Zirconium Hydrazinediido Complexes Derived from Cyclic Hydrazines and Their Role in the Catalytic Synthesis of 1,7-Annulated Indoles
Scholl, Solveig A.; Wadepohl, Hubert; Gade, Lutz H.; Organometallics 32 (2013) 937–; doi:10.1021/om301235d

data_4080049
_publ_section_title
;
 Zirconium Hydrazinediido Complexes Derived from Cyclic Hydrazines and
 Their Role in the Catalytic Synthesis of 1,7-Annulated Indoles
;
_journal_issue                   3
_journal_name_full               Organometallics
_journal_page_first              937
_journal_paper_doi               10.1021/om301235d
_journal_volume                  32
_journal_year                    2013
_chemical_absolute_configuration syn
_chemical_formula_sum            'C15 H19 N'
_chemical_formula_weight         213.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ss43
_audit_creation_date
;
'Thu Oct 25 17:08:02 2012'
;
_audit_creation_method           SHELXL-2012
_audit_update_record             'Fri Nov  9 16:37:51 CET 2012'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.86410(10)
_cell_length_b                   9.08232(10)
_cell_length_c                   16.97075(19)
_cell_measurement_reflns_used    16278
_cell_measurement_temperature    115.00(10)
_cell_measurement_theta_max      71.8830
_cell_measurement_theta_min      4.8652
_cell_volume                     1212.12(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_publication_material
'encif (Wadepohl, 2012); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      115.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            'Agilent EOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega  -24.00    4.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000 -150.0000 28

  2 omega   21.00   66.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   30.0000 45

  3 omega  -20.00   16.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   30.0000 36

  4 omega  -67.00  -40.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000 -150.0000 27

  5 omega   47.00   74.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0000   77.0000   99.2833 27

  6 omega   -9.00   25.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0000   77.0000   99.2833 34

  7 omega   -6.00   40.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.0000   76.0000  -46.7157 46

  8 omega   11.00   42.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   79.0000   42.9506 31

  9 omega   12.00   37.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   80.0000  -17.4051 25

 10 omega  -53.00   24.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   64.0000  -90.0000 77

 11 omega  -45.00   29.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000 -150.0000 74

 12 omega  -43.00   28.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   25.0000    0.0000 71

 13 omega  -43.00  -13.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  120.0000 30

 14 omega  -39.00  -13.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  150.0000 26

 15 omega   16.00   47.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   78.0000 -100.5272 31

 16 omega   14.00   39.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   80.0000   88.9990 25

 17 omega   15.00   40.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   79.0000 -173.1813 25

 18 omega   19.00   44.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000  -73.1774 25

 19 omega   19.00   44.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000  -37.8861 25

 20 omega   25.00   54.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   75.0000 -152.9587 29

 21 omega  -15.00   87.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       55.1171  -80.0000   58.9345 102

 22 omega   34.00   60.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       55.1171   73.0000   -3.4870 26

 23 omega   25.00   52.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       55.1171   77.0000  -30.0000 27

 24 omega   27.00   53.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       55.1171   77.0000  120.0000 26

 25 omega   36.00   62.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000   98.4736 26

 26 omega   31.00   57.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000  125.7185 26

 27 omega   96.00  123.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000  -83.2325 27

 28 omega   31.00   57.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000  -83.2325 26

 29 omega   34.00   63.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000 -130.7837 29

 30 omega   28.00   55.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000   33.2991 27

 31 omega   35.00   61.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   74.0000  -23.8090 26

 32 omega   34.00   65.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   74.0000   84.2213 31

 33 omega   41.00   80.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   61.0000  174.0216 39

 34 omega   39.00   72.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   69.0000  -47.5426 33

 35 omega   94.00  122.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   61.0000  174.0216 28

 36 omega   34.00   60.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   77.0000 -171.8345 26

 37 omega   51.00   82.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   58.0000  -75.2462 31

 38 omega   44.00   75.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   70.0000   -2.6899 31

 39 omega   51.00  110.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   55.0000  -90.7742 59

 40 omega   52.00   78.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   63.0000   63.2816 26

 41 omega   51.00  104.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   66.0000   40.8565 53

 42 omega  118.00  144.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   76.0000 -151.2688 26

 43 omega   45.00   74.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   76.0000 -151.2688 29

 44 omega   58.00   84.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   57.0000  146.0801 26

 45 omega   53.00  100.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   46.0000  -54.4846 47

 46 omega   54.00   80.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   58.0000  122.1699 26

 47 omega   49.00   77.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   70.0000  -37.9070 28

 48 omega   53.00  123.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   60.0000 -179.9575 70

 49 omega   75.00  101.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   60.0000   -4.1355 26

 50 omega   49.00   79.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   75.0000 -151.0263 30

