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_1570623
_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         '2(C47 H45 N)'
_chemical_formula_sum            'C94 H90 N2'
_chemical_formula_weight         1247.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-06
_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                 91.9370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.4355(3)
_cell_length_b                   7.95430(10)
_cell_length_c                   31.2422(3)
_cell_measurement_reflns_used    31506
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      74.1780
_cell_measurement_theta_min      4.2040
_cell_volume                     6814.10(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      123(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.984
_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    -13.00  22.00   0.50    0.09    --   42.80 -77.00  57.00   70
  2  \w     30.00  55.00   0.50    0.35    --   76.50 -77.00  57.00   50
  3  \w    -13.00  31.00   0.50    0.09    --  -42.80  77.00-176.00   88
  4  \w    -65.00   3.00   0.50    0.09    --  -42.80  57.00  90.00  136
  5  \w    -56.00 -28.00   0.50    0.35    -- -106.00  37.00  60.00   56
  6  \w    -84.00 -58.00   0.50    0.35    -- -106.00  77.00 150.00   52
  7  \w    -83.00 -33.00   0.50    0.35    -- -106.00 125.00 150.00  100
  8  \w    -95.00 -68.00   0.50    0.35    -- -106.00  37.00  60.00   54
  9  \w   -115.00 -33.00   0.50    0.35    -- -106.00  57.00 150.00  164
 10  \w    -92.00 -66.00   0.50    0.35    -- -106.00  77.00 -30.00   52
 11  \w   -105.00 -36.00   0.50    0.35    -- -106.00 125.00 -60.00  138
 12  \w    -96.00 -11.00   0.50    0.09    --  -42.80 125.00-180.00  170
 13  \w    -67.00 -36.00   0.50    0.35    -- -106.00 125.00-180.00   62
 14  \w   -113.00 -32.00   0.50    0.35    -- -106.00 125.00 -90.00  162
 15  \w   -110.00 -60.00   0.50    0.35    -- -106.00  37.00-180.00  100
 16  \w   -121.00 -35.00   0.50    0.35    -- -106.00  77.00-176.00  172
 17  \w   -107.00 -77.00   0.50    0.35    -- -106.00 125.00-180.00   60
 18  \w   -133.00 -27.00   0.50    0.35    -- -106.00  19.00-180.00  212
 19  \w   -111.00 -72.00   0.50    0.09    --  -42.80-125.00 -30.00   78
 20  \w   -138.00-113.00   0.50    0.35    -- -106.00 -77.00  57.00   50
 21  \w   -165.00 -83.00   0.50    0.35    -- -106.00 -57.00  60.00  164
 22  \w   -106.00 -70.00   0.50    0.09    --  -42.80-125.00 120.00   72
 23  \w   -155.00 -80.00   0.50    0.35    -- -106.00 -19.00 -60.00  150
 24  \w   -173.00 -84.00   0.50    0.35    -- -106.00 -99.00  30.00  178
 25  \w   -124.00 -99.00   0.50    0.35    -- -106.00  77.00 150.00   50
 26  \w     67.00  92.00   0.50    0.09    --   42.80  77.00-176.00   50
 27  \w     75.00 100.00   0.50    0.35    --   76.50  77.00-176.00   50
 28  \w     71.00 117.00   0.50    0.09    --   42.80 125.00  30.00   92
;
_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      0.0507544000
_diffrn_orient_matrix_UB_12      0.0824650000
_diffrn_orient_matrix_UB_13      -0.0010476000
_diffrn_orient_matrix_UB_21      0.0170498000
_diffrn_orient_matrix_UB_22      -0.1395103000
_diffrn_orient_matrix_UB_23      -0.0301937000
_diffrn_orient_matrix_UB_31      -0.0170195000
_diffrn_orient_matrix_UB_32      0.1060835000
_diffrn_orient_matrix_UB_33      -0.0390054000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0327
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            58837
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.165
_diffrn_reflns_theta_min         4.219
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.520
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89198
_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    1.216
_exptl_crystal_description       prism
_exptl_crystal_F_000             2672
_exptl_crystal_size_max          0.352
_exptl_crystal_size_mid          0.285
_exptl_crystal_size_min          0.272
_refine_diff_density_max         1.153
_refine_diff_density_min         -0.442
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     914
_refine_ls_number_reflns         13645
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0590
_refine_ls_R_factor_gt           0.0548
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0653P)^2^+4.1452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1401
_refine_ls_wR_factor_ref         0.1435
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12364
_reflns_number_total             13645
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_210306
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_database_code               1570623
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C47 H45 N'
_reflns_odcompleteness_completeness 99.34
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Others
 Sof(H90C)=Sof(H90D)=Sof(H88C)=Sof(H88D)=Sof(H92C)=Sof(H92D)=Sof(H86C)=
 Sof(H86D)=Sof(C87A)=Sof(H87C)=Sof(H87D)=Sof(C89A)=Sof(H89C)=Sof(H89D)=
 Sof(C91A)=Sof(H91C)=Sof(H91D)=1-FVAR(1)
 Sof(H90A)=Sof(H90B)=Sof(H88A)=Sof(H88B)=Sof(H92A)=Sof(H92B)=Sof(H86A)=
 Sof(H86B)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(C91)=
 Sof(H91A)=Sof(H91B)=FVAR(1)
 Sof(H94C)=Sof(H94D)=Sof(H96D)=Sof(H96E)=Sof(H96F)=Sof(C95A)=Sof(H95C)=
 Sof(H95D)=Sof(C93A)=Sof(H93C)=Sof(H93D)=1-FVAR(2)
 Sof(H94A)=Sof(H94B)=Sof(H96A)=Sof(H96B)=Sof(H96C)=Sof(C93)=Sof(H93A)=
 Sof(H93B)=Sof(C95)=Sof(H95A)=Sof(H95B)=FVAR(2)
3.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C38(H38A,H38B), C43(H43A,H43B), C40(H40A,H40B), C44(H44A,
 H44B), C42(H42A,H42B), C46(H46A,H46B), C85(H85A,H85B), C39(H39A,H39B),
 C41(H41A,H41B), C90(H90A,H90B), C90(H90C,H90D), C45(H45A,H45B), C47(H47A,H47B),
  C88(H88A,H88B), C88(H88C,H88D), C92(H92A,H92B), C92(H92C,H92D), C94(H94A,
 H94B), C94(H94C,H94D), C86(H86A,H86B), C86(H86C,H86D), C87(H87A,H87B),
 C89(H89A,H89B), C91(H91A,H91B), C93(H93A,H93B), C95(H95A,H95B), C87A(H87C,
 H87D), C89A(H89C,H89D), C91A(H91C,H91D), C95A(H95C,H95D), C93A(H93C,H93D)
3.b Aromatic/amide H refined with riding coordinates:
 C24(H24), C14(H14), C22(H22), C21(H21), C51(H51), C68(H68), C33(H33), C7(H7),
 C16(H16), C23(H23), C5(H5), C62(H62), C72(H72), C65(H65), C66(H66), C81(H81),
 C64(H64), C26(H26), C74(H74), C63(H63), C6(H6), C67(H67), C19(H19), C71(H71),
 C69(H69), C17(H17), C36(H36), C70(H70), C77(H77), C29(H29), C27(H27), C18(H18),
  C84(H84), C35(H35), C82(H82), C34(H34), C76(H76), C28(H28), C83(H83), C75(H75)
3.c Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C96(H96A,H96B,H96C), C96(H96D,H96E,H96F)
;
_shelx_res_checksum              56489
_shelx_hkl_checksum              61972
_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 1.234
_oxdiff_exptl_absorpt_empirical_full_min 0.863