Direct synthesis of spirobifluorenes by formal dehydrative coupling of biaryls and fluorenones.
Kato, Yugo; Nishimura, Kazutoshi; Nishii, Yuji; Hirano, Koji; Chemical science 15 (2024) 2112–2117; doi:10.1039/d3sc05977d

data_1570621
_publ_section_title
;
 Direct synthesis of spirobifluorenes by formal dehydrative coupling of
 biaryls and fluorenones.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              2112
_journal_page_last               2117
_journal_paper_doi               10.1039/d3sc05977d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C29 H18 F3 N'
_chemical_formula_sum            'C29 H18 F3 N'
_chemical_formula_weight         437.44
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-11-02 deposited with the CCDC.	2024-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.8051(3)
_cell_length_b                   22.8051(3)
_cell_length_c                   8.2792(2)
_cell_measurement_reflns_used    7818
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.0870
_cell_measurement_theta_min      3.8290
_cell_volume                     4305.78(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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     82.00 131.00   0.50    0.40    --   76.50  89.00 168.00   98
  2  \w   -176.00 -85.00   0.50    0.40    -- -106.00 -93.00 -46.00  182
  3  \w    -71.00 -46.00   0.50    0.40    -- -106.00  46.00 -42.00   50
  4  \w   -127.00-101.00   0.50    0.40    -- -106.00  46.00 -42.00   52
  5  \w    -62.00  33.00   0.50    0.12    --  -42.80  46.00 -42.00  190
  6  \w   -116.00 -87.00   0.50    0.12    --  -42.80-125.00 -30.00   58
  7  \w   -107.00 -70.00   0.50    0.12    --  -42.80-125.00  90.00   74
  8  \w     30.00  75.00   0.50    0.12    --   42.80-125.00-180.00   90
  9  \w    -65.00 -35.00   0.50    0.40    -- -106.00 125.00  30.00   60
 10  \w   -117.00 -75.00   0.50    0.40    -- -106.00 125.00  30.00   84
 11  \w    -91.00 -65.00   0.50    0.40    -- -106.00 125.00 120.00   52
 12  \w   -156.00-130.00   0.50    0.40    -- -106.00 -37.00 120.00   52
 13  \w   -177.00 -83.00   0.50    0.40    -- -106.00 -99.00   0.00  188
 14  \w   -163.00 -83.00   0.50    0.40    -- -106.00 -37.00   0.00  160
 15  \w    -97.00 -64.00   0.50    0.40    -- -106.00  57.00-180.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0212630000
_diffrn_orient_matrix_UB_12      0.0176673000
_diffrn_orient_matrix_UB_13      -0.1697788000
_diffrn_orient_matrix_UB_21      -0.0573166000
_diffrn_orient_matrix_UB_22      0.0344070000
_diffrn_orient_matrix_UB_23      -0.0274186000
_diffrn_orient_matrix_UB_31      0.0287116000
_diffrn_orient_matrix_UB_32      0.0554080000
_diffrn_orient_matrix_UB_33      0.0710069000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            18566
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.249
_diffrn_reflns_theta_min         3.877
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.796
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58822
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (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    1.350
_exptl_crystal_description       prism
_exptl_crystal_F_000             1808
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.247
_exptl_crystal_size_min          0.182
_refine_diff_density_max         0.958
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     390
_refine_ls_number_reflns         4300
_refine_ls_number_restraints     158
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0997
_refine_ls_R_factor_gt           0.0918
_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^)+(0.1706P)^2^+3.1964P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2877
_refine_ls_wR_factor_ref         0.2963
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3654
_reflns_number_total             4300
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_200909_1
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_original_cell_volume        4305.78(15)
_cod_original_sg_symbol_H-M      'P 42/n'
_cod_database_code               1570621
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C29 H18 F3 N'
_reflns_odcompleteness_completeness 99.32
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C20, C15, C16, C17, C18, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C15A, C16A, C17A, C18A, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21A, C22A, C23A, C24A, C14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C14, C13, C21, C22, C23, C24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C20 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C21A \\sim C22A \\sim C23A \\sim C24A \\sim C14A: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C13 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C14: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(H24A)=Sof(C14A)=Sof(C15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=1-FVAR(1)
 Sof(C15)=Sof(C14)=Sof(C19)=Sof(H19)=Sof(C21)=Sof(H21)=Sof(C24)=Sof(H24)=
 Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C16)=Sof(H16)=Sof(C23)=Sof(H23)=
 Sof(C22)=Sof(H22)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C27(H27), C28(H28), C4(H4), C19(H19), C21(H21), C25(H25),
 C24(H24), C26(H26), C17(H17), C18(H18), C16(H16), C23(H23), C22(H22),
 C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C16A(H16A), C17A(H17A),
 C18A(H18A), C19A(H19A)
5.b Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C)
;
_shelx_res_checksum              76604
_shelx_hkl_checksum              56218
_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 4.728
_oxdiff_exptl_absorpt_empirical_full_min 0.590