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_1570626
_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(C26 H21)'
_chemical_formula_sum            'C52 H42'
_chemical_formula_weight         666.85
_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             2021-02-10
_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                63.792(5)
_cell_angle_beta                 67.462(4)
_cell_angle_gamma                77.789(4)
_cell_formula_units_Z            2
_cell_length_a                   12.0253(5)
_cell_length_b                   14.2850(8)
_cell_length_c                   15.2395(6)
_cell_measurement_reflns_used    10135
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      73.8600
_cell_measurement_theta_min      3.7680
_cell_volume                     2166.5(2)
_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      273(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 0.986
_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    -35.00  65.00   0.50    1.72    --   42.80 -37.00 120.00  200
  2  \w     62.00  92.00   0.50    1.72    --   42.80-117.00   3.00   60
  3  \w     34.00  59.00   0.50    7.06    --   76.50-117.00   3.00   50
  4  \w    -10.00  61.00   0.50    1.72    --   42.80 -57.00  60.00  142
  5  \w     54.00 126.00   0.50    7.06    --   76.50  37.00 -90.00  144
  6  \w     69.00  97.00   0.50    1.72    --   42.80 161.00-118.00   56
  7  \w     75.00 100.00   0.50    7.06    --   76.50 161.00-118.00   50
  8  \w    103.00 150.00   0.50    7.06    --   76.50 117.00  90.00   94
  9  \w     79.00 116.00   0.50    1.72    --   42.80 125.00 120.00   74
 10  \w     72.00 116.00   0.50    1.72    --   42.80 125.00 150.00   88
 11  \w    -58.00 -29.00   0.50    7.06    -- -106.00  37.00 120.00   58
 12  \w    -72.00 -47.00   0.50    1.72    --  -42.80 117.00  90.00   50
 13  \w   -112.00 -84.00   0.50    7.06    -- -106.00 117.00  90.00   56
 14  \w   -113.00 -32.00   0.50    7.06    -- -106.00 125.00 120.00  162
 15  \w   -115.00 -54.00   0.50    7.06    -- -106.00 125.00 150.00  122
 16  \w   -123.00 -97.00   0.50    7.06    -- -106.00  37.00 120.00   52
 17  \w   -123.00 -33.00   0.50    7.06    -- -106.00  77.00 120.00  180
 18  \w   -114.00 -51.00   0.50    7.06    -- -106.00 125.00   0.00  126
 19  \w   -103.00 -50.00   0.50    7.06    -- -106.00  77.00 -30.00  106
 20  \w    -93.00 -32.00   0.50    7.06    -- -106.00  57.00 -60.00  122
 21  \w    -85.00 -42.00   0.50    7.06    -- -106.00 125.00-180.00   86
 22  \w    -98.00 -73.00   0.50    1.72    --  -42.80 161.00-118.00   50
 23  \w   -121.00 -78.00   0.50    7.06    -- -106.00 161.00-118.00   86
 24  \w   -117.00 -33.00   0.50    7.06    -- -106.00 125.00-150.00  168
 25  \w   -112.00 -33.00   0.50    7.06    -- -106.00 125.00 -60.00  158
 26  \w   -125.00 -27.00   0.50    7.06    -- -106.00  19.00-120.00  196
 27  \w   -121.00 -95.00   0.50    7.06    -- -106.00 -57.00-150.00   52
 28  \w   -130.00 -84.00   0.50    7.06    -- -106.00 -37.00-150.00   92
 29  \w   -142.00-116.00   0.50    7.06    -- -106.00 -57.00 -90.00   52
 30  \w   -156.00 -93.00   0.50    7.06    -- -106.00 -99.00 -30.00  126
 31  \w   -141.00-115.00   0.50    7.06    -- -106.00 -37.00  60.00   52
 32  \w   -159.00-126.00   0.50    7.06    -- -106.00-117.00   3.00   66
 33  \w   -167.00-125.00   0.50    7.06    -- -106.00-125.00  60.00   84
 34  \w   -174.00 -83.00   0.50    7.06    -- -106.00 -57.00  60.00  182
 35  \w   -108.00 -70.00   0.50    1.72    --  -42.80-125.00  60.00   76
 36  \w   -115.00 -73.00   0.50    1.72    --  -42.80-125.00  90.00   84
 37  \w   -176.00 -89.00   0.50    7.06    -- -106.00 -37.00 -60.00  174
 38  \w   -112.00 -32.00   0.50    7.06    -- -106.00  57.00  30.00  160
 39  \w   -120.00 -63.00   0.50    7.06    -- -106.00  57.00 120.00  114
 40  \w   -117.00 -91.00   0.50    7.06    -- -106.00 125.00 -90.00   52
 41  \w   -116.00 -62.00   0.50    7.06    -- -106.00  57.00-150.00  108
