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_7132224
_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         'C36 H12 F12, 2(C4 H8 O)'
_chemical_formula_sum            'C44 H28 F12 O2'
_chemical_formula_weight         816.66
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                112.645(5)
_cell_angle_beta                 100.614(4)
_cell_angle_gamma                109.590(4)
_cell_formula_units_Z            1
_cell_length_a                   9.9513(5)
_cell_length_b                   10.4272(5)
_cell_length_c                   10.5475(5)
_cell_measurement_reflns_used    5271
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.9520
_cell_measurement_theta_min      2.2620
_cell_volume                     887.70(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.817
_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      8.00  36.00   0.50  100.00    --   -2.77  81.00 -25.00   56
  2  \w    -42.00   8.00   0.50  100.00    --   -2.77 -81.00-148.00  100
  3  \w    -29.00  28.00   0.50  100.00    --    3.32 -81.00-148.00  114
  4  \w    -17.00   8.00   0.50  100.00    --    3.32  81.00 -25.00   50
  5  \w    -62.00   8.00   0.50  100.00    --   -2.77 -37.00   0.00  140
  6  \w    -12.00  38.00   0.50  100.00    --    3.32 -99.00   0.00  100
  7  \w    -56.00  20.00   0.50  100.00    --    3.32 -57.00 120.00  152
  8  \w    -11.00  34.00   0.50  100.00    --    3.32  57.00 -30.00   90
  9  \w     50.00  76.00   0.50  100.00    --    3.32  57.00 -30.00   52
 10  \w    -12.00  14.00   0.50  100.00    --    3.32 -99.00  90.00   52
;
_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      -0.0715386000
_diffrn_orient_matrix_UB_12      -0.0495340000
_diffrn_orient_matrix_UB_13      -0.0036467000
_diffrn_orient_matrix_UB_21      0.0365287000
_diffrn_orient_matrix_UB_22      0.0051069000
_diffrn_orient_matrix_UB_23      0.0674062000
_diffrn_orient_matrix_UB_31      -0.0112103000
_diffrn_orient_matrix_UB_32      0.0656914000
_diffrn_orient_matrix_UB_33      0.0393010000
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.0602
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.817
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            13568
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.817
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.821
_diffrn_reflns_theta_min         2.243
_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    0.136
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81504
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_description       block
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.546
_refine_diff_density_min         -1.070
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     353
_refine_ls_number_reflns         4167
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.1062
_refine_ls_R_factor_gt           0.0816
_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^)+(0.1354P)^2^+1.5167P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2272
_refine_ls_wR_factor_ref         0.2456
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3064
_reflns_number_total             4167
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04887j2.cif
_cod_data_source_block           compound_2
_cod_original_cell_volume        887.69(8)
_cod_database_code               7132224
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H F O'
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.987
_diffrn_oxdiff_digest_frames
;
012bd3b97bb30e8346fe8608ded00030ec0002579c7
;
_diffrn_oxdiff_digest_hkl
;
011ac45113019dc11d2fed5fbef856fa9e8d10
;
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C33-C32 = C31-C32 = C31-C30
 1.54 with sigma of 0.01
 O34-C30 = O34-C33
 1.43 with sigma of 0.01
 C33-C30
 2.4 with sigma of 0.01
 O34-C31
 2.4 with sigma of 0.01
 C30-C32
 2.4 with sigma of 0.01
 C31-C33
 2.4 with sigma of 0.01
 C32-O34
 2.4 with sigma of 0.01
 C38-C37
 1.54 with sigma of 0.01
 C36-C37 = C35-C36
 1.54 with sigma of 0.01
 O39-C35 = O39-C38
 1.43 with sigma of 0.01
 O39-C37
 2.4 with sigma of 0.01
 C38-C36
 2.4 with sigma of 0.01
 C37-C35
 2.4 with sigma of 0.01
 C36-O39
 2.4 with sigma of 0.01
 C35-C38
 2.4 with sigma of 0.01
 C27-C26 = C27-C28 = C26-C25
 1.54 with sigma of 0.01
 O29-C28 = O29-C25
 1.43 with sigma of 0.01
 O29-C26
 2.4 with sigma of 0.01
 C25-C27
 2.4 with sigma of 0.01
 C26-C28
 2.4 with sigma of 0.01
 C27-O29
 2.4 with sigma of 0.01
 C28-C25
 2.4 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C28 \\sim C27 \\sim C26 \\sim C25 \\sim O29 \\sim C33 \\sim O39 \\sim O34 \\sim
C30 \\sim C35 \\sim C31 \\sim C36 \\sim C32 \\sim C37 \\sim C38: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(O29) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(O34) \\sim Ueq,
Uanis(O39) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C26)=Sof(H0AC)=Sof(H0AD)=Sof(C25)=Sof(H00C)=Sof(H00D)=Sof(O29)=Sof(C28)=
 Sof(H1AA)=Sof(H1AB)=Sof(C27)=Sof(H1AC)=Sof(H1AD)=0.66667*(1-FVAR(2))
 Sof(O39)=Sof(C38)=Sof(H2AA)=Sof(H2AB)=Sof(C37)=Sof(H3AA)=Sof(H3AB)=Sof(C36)=
 Sof(H4AA)=Sof(H4AB)=Sof(C35)=Sof(H5AA)=Sof(H5AB)=0.66667*FVAR(2)
 Fixed Sof: O34(0.33333) C32(0.33333) H6AA(0.33333) H6AB(0.33333) C30(0.33333)
 H00A(0.33333) H00B(0.33333) C31(0.33333) H1A(0.33333) H1B(0.33333)
 C33(0.33333) H0AA(0.33333) H0AB(0.33333)
5.a Secondary CH2 refined with riding coordinates:
 C32(H6AA,H6AB), C30(H00A,H00B), C31(H1A,H1B), C33(H0AA,H0AB), C26(H0AC,H0AD),
 C25(H00C,H00D), C28(H1AA,H1AB), C27(H1AC,H1AD), C38(H2AA,H2AB), C37(H3AA,H3AB),
  C36(H4AA,H4AB), C35(H5AA,H5AB)
5.b Aromatic/amide H refined with riding coordinates:
 C22(H00J), C21(H00K), C10(H00L), C5(H00M), C6(H00N), C11(H00O)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              86619
_shelx_hkl_checksum              18201
_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 3.963
_oxdiff_exptl_absorpt_empirical_full_min 0.212