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_1570629
_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         'C84 H92 S2'
_chemical_formula_sum            'C84 H92 S2'
_chemical_formula_weight         1165.69
_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             2021-01-25
_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                 112.159(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.0314(4)
_cell_length_b                   12.4409(2)
_cell_length_c                   26.6247(4)
_cell_measurement_reflns_used    38469
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      73.9500
_cell_measurement_theta_min      3.4360
_cell_volume                     6758.6(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      173(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    -54.00  32.00   0.50    0.47    --  -42.80  49.00  37.00  172
  2  \w    -19.00  17.00   0.50    0.47    --   42.80 -49.00-109.00   72
  3  \w     26.00  51.00   0.50    1.93    --   76.50 -49.00-109.00   50
  4  \w     12.00  64.00   0.50    0.47    --   42.80 -57.00-180.00  104
  5  \w     14.00  89.00   0.50    0.47    --   42.80-125.00-180.00  150
  6  \w     69.00  94.00   0.50    0.47    --   42.80  49.00  37.00   50
  7  \w     97.00 123.00   0.50    1.93    --   76.50  49.00  37.00   52
  8  \w     87.00 116.00   0.50    0.47    --   42.80 125.00  90.00   58
  9  \w     71.00 126.00   0.50    1.93    --   76.50 125.00 -60.00  110
 10  \w    -55.00 -30.00   0.50    1.93    -- -106.00  19.00-120.00   50
 11  \w    -90.00 -32.00   0.50    1.93    -- -106.00  77.00 -90.00  116
 12  \w    -72.00 -32.00   0.50    1.93    -- -106.00 125.00-180.00   80
 13  \w    -84.00 -58.00   0.50    1.93    -- -106.00 125.00-150.00   52
 14  \w    -91.00 -32.00   0.50    1.93    -- -106.00  77.00-120.00  118
 15  \w    -85.00 -59.00   0.50    1.93    -- -106.00  49.00  37.00   52
 16  \w    -72.00 -40.00   0.50    1.93    -- -106.00  77.00  60.00   64
 17  \w    -95.00 -69.00   0.50    1.93    -- -106.00 125.00  60.00   52
 18  \w    -88.00 -62.00   0.50    1.93    -- -106.00  77.00  30.00   52
 19  \w   -111.00 -33.00   0.50    1.93    -- -106.00 125.00  90.00  156
 20  \w    -95.00 -10.00   0.50    0.47    --  -42.80 125.00  30.00  170
 21  \w   -117.00 -92.00   0.50    1.93    -- -106.00 125.00-180.00   50
 22  \w   -116.00 -32.00   0.50    1.93    -- -106.00 125.00-120.00  168
 23  \w   -107.00 -32.00   0.50    1.93    -- -106.00 125.00  30.00  150
 24  \w   -126.00 -82.00   0.50    1.93    -- -106.00  77.00  60.00   88
 25  \w   -125.00 -62.00   0.50    1.93    -- -106.00  57.00 150.00  126
 26  \w   -127.00 -94.00   0.50    1.93    -- -106.00 139.00 160.14   66
 27  \w   -129.00 -34.00   0.50    1.93    -- -106.00 142.00  80.73  190
 28  \w   -124.00 -38.00   0.50    1.93    -- -106.00 134.00 -83.91  172
 29  \w   -115.00 -63.00   0.50    1.93    -- -106.00 125.00 -90.00  104
 30  \w   -127.00 -79.00   0.50    1.93    -- -106.00  57.00 -90.00   96
 31  \w   -128.00-102.00   0.50    1.93    -- -106.00  19.00-120.00   52
 32  \w   -126.00 -61.00   0.50    1.93    -- -106.00  57.00-120.00  130
 33  \w   -127.00 -33.00   0.50    1.93    -- -106.00 139.00 -32.03  188
 34  \w   -135.00-110.00   0.50    1.93    -- -106.00  77.00-150.00   50
 35  \w   -131.00 -99.00   0.50    1.93    -- -106.00 145.00  -3.03   64
 36  \w   -135.00 -91.00   0.50    1.93    -- -106.00  77.00  30.00   88
 37  \w   -117.00 -20.00   0.50    0.47    --  -42.80 -49.00-109.00  194
 38  \w   -112.00 -78.00   0.50    0.47    --  -42.80-125.00-150.00   68
 39  \w   -139.00-113.00   0.50    1.93    -- -106.00 -49.00-109.00   52
 40  \w   -137.00-111.00   0.50    1.93    -- -106.00 -57.00 -90.00   52
 41  \w   -141.00 -84.00   0.50    1.93    -- -106.00 -99.00 -30.00  114
 42  \w   -127.00 -77.00   0.50    1.93    -- -106.00 -77.00  30.00  100
 43  \w   -177.00 -98.00   0.50    1.93    -- -106.00 -57.00-150.00  158
 44  \w   -177.00 -90.00   0.50    1.93    -- -106.00 -57.00-180.00  174
 45  \w   -176.00-150.00   0.50    1.93    -- -106.00 -57.00 -90.00   52
 46  \w   -166.00-141.00   0.50    1.93    -- -106.00 -77.00  30.00   50
 47  \w   -175.00 -83.00   0.50    1.93    -- -106.00 -37.00  60.00  184