 42  \w   -169.00-144.00   0.50    7.06    -- -106.00 -57.00-150.00   50
 43  \w   -171.00 -75.00   0.50    7.06    -- -106.00 -19.00 -30.00  192
 44  \w   -103.00 -76.00   0.50    1.72    --  -42.80-161.00-147.00   54
 45  \w     50.00  75.00   0.50    1.72    --   42.80-161.00-147.00   50
 46  \w     60.00  85.00   0.50    7.06    --   76.50-161.00-147.00   50
 47  \w   -127.00-102.00   0.50    7.06    -- -106.00-161.00-147.00   50
;
_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      0.0643990000
_diffrn_orient_matrix_UB_12      -0.0369213000
_diffrn_orient_matrix_UB_13      0.0806631000
_diffrn_orient_matrix_UB_21      -0.1144327000
_diffrn_orient_matrix_UB_22      -0.0534026000
_diffrn_orient_matrix_UB_23      0.0861241000
_diffrn_orient_matrix_UB_31      0.0452419000
_diffrn_orient_matrix_UB_32      -0.1013470000
_diffrn_orient_matrix_UB_33      -0.0181377000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0481
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32393
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.217
_diffrn_reflns_theta_min         3.425
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.434
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88352
_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    1.022
_exptl_crystal_description       prism
_exptl_crystal_F_000             708
_exptl_crystal_size_max          0.167
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         8698
_refine_ls_number_restraints     214
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0649
_refine_ls_R_factor_gt           0.0539
_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^)+(0.0984P)^2^+0.1584P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1612
_refine_ls_wR_factor_ref         0.1699
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6871
_reflns_number_total             8698
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_210209_1
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_database_code               1570626
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C52 H42'
_reflns_odcompleteness_completeness 99.85
_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
 C0, C1AA, C2AA, C3AA, C4AA, C5AA, C2, C6AA, C3, C7AA, C8AA, C9AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C00L, C00Q, C00W, C010, C014, C019, C01B, C01D, C01F, C01G, C01H, C01I
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C0 \\sim C1AA \\sim C2AA \\sim C3AA \\sim C4AA \\sim C5AA \\sim C2 \\sim C6AA
\\sim C3 \\sim C7AA \\sim C8AA \\sim C9AA: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C00L \\sim C00Q \\sim C00W \\sim C010 \\sim C014 \\sim C019 \\sim C01B \\sim
C01D \\sim C01F \\sim C01G \\sim C01H \\sim C01I: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(C0)=Sof(H0)=Sof(C1AA)=Sof(H1AA)=Sof(C2AA)=Sof(H2AA)=Sof(C3AA)=Sof(H3AA)=
 Sof(C4AA)=Sof(C5AA)=Sof(C2)=Sof(C6AA)=Sof(C3)=Sof(H3)=Sof(C7AA)=Sof(H7AA)=
 Sof(C8AA)=Sof(H8AA)=Sof(C9AA)=Sof(H9AA)=1-FVAR(1)
 Sof(C00L)=Sof(C00Q)=Sof(C00W)=Sof(C010)=Sof(C014)=Sof(H014)=Sof(C019)=
 Sof(H019)=Sof(C01B)=Sof(H01J)=Sof(C01D)=Sof(H01K)=Sof(C01F)=Sof(H01L)=
 Sof(C01G)=Sof(H01M)=Sof(C01H)=Sof(H01N)=Sof(C01I)=Sof(H01O)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C007(H007), C008(H008), C009(H009), C00E(H00E), C00J(H00J), C00M(H00M),
 C00O(H00O), C00P(H00P), C00R(H00R), C00U(H00U), C00V(H00V), C00X(H00X),
 C00Y(H00Y), C00Z(H00Z), C013(H013), C014(H014), C016(H016), C019(H019),
 C01B(H01J), C01D(H01K), C01F(H01L), C01G(H01M), C01H(H01N), C01I(H01O), C0(H0),
  C1AA(H1AA), C2AA(H2AA), C3AA(H3AA), C3(H3), C7AA(H7AA), C8AA(H8AA), C9AA(H9AA)
5.b Idealised Me refined as rotating group:
 C011(H01A,H01B,H01C), C012(H01D,H01E,H01F), C017(H01P,H01Q,H01R), C01A(H01G,
 H01H,H01I), C01C(H01S,H01T,H01U), C01E(H01V,H01W,H01X)
;
_shelx_res_checksum              74971
_shelx_hkl_checksum              95676
_shelx_fab_checksum              23073
_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 4.341
_oxdiff_exptl_absorpt_empirical_full_min 0.476