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_7132225
_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         'C112 H80 N16, 2(C7 H8), 2(C5 H12)'
_chemical_formula_sum            'C136 H120 N16'
_chemical_formula_weight         1978.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/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
;
2022-11-11 deposited with the CCDC.	2023-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.363(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.1737(8)
_cell_length_b                   23.2224(7)
_cell_length_c                   25.1475(12)
_cell_measurement_reflns_used    12784
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      22.6340
_cell_measurement_theta_min      1.7210
_cell_volume                     10847.2(8)
_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 0.999
_diffrn_measured_fraction_theta_max 0.826
_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    -78.00  -3.00   0.50   20.00    --  -10.74 -53.00  73.00  150
  2  \w    -14.00  29.00   0.50   20.00    --  -10.74 -99.00 -30.00   86
  3  \w     -1.00  32.00   0.50   20.00    --  -10.74 -99.00-150.00   66
  4  \w    -42.00  67.00   0.50   20.00    --  -10.74  53.00-141.00  218
  5  \w     51.00  84.00   0.50   20.00    --   11.29 179.00  90.00   66
;
_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      0.0048125000
_diffrn_orient_matrix_UB_12      -0.0163346000
_diffrn_orient_matrix_UB_13      -0.0226560000
_diffrn_orient_matrix_UB_21      0.0355745000
_diffrn_orient_matrix_UB_22      0.0108359000
_diffrn_orient_matrix_UB_23      0.0043035000
_diffrn_orient_matrix_UB_31      0.0130536000
_diffrn_orient_matrix_UB_32      -0.0234154000
_diffrn_orient_matrix_UB_33      0.0177722000
_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  0.0643
_diffrn_reflns_av_unetI/netI     0.1029
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.826
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            64373
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.826
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.975
_diffrn_reflns_theta_min         1.672
_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    0.072
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37750
_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    1.211
_exptl_crystal_description       block
_exptl_crystal_F_000             4192
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.826
_refine_diff_density_min         -0.494
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1414
_refine_ls_number_reflns         21583
_refine_ls_number_restraints     457
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1987
_refine_ls_R_factor_gt           0.1080
_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^)+(0.1759P)^2^+8.6413P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2810
_refine_ls_wR_factor_ref         0.3371
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10831
_reflns_number_total             21583
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04887j2.cif
_cod_data_source_block           compound_5
_cod_database_code               7132225
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N'
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.986
_diffrn_oxdiff_digest_frames
;
01291c0e4f1faa6ce2a51f72243caa8e7d00025f382
;
_diffrn_oxdiff_digest_hkl
;
01f632028de194851e7b7c5a7e6f6974a24c39
;
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.01
_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
 C136-C137 = C138-C137 = C138-C139 = C140-C139
 1.54 with sigma of 0.01
 C150-C152
 2.56 with sigma of 0.01
 C148-C150
 2.56 with sigma of 0.01
 C149-C148 = C150-C149 = C151-C150 = C152-C151
 1.56 with sigma of 0.01
 C149-C151
 2.56 with sigma of 0.01
 C155-C157
 2.56 with sigma of 0.01
 C153-C155
 2.56 with sigma of 0.01
 C154-C153 = C155-C154 = C156-C155 = C157-C156
