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_1570627
_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         'C2 H4 Cl2, C56 H41 N'
_chemical_formula_sum            'C58 H45 Cl2 N'
_chemical_formula_weight         826.85
_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     dual
_audit_creation_date             2021-03-02
_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                94.9290(10)
_cell_angle_beta                 102.9010(10)
_cell_angle_gamma                107.0460(10)
_cell_formula_units_Z            2
_cell_length_a                   10.38100(10)
_cell_length_b                   14.3480(2)
_cell_length_c                   15.61030(10)
_cell_measurement_reflns_used    17419
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      74.1000
_cell_measurement_theta_min      4.0130
_cell_volume                     2138.07(4)
_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      173(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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    -29.00  64.00   0.50    0.27    --   42.80 -57.00  60.00  186
  2  \w     56.00  84.00   0.50    0.27    --   42.80-130.00 -24.00   56
  3  \w     42.00  67.00   0.50    1.08    --   76.50-130.00 -24.00   50
  4  \w     54.00  89.00   0.50    0.27    --   42.80-140.00 161.00   70
  5  \w     49.00  74.00   0.50    1.08    --   76.50-140.00 161.00   50
  6  \w    116.00 151.00   0.50    1.08    --   76.50  77.00   0.00   70
  7  \w     85.00 110.00   0.50    1.08    --   76.50 130.00  47.00   50
  8  \w     68.00  93.00   0.50    0.27    --   42.80 130.00  47.00   50
  9  \w     54.00 111.00   0.50    1.08    --   76.50  77.00   0.00  114
 10  \w     71.00 102.00   0.50    0.27    --   42.80 125.00 -60.00   62
 11  \w     62.00 113.00   0.50    0.27    --   42.80 140.00-138.00  102
 12  \w     82.00 107.00   0.50    1.08    --   76.50 140.00-138.00   50
 13  \w    -61.00 -34.00   0.50    1.08    -- -106.00 125.00 -90.00   54
 14  \w    -63.00 -37.00   0.50    1.08    -- -106.00 125.00-150.00   52
 15  \w    -77.00 -35.00   0.50    1.08    -- -106.00  77.00 -90.00   84
 16  \w   -104.00 -21.00   0.50    0.27    --  -42.80 140.00-138.00  166
 17  \w    -86.00 -58.00   0.50    0.27    --  -42.80 130.00  47.00   56
 18  \w   -111.00 -40.00   0.50    1.08    -- -106.00 130.00  47.00  142
 19  \w    -67.00 -32.00   0.50    1.08    -- -106.00 125.00  90.00   70
 20  \w    -57.00 -32.00   0.50    1.08    -- -106.00  77.00  90.00   50
 21  \w    -86.00 -40.00   0.50    1.08    -- -106.00 125.00  30.00   92
 22  \w   -103.00 -77.00   0.50    1.08    -- -106.00 125.00 -90.00   52
 23  \w   -104.00 -78.00   0.50    1.08    -- -106.00 140.00-138.00   52
 24  \w   -115.00 -33.00   0.50    1.08    -- -106.00 125.00 -60.00  164
 25  \w   -101.00 -76.00   0.50    1.08    -- -106.00 125.00 -30.00   50
 26  \w   -126.00 -71.00   0.50    1.08    -- -106.00  57.00 -90.00  110
 27  \w   -128.00 -81.00   0.50    1.08    -- -106.00  77.00 -90.00   94
 28  \w   -112.00 -86.00   0.50    1.08    -- -106.00 125.00-150.00   52
 29  \w   -117.00 -82.00   0.50    1.08    -- -106.00 125.00-120.00   70
 30  \w   -128.00 -32.00   0.50    1.08    -- -106.00  57.00 -30.00  192
 31  \w    -99.00 -58.00   0.50    1.08    -- -106.00  57.00  90.00   82
 32  \w   -106.00 -75.00   0.50    1.08    -- -106.00  77.00  90.00   62
 33  \w   -104.00 -31.00   0.50    1.08    -- -106.00  37.00  90.00  146
 34  \w    -94.00 -60.00   0.50    1.08    -- -106.00 125.00 150.00   68
 35  \w   -114.00 -77.00   0.50    1.08    -- -106.00 125.00  90.00   74
 36  \w   -129.00 -35.00   0.50    1.08    -- -106.00 142.00  -4.72  188
