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_1570624
_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(C32 H21 N)'
_chemical_formula_sum            'C64 H42 N2'
_chemical_formula_weight         838.99
_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             2020-09-17
_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                 101.487(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.7190(3)
_cell_length_b                   8.36430(10)
_cell_length_c                   33.8437(5)
_cell_measurement_reflns_used    17855
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      74.1340
_cell_measurement_theta_min      4.3840
_cell_volume                     4360.59(12)
_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 0.999
_diffrn_measured_fraction_theta_max 0.975
_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    -65.00  31.00   0.50    0.46    --  -42.80  57.00   0.00  192
  2  \w     66.00  92.00   0.50    0.46    --   42.80 157.00 -78.00   52
  3  \w     76.00 101.00   0.50    1.96    --   76.50 157.00 -78.00   50
  4  \w     72.00 112.00   0.50    0.46    --   42.80 125.00  60.00   80
  5  \w     88.00 113.00   0.50    1.96    --   76.50 119.00 126.00   50
  6  \w     77.00 117.00   0.50    0.46    --   42.80 125.00  90.00   80
  7  \w     26.00  51.00   0.50    0.46    --   42.80-119.00  41.00   50
  8  \w     46.00 113.00   0.50    0.46    --   42.80-157.00-114.00  134
  9  \w     58.00  83.00   0.50    1.96    --   76.50-157.00-114.00   50
 10  \w    -85.00 -32.00   0.50    1.96    -- -106.00  77.00 150.00  106
 11  \w    -86.00 -60.00   0.50    1.96    -- -106.00  77.00  90.00   52
 12  \w   -110.00 -84.00   0.50    1.96    -- -106.00 119.00 126.00   52
 13  \w   -130.00 -94.00   0.50    1.96    -- -106.00  77.00 150.00   72
 14  \w   -134.00-109.00   0.50    1.96    -- -106.00  77.00  90.00   50
 15  \w    -68.00 -35.00   0.50    1.96    -- -106.00 125.00   0.00   66
 16  \w    -95.00 -70.00   0.50    0.46    --  -42.80 157.00 -78.00   50
 17  \w   -138.00 -33.00   0.50    1.96    -- -106.00 157.00 -78.00  210
 18  \w    -74.00 -32.00   0.50    1.96    -- -106.00 125.00-150.00   84
 19  \w    -68.00 -32.00   0.50    1.96    -- -106.00  77.00-180.00   72
 20  \w   -104.00 -78.00   0.50    1.96    -- -106.00 125.00-150.00   52
 21  \w   -131.00 -73.00   0.50    1.96    -- -106.00  77.00-180.00  116
 22  \w   -111.00 -73.00   0.50    1.96    -- -106.00 125.00   0.00   76
 23  \w   -177.00 -83.00   0.50    1.96    -- -106.00 -37.00  60.00  188
 24  \w   -135.00 -83.00   0.50    1.96    -- -106.00 -57.00  30.00  104
 25  \w   -105.00 -77.00   0.50    1.96    -- -106.00 -77.00 -30.00   56
 26  \w   -119.00 -84.00   0.50    1.96    -- -106.00 -99.00-120.00   70
 27  \w   -106.00 -81.00   0.50    0.46    --  -42.80-157.00-114.00   50
 28  \w   -116.00 -73.00   0.50    0.46    --  -42.80-125.00   0.00   86
 29  \w   -112.00 -85.00   0.50    0.46    --  -42.80-125.00 -30.00   54
 30  \w   -141.00-116.00   0.50    1.96    -- -106.00-119.00  41.00   50
 31  \w   -139.00 -70.00   0.50    1.96    -- -106.00-125.00  30.00  138
 32  \w   -110.00 -85.00   0.50    0.46    --  -42.80-125.00 120.00   50
 33  \w   -154.00-110.00   0.50    1.96    -- -106.00 -37.00  90.00   88
 34  \w   -132.00 -83.00   0.50    1.96    -- -106.00 -99.00 150.00   98
 35  \w   -159.00-125.00   0.50    1.96    -- -106.00 -77.00 -30.00   68
 36  \w   -174.00-149.00   0.50    1.96    -- -106.00-125.00  30.00   50
 37  \w   -176.00-150.00   0.50    1.96    -- -106.00 -99.00 150.00   52
;
_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      0.0078230000
_diffrn_orient_matrix_UB_12      -0.0203626000
_diffrn_orient_matrix_UB_13      0.0458088000
_diffrn_orient_matrix_UB_21      0.0119845000
_diffrn_orient_matrix_UB_22      -0.1814850000
_diffrn_orient_matrix_UB_23      -0.0042992000
_diffrn_orient_matrix_UB_31      0.0990354000
_diffrn_orient_matrix_UB_32      0.0237241000
_diffrn_orient_matrix_UB_33      0.0062571000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0648
_diffrn_reflns_av_unetI/netI     0.0457
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            38978
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.612
_diffrn_reflns_theta_min         3.396
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.562
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45276
_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    1.278
_exptl_crystal_description       prism
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.364
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     709
_refine_ls_number_reflns         8727
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0691
_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^)+(0.0380P)^2^+4.1008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1621
_refine_ls_wR_factor_ref         0.1659
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7828
_reflns_number_total             8727
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_200917
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_database_code               1570624
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C32 N H21'
_reflns_odcompleteness_completeness 99.40
_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
 C21, N20, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5A, C4A, C3A, N20A, C21A, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C21 \\sim N20 \\sim C2 \\sim C3 \\sim C5 \\sim C4: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C5A \\sim C4A \\sim C3A \\sim C2A \\sim N20A \\sim C21A: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(N20A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(H5A)=1-FVAR(1)
 Sof(N20)=Sof(C3)=Sof(C2)=Sof(C5)=Sof(H5)=Sof(C4)=Sof(H4)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=FVAR(1)
 Sof(C67A)=Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C1BB)=Sof(N66A)=Sof(C45A)=
 Sof(C46A)=Sof(H46A)=Sof(C4AB)=Sof(H4AB)=1-FVAR(2)
 Sof(N66)=Sof(C45)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C46)=Sof(H46)=
 Sof(C4AA)=Sof(H4AA)=Sof(C1BA)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C28(H28), C27(H27), C33(H33), C25(H25), C26(H26), C49(H49), C32(H32),
 C30(H30), C52(H52), C36(H36), C31(H31), C7(H7), C50(H50), C64(H64), C56(H56),
 C59(H59), C51(H51), C18(H18), C57(H57), C58(H58), C63(H63), C39(H39), C15(H15),
  C62(H62), C61(H61), C10(H10), C8(H8), C17(H17), C37(H37), C9(H9), C16(H16),
 C38(H38), C5(H5), C4(H4), C46(H46), C4AA(H4AA), C4A(H4A), C5A(H5A), C46A(H46A),
  C4AB(H4AB)
5.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C67(H67A,H67B,H67C), C21A(H21D,H21E,H21F), C67A(H67D,
 H67E,H67F)
;
_shelx_res_checksum              21193
_shelx_hkl_checksum              20083
_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 3.164
_oxdiff_exptl_absorpt_empirical_full_min 0.458