 1.56 with sigma of 0.01
 C154-C156
 2.56 with sigma of 0.01
 C142-C141 = C146-C141 = C146-C145 = C145-C144 = C144-C143 = C143-C142
 1.39 with sigma of 0.01
3. Restrained planarity
 C143, C144, C145, C146, C141, C142, C147
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C149 \\sim C152 \\sim C150 \\sim C148 \\sim C151 \\sim C156 \\sim C153 \\sim
C155 \\sim C157 \\sim C154: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.01
Uanis(C148) \\sim Ueq, Uanis(C149) \\sim Ueq, Uanis(C150) \\sim Ueq,
Uanis(C151) \\sim Ueq, Uanis(C152) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.02
Uanis(N119) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C121) \\sim Ueq, Uanis(C120) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N124) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(C127) \\sim Ueq,
Uanis(C126) \\sim Ueq, Uanis(C125) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C136) \\sim Ueq, Uanis(C137) \\sim Ueq, Uanis(C138) \\sim Ueq,
Uanis(C139) \\sim Ueq, Uanis(C140) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C142) \\sim Ueq, Uanis(C143) \\sim Ueq, Uanis(C144) \\sim Ueq,
Uanis(C146) \\sim Ueq, Uanis(C145) \\sim Ueq, Uanis(C141) \\sim Ueq,
Uanis(C147) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C130) \\sim Ueq,
Uanis(C131) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C133) \\sim Ueq,
Uanis(C134) \\sim Ueq, Uanis(C135) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(N44) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C149) \\sim Ueq, Uanis(C152) \\sim Ueq, Uanis(C150) \\sim Ueq,
Uanis(C148) \\sim Ueq, Uanis(C151) \\sim Ueq, Uanis(C156) \\sim Ueq,
Uanis(C153) \\sim Ueq, Uanis(C155) \\sim Ueq, Uanis(C157) \\sim Ueq,
Uanis(C154) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C152, C151, C150, C149, C148
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Others
 Fixed Sof: C149(0.5) H14D(0.5) H14E(0.5) C152(0.5) H15A(0.5) H15B(0.5)
 H15C(0.5) C150(0.5) H15D(0.5) H15E(0.5) C148(0.5) H14F(0.5) H14G(0.5)
 H14H(0.5) C151(0.5) H15F(0.5) H15G(0.5) C156(0.5) H15H(0.5) H15I(0.5)
 C153(0.5) H15J(0.5) H15K(0.5) H15L(0.5) C155(0.5) H15M(0.5) H15N(0.5)
 C157(0.5) H15O(0.5) H15P(0.5) H15Q(0.5) C154(0.5) H15R(0.5) H15S(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C137(H13A,H13B), C138(H13C,H13D), C139(H13H,H13I), C149(H14D,H14E), C150(H15D,
 H15E), C151(H15F,H15G), C156(H15H,H15I), C155(H15M,H15N), C154(H15R,H15S)
7.b Me refined with riding coordinates:
 C135(H13J,H13K,H13L), C147(H14I,H14J,H14K), C136(H13E,H13F,H13G), C140(H14A,
 H14B,H14C), C152(H15A,H15B,H15C), C148(H14F,H14G,H14H), C153(H15J,H15K,H15L),
 C157(H15O,H15P,H15Q)
7.c Aromatic/amide H refined with riding coordinates:
 C69(H69), C70(H70), C100(H100), C101(H101), C83(H83), C107(H107), C3(H3),
 C82(H82), C4(H4), C104(H104), C91(H91), C112(H112), C109(H109), C77(H77),
 C96(H96), C24(H24), C111(H111), C21(H21), C80(H80), C27(H27), C115(H115),
 C88(H88), C53(H53), C22(H22), C95(H95), C93(H93), C114(H114), C25(H25),
 C75(H75), C94(H94), C106(H106), C38(H38), C105(H105), C73(H73), C64(H64),
 C110(H110), C72(H72), C61(H61), C43(H43), C79(H79), C78(H78), C37(H37),
 C26(H26), C90(H90), C40(H40), C54(H54), C74(H74), C41(H41), C89(H89), C42(H42),
  C63(H63), C32(H32), C123(H123), C62(H62), C31(H31), C29(H29), C120(H120),
 C59(H59), C128(H128), C125(H125), C56(H56), C122(H122), C11(H11), C47(H47),
 C45(H45), C30(H30), C126(H126), C121(H121), C8(H8), C57(H57), C48(H48),
 C13(H13), C127(H127), C58(H58), C16(H16), C46(H46), C10(H10), C9(H9), C14(H14),
  C15(H15), C130(H130), C134(H134), C133(H133), C131(H131), C132(H132),
 C144(H144), C143(H143), C142(H142), C145(H145), C146(H146)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              96165
_shelx_hkl_checksum              90589
_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 2.315
_oxdiff_exptl_absorpt_empirical_full_min 0.557