Isolation and structural characterization of a titanacyclopropane as key intermediate in the double aryl Grignard addition to 2-(arylethynyl)pyridine derivatives.
Foschi, Francesco; Roth, Torsten; Enders, Markus; Wadepohl, Hubert; Clot, Eric; Gade, Lutz H.; Chemical communications (Cambridge, England) 54 (2018) 2228–2231; doi:10.1039/c8cc00478a

data_7121239
_publ_section_title
;
 Isolation and structural characterization of a titanacyclopropane as key
 intermediate in the double aryl Grignard addition to
 2-(arylethynyl)pyridine derivatives.
;
_journal_issue                   18
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2228
_journal_page_last               2231
_journal_paper_doi               10.1039/c8cc00478a
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C45 H27 F6 N'
_chemical_formula_sum            'C45 H27 F6 N'
_chemical_formula_weight         695.67
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ff20
_audit_creation_date             2017-10-25
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:44:14 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-17 deposited with the CCDC.
2018-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.803(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
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_cell_length_b                   10.2929(3)
_cell_length_c                   20.6155(5)
_cell_measurement_reflns_used    10025
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      29.6050
_cell_measurement_theta_min      2.5380
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_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
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_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -43.00  57.00   0.50   20.00    --   26.87 -77.00 -30.00  200
  2  \w    -20.00  69.00   0.50   20.00    --   26.87 -99.00 150.00  178
  3  \w    -42.00  48.00   0.50   20.00    --   26.87 -57.00-150.00  180
  4  \w      6.00  96.00   0.50   20.00    --   26.87  57.00-180.00  180
  5  \w    -42.00  48.00   0.50   20.00    --   26.87 -57.00  30.00  180
  6  \w     -3.00  97.00   0.50   20.00    --   26.87  77.00 -90.00  200
  7  \w     -3.00  97.00   0.50   20.00    --   26.87  77.00  60.00  200
  8  \w      6.00  96.00   0.50   20.00    --   26.87  57.00   0.00  180
  9  \w      6.00  67.00   0.50   20.00    --   26.87  57.00-120.00  122
 10  \w    -20.00  69.00   0.50   20.00    --   26.87 -99.00 -60.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0378916000
_diffrn_orient_matrix_UB_12      0.0069613000
_diffrn_orient_matrix_UB_13      0.0167540000
_diffrn_orient_matrix_UB_21      -0.0073493000
_diffrn_orient_matrix_UB_22      -0.0676652000
_diffrn_orient_matrix_UB_23      -0.0031496000
_diffrn_orient_matrix_UB_31      0.0211436000
_diffrn_orient_matrix_UB_32      -0.0110293000
_diffrn_orient_matrix_UB_33      0.0298975000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0795
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            73029
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.545
_diffrn_reflns_theta_min         2.212
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.101
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.804
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
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    1.351
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1432
_exptl_crystal_size_max          0.144
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.070
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     550
_refine_ls_number_reflns         10459
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0967
_refine_ls_R_factor_gt           0.0574
_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^)+(0.0352P)^2^+1.9980P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1125
_refine_ls_wR_factor_ref         0.1288
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6833
_reflns_number_total             10459
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc00478a2.cif
_cod_data_source_block           ga_ff20
_cod_depositor_comments
'Adding full bibliography for 7121234--7121240.cif.'
_cod_original_cell_volume        3419.27(14)
_cod_database_code               7121239
_audit_block_refno               2966
_audit_block_usercomment         'FF459, irregular, colourless'
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.990
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_shelxl_version_number           2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
;
_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 1.092
_oxdiff_exptl_absorpt_empirical_full_min 0.911
_shelx_res_checksum              11226
_cell_oxdiff_length_a            16.1184(6)
_cell_oxdiff_length_b            10.2930(2)
_cell_oxdiff_length_c            20.6114(8)
_cell_oxdiff_angle_alpha         90.000(3)
_cell_oxdiff_angle_beta          90.774(3)
_cell_oxdiff_angle_gamma         90.006(3)
_cell_oxdiff_volume              3419.3(2)
_cell_oxdiff_measurement_reflns_used 10025