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_4130523
_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
'2(C36 H32 N4), 2(C28 H30 N2), 9(C2 H3 N), 7(F6 P)'
_chemical_formula_sum            'C146 H151 F42 N21 P7'
_chemical_formula_weight         3214.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2015-03-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.147(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6492(7)
_cell_length_b                   19.7296(9)
_cell_length_c                   22.6647(10)
_cell_measurement_reflns_used    4902
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      64.832
_cell_measurement_theta_min      2.974
_cell_volume                     7414.9(6)
_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 0.935
_diffrn_measured_fraction_theta_max 0.987
_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  0.0514
_diffrn_reflns_av_unetI/netI     0.0529
_diffrn_reflns_Laue_measured_fraction_full 0.935
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            35068
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.189
_diffrn_reflns_theta_min         2.975
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.751
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6324
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0651 before and 0.0522 after correction.
The Ratio of minimum to maximum transmission is 0.8403.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_description       lath
_exptl_crystal_F_000             3314
_exptl_crystal_size_max          0.149
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.019
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1108
_refine_ls_number_reflns         12522
_refine_ls_number_restraints     1063
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0909
_refine_ls_R_factor_gt           0.0582
_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^)+(0.0980P)^2^+2.2498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1523
_refine_ls_wR_factor_ref         0.1747
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8463
_reflns_number_total             12522
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04343_si_002.cif
_cod_data_source_block           cx0324
_cod_database_code               4130523
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.780
_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
 F19-F21 \\sim F19-F22 \\sim F19-F23 \\sim F19-F24 \\sim F20-F21 \\sim F20-F22
\\sim F20-F23 \\sim F20-F24
 \\sim F21-F22 \\sim F21-F24 \\sim F22-F23 \\sim F23-F24
 with sigma of 0.04
 P4-F19 \\sim P4-F20 \\sim P4-F21 \\sim P4-F22 \\sim P4-F23 \\sim P4-F24
 with sigma of 0.02
 F21A-F24A \\sim F21A-F20A \\sim F21A-F19A \\sim F21A-F22A \\sim F24A-F20A
\\sim F24A-F19A \\sim F24A-
 F23A \\sim F20A-F22A \\sim F20A-F23A \\sim F19A-F22A \\sim F19A-F23A \\sim
F22A-F23A
 with sigma of 0.04
 P4A-F21A \\sim P4A-F24A \\sim P4A-F20A \\sim P4A-F19A \\sim P4A-F22A \\sim
P4A-F23A
 with sigma of 0.02
 C6S-C5S \\sim C6T-C5S
 with sigma of 0.02
3. 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
4. Others
 Sof(P4A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(1)
 Sof(P4)=Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=FVAR(1)
 Sof(C8T)=Sof(H8TA)=Sof(H8TB)=Sof(H8TC)=1-FVAR(2)
 Sof(C8S)=Sof(H8SA)=Sof(H8SB)=Sof(H8SC)=FVAR(2)
 Sof(C6T)=Sof(H6TA)=Sof(H6TB)=Sof(H6TC)=1-FVAR(3)
 Sof(C6S)=Sof(H6SA)=Sof(H6SB)=Sof(H6SC)=FVAR(3)
 Fixed Sof: P3(0.5) F13(0.5) F14(0.5) F15(0.5) F16(0.5) F17(0.5) F18(0.5)
 N5S(0.5) C9S(0.5) C10S(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C12(H12A,H12B), C33(H33A,H33B), C44(H44A,H44B), C24(H24A,H24B),
 C56(H56A,H56B)
5.b Me refined with riding coordinates:
 C8S(H8SA,H8SB,H8SC), C8T(H8TA,H8TB,H8TC), C6S(H6SA,H6SB,H6SC), C6T(H6TA,H6TB,
 H6TC)
5.c 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), C34(H34), C35(H35), C37(H37), C38(H38), C40(H40),
  C41(H41), C42(H42), C43(H43), C46(H46), C47(H47), C49(H49), C50(H50),
 C19(H19), C20(H20), C22(H22), C23(H23), C26(H26), C28(H28), C30(H30), C51(H51),
  C52(H52), C54(H54), C55(H55), C58(H58), C60(H60), C62(H62)
5.d Idealised Me refined with riding coordinates:
 C10S(H10A,H10B,H10C)
5.e Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C), C4S(H4SA,H4SB,H4SC), C2S(H2SA,H2SB,H2SC)
;
_shelx_res_checksum              9779
_shelx_hkl_checksum              86787
_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'