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_7121237
_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 H33 N, 0.5(C5 H12)'
_chemical_formula_sum            'C47.5 H39 N'
_chemical_formula_weight         623.79
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ff22
_audit_creation_date             2017-11-22
_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                 107.3819(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.51974(11)
_cell_length_b                   9.24966(5)
_cell_length_c                   22.74222(19)
_cell_measurement_reflns_used    56452
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.8480
_cell_measurement_theta_min      3.7810
_cell_volume                     3517.12(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2014 (Giacovazzo et al., 2014)'
_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 0.997
_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    -72.00  26.00   1.00    1.00    --    0.00 -38.00  90.00   98
  2  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00 120.00   90
  3  \w    -26.00  72.00   1.00    1.00    --    0.00  38.00 -60.00   98
  4  \w    -69.00  21.00   1.00    1.00    --    0.00 -57.00 -30.00   90
  5  \w    -42.00   5.00   1.00    1.00    --   10.00 117.00  -7.56   47
  6  \w    -35.00  -1.00   1.00    1.00    --   22.00 124.00 -84.15   34
  7  \w    -22.00   5.00   1.00    4.00    --   30.00 117.00  93.35   27
  8  \w      5.00  32.00   1.00    4.00    --   42.00  90.00 178.70   27
  9  \w      5.00  32.00   1.00    4.00    --   42.00  90.00  26.50   27
 10  \w      5.00  32.00   1.00    4.00    --   42.00  90.00 -82.97   27
 11  \w     13.00  45.00   1.00    4.00    --   46.00  82.00-134.42   32
 12  \w     12.00  38.00   1.00    4.00    --   46.00  84.00 -36.66   26
 13  \w     13.00  40.00   1.00    4.00    --   46.00  83.00  83.48   27
 14  \w     12.00  38.00   1.00    4.00    --   46.00  84.00 137.07   26
 15  \w     12.00  38.00   1.00    4.00    --   46.00  84.00 -84.40   26
 16  \w     13.00  40.00   1.00    4.00    --   46.00  83.00  27.55   27
 17  \w     21.00 120.00   1.00    4.00    --   50.00  76.00  68.75   99
 18  \w     17.00  45.00   1.00    4.00    --   50.00  82.00 -13.42   28
 19  \w     18.00  46.00   1.00    4.00    --   50.00  81.00 119.50   28
 20  \w     17.00  45.00   1.00    4.00    --   50.00  82.00-177.85   28
 21  \w     17.00  45.00   1.00    4.00    --   50.00  82.00  34.00   28
 22  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -30.00  100
 23  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-120.00  100
 24  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  90.00  100
 25  \w     24.00 124.00   1.00    4.00    --   54.00  77.00   0.00  100
 26  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -90.00  100
 27  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 120.00  100
 28  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00  30.00   90
 29  \w     24.00 124.00   1.00    4.00    --   54.00  77.00-150.00  100
 30  \w     23.00 111.00   1.00    4.00    --   54.00-125.00-150.00   88
 31  \w    -15.00  75.00   1.00    4.00    --   54.00 -57.00 -60.00   90
 32  \w     25.00 124.00   1.00    4.00    --   54.00  75.00 145.70   99
 33  \w      1.00  96.00   1.00    4.00    --   54.00 -99.00-150.00   95
 34  \w     24.00 124.00   1.00    4.00    --   54.00  77.00  30.00  100
 35  \w     24.00 124.00   1.00    4.00    --   54.00  77.00 -60.00  100
 36  \w     35.00 125.00   1.00    4.00    --   58.00  64.00 -35.86   90
 37  \w     34.00 126.00   1.00    4.00    --   58.00  68.00 144.39   92
 38  \w     29.00 128.00   1.00    4.00    --   58.00  75.00  29.59   99
 39  \w     31.00 127.00   1.00    4.00    --   58.00  71.00  61.73   96
 40  \w     35.00 126.00   1.00    4.00    --   58.00  66.00  85.44   91
 41  \w     28.00 128.00   1.00    4.00    --   58.00  77.00 167.92  100
 42  \w     35.00 131.00   1.00    4.00    --   62.00  72.00  -3.57   96
 43  \w     37.00 130.00   1.00    4.00    --   62.00  69.00-129.42   93
 44  \w     39.00 130.00   1.00    4.00    --   62.00  65.00-170.05   91
 45  \w     41.00 131.00   1.00    4.00    --   62.00  54.00 -57.75   90
 46  \w     33.00 132.00   1.00    4.00    --   62.00  76.00 150.25   99
 47  \w     37.00 136.00   1.00    4.00    --   66.00  76.00  24.37   99
 48  \w     41.00 134.00   1.00    4.00    --   66.00  69.00  55.28   93
