Combining Intra- and Intermolecular Charge Transfer with Polycationic Cyclophanes to Design 2D Tessellations.
Cetin, Muhammet Mustafa; Beldjoudi, Yassine; Roy, Indranil; Anamimoghadam, Ommid; Bae, Youn Jue; Young, Ryan M.; Krzyaniak, Matthew D.; Stern, Charlotte L.; Philp, Douglas; Alsubaie, Fehaid M.; Wasielewski, Michael R.; Stoddart, J. Fraser; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b07877

data_4129153
_publ_section_title
;
 Combining Intra- and Intermolecular Charge Transfer with Polycationic
 Cyclophanes to Design 2D Tessellations.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b07877
_journal_year                    2019
_chemical_formula_moiety         'C66 H54 N6, 6(F6 P), 3(C2 H3 N)'
_chemical_formula_sum            'C72 H63 F36 N9 P6'
_chemical_formula_weight         1924.13
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   70.029(5)
_cell_length_b                   70.029(5)
_cell_length_c                   9.1062(7)
_cell_measurement_reflns_used    4108
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      53.837
_cell_measurement_theta_min      2.524
_cell_volume                     38674(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.939
_diffrn_measured_fraction_theta_max 0.990
_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  0.0988
_diffrn_reflns_av_unetI/netI     0.1094
_diffrn_reflns_Laue_measured_fraction_full 0.939
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       82
_diffrn_reflns_limit_h_min       -76
_diffrn_reflns_limit_k_max       60
_diffrn_reflns_limit_k_min       -82
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            49379
_diffrn_reflns_point_group_measured_fraction_full 0.939
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.291
_diffrn_reflns_theta_min         1.262
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    2.294
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.5749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1280 before and 0.0604 after correction. The Ratio of minimum to maximum transmission is 0.7639. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.487
_exptl_crystal_description       needle
_exptl_crystal_F_000             17496
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.303
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.327
_refine_diff_density_min         -0.621
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.180
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1492
_refine_ls_number_reflns         14595
_refine_ls_number_restraints     2861
_refine_ls_restrained_S_all      2.353
_refine_ls_R_factor_all          0.2232
_refine_ls_R_factor_gt           0.1402
_refine_ls_shift/su_max          0.001
_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          0.3522
_refine_ls_wR_factor_ref         0.4130
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6535
_reflns_number_total             14595
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            4(6PF6).cif
_cod_data_source_block           cx1172
_cod_original_cell_volume        38674(6)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               4129153
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.543
_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
 P4A-F16A = P4A-F15A = P4A-F14A = P4A-F18A = P4A-F17A = P4A-F13A
 1.6 with sigma of 0.01
 P4-F13 = P4-F18 = P4-F14 = P4-F15 = P4-F16 = P4-F17
 1.6 with sigma of 0.01
 P8-F39 = P8-F38 = P8-F40 = P8-F37 = P8-F42 = P8-F41
 1.6 with sigma of 0.01
 P1-F4 = P1-F3 = P1-F6 = P1-F5 = P1-F2 = P1-F1
 1.6 with sigma of 0.01
 F17-F16 \\sim F17-F13 \\sim F17-F18 \\sim F17-F14 \\sim F16-F13 \\sim F16-F14
\\sim F16-F15 \\sim F13-F18
 \\sim F13-F15 \\sim F18-F14 \\sim F18-F15 \\sim F14-F15
 with sigma of 0.02
 P4-F17 \\sim P4-F16 \\sim P4-F13 \\sim P4-F18 \\sim P4-F14 \\sim P4-F15
 with sigma of 0.01
 F13A-F15A \\sim F13A-F16A \\sim F13A-F17A \\sim F13A-F18A \\sim F15A-F16A
