Half-substituted fluorocycloparaphenylenes with high symmetry: Synthesis, properties and derivatization to densely substituted carbon nanorings
Shudo, Hiroki; Kuwayama, Motonobu; Segawa, Yasutomo; Yagi, Akiko; Itami, Kenichiro; Chemical Communications  (2023) –; doi:10.1039/D3CC04887J

data_7132223
_publ_section_title
;
 Half-substituted fluorocycloparaphenylenes with high symmetry: Synthesis,
 properties and derivatization to densely substituted carbon nanorings
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04887J
_journal_year                    2023
_chemical_formula_moiety         '4(C24 H8 F8), 8(C3 H3)'
_chemical_formula_sum            'C120 H56 F32'
_chemical_formula_weight         2105.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-10-21
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.05 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5625)
;
_audit_update_record
;
2023-02-16 deposited with the CCDC.	2023-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.529(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8837(5)
_cell_length_b                   18.2597(4)
_cell_length_c                   27.4771(8)
_cell_measurement_reflns_used    19126
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      26.5330
_cell_measurement_theta_min      1.9240
_cell_volume                     9342.6(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.882
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -31.00  17.00   0.50   70.00    --   20.11 -67.00 -72.00   96
  2  \w    -71.00 -46.00   0.50   70.00    --  -19.64 -67.00 -72.00   50
  3  \w    -78.00 -44.00   0.50   70.00    --   20.11-179.00 -60.00   68
  4  \w    -91.00 -47.00   0.50   70.00    --   20.11-179.00  30.00   88
  5  \w   -119.00 -13.00   0.50   70.00    --  -19.64 -57.00 150.00  212
  6  \w    -31.00 104.00   0.50   70.00    --   20.11  67.00  62.00  270
  7  \w     38.00  93.00   0.50   70.00    --   20.11 179.00 -30.00  110
  8  \w     54.00  79.00   0.50   70.00    --   20.11 179.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0222406000
_diffrn_orient_matrix_UB_12      0.0295451000
_diffrn_orient_matrix_UB_13      0.0016614000
_diffrn_orient_matrix_UB_21      -0.0191746000
_diffrn_orient_matrix_UB_22      -0.0025623000
_diffrn_orient_matrix_UB_23      -0.0271091000
_diffrn_orient_matrix_UB_31      -0.0242538000
_diffrn_orient_matrix_UB_32      -0.0250946000
_diffrn_orient_matrix_UB_33      0.0047220000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.882
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            58989
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.094
_diffrn_reflns_theta_min         1.562
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.131
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80207
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       block
_exptl_crystal_F_000             4256
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.427
_refine_diff_density_min         -0.663
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1703
_refine_ls_number_reflns         18190
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.1261
_refine_ls_R_factor_gt           0.0894
_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^)+(0.1730P)^2^+11.2567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2678
_refine_ls_wR_factor_ref         0.3037
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12019
_reflns_number_total             18190
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04887j2.cif
_cod_data_source_block           compound_1
_cod_original_cell_volume        9342.6(4)
_cod_database_code               7132223
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H F'
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.987
_diffrn_oxdiff_digest_frames
;
01ca4c5ba295477fb6f7647b30025ff8a100025dc65
;
_diffrn_oxdiff_digest_hkl
;
015665702ce445aa079c89dbe49442cb5d30fd
;
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C125-C126 = C125-C124 = C124-C123 = C122-C123 = C121-C122 = C121-C126 = C132-