 48  \w   -177.00 -86.00   0.50    1.93    -- -106.00 -37.00  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      -0.0038246000
_diffrn_orient_matrix_UB_12      -0.1066226000
_diffrn_orient_matrix_UB_13      -0.0304744000
_diffrn_orient_matrix_UB_21      0.0753906000
_diffrn_orient_matrix_UB_22      -0.0055881000
_diffrn_orient_matrix_UB_23      0.0221629000
_diffrn_orient_matrix_UB_31      -0.0001791000
_diffrn_orient_matrix_UB_32      -0.0627383000
_diffrn_orient_matrix_UB_33      0.0498410000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1631
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            100922
_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         74.927
_diffrn_reflns_theta_min         3.418
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.039
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85939
_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    1.146
_exptl_crystal_description       prism
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.146
_exptl_crystal_size_min          0.092
_refine_diff_density_max         1.324
_refine_diff_density_min         -0.725
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.384
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     890
_refine_ls_number_reflns         13697
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.382
_refine_ls_R_factor_all          0.1079
_refine_ls_R_factor_gt           0.0946
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2904
_refine_ls_wR_factor_ref         0.3334
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10865
_reflns_number_total             13697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_210123_1
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_database_code               1570629
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C84 S2 H92'
_reflns_odcompleteness_completeness 99.92
_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. Rigid bond restraints
 C67, C66, C65, C64, C63, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Rigid body (RIGU) restrains
 C62, C63, C64, C65, C66, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H61C)=Sof(H61D)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C67)=Sof(H67A)=
 Sof(H67B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C64)=
 Sof(H64A)=Sof(H64B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 1-FVAR(1)
 Sof(H61A)=Sof(H61B)=Sof(C01U)=Sof(H01E)=Sof(H01F)=Sof(C01V)=Sof(H01G)=
 Sof(H01H)=Sof(C01X)=Sof(H01K)=Sof(H01L)=Sof(H01M)=Sof(C020)=Sof(H02A)=
 Sof(H02B)=Sof(C021)=Sof(H02C)=Sof(H02D)=Sof(C022)=Sof(H02E)=Sof(H02F)=
 Sof(C023)=Sof(H02G)=Sof(H02H)=FVAR(1)
 Fixed Sof: H02K(0.5) H02L(0.5) H02I(0.5) H02J(0.5) C7AA(0.5) H7AA(0.5)
 H7AB(0.5) C4AA(0.5) H4AA(0.5) H4AB(0.5) H4AC(0.5) C5AA(0.5) H5AA(0.5)
 H5AB(0.5) C6AA(0.5) H6AA(0.5) H6AB(0.5) C0AA(0.5) H0AA(0.5) H0AB(0.5)
 C1BA(0.5) H1BA(0.5) H1BB(0.5) C3BA(0.5) H3BA(0.5) H3BB(0.5) H3BC(0.5)
 C9AA(0.5) H9AA(0.5) H9AB(0.5) C2BA(0.5) H2BA(0.5) H2BB(0.5) C0BA(0.5)
 H0BA(0.5) H0BB(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C54(H54A,H54B), C55(H55A,H55B), C58(H58A,H58B), C53(H53A,
 H53B), C57(H57A,H57B), C59(H59A,H59B), C01Q(H01A,H01B), C01R(H01C,H01D),
 C61(H61A,H61B), C61(H61C,H61D), C01U(H01E,H01F), C01V(H01G,H01H), C01W(H01I,
 H01J), C01Y(H01N,H01O), C01Z(H01P,H01Q), C020(H02A,H02B), C021(H02C,H02D),
 C022(H02E,H02F), C023(H02G,H02H), C029(H02K,H02L), C029(H02I,H02J), C02A(H02M,
 H02N), C7AA(H7AA,H7AB), C5AA(H5AA,H5AB), C6AA(H6AA,H6AB), C0AA(H0AA,H0AB),
 C67(H67A,H67B), C66(H66A,H66B), C65(H65A,H65B), C64(H64A,H64B), C63(H63A,H63B),
  C62(H62A,H62B), C3AA(H3AA,H3AB), C1AA(H1AA,H1AB), C2AA(H2AA,H2AB), C1BA(H1BA,
 H1BB), C9AA(H9AA,H9AB), C2BA(H2BA,H2BB), C0BA(H0BA,H0BB)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C16(H16), C17(H17), C13(H13), C42(H42), C30(H30), C3(H3), C6(H6),
 C49(H49), C24(H24), C39(H39), C2(H2), C27(H27), C36(H36), C51(H51), C1(H1),
 C25(H25), C33(H33), C43(H43), C26(H26), C52(H52), C32(H32), C45(H45), C37(H37)
5.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C01X(H01K,H01L,H01M), C4AA(H4AA,H4AB,H4AC), C68(H68A,
 H68B,H68C), C8AA(H8AA,H8AB,H8AC), C3BA(H3BA,H3BB,H3BC)
;
_shelx_res_checksum              34180
_shelx_hkl_checksum              93035
_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 2.825
_oxdiff_exptl_absorpt_empirical_full_min 0.469