F6 P), C36 H32 N4, C28 H34 N4, 4(C2 H3 N)'
_chemical_formula_sum            'C72 H78 F30 N12 P5'
_chemical_formula_weight         1836.34
_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     iterative
_audit_creation_date             2013-10-28
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                87.542(5)
_cell_angle_beta                 74.700(6)
_cell_angle_gamma                83.934(6)
_cell_formula_units_Z            2
_cell_length_a                   13.9238(14)
_cell_length_b                   18.0258(17)
_cell_length_c                   19.2008(18)
_cell_measurement_reflns_used    9929
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.138
_cell_measurement_theta_min      4.776
_cell_volume                     4621.8(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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard, H. Puschmann, in preparation (2013)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.882
_diffrn_measured_fraction_theta_max 0.970
_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  0.0624
_diffrn_reflns_av_unetI/netI     0.0910
_diffrn_reflns_Laue_measured_fraction_full 0.882
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            31230
_diffrn_reflns_point_group_measured_fraction_full 0.882
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         63.68
_diffrn_reflns_theta_min         2.39
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.858
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.5858
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1116 before and 0.0653 after correction.
The Ratio of minimum to maximum transmission is 0.7784.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       needle
_exptl_crystal_F_000             1878
_exptl_crystal_size_max          0.819
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.544
_refine_diff_density_min         -0.982
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.700
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1187
_refine_ls_number_reflns         14749
_refine_ls_number_restraints     625
_refine_ls_restrained_S_all      1.698
_refine_ls_R_factor_all          0.2417
_refine_ls_R_factor_gt           0.1656
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_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          0.4604
_refine_ls_wR_factor_ref         0.5072
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7078
_reflns_number_total             14749
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04343_si_005.cif
_cod_data_source_block           n3046a
_cod_database_code               4130525
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.311
_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
 P2-F11A \\sim P2-F11 \\sim P2-F12A \\sim P2-F12 \\sim P2-F8A \\sim P2-F8 \\sim
P2-F9A \\sim P2-F9 \\sim P2-F7
 \\sim P2-F7A \\sim P2-F10A \\sim P2-F10
 with sigma of 0.01
 F25-F27 \\sim F29-F28 \\sim F30-F26 \\sim F8-F7 \\sim F11-F9 \\sim F10-F12
\\sim F25A-F26A \\sim F27A-
 F29A \\sim F28A-F30A \\sim F9A-F11A \\sim F10A-F12A \\sim F7A-F8A
 with sigma of 0.01
 F25-F28 \\sim F27-F30 \\sim F29-F26 \\sim F8-F9 \\sim F10-F11 \\sim F7-F12
\\sim F25A-F27A \\sim F28A-
 F26A \\sim F29A-F30A \\sim F9A-F12A \\sim F11A-F8A \\sim F10A-F7A \\sim
F28-F26 \\sim F27-F29 \\sim F30-
 F25 \\sim F28-F30 \\sim F25-F29 \\sim F26-F27 \\sim F16-F17 \\sim F14-F15
\\sim F13-F18
 with sigma of 0.01
 P5-F27 \\sim P5-F29 \\sim P5-F30 \\sim P5A-F30A \\sim P5-F25 \\sim P5A-F29A
\\sim P5A-F25A \\sim P5A-F28A
 \\sim P5A-F27A \\sim P5A-F26A \\sim P5-F26 \\sim P5-F28
 with sigma of 0.01
3. Rigid bond restraints
 F25A, F26A, F27A, F30A, F28A, F29A, F25, F26, F27, F28, F29, F30
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 P5A, P5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10A, F7A, F10, F12, F9, F11A, F7, F12A, F8, F9A, F11, F8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 P5A, P5, P6, P4, P1, P3, P2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F25A, F26A, F27A, F28A, F29A, F30A, F25, F26, F27, F28, F29, F30, F1, F2, F3,
 F4, F5, F6, F31, F32, F33, F34, F35, F36, F7, F8, F9, F10, F11, F12, F10A,
 F12A, F9A, F7A, F8A, F11A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F25A \\sim F26A \\sim F27A \\sim F30A \\sim F28A \\sim F29A \\sim F25 \\sim F26
\\sim F27 \\sim F28 \\sim F29 \\sim F30: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
P5A \\sim P5: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
F10A \\sim F7A \\sim F10 \\sim F12 \\sim F9 \\sim F11A \\sim F7 \\sim F12A
\\sim F8 \\sim F9A \\sim F11 \\sim F8A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
P5A \\sim P5 \\sim P6 \\sim P4 \\sim P1 \\sim P3 \\sim P2: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
F25A \\sim F26A \\sim F27A \\sim F28A \\sim F29A \\sim F30A \\sim F25 \\sim F26
\\sim F27 \\sim F28 \\sim F29 \\sim F30 \\sim F1 \\sim F2 \\sim F3 \\sim F4
\\sim F5 \\sim F6 \\sim F31 \\sim F32 \\sim F33 \\sim F34 \\sim F35 \\sim F36
\\sim F7 \\sim F8 \\sim F9 \\sim F10 \\sim F11 \\sim F12 \\sim F10A \\sim F12A
\\sim F9A \\sim F7A \\sim F8A \\sim F11A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(P5) = Uanis(P5A)
Uanis(F29) = Uanis(F25) = Uanis(F30) = Uanis(F28) = Uanis(F26) = Uanis(F27) =
Uanis(F26A) = Uanis(F25A) = Uanis(F28A) = Uanis(F30A) = Uanis(F29A) =
Uanis(F27A)
5. Rigid body (RIGU) restrains
 C43, C42, C64, C63, C37, C38, C39, C40, C41, C58, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 1*[Sof(P5)+Sof(F25)+Sof(F26)+Sof(F27)+Sof(F28)+Sof(F29)+Sof(F30)]+1*[Sof(P1)+
 Sof(F1)+Sof(F2)+Sof(F3)+Sof(F4)+Sof(F5)+Sof(F6)]+1*[Sof(P6)+Sof(F31)+Sof(F32)+
 Sof(F33)+Sof(F34)+Sof(F35)+Sof(F36)]+1*[Sof(P5A)+Sof(F25A)+Sof(F26A)+Sof(F27A)+
 Sof(F28A)+Sof(F29A)+Sof(F30A)]=2.5 with esd of 0.001
 Sof(P5)=Sof(F25)=Sof(F26)=Sof(F27)=Sof(F28)=Sof(F29)=Sof(F30)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(3)
 Sof(P6)=Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=Sof(F36)=FVAR(4)
 Sof(P5A)=Sof(F25A)=Sof(F26A)=Sof(F27A)=Sof(F28A)=Sof(F29A)=Sof(F30A)=FVAR(5)
 Fixed Sof: P3(0.5) F13(0.5) F14(0.5) F15(0.5) F16(0.5) F17(0.5) F18(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C19(H19A,H19B), C26(H26A,H26B), C44(H44A,H44B),
 C45(H45A,H45B), C56(H56A,H56B), C57(H57A,H57B)
7.b Me refined with riding coordinates:
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C68(H68A,H68B,
 H68C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C24(H24), C25(H25),
  C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35),
 C36(H36), C37(H37), C39(H39), C41(H41), C46(H46), C47(H47), C49(H49), C50(H50),
  C52(H52), C53(H53), C54(H54), C55(H55), C58(H58), C60(H60), C62(H62)
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 = 488.2 Ang^3^ [10.6%]
Total electron count / cell = 34.8
;
_shelx_res_checksum              9588
_shelx_hkl_checksum              73014