 C127 = C132-C131 = C130-C131 = C130-C129 = C129-C128 = C127-C128
 1.39 with sigma of 0.02
 C67-C72 = C68-C67 = C68-C69 = C69-C70 = C71-C70 = C71-C72
 1.39 with sigma of 0.02
 C139-C140 = C140-C141
 1.39 with sigma of 0.02
 C4-C3 = C3-C2 = C1-C2 = C1-C6 = C6-C5 = C5-C4 = C7-C12 = C8-C7 = C8-C9 = C10-
 C9 = C10-C11 = C12-C11 = C15-C14 = C16-C15 = C16-C17 = C17-C18 = C18-C13 = C14-
 C13 = C24-C19 = C24-C23 = C22-C23 = C21-C20 = C21-C22 = C20-C19 = C26-C25 =
 C27-C26 = C27-C28 = C29-C28 = C29-C30 = C30-C25 = C36-C31 = C35-C36 = C34-C35 =
  C34-C33 = C33-C32 = C32-C31 = C41-C42 = C40-C41 = C40-C39 = C39-C38 = C38-C37
 = C42-C37 = C44-C45 = C43-C44 = C43-C48 = C48-C47 = C47-C46 = C45-C46
 1.39 with sigma of 0.02
 F10-C27 = F9-C26 = F7-C24 = F8-C23 = F11-C36 = F12-C35 = F14-C39 = F13-C38 =
 F15-C48 = F16-C47 = F1-C2 = F2-C3 = F3-C8 = F4-C9 = F5-C14 = F6-C15
 1.35 with sigma of 0.02
 C133_$1-C133 = C134-C133 = C135-C134
 1.39 with sigma of 0.005
 C137-C136 = C138-C137 = C138-C136_$1
 1.39 with sigma of 0.005
 C145-C144 = C146-C145 = C147-C146 = C147-C142 = C143-C142 = C144-C143
 1.39 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C14) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.002
Uanis(C144) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C125) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C123) \\sim Ueq,
Uanis(C122) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C128) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C132) \\sim Ueq,
Uanis(C131) \\sim Ueq, Uanis(C130) \\sim Ueq, Uanis(C129) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.02
Uanis(C135) \\sim Ueq, Uanis(C134) \\sim Ueq, Uanis(C133) \\sim Ueq,
Uanis(C141) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C139) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 F29, C86
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F18, C51
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C144, C143, C142, C147, C146, C145
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H113)=Sof(H114)=Sof(F37)=Sof(F38)=1-FVAR(1)
 Sof(F41)=Sof(F42)=Sof(H111)=Sof(H110)=FVAR(1)
 Fixed Sof: C2(0.5) C3(0.5) C4(0.5) C5(0.5) H5(0.5) C6(0.5) H6(0.5) C1(0.5)
 C7(0.5) C8(0.5) C12(0.5) H12(0.5) C9(0.5) C11(0.5) H11(0.5) C10(0.5) C46(0.5)
 C45(0.5) H45(0.5) C47(0.5) C44(0.5) H44(0.5) C48(0.5) C43(0.5) C13(0.5)
 C14(0.5) C18(0.5) H18(0.5) C15(0.5) C17(0.5) H17(0.5) C16(0.5) C19(0.5)
 C24(0.5) C20(0.5) H20(0.5) C23(0.5) C22(0.5) C25(0.5) C26(0.5) C30(0.5)
 H30(0.5) C27(0.5) C29(0.5) H29(0.5) C28(0.5) C31(0.5) C36(0.5) C32(0.5)
 H32(0.5) C35(0.5) C33(0.5) H33(0.5) C34(0.5) C37(0.5) C38(0.5) C42(0.5)
 H42(0.5) C39(0.5) C41(0.5) H41(0.5) C40(0.5) C21(0.5) H21(0.5) F3(0.5) F4(0.5)
 F7(0.5) F8(0.5) F11(0.5) F12(0.5) F10(0.5) F13(0.5) F14(0.5) F15(0.5) F16(0.5)
 F5(0.5) F6(0.5) F9(0.5) F2(0.5) F1(0.5) C144(0.5) H144(0.5) C143(0.5)
 H143(0.5) C142(0.5) H142(0.5) C147(0.5) H147(0.5) C146(0.5) H146(0.5)
 C145(0.5) H145(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C93(H93), C92(H92), C78(H78), C77(H77), C68(H68), C80(H80), C81(H81),
 C69(H69), C66(H66), C56(H56), C89(H89), C53(H53), C65(H65), C57(H57), C90(H90),
  C54(H54), C116(H116), C117(H117), C107(H107), C102(H102), C111(H111),
 C108(H108), C101(H101), C113(H113), C110(H110), C114(H114), C136(H136),
 C138(H138), C137(H137), C128(H128), C126(H126), C131(H131), C121(H121),
 C130(H130), C129(H129), C124(H124), C127(H127), C123(H123), C132(H132),
 C125(H125), C122(H122), C135(H135), C134(H134), C133(H133), C5(H5), C6(H6),
 C12(H12), C11(H11), C45(H45), C44(H44), C18(H18), C17(H17), C20(H20), C30(H30),
  C29(H29), C32(H32), C33(H33), C42(H42), C41(H41), C21(H21), C140(H140),
 C141(H141), C139(H139), C144(H144), C143(H143), C142(H142), C147(H147),
 C146(H146), C145(H145)
;
_shelx_res_checksum              18186
_shelx_hkl_checksum              17833
_olex2_exptl_crystal_mounting_method loop
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.734