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_4130520
_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, C26 H26 N2, 3(F6 P), 0.5(C4 H6 N2)'
_chemical_formula_sum            'C64 H61 F18 N7 P3'
_chemical_formula_weight         1363.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2015-03-17
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 121.019(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.8633(18)
_cell_length_b                   19.6876(13)
_cell_length_c                   14.3635(9)
_cell_measurement_reflns_used    7272
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.226
_cell_measurement_theta_min      2.909
_cell_volume                     6752.5(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.933
_diffrn_measured_fraction_theta_max 0.993
_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  0.0279
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.933
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            23953
_diffrn_reflns_point_group_measured_fraction_full 0.933
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.084
_diffrn_reflns_theta_min         3.591
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.635
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6650
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0754 before and 0.0447 after correction.
The Ratio of minimum to maximum transmission is 0.8831.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       lath
_exptl_crystal_F_000             2804
_exptl_crystal_size_max          0.155
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.563
_refine_diff_density_min         -1.399
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         5897
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      1.632
_refine_ls_R_factor_all          0.1135
_refine_ls_R_factor_gt           0.1005
_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^)+(0.1671P)^2^+23.6933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2952
_refine_ls_wR_factor_ref         0.3082
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4770
_reflns_number_total             5897
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04343_si_003.cif
_cod_data_source_block           cx0325
_cod_database_code               4130520
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.786
_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
 P3-F15 \\sim P3-F12 \\sim P3-F14 \\sim P3-F13_$1 \\sim P3-F11_$1 \\sim P3-F10
 with sigma of 0.02
 F13-F15_$1 \\sim F10_$1-F12_$1 \\sim F15_$1-F12_$1 \\sim F13-F10_$1
 with sigma of 0.02
 F15-F10 \\sim F13-F12 \\sim F11-F14
 with sigma of 0.02
 F11-F13 \\sim F15-F14 \\sim F13-F14 \\sim F15-F11 \\sim F12-F14 \\sim F10-F11
\\sim F10-F14 \\sim F12-F11
 with sigma of 0.02
 F13-F15 \\sim F10-F12 \\sim F13-F10 \\sim F15-F12
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(P3) = Uanis(F10) = Uanis(F11) = Uanis(F12) = Uanis(F13) = Uanis(F14) =
Uanis(F15)
4. Others
 Fixed Sof: F10(0.5) F11(0.5) F12(0.5) F13(0.5) F14(0.5) F15(0.5) H2SA(0.5)
 H2SB(0.5) H2SC(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C12(H12A,H12B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25),
  C27(H27), C29(H29)
5.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C2S(H2SA,H2SB,H2SC)
;
_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 = 860.5 Ang^3^ [12.7%]
Total electron count / cell = 174.1
;
_shelx_res_checksum              50016
_shelx_hkl_checksum              40841
_olex2_date_sample_data_collection 2015-03-16
_olex2_date_sample_submission    2015-03-09
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in oil'
_olex2_submission_original_sample_id ccy_9_57_12
_olex2_submission_special_instructions 'No special instructions were received'