Zirconium and Hafnium Hydrazinediido Half-Sandwich Complexes: Synthesis and Reactivity
Schweizer, Peter D.; Wadepohl, Hubert; Gade, Lutz H.; Organometallics 33 (2014) 1726–; doi:10.1021/om500087s

data_4082801
_publ_section_title
;
 Zirconium and Hafnium Hydrazinediido Half-Sandwich Complexes: Synthesis
 and Reactivity
;
_journal_issue                   7
_journal_name_full               Organometallics
_journal_page_first              1726
_journal_paper_doi               10.1021/om500087s
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C41 H50 N6 Zr'
_chemical_formula_sum            'C41 H50 N6 Zr'
_chemical_formula_weight         718.09
_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_psch18
_audit_creation_date
;
'Tue Apr 30 15:27:36 2013'
;
_audit_update_record             'Tue Nov 26 16:51:35 CET 2013'
_cell_angle_alpha                90
_cell_angle_beta                 101.2742(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.33688(7)
_cell_length_b                   15.94563(5)
_cell_length_c                   24.70487(10)
_cell_measurement_reflns_used    150362
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      32.3450
_cell_measurement_theta_min      3.3220
_cell_volume                     7470.47(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-13); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      110(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9241
_diffrn_detector_type            'Agilent EOS'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.944
_diffrn_measurement_details
;
  1 omega  -26.00    4.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245  -77.0000   30.0000 60

  2 omega  -33.00   -1.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245  -38.0000   30.0000 64

  3 omega  -28.00   -3.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245  -77.0000  -60.0000 50

  4 omega  -61.00  -10.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245   79.0000 -124.9998 102

  5 omega  -13.00   30.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245   57.0000  -60.0000 86

  6 omega   28.00   99.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   77.0000  -60.0000 142

  7 omega  -39.00   27.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -57.0000   30.0000 132

  8 omega   -5.00   22.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   80.0000 -167.5568 54

  9 phi      0.00   43.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
  28.0026   28.0026  -20.0000     -     86

 10 omega    2.00   28.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   77.0000  -30.0000 52

 11 omega    6.00   90.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000  150.0000 168

 12 omega    6.00   54.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000 -120.0000 96

 13 omega    7.00   88.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000   60.0000 162

 14 omega   11.00   60.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -77.0000  -30.0000 98

 15 omega   69.00   95.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   77.0000  -30.0000 52

 16 omega   11.00   99.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   77.0000 -120.0000 176

 17 omega  -45.00    1.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -38.0000 -180.0000 92

 18 omega   29.00   60.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -77.0000   60.0000 62

 19 omega  -41.00   -7.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -79.0000   10.2087 68

 20 omega   28.00   63.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -79.0000   10.2087 70

 21 omega  -41.00   63.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -79.0000  -85.1211 208

 22 omega  -20.00   63.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -80.0000  145.3023 166

 23 omega -100.00   -1.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245  -38.0000  -90.0000 198

 24 omega  -61.00   25.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245   79.0000 -124.9998 172

 25 omega  -60.00   43.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245   77.0000  -30.0000 206

 26 omega  -99.00    4.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245  -77.0000   60.0000 206

 27 omega  -41.00   50.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -57.0000  150.0000 182

 28 omega  -43.00   60.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -77.0000   90.0000 206

 29 omega    6.00   97.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000 -120.0000 182

 30 phi    120.00  240.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
  40.0000   28.0026    0.0000     -     240

 31 omega  -46.00  102.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026    0.0000    0.0000 296

 32 omega    6.00   97.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000   30.0000 182

 33 omega   -4.00   99.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   77.0000  -90.0000 206

 34 omega   -4.00   99.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   77.0000    0.0000 206

 35 omega    6.00   97.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000 -180.0000 182

 36 omega  -43.00   60.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026  -77.0000 -150.0000 206

 37 omega    6.00   97.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026   57.0000  -60.0000 182

 38 omega  -41.00   63.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -80.0000  145.3023 208

 39 omega  -41.00   63.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -79.0000   10.2087 208

 40 omega  -41.00   63.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -79.0000  -85.1211 208

 41 omega -102.00   -2.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.9245    0.0000    0.0000 200

 42 omega  -46.00  102.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026    0.0000  240.0000 296

 43 omega  -46.00  102.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0026    0.0000  120.0000 296

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w and \p scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0358979000
_diffrn_orient_matrix_UB_12      0.0121747000
_diffrn_orient_matrix_UB_13      0.0038243000
_diffrn_orient_matrix_UB_21      0.0082687000
_diffrn_orient_matrix_UB_22      -0.0386567000
_diffrn_orient_matrix_UB_23      -0.0114504000
_diffrn_orient_matrix_UB_31      -0.0064242000
_diffrn_orient_matrix_UB_32      0.0183351000
_diffrn_orient_matrix_UB_33      -0.0266779000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0623
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            608488
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.130
_diffrn_reflns_theta_min         3.195
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.331
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95120
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            bronze
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3024
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1021
_refine_ls_number_reflns         26873
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0325
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0308P)^2^+3.2842P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0738
_refine_ls_wR_factor_ref         0.0773
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23239
_reflns_number_total             26873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500087s_si_002.cif
_cod_data_source_block           complex_3a
_cod_depositor_comments          'Adding full bibliography for 4082801.cif.'
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4082801
_audit_block_refno               1762
_audit_block_usercomment         'PD446_2, irregular, bronze'
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C41 H50 N6 Zr'
_chemical_oxdiff_usercomment     'PD446_2, irregular, bronze'
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.968
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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.a Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C80(H81A,H81B,H81C), C81(H80A,H80B,
 H80C), C87(H87A,H87B,H87C), C88(H91A,H91B,H91C), C89(H90A,H90B,H90C), C90(H89A,
 H89B,H89C), C91(H88A,H88B,H88C), C30(H30A,H30B,H30C), C12(H12A,H12B,H12C),
 C11(H11A,H11B,H11C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C31(H31A,H31B,H31C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              95685
_cell_oxdiff_length_a            19.34131(13)
_cell_oxdiff_length_b