 49  \w     37.00 136.00   1.00    4.00    --   66.00  76.00  91.35   99
 50  \w     39.00 135.00   1.00    4.00    --   66.00  71.00-154.18   96
 51  \w     44.00 134.00   1.00    4.00    --   66.00  63.00 -68.49   90
 52  \w     45.00 135.00   1.00    4.00    --   66.00  56.00-176.36   90
 53  \w     46.00 138.00   1.00    4.00    --   70.00  67.00  70.46   92
 54  \w     48.00 138.00   1.00    4.00    --   70.00  61.00 -96.93   90
 55  \w     45.00 142.00   1.00    4.00    --   70.00  41.00   5.88   97
 56  \w     42.00 140.00   1.00    4.00    --   70.00  74.00-146.12   98
 57  \w     44.00 144.00   1.00    4.00    --   74.00  77.00-143.80  100
 58  \w     53.00 143.00   1.00    4.00    --   74.00  55.00 179.59   90
 59  \w     46.00 144.00   1.00    4.00    --   74.00  74.00-177.70   98
 60  \w     49.00 142.00   1.00    4.00    --   74.00  69.00 -86.32   93
 61  \w     55.00 146.00   1.00    4.00    --   78.00  65.00 127.83   91
 62  \w     57.00 147.00   1.00    4.00    --   78.00  58.00 -29.71   90
 63  \w     49.00 148.00   1.00    4.00    --   78.00  75.00  71.58   99
 64  \w     48.00 148.00   1.00    4.00    --   78.00  77.00  -4.02  100
 65  \w     48.00 148.00   1.00    4.00    --   78.00  77.00 166.80  100
 66  \w     49.00 148.00   1.00    4.00    --   78.00  75.00 129.00   99
 67  \w     60.00 150.00   1.00   10.00    --   82.00  61.00-175.37   90
 68  \w     59.00 153.00   1.00   10.00    --   82.00  48.00  38.56   94
 69  \w     55.00 151.00   1.00   10.00    --   82.00  71.00-140.33   96
 70  \w     55.00 151.00   1.00   10.00    --   82.00  71.00  47.28   96
 71  \w     54.00 152.00   1.00   10.00    --   82.00  74.00  87.96   98
 72  \w     58.00 156.00   1.00   10.00    --   86.00  74.00-155.58   98
 73  \w     56.00 156.00   1.00   10.00    --   86.00  77.00  17.57  100
 74  \w     59.00 155.00   1.00   10.00    --   86.00  72.00 -38.82   96
 75  \w     57.00 156.00   1.00   10.00    --   86.00  75.00 -90.21   99
 76  \w     57.00 156.00   1.00   10.00    --   86.00  76.00 -45.91   99
 77  \w     61.00 160.00   1.00   10.00    --   90.00  75.00   8.45   99
 78  \w     61.00 160.00   1.00   10.00    --   90.00  76.00 157.31   99
 79  \w     62.00 159.00   1.00   10.00    --   90.00  73.00-139.41   97
 80  \w     61.00 160.00   1.00   10.00    --   90.00  76.00 -25.36   99
 81  \w     65.00 164.00   1.00   10.00    --   94.00  75.00-111.25   99
 82  \w     76.00 166.00   1.00   10.00    --   98.00  61.00 146.63   90
 83  \w     77.00 167.00   1.00   10.00    --   98.00  55.00 143.70   90
 84  \w     75.00 171.00   1.00   10.00    --  102.00  71.00  60.88   96
 85  \w     79.00 173.00   1.00   10.00    --  102.00  48.00 -29.19   94
 86  \w     80.00 177.00   1.00   10.00    --  108.00  73.00 145.96   97
 87  \w     85.00 176.00   1.00   10.00    --  108.00  65.00-100.72   91
 88  \w     81.00 177.00   1.00   10.00    --  108.00  71.00 -67.83   96
 89  \w     36.00 116.00   1.00   10.00    --  108.00-111.00-180.00   80
 90  \w     82.00 178.00   1.00   10.00    --  108.00  38.00 150.00   96
 91  \w     36.00 116.00   1.00   10.00    --  108.00-111.00  30.00   80
 92  \w     85.00 175.00   1.00   10.00    --  108.00  64.00-180.00   90
 93  \w     85.00 175.00   1.00   10.00    --  108.00  64.00  90.00   90
 94  \w     85.00 175.00   1.00   10.00    --  108.00  64.00 -30.00   90
 95  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 150.00  100
 96  \w     78.00 178.00   1.00   10.00    --  108.00  77.00-150.00  100
 97  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 -60.00  100
 98  \w     78.00 178.00   1.00   10.00    --  108.00  77.00  60.00  100
 99  \w     78.00 178.00   1.00   10.00    --  108.00  77.00  30.00  100
100  \w     78.00 178.00   1.00   10.00    --  108.00  77.00-120.00  100
101  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 -90.00  100
102  \w     78.00 178.00   1.00   10.00    --  108.00  77.00   0.00  100
103  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 120.00  100
104  \w     78.00 178.00   1.00   10.00    --  108.00  77.00-180.00  100
105  \w     36.00 116.00   1.00   10.00    --  108.00-111.00 120.00   80
106  \w    100.00 178.00   1.00   10.00    --  108.00 111.00 150.00   78
107  \w     36.00 146.00   1.00   10.00    --  108.00 -92.00-180.00  110
108  \w     85.00 175.00   1.00   10.00    --  108.00  64.00  30.00   90