 37  \w   -127.00-101.00   0.50    1.08    -- -106.00 139.00 128.10   52
 38  \w   -177.00 -75.00   0.50    1.08    -- -106.00 -19.00-120.00  204
 39  \w   -117.00 -84.00   0.50    1.08    -- -106.00 -37.00-150.00   66
 40  \w   -133.00 -28.00   0.50    1.08    -- -106.00  19.00-150.00  210
 41  \w   -115.00 -15.00   0.50    0.27    --  -42.80 -77.00 -30.00  200
 42  \w    -99.00 -70.00   0.50    1.08    -- -106.00-125.00   0.00   58
 43  \w   -116.00 -88.00   0.50    1.08    -- -106.00-130.00 -24.00   56
 44  \w   -130.00-105.00   0.50    1.08    -- -106.00-125.00   0.00   50
 45  \w   -143.00 -99.00   0.50    1.08    -- -106.00 -77.00  60.00   88
 46  \w   -123.00 -98.00   0.50    1.08    -- -106.00-140.00 161.00   50
 47  \w   -112.00 -87.00   0.50    0.27    --  -42.80-140.00 161.00   50
 48  \w   -115.00 -70.00   0.50    0.27    --  -42.80-125.00  60.00   90
 49  \w   -108.00 -83.00   0.50    0.27    --  -42.80-130.00 -24.00   50
 50  \w   -112.00 -71.00   0.50    1.08    -- -106.00-125.00-150.00   82
 51  \w   -173.00-137.00   0.50    1.08    -- -106.00-125.00   0.00   72
 52  \w   -174.00-115.00   0.50    1.08    -- -106.00-125.00-150.00  118
 53  \w   -177.00 -84.00   0.50    1.08    -- -106.00 -37.00-180.00  186
 54  \w   -166.00-125.00   0.50    1.08    -- -106.00 -37.00-150.00   82
;
_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      -0.0684576000
_diffrn_orient_matrix_UB_12      -0.0354427000
_diffrn_orient_matrix_UB_13      -0.1003888000
_diffrn_orient_matrix_UB_21      0.1326946000
_diffrn_orient_matrix_UB_22      0.0649464000
_diffrn_orient_matrix_UB_23      -0.0209309000
_diffrn_orient_matrix_UB_31      0.0596509000
_diffrn_orient_matrix_UB_32      -0.0864867000
_diffrn_orient_matrix_UB_33      0.0034904000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33580
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.235
_diffrn_reflns_theta_min         3.265
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73545
_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    1.284
_exptl_crystal_description       prism
_exptl_crystal_F_000             868
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     570
_refine_ls_number_reflns         8587
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0547P)^2^+0.6346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1069
_refine_ls_wR_factor_ref         0.1104
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7638
_reflns_number_total             8587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_210302_1
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_database_code               1570627
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C58 H45 N Cl2'
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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. Others
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=1-FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C2)=Sof(H2A)=Sof(H2B)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,
 H60B), C3(H3A,H3B), C2(H2A,H2B), C2A(H2AA,H2AB), C3A(H3AA,H3AB)
3.b Aromatic/amide H refined with riding coordinates:
 C34(H34), C31(H31), C12(H12), C9(H9), C29(H29), C47(H47), C28(H28), C21(H21),
 C39(H39), C18(H18), C24(H24), C27(H27), C52(H52), C42(H42), C22(H22), C15(H15),
  C23(H23), C26(H26), C50(H50), C48(H48), C41(H41), C17(H17), C40(H40),
 C55(H55), C53(H53), C16(H16), C49(H49), C54(H54)
3.c Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C)
;
_shelx_res_checksum              83950
_shelx_hkl_checksum              75820
_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 1.609
_oxdiff_exptl_absorpt_empirical_full_min 0.710