\\sim F15A-F17A \\sim F15A-
 F18A \\sim F15A-F14A \\sim F16A-F17A \\sim F16A-F18A \\sim F16A-F14A \\sim
F17A-F18A \\sim F17A-F14A ~
 F18A-F14A
 with sigma of 0.02
 P4A-F13A \\sim P4A-F15A \\sim P4A-F16A \\sim P4A-F17A \\sim P4A-F18A \\sim
P4A-F14A
 with sigma of 0.01
 F50A-F53A \\sim F50A-F54A \\sim F50A-F52A \\sim F50A-F51A \\sim F53A-F54A
\\sim F53A-F52A \\sim F53A-
 F49A \\sim F54A-F49A \\sim F54A-F51A \\sim F52A-F49A \\sim F52A-F51A \\sim
F49A-F51A
 with sigma of 0.02
 P3-F50A \\sim P3-F53A \\sim P3-F54A \\sim P3-F52A \\sim P3-F49A \\sim P3-F51A
 with sigma of 0.01
 F50-F52 \\sim F50-F53 \\sim F50-F51 \\sim F50-F54 \\sim F52-F53 \\sim F52-F51
\\sim F52-F49 \\sim F53-F49
 \\sim F53-F54 \\sim F51-F49 \\sim F51-F54 \\sim F49-F54
 with sigma of 0.02
 P3A-F50 \\sim P3A-F52 \\sim P3A-F53 \\sim P3A-F51 \\sim P3A-F49 \\sim P3A-F54
 with sigma of 0.01
 F21-F22 \\sim F21-F20 \\sim F21-F24 \\sim F21-F19 \\sim F22-F20 \\sim F22-F23
\\sim F22-F19 \\sim F20-F24
 \\sim F20-F23 \\sim F24-F23 \\sim F24-F19 \\sim F23-F19
 with sigma of 0.02
 P5-F21 \\sim P5-F22 \\sim P5-F20 \\sim P5-F24 \\sim P5-F23 \\sim P5-F19
 with sigma of 0.01
 F21A-F22A \\sim F21A-F20A \\sim F21A-F24A \\sim F21A-F19A \\sim F22A-F20A
\\sim F22A-F23A \\sim F22A-
 F19A \\sim F20A-F24A \\sim F20A-F23A \\sim F24A-F23A \\sim F24A-F19A \\sim
F23A-F19A
 with sigma of 0.02
 P5A-F21A \\sim P5A-F22A \\sim P5A-F20A \\sim P5A-F24A \\sim P5A-F23A \\sim
P5A-F19A
 with sigma of 0.01
 F41-F40 \\sim F41-F37 \\sim F41-F42 \\sim F41-F38 \\sim F40-F39 \\sim F40-F37
\\sim F40-F38 \\sim F39-F37
 \\sim F39-F42 \\sim F39-F38 \\sim F37-F42 \\sim F42-F38
 with sigma of 0.02
 P8-F41 \\sim P8-F40 \\sim P8-F39 \\sim P8-F37 \\sim P8-F42 \\sim P8-F38
 with sigma of 0.01
 F4-F3 \\sim F4-F5 \\sim F4-F1 \\sim F4-F2 \\sim F3-F5 \\sim F3-F6 \\sim F3-F1
\\sim F3-F2 \\sim F5-F6 \\sim F5-F1
 \\sim F5-F2 \\sim F6-F1 \\sim F6-F2 \\sim F1-F2
 with sigma of 0.04
 P1-F4 \\sim P1-F3 \\sim P1-F5 \\sim P1-F6 \\sim P1-F1 \\sim P1-F2
 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 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
5. Others
 Sof(P4A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(1)
 Sof(P4)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(1)
 Sof(P3)=Sof(F49A)=Sof(F50A)=Sof(F51A)=Sof(F52A)=Sof(F53A)=Sof(F54A)=1-FVAR(2)
 Sof(P3A)=Sof(F49)=Sof(F50)=Sof(F51)=Sof(F52)=Sof(F53)=Sof(F54)=FVAR(2)
 Sof(P5A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(3)
 Sof(P5)=Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=FVAR(3)
 Fixed Sof: P1(0.25) F1(0.25) F2(0.25) F3(0.25) F4(0.25) F5(0.25) F6(0.25)
 P6(0.5) F25(0.5) F26(0.5) F27(0.5) F28(0.5) F29(0.5) F30(0.5) P7(0.5) F31(0.5)
 F32(0.5) F33(0.5) F34(0.5) F35(0.5) F36(0.5) P8(0.25) F37(0.25) F38(0.25)
 F39(0.25) F40(0.25) F41(0.25) F42(0.25) P9(0.5) F43(0.5) F44(0.5) F45(0.5)
 F46(0.5) F47(0.5) F48(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C22(H22A,H22B), C33(H33A,H33B), C44(H44A,H44B), C55(H55A,
 H55B), C66(H66A,H66B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C24(H24), C26(H26),
  C28(H28), C29(H29), C31(H31), C32(H32), C34(H34), C35(H35), C37(H37),
 C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C46(H46), C48(H48), C50(H50),
  C51(H51), C53(H53), C54(H54), C56(H56), C57(H57), C59(H59), C60(H60),
 C62(H62), C63(H63), C64(H64), C65(H65)
6.c Idealised Me refined as rotating group:
 C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C6S(H6SA,H6SB,H6SC)
;
_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 = 3084.2 Ang^3^ [8.0%]
Total electron count / cell = 1179.3
;
_shelx_res_checksum              30236
_shelx_hkl_checksum              91626
_shelx_fab_checksum              52250
_olex2_date_sample_data_collection 2018-01-18
_olex2_date_sample_submission    2018-01-17
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1172
_olex2_submission_special_instructions 'No special instructions were received'