 51 omega   20.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000  -80.0000  -78.7964 89

 52 omega   51.00   77.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   73.0000  110.3418 26

 53 omega   62.00   90.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   45.0000   85.9612 28

 54 omega   75.00  101.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000   57.0000 -135.9164 26

 55 omega   11.00   87.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000  -80.0000  131.6608 76

 56 omega   55.00   85.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000   72.0000  -34.3132 30

 57 omega   77.00  104.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000  -80.0000   15.7956 27

 58 omega   59.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       86.0000   72.0000  141.5837 31

 59 omega   68.00  128.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000   68.0000  -79.6478 60

 60 omega   71.00   97.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000   60.0000  152.5867 26

 61 omega   64.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000  -80.0000 -132.5694 26

 62 omega   73.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       94.0000   58.0000  -28.6643 31

 63 omega   71.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   74.0000 -172.9097 35

 64 omega   70.00   97.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   74.0000   88.3378 27

 65 omega   90.00  127.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000    0.0000 37

 66 omega  100.00  127.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   50.0000  -60.0000 27

 67 omega   81.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -30.0000 97

 68 omega   89.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000   60.0000 88

 69 omega   98.00  147.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   50.0000   30.0000 49

 70 omega   92.00  118.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -77.0000    0.0000 26

 71 omega   74.00  140.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -63.3459 66

 72 omega   43.00   69.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -63.3459 26

 73 omega   55.00  103.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -79.0000   52.3221 48

 74 omega   86.00  145.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   38.0000  -90.0000 59

 75 omega   90.00  116.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000  120.0000 26

 76 omega   89.00  170.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000   90.0000 81

 77 omega   89.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000  -90.0000 88

 78 omega   89.00  114.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000 -120.0000 25

 79 omega   81.00  107.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000    0.0000 26

 80 omega   81.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -150.0000 25

 81 omega   88.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000   30.0000 89

 82 omega   85.00  157.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -180.0000 72

 83 omega   81.00  172.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  120.0000 91

 84 omega   40.00  141.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  146.1785 101

 85 omega   90.00  139.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -77.0000 -150.0000 49

 86 omega   81.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000   60.0000 25

 87 omega   83.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -90.0000 26

 88 omega  115.00  172.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -60.0000 57

 89 omega   63.00   89.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -79.0000  -22.6325 26

 90 omega   80.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -60.0000 28

 91 omega  136.00  174.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -120.0000 38

 92 omega   80.00  107.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000   90.6586 27

 93 omega   85.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   38.0000    0.0000 26

 94 omega   80.00  107.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -120.0000 27

 95 omega   81.00  107.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000   90.0000 26

 96 omega   82.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000   30.0000 27

 97 omega   90.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000 -150.0000 87

 98 omega   81.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  150.0000 97

 99 omega  134.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000    0.0000 44

;
_diffrn_measurement_device       '\k-geometry 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      0.0016945000
_diffrn_orient_matrix_UB_12      -0.0555761000
_diffrn_orient_matrix_UB_13      -0.0857440000
_diffrn_orient_matrix_UB_21      -0.0993040000
_diffrn_orient_matrix_UB_22      -0.1383788000
_diffrn_orient_matrix_UB_23      0.0252915000
_diffrn_orient_matrix_UB_31      -0.1688529000
_diffrn_orient_matrix_UB_32      0.0808958000
_diffrn_orient_matrix_UB_33      -0.0156898000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0565
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            22409
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.029
_diffrn_reflns_theta_min         5.213
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.506
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       plate
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.2147
_exptl_crystal_size_mid          0.1731
_exptl_crystal_size_min          0.0614
_refine_diff_density_max         0.110
_refine_diff_density_min         -0.183
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 962 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     188
_refine_ls_number_reflns         2368
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0333P)^2^+0.1957P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0691
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.702
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                2338
_reflns_number_total             2368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om301235d_si_002.cif
_cod_data_source_block           Ind3
_cod_original_cell_volume        1212.12(3)
_cod_database_code               4080049
_audit_block_refno               1621
_audit_block_usercomment         'SOSJW27, plate, colourless'
_shelx_estimated_absorpt_t_min   0.899
_shelx_estimated_absorpt_t_max   0.970
_shelxl_version_number           2012-6
_cell_oxdiff_length_a            7.86416(19)
_cell_oxdiff_length_b            9.0808(2)
_cell_oxdiff_length_c            16.9735(3)
_cell_oxdiff_angle_alpha         89.9861(17)
_cell_oxdiff_angle_beta          89.9756(18)
_cell_oxdiff_angle_gamma         89.9791(19)
_cell_oxdiff_volume              1212.12(5)
_cell_oxdiff_measurement_reflns_used 16278
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_theta     66.97
_reflns_odcompleteness_iscentric 1