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_1570622
_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         'C38 H39 N'
_chemical_formula_sum            'C38 H39 N'
_chemical_formula_weight         509.70
_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             2021-01-14
_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                116.431(3)
_cell_angle_beta                 95.048(2)
_cell_angle_gamma                94.470(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9754(2)
_cell_length_b                   12.1150(4)
_cell_length_c                   12.3347(3)
_cell_measurement_reflns_used    8423
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      74.0890
_cell_measurement_theta_min      4.0260
_cell_volume                     1450.31(8)
_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      223(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 0.983
_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     43.00 121.00   0.50    0.73    --   42.80  35.00 -20.00  156
  2  \w    101.00 127.00   0.50    2.92    --   76.50  35.00 -20.00   52
  3  \w     70.00  96.00   0.50    2.92    --   76.50  35.00 -20.00   52
  4  \w     98.00 124.00   0.50    2.92    --   76.50 125.00-150.00   52
  5  \w     85.00 117.00   0.50    0.73    --   42.80 125.00-180.00   64
  6  \w     25.00  50.00   0.50    2.92    --   76.50 -35.00-177.00   50
  7  \w    -32.00  59.00   0.50    0.73    --   42.80 -35.00-177.00  182
  8  \w    -15.00  21.00   0.50    0.73    --  -42.80  35.00 -20.00   72
  9  \w    -62.00 -28.00   0.50    2.92    -- -106.00  35.00 -20.00   68
 10  \w    -77.00 -51.00   0.50    2.92    -- -106.00  57.00 -90.00   52
 11  \w    -98.00 -69.00   0.50    2.92    -- -106.00  37.00-180.00   58
 12  \w    -74.00 -33.00   0.50    2.92    -- -106.00  57.00-180.00   82
 13  \w    -67.00 -41.00   0.50    2.92    -- -106.00 125.00 -90.00   52
 14  \w    -69.00 -34.00   0.50    2.92    -- -106.00 125.00 -30.00   70
 15  \w    -59.00 -32.00   0.50    2.92    -- -106.00 125.00  60.00   54
 16  \w    -96.00 -59.00   0.50    0.73    --  -42.80 125.00 150.00   74
 17  \w   -127.00 -68.00   0.50    2.92    -- -106.00  57.00  90.00  118
 18  \w    -84.00 -29.00   0.50    2.92    -- -106.00  19.00 120.00  110
 19  \w   -111.00 -32.00   0.50    2.92    -- -106.00 125.00 150.00  158
 20  \w   -114.00 -35.00   0.50    2.92    -- -106.00 125.00  30.00  158
 21  \w   -117.00 -75.00   0.50    2.92    -- -106.00 125.00 -90.00   84
 22  \w   -115.00 -63.00   0.50    2.92    -- -106.00 125.00-120.00  104
 23  \w   -105.00 -50.00   0.50    2.92    -- -106.00  77.00 -90.00  110
 24  \w   -119.00 -93.00   0.50    2.92    -- -106.00  35.00 -20.00   52
 25  \w   -113.00 -32.00   0.50    2.92    -- -106.00  77.00  30.00  162
 26  \w   -108.00 -83.00   0.50    2.92    -- -106.00 125.00  90.00   50
 27  \w   -108.00 -65.00   0.50    2.92    -- -106.00 125.00  60.00   86
 28  \w   -117.00 -61.00   0.50    2.92    -- -106.00 125.00   0.00  112
 29  \w   -118.00 -81.00   0.50    2.92    -- -106.00  57.00 -90.00   74
 30  \w   -114.00 -35.00   0.50    2.92    -- -106.00 125.00-180.00  158
 31  \w   -113.00 -88.00   0.50    2.92    -- -106.00  57.00-180.00   50
 32  \w   -120.00 -63.00   0.50    0.73    --  -42.80 -35.00-177.00  114
 33  \w      2.00 102.00   0.50    2.92    --   76.50 -77.00  30.00  200
 34  \w    -44.00 -19.00   0.50    0.73    --  -42.80 -35.00-177.00   50
 35  \w   -115.00 -71.00   0.50    0.73    --  -42.80-125.00-180.00   88
 36  \w   -152.00 -95.00   0.50    2.92    -- -106.00 -35.00-177.00  114
 37  \w   -155.00-130.00   0.50    2.92    -- -106.00 -37.00-120.00   50
 38  \w   -177.00 -75.00   0.50    2.92    -- -106.00 -19.00-120.00  204
 39  \w   -136.00 -83.00   0.50    2.92    -- -106.00-125.00  30.00  106
 40  \w   -101.00 -75.00   0.50    0.73    --  -42.80-125.00 120.00   52
