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_1570625
_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         '0.25(C72 H76 N2)'
_chemical_formula_sum            'C18 H19 N0.5'
_chemical_formula_weight         242.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-27
_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                 97.3120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.0249(2)
_cell_length_b                   11.65340(10)
_cell_length_c                   16.3566(2)
_cell_measurement_reflns_used    25676
_cell_measurement_temperature    263(2)
_cell_measurement_theta_max      73.8440
_cell_measurement_theta_min      3.7420
_cell_volume                     2840.61(6)
_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      263(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 0.994
_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    -42.00 -17.00   0.50    0.13    --  -42.93  22.00-102.00   50
  2  \w    -86.00 -60.00   0.50    0.13    --  -42.93 -22.00  91.00   52
  3  \w     15.00  40.00   0.50    0.13    --   42.93 -22.00  91.00   50
  4  \w     16.00  79.00   0.50    0.13    --   42.93  22.00-102.00  126
  5  \w     82.00 108.00   0.50    0.48    --   76.50  22.00-102.00   52
  6  \w     27.00  52.00   0.50    0.48    --   76.50 -22.00  91.00   50
  7  \w    -55.00 -30.00   0.50    0.48    -- -106.00  22.00-102.00   50
  8  \w   -127.00 -93.00   0.50    0.48    -- -106.00 -22.00  91.00   68
  9  \w    -93.00 -12.00   0.50    0.13    --  -42.93 125.00 -30.00  162
 10  \w   -115.00 -70.00   0.50    0.13    --  -42.93-125.00-120.00   90
 11  \w     94.00 120.00   0.50    0.13    --   42.93  37.00 -30.00   52
 12  \w     65.00  91.00   0.50    0.13    --   42.93  37.00 -30.00   52
 13  \w     16.00  74.00   0.50    0.13    --   42.93  77.00 -30.00  116
 14  \w     16.00 116.00   0.50    0.13    --   42.93  77.00  30.00  200
 15  \w     29.00  60.00   0.50    0.13    --   42.93  37.00 -30.00   62
 16  \w     49.00  87.00   0.50    0.48    --   76.50  77.00 -60.00   76
 17  \w     48.00  84.00   0.50    0.48    --   76.50  77.00 -30.00   72
 18  \w     49.00  75.00   0.50    0.48    --   76.50  77.00  60.00   52
 19  \w     48.00 136.00   0.50    0.48    --   76.50  77.00  90.00  176
 20  \w     48.00  73.00   0.50    0.48    --   76.50  77.00  30.00   50
 21  \w     48.00 140.00   0.50    0.48    --   76.50  77.00   0.00  184
 22  \w     52.00  92.00   0.50    0.48    --   76.50  67.00  63.12   80
 23  \w     54.00  80.00   0.50    0.48    --   76.50  57.00  60.00   52
 24  \w    -99.00 -74.00   0.50    0.48    -- -106.00 -83.00 -11.83   50
 25  \w   -175.00-149.00   0.50    0.48    -- -106.00 -83.00 -11.83   52
 26  \w   -128.00 -80.00   0.50    0.48    -- -106.00  37.00  90.00   96
 27  \w   -100.00 -75.00   0.50    0.48    -- -106.00 -81.00  51.78   50
 28  \w   -135.00 -84.00   0.50    0.48    -- -106.00  77.00  30.00  102
 29  \w   -176.00-137.00   0.50    0.48    -- -106.00 -81.00  51.78   78
 30  \w    -76.00 -41.00   0.50    0.48    -- -106.00 125.00 -90.00   70
 31  \w   -119.00 -80.00   0.50    0.48    -- -106.00 -70.00  44.16   78
 32  \w    -78.00 -52.00   0.50    0.48    -- -106.00  77.00  30.00   52
 33  \w   -176.00 -82.00   0.50    0.48    -- -106.00 -69.00 -16.86  188
 34  \w   -175.00 -77.00   0.50    0.48    -- -106.00 -77.00  60.00  196
 35  \w   -173.00 -82.00   0.50    0.48    -- -106.00 -65.00  24.26  182
 36  \w   -106.00 -77.00   0.50    0.48    -- -106.00 -79.00  35.95   58
 37  \w   -177.00-151.00   0.50    0.48    -- -106.00 -77.00   0.00   52
 38  \w   -113.00 -79.00   0.50    0.48    -- -106.00 -77.00   0.00   68
 39  \w   -102.00 -77.00   0.50    0.48    -- -106.00 -76.00 -37.73   50
 40  \w   -101.00 -76.00   0.50    0.48    -- -106.00 -79.00 -22.45   50
 41  \w   -156.00-130.00   0.50    0.48    -- -106.00 -76.00 -37.73   52
 42  \w   -125.00 -42.00   0.50    0.48    -- -106.00  57.00-120.00  166
 43  \w   -107.00 -78.00   0.50    0.48    -- -106.00 -75.00  17.43   58
 44  \w   -167.00 -80.00   0.50    0.48    -- -106.00 -71.00   3.31  174
 45  \w   -166.00-128.00   0.50    0.48    -- -106.00 -77.00  90.00   76
 46  \w   -147.00-110.00   0.50    0.48    -- -106.00 -75.00  17.43   74
 47  \w   -177.00 -93.00   0.50    0.48    -- -106.00 -99.00  90.00  168
 48  \w   -109.00 -50.00   0.50    0.48    -- -106.00  37.00  30.00  118
 49  \w   -168.00 -79.00   0.50    0.48    -- -106.00 -72.00 -72.33  178
 50  \w   -173.00-147.00   0.50    0.48    -- -106.00 -79.00 -22.45   52
 51  \w   -102.00 -77.00   0.50    0.48    -- -106.00 -79.00  28.86   50
 52  \w    -80.00 -35.00   0.50    0.48    -- -106.00 125.00-150.00   90
