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_4080051
_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_formula_sum            'C58.5 H71 N9 Zr'
_chemical_formula_weight         991.46
_chemical_properties_physical    air-sensitive
_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_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ss33
_audit_creation_date
;
'Mon Feb 13 18:43:13 2012'
;
_audit_creation_method           SHELXL-2012
_audit_update_record             'Fri Nov  9 16:58:09 CET 2012'
_cell_angle_alpha                90
_cell_angle_beta                 105.3627(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8426(2)
_cell_length_b                   15.35907(16)
_cell_length_c                   18.8516(2)
_cell_measurement_reflns_used    22303
_cell_measurement_temperature    114.97(11)
_cell_measurement_theta_max      71.8410
_cell_measurement_theta_min      3.7645
_cell_volume                     5260.80(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_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      114.97(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9241
_diffrn_detector_type            'Agilent EOS'
_diffrn_measured_fraction_theta_full 0.942
_diffrn_measured_fraction_theta_max 0.905
_diffrn_measurement_details
;
  1 omega  -65.00  -40.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   90.0000 25

  2 omega   -7.00   19.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   90.0000 26

  3 omega  -17.00   10.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   38.0000 -150.0000 27

  4 omega   26.00   65.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   90.0000 39

  5 omega  -17.00   38.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -120.0000 55

  6 omega  -17.00   15.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   90.0000 32

  7 omega   -5.00   30.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -       14.0000   78.0000  155.0000 35

  8 omega   -8.00   19.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -       22.0000   80.0000   11.0000 27

  9 omega   10.00   46.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   80.0000 -102.0000 36

 10 omega  -56.00   27.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   77.0000  -30.0000 83

 11 omega  -41.00   29.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000   60.0000 70

 12 omega  -38.00  -13.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000 -180.0000 25

 13 omega  -44.00  -12.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  120.0000 32

 14 omega  -47.00  -12.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  -60.0000 35

 15 omega  -41.00  -13.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   60.0000 28

 16 omega  -50.00   30.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000 -180.0000 80

 17 omega   14.00   39.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   80.0000  -55.0000 25

 18 omega   15.00   40.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   79.0000  112.0000 25

 19 omega   14.00   44.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   80.0000   52.0000 30

 20 omega   18.00   43.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000 -128.0000 25

 21 omega   19.00   44.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000  169.0000 25

 22 omega   21.00   46.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000   -8.0000 25

 23 omega   18.00   43.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000   42.0000 25

 24 omega   22.00   47.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   78.0000   67.0000 25

 25 omega   19.00   44.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000  123.0000 25

 26 omega   19.00   44.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000  -22.0000 25

 27 omega   18.00   43.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000  -94.0000 25

 28 omega   23.00   48.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   78.0000 -162.0000 25

 29 omega   23.00   48.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   78.0000  140.0000 25

 30 omega   75.00  124.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   88.0000 49

 31 omega   27.00   96.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   76.0000  171.0000 69

 32 omega   25.00   51.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   75.0000  -76.0000 26

 33 omega   25.00   51.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   88.0000 26

 34 omega  -15.00   85.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       55.0790  -80.0000 -142.0000 100

 35 omega   29.00   55.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  -98.0000 26

 36 omega   29.00   62.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   75.0000  111.0000 33

 37 omega   30.00   56.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000   13.0000 26

 38 omega   71.00  127.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000 -123.0000 56

 39 omega   29.00   55.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000 -123.0000 26

 40 omega   29.00  109.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  -27.0000 80

 41 omega   29.00   60.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000   33.0000 31

 42 omega   33.00   79.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  145.0000 46

 43 omega   36.00  118.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   71.0000  -91.0000 82

 44 omega   35.00  110.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   73.0000    8.0000 75

 45 omega   36.00  119.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   71.0000   56.0000 83

 46 omega   33.00   95.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   75.0000 -167.0000 62

 47 omega   63.00   89.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000  -80.0000   94.0000 26

 48 omega   10.00   36.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000  -80.0000   94.0000 26

 49 omega   18.00  107.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000  -79.0000   15.0000 89

 50 omega   72.00  122.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000  -80.0000  166.0000 50

 51 omega   36.00   85.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000  -80.0000  -21.0000 49

 52 omega  111.00  178.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000   30.0000 67

 53 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000   30.0000 26

 54 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000 -120.0000 26

 55 omega  140.00  166.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000 -180.0000 26

 56 omega   96.00  122.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   50.0000  -30.0000 26

 57 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000 -180.0000 26

 58 omega   89.00  116.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   63.0000   60.0000 27

 59 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000   90.0000 26

 60 omega   80.00  112.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   25.0000  -60.0000 32

 61 omega   81.00  107.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000  -60.0000 26

 62 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000 -150.0000 26

 63 omega  125.00  167.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000   60.0000 42

 64 omega   91.00  118.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   50.0000 -180.0000 27

 65 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000   60.0000 26

 66 omega   89.00  115.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   63.0000 -180.0000 26

 67 omega  138.00  176.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000  -90.0000 38

 68 omega   80.00  105.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000  -90.0000 25

 69 omega  124.00  158.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000    0.0000 34

 70 omega   86.00  145.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   38.0000 -120.0000 59

 71 omega   80.00  106.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   77.0000    0.0000 26

 72 omega   90.00  115.00   1.0000   35.0000
omega____ theta____ kappa____ phi______ frames
    -      110.1580   50.0000   30.0000 25

;
_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      0.0600489000
_diffrn_orient_matrix_UB_12      0.0075478000
_diffrn_orient_matrix_UB_13      0.0732882000
_diffrn_orient_matrix_UB_21      0.0095664000
_diffrn_orient_matrix_UB_22      -0.0996556000
_diffrn_orient_matrix_UB_23      0.0019185000
_diffrn_orient_matrix_UB_31      0.0591428000
_diffrn_orient_matrix_UB_32      0.0085262000
_diffrn_orient_matrix_UB_33      -0.0424668000
_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  0.0507
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.942
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            59622
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         71.987
_diffrn_reflns_theta_min         3.768
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.065
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73059
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       needle
_exptl_crystal_F_000             2100
_exptl_crystal_size_max          0.2634
_exptl_crystal_size_mid          0.0777
_exptl_crystal_size_min          0.0488
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     731
_refine_ls_number_reflns         9353
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0331
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0317P)^2^+3.9709P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0795
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7774
_reflns_number_total             9353
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om301235d_si_002.cif
_cod_data_source_block           Zr-complex_2
_cod_original_cell_volume        5260.79(11)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_original_formula_sum        'C58.50 H71 N9 Zr'
_cod_database_code               4080051
_audit_block_refno               1437
_audit_block_usercomment         SOS534_3_2,needle,orange
_shelx_estimated_absorpt_t_min   0.820
_shelx_estimated_absorpt_t_max   0.820
_shelxl_version_number           2012-6
_cell_oxdiff_length_a            18.8374(5)
_cell_oxdiff_length_b            15.3589(4)
_cell_oxdiff_length_c            18.8597(5)
_cell_oxdiff_angle_alpha         89.992(2)
_cell_oxdiff_angle_beta          105.393(2)
_cell_oxdiff_angle_gamma         90.029(2)
_cell_oxdiff_volume              5260.8(2)
_cell_oxdiff_measurement_reflns_used 22303
_reflns_odcompleteness_completeness 93.20
_reflns_odcompleteness_theta     66.97
_reflns_odcompleteness_iscentric 1