 41  \w   -171.00-144.00   0.50    2.92    -- -106.00-125.00  30.00   54
 42  \w   -174.00 -85.00   0.50    2.92    -- -106.00 -99.00   0.00  178
 43  \w   -172.00-112.00   0.50    2.92    -- -106.00 -37.00 120.00  120
 44  \w   -134.00-109.00   0.50    2.92    -- -106.00  19.00 120.00   50
 45  \w   -176.00-149.00   0.50    2.92    -- -106.00 -99.00 150.00   54
 46  \w   -177.00-111.00   0.50    2.92    -- -106.00 -57.00-150.00  132
;
_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      0.1384506000
_diffrn_orient_matrix_UB_12      -0.0055991000
_diffrn_orient_matrix_UB_13      -0.0105080000
_diffrn_orient_matrix_UB_21      -0.0239376000
_diffrn_orient_matrix_UB_22      -0.1431321000
_diffrn_orient_matrix_UB_23      -0.0628264000
_diffrn_orient_matrix_UB_31      -0.0215111000
_diffrn_orient_matrix_UB_32      -0.0010266000
_diffrn_orient_matrix_UB_33      -0.1255808000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            20471
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.274
_diffrn_reflns_theta_min         4.041
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.498
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63235
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.167
_exptl_crystal_description       plate
_exptl_crystal_F_000             548
_exptl_crystal_size_max          0.371
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.575
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     462
_refine_ls_number_reflns         5815
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0829
_refine_ls_R_factor_gt           0.0723
_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^)+(0.1129P)^2^+0.4895P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2040
_refine_ls_wR_factor_ref         0.2161
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4776
_reflns_number_total             5815
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           210114_1
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_original_cell_volume        1450.31(7)
_cod_database_code               1570622
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C56 H34 N2'
_reflns_odcompleteness_completeness 99.77
_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
 Fixed Sof: C21(0.5) H21A(0.5) H21B(0.5) C29(0.5) H29A(0.5) H29B(0.5)
 C9AA(0.5) H9AA(0.5) H9AB(0.5) C5AA(0.5) H5AA(0.5) H5AB(0.5) C2AA(0.5)
 H2AA(0.5) H2AB(0.5) C4AA(0.5) H4AA(0.5) H4AB(0.5) C1AA(0.5) H1AA(0.5)
 H1AB(0.5) C7AA(0.5) H7AA(0.5) H7AB(0.5) C6AA(0.5) H6AA(0.5) H6AB(0.5)
 C8AA(0.5) H8AA(0.5) H8AB(0.5) C0BA(0.5) H0BA(0.5) H0BB(0.5) C2BA(0.5)
 H2BA(0.5) H2BB(0.5) H2BC(0.5) C4BA(0.5) H4BA(0.5) H4BB(0.5) C7BA(0.5)
 H7BA(0.5) H7BB(0.5) C6BA(0.5) H6BA(0.5) H6BB(0.5) C8BA(0.5) H8BA(0.5)
 H8BB(0.5) H8BC(0.5) C5BA(0.5) H5BA(0.5) H5BB(0.5) C1CA(0.5) H1CA(0.5)
 H1CB(0.5) C0CA(0.5) H0CA(0.5) H0CB(0.5) C9BA(0.5) H9BA(0.5) H9BB(0.5)
 C2CA(0.5) H2CA(0.5) H2CB(0.5) C3CA(0.5) H3CA(0.5) H3CB(0.5) C4CA(0.5)
 H4CA(0.5) H4CB(0.5) C5CA(0.5) H5CA(0.5) H5CB(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C29(H29A,H29B), C9AA(H9AA,H9AB), C5AA(H5AA,H5AB), C2AA(H2AA,
 H2AB), C4AA(H4AA,H4AB), C1AA(H1AA,H1AB), C7AA(H7AA,H7AB), C6AA(H6AA,H6AB),
 C8AA(H8AA,H8AB), C0BA(H0BA,H0BB), C4BA(H4BA,H4BB), C7BA(H7BA,H7BB), C6BA(H6BA,
 H6BB), C5BA(H5BA,H5BB), C1CA(H1CA,H1CB), C0CA(H0CA,H0CB), C9BA(H9BA,H9BB),
 C2CA(H2CA,H2CB), C3CA(H3CA,H3CB), C4CA(H4CA,H4CB), C5CA(H5CA,H5CB)
3.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C24(H24), C25(H25), C5(H5), C28(H28), C8(H8), C26(H26), C27(H27),
 C7(H7), C6(H6), C0AA(H0AA), C3AA(H3AA), C3BA(H3BA), C1BA(H1BA)
3.c Idealised Me refined as rotating group:
 C2BA(H2BA,H2BB,H2BC), C8BA(H8BA,H8BB,H8BC)
;
_shelx_res_checksum              2459
_shelx_hkl_checksum              58301
_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 1.735
_oxdiff_exptl_absorpt_empirical_full_min 0.538