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_1570628
_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         'C42 H24 S, 2(C H Cl3)'
_chemical_formula_sum            'C44 H26 Cl6 S'
_chemical_formula_weight         799.41
_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             2021-02-12
_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                 98.248(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2354(4)
_cell_length_b                   14.2615(4)
_cell_length_c                   20.8253(6)
_cell_measurement_reflns_used    12940
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.9840
_cell_measurement_theta_min      2.2940
_cell_volume                     3596.33(19)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.798
_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      7.00  67.00   0.50    6.87    --   -8.74  46.00  74.00  120
  2  \w    -25.00   1.00   0.50    6.87    --   -8.74 -99.00-120.00   52
  3  \w    -26.00  28.00   0.50    6.87    --   -8.74 -99.00   0.00  108
  4  \w    -19.00  31.00   0.50    6.87    --   -8.74 -99.00 150.00  100
  5  \w    -84.00   5.00   0.50    6.87    --   -8.74 -46.00 -75.00  178
;
_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      -0.0477635000
_diffrn_orient_matrix_UB_12      -0.0285101000
_diffrn_orient_matrix_UB_13      -0.0016895000
_diffrn_orient_matrix_UB_21      0.0050558000
_diffrn_orient_matrix_UB_22      -0.0002099000
_diffrn_orient_matrix_UB_23      0.0343793000
_diffrn_orient_matrix_UB_31      -0.0334586000
_diffrn_orient_matrix_UB_32      0.0407564000
_diffrn_orient_matrix_UB_33      -0.0010173000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0529
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.798
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            28944
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.798
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.211
_diffrn_reflns_theta_min         1.976
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.570
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67386
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.476
_exptl_crystal_description       block
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.199
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.858
_refine_diff_density_min         -1.014
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         8538
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0759
_refine_ls_R_factor_gt           0.0564
_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^)+(0.0923P)^2^+3.1146P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1565
_refine_ls_wR_factor_ref         0.1728
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6525
_reflns_number_total             8538
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05977d2.cif
_cod_data_source_block           kato_210212_1
_cod_depositor_comments
'Adding full bibliography for 1570621--1570629.cif.'
_cod_database_code               1570628
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C44 H26 S Cl6'
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C2EA(H2EA), C3EA(H3EA)
2.b Aromatic/amide H refined with riding coordinates:
 C8AA(H8AA), C6BA(H6BA), C7BA(H7BA), C8BA(H8BA), C1CA(H1CA), C3CA(H3CA),
 C4CA(H4CA), C5CA(H5CA), C6CA(H6CA), C7CA(H7CA), C8CA(H8CA), C9CA(H9CA),
 C0DA(H0DA), C1DA(H1DA), C2DA(H2DA), C3DA(H3DA), C4DA(H4DA), C5DA(H5DA),
 C6DA(H6DA), C7DA(H7DA), C8DA(H8DA), C9DA(H9DA), C0EA(H0EA), C1EA(H1EA)
;
_shelx_res_checksum              19365
_shelx_hkl_checksum              96267
_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 1.628
_oxdiff_exptl_absorpt_empirical_full_min 0.680