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_7121235
_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_absolute_configuration unk
_chemical_formula_moiety         'C24 H16 F2 N2'
_chemical_formula_sum            'C24 H16 F2 N2'
_chemical_formula_weight         370.39
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_symmetry_space_group_name_Hall  'P 32'
_symmetry_space_group_name_H-M   'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_tro67
_audit_creation_date
;
'Thu Apr 10 16:53:26 2014'
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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
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   28.9605(16)
_cell_length_b                   28.9605(16)
_cell_length_c                   5.6946(3)
_cell_measurement_reflns_used    3963
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      19.2960
_cell_measurement_theta_min      3.6490
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_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
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'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
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_computing_structure_solution    'SHELXD (Sheldrick, 2000-2008)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
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_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
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_diffrn_measured_fraction_theta_full 0.998
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_diffrn_measurement_details
;
  1 omega  -49.00    1.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.5380   77.0000 -120.0000 100

  2 omega  -78.00   10.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.5380  -77.0000   30.0000 176

  3 omega  -49.00  -23.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.5380   77.0000   60.0000 52

  4 omega  -50.00   11.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.5380   79.0000  109.9258 122

  5 omega    8.00   51.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.5380   77.0000   60.0000 86

  6 omega   24.00   49.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000 -150.0000 50

  7 omega  -23.00   49.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000  -60.0000 144

  8 omega   -3.00   84.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000  -30.0000 174

  9 omega  -50.00   12.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000 -180.0000 124

 10 omega  -52.00   49.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000   30.0000 202

 11 omega   -1.00   80.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000 -180.0000 162

 12 omega    2.00   59.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   77.0000 -120.0000 114

 13 omega  -25.00   74.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   19.0000  150.0000 198

 14 omega   24.00   49.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000  -30.0000 50

 15 omega   21.00   50.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -79.0000  155.8710 58

 16 omega  -50.00    4.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -57.0000  -90.0000 108

 17 omega  -25.00   92.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   19.0000  -30.0000 234

;
_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_UB_11      0.0050120000
_diffrn_orient_matrix_UB_12      0.0266052000
_diffrn_orient_matrix_UB_13      -0.0010607000
_diffrn_orient_matrix_UB_21      -0.0276806000
_diffrn_orient_matrix_UB_22      -0.0094778000
_diffrn_orient_matrix_UB_23      0.0128754000
_diffrn_orient_matrix_UB_31      0.0029207000
_diffrn_orient_matrix_UB_32      0.0012136000
_diffrn_orient_matrix_UB_33      0.1238788000
_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  0.1830
_diffrn_reflns_av_unetI/netI     0.1180
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_number            76183
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.155
_diffrn_reflns_theta_max         25.155
_diffrn_reflns_theta_min         3.249
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  0.987
_exptl_absorpt_correction_T_min  0.956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       needle
_exptl_crystal_F_000             1728
_exptl_crystal_size_max          0.291
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 2389 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(7)
_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     758
_refine_ls_number_reflns         9873
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.1034
_refine_ls_R_factor_gt           0.0742
_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^)+(0.0362P)^2^+0.1453P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1207
_refine_ls_wR_factor_ref         0.1330
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                7376
_reflns_number_total             9873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc00478a2.cif
_cod_data_source_block           ga_tro67
_cod_depositor_comments
'Adding full bibliography for 7121234--7121240.cif.'
_cod_original_cell_volume        4136.3(5)
_cod_database_code               7121235
_audit_block_refno               2008
_audit_block_usercomment         'tr1218, needle, colourless'
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.973
_shelxl_version_number           2018/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.921(2)
 0.079(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24),
  C34(H34), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C42(H42),
 C43(H43), C45(H45), C46(H46), C47(H47), C48(H48), C50(H50), C51(H51), C53(H53),
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 C72(H72), C73(H73), C75(H75), C76(H76), C77(H77), C78(H78), C80(H80), C81(H81),
  C83(H83), C84(H84)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_res_checksum              52712
_cell_oxdiff_length_a            28.9472(11)
_cell_oxdiff_length_b            28.9603(13)
_cell_oxdiff_length_c            5.6949(2)
_cell_oxdiff_angle_alpha         90.001(4)
_cell_oxdiff_angle_beta          90.001(3)
_cell_oxdiff_angle_gamma         119.958(4)
_cell_oxdiff_volume              4136.3(3)
_cell_oxdiff_measurement_reflns_used 3963
_reflns_odcompleteness_completeness 87.99
_reflns_odcompleteness_theta     26.32
_reflns_odcompleteness_iscentric 1