 53  \w   -112.00 -87.00   0.50    0.48    -- -106.00 125.00 -30.00   50
 54  \w    -66.00 -41.00   0.50    0.48    -- -106.00 125.00 -30.00   50
 55  \w   -170.00-144.00   0.50    0.48    -- -106.00 -79.00  28.86   52
 56  \w   -126.00 -81.00   0.50    0.48    -- -106.00 -75.00 -42.88   90
 57  \w   -103.00 -78.00   0.50    0.48    -- -106.00 -77.00 -30.00   50
 58  \w   -177.00-108.00   0.50    0.48    -- -106.00 -89.00 -36.55  138
 59  \w   -101.00 -76.00   0.50    0.48    -- -106.00 -89.00 -36.55   50
 60  \w   -170.00-145.00   0.50    0.48    -- -106.00 -84.00  73.94   50
 61  \w   -102.00 -77.00   0.50    0.48    -- -106.00 -84.00  73.94   50
 62  \w   -103.00 -77.00   0.50    0.48    -- -106.00 -77.00 -60.00   52
 63  \w   -149.00-113.00   0.50    0.48    -- -106.00 -77.00 -60.00   72
 64  \w   -114.00 -75.00   0.50    0.48    -- -106.00 125.00-120.00   78
 65  \w    -71.00 -40.00   0.50    0.48    -- -106.00  37.00  90.00   62
 66  \w   -104.00 -79.00   0.50    0.48    -- -106.00 -74.00  48.18   50
 67  \w   -103.00 -78.00   0.50    0.48    -- -106.00 -74.00   0.45   50
 68  \w   -103.00 -78.00   0.50    0.48    -- -106.00 -74.00 -18.07   50
 69  \w   -104.00 -79.00   0.50    0.48    -- -106.00 -77.00  17.44   50
 70  \w   -101.00 -76.00   0.50    0.48    -- -106.00 -89.00  74.68   50
 71  \w   -125.00 -34.00   0.50    0.48    -- -106.00  57.00  90.00  182
;
_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      0.0026383000
_diffrn_orient_matrix_UB_12      -0.0387312000
_diffrn_orient_matrix_UB_13      0.0903505000
_diffrn_orient_matrix_UB_21      -0.1032730000
_diffrn_orient_matrix_UB_22      0.0039229000
_diffrn_orient_matrix_UB_23      -0.0087193000
_diffrn_orient_matrix_UB_31      -0.0040326000
_diffrn_orient_matrix_UB_32      -0.1263099000
_diffrn_orient_matrix_UB_33      -0.0279267000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            54897
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.170
_diffrn_reflns_theta_min         4.672
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.484
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62426
_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    1.133
_exptl_crystal_description       prism
_exptl_crystal_F_000             1044
_exptl_crystal_size_max          0.482
_exptl_crystal_size_mid          0.275
_exptl_crystal_size_min          0.129
_refine_diff_density_max         0.213
_refine_diff_density_min         -0.289
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     436
_refine_ls_number_reflns         5760
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0581
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0791P)^2^+0.3871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1437
_refine_ls_wR_factor_ref         0.1500
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5029
_reflns_number_total             5760
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_201027_2
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_original_formula_sum        'C18 H19 N0.50'
_cod_database_code               1570625
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C17 H18 N2'
_reflns_odcompleteness_completeness 99.95
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C0AA) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C9)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
3. Others
 Sof(H00C)=Sof(H00D)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C0AA)=Sof(H0AB)=
 Sof(H0AC)=Sof(H0AD)=1-FVAR(1)
 Sof(H00A)=Sof(H00B)=Sof(C00R)=Sof(H00H)=Sof(H00R)=Sof(C00S)=Sof(H00S)=
 Sof(H00T)=Sof(C00T)=Sof(H00U)=Sof(H00V)=Sof(C00U)=Sof(H00W)=Sof(H00X)=
 Sof(C00V)=Sof(H00Y)=Sof(H)=Sof(C00W)=Sof(H00Z)=Sof(HA)=Sof(C00X)=Sof(H00)=
 Sof(HB)=Sof(C00Y)=Sof(H0AA)=Sof(HC)=Sof(C00Z)=Sof(H1AA)=Sof(HD)=Sof(C010)=
 Sof(H01A)=Sof(H01B)=Sof(C011)=Sof(H01C)=Sof(H01D)=Sof(H01E)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C00H(H00A,H00B), C00H(H00C,H00D), C00R(H00H,H00R), C00S(H00S,H00T), C00T(H00U,
 H00V), C00U(H00W,H00X), C00V(H00Y,H), C00W(H00Z,HA), C00X(H00,HB), C00Y(H0AA,
 HC), C00Z(H1AA,HD), C010(H01A,H01B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C11(H11A,H11B)
4.b Aromatic/amide H refined with riding coordinates:
 C004(H004), C00E(H00E), C00F(H00F), C00G(H00G), C00I(H00I), C00J(H00J),
 C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P),
 C00Q(H00Q)
4.c Idealised Me refined as rotating group:
 C011(H01C,H01D,H01E), C0AA(H0AB,H0AC,H0AD)
;
_shelx_res_checksum              5727
_shelx_hkl_checksum              41909
_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 2.416
_oxdiff_exptl_absorpt_empirical_full_min 0.534