109  \w     85.00 175.00   1.00   10.00    --  108.00  64.00-150.00   90
110  \w     85.00 175.00   1.00   10.00    --  108.00  64.00   0.00   90
111  \w     85.00 175.00   1.00   10.00    --  108.00  64.00 120.00   90
112  \w     78.00 178.00   1.00   10.00    --  108.00  77.00  90.00  100
113  \w    100.00 178.00   1.00   10.00    --  108.00 111.00  30.00   78
114  \w     78.00 178.00   1.00   10.00    --  108.00  77.00 -30.00  100
115  \w    100.00 178.00   1.00   10.00    --  108.00 111.00-180.00   78
116  \w     36.00 146.00   1.00   10.00    --  108.00 -92.00 120.00  110
117  \w     82.00 178.00   1.00   10.00    --  108.00  38.00 120.00   96
118  \w     36.00 116.00   1.00   10.00    --  108.00-111.00   0.00   80
119  \w     82.00 178.00   1.00   10.00    --  108.00  38.00  60.00   96
120  \w     82.00 178.00   1.00   10.00    --  108.00  38.00 -30.00   96
121  \w     82.00 178.00   1.00   10.00    --  108.00  38.00-120.00   96
122  \w     85.00 175.00   1.00   10.00    --  108.00  64.00-120.00   90
123  \w    100.00 178.00   1.00   10.00    --  108.00 111.00 -30.00   78
124  \w     80.00 178.00   1.00   10.00    --  108.00  74.00 -19.83   98
125  \f      0.00  97.00   1.00    1.00   0.00   0.00 -40.00    --    97
126  \f      0.00 270.00   1.00    0.20   0.00   0.00   0.00    --   270
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0779749000
_diffrn_orient_matrix_UB_12      -0.0063661000
_diffrn_orient_matrix_UB_13      0.0180867000
_diffrn_orient_matrix_UB_21      0.0085173000
_diffrn_orient_matrix_UB_22      -0.1653256000
_diffrn_orient_matrix_UB_23      0.0071041000
_diffrn_orient_matrix_UB_31      0.0483596000
_diffrn_orient_matrix_UB_32      0.0189206000
_diffrn_orient_matrix_UB_33      0.0682671000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0134
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            175052
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.926
_diffrn_reflns_theta_min         3.789
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.508
_exptl_absorpt_correction_T_max  1.155
_exptl_absorpt_correction_T_min  0.924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
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    1.178
_exptl_crystal_description       plate
_exptl_crystal_F_000             1324
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.698
_refine_diff_density_min         -0.668
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         6766
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0497
_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^)+(0.0468P)^2^+2.4013P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1152
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6216
_reflns_number_total             6766
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc00478a2.cif
_cod_data_source_block           ga_ff22
_cod_depositor_comments
'Adding full bibliography for 7121234--7121240.cif.'
_cod_original_formula_sum        'C47.50 H39 N'
_cod_database_code               7121237
_audit_block_refno               2982
_audit_block_usercomment         'FF465, plate, colourless'
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.951
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C81-C82 = C84-C85
 1.5 with sigma of 0.01
 C82-C83 = C83-C84
 1.5 with sigma of 0.01
 C81-C83 = C82-C84 = C83-C85
 2.53 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C81, C82, C83, C84
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) C82(0.5) H82A(0.5)
 H82B(0.5) C83(0.5) H83A(0.5) H83B(0.5) C84(0.5) H84A(0.5) H84B(0.5) C85(0.5)
 H85A(0.5) H85B(0.5) H85C(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B)
5.b Me refined with riding coordinates:
 C81(H81A,H81B,H81C), C85(H85A,H85B,H85C)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24), C25(H25), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43),
  C44(H44), C45(H45)
;
_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
- Detector area scaling
;
_shelx_res_checksum              43813
_cell_oxdiff_length_a            17.5162(3)
_cell_oxdiff_length_b            9.25115(10)
_cell_oxdiff_length_c            22.7404(4)
_cell_oxdiff_angle_alpha         90.0065(11)
_cell_oxdiff_angle_beta          107.3603(14)
_cell_oxdiff_angle_gamma         90.0097(11)
_cell_oxdiff_volume              3517.12(9)
_cell_oxdiff_measurement_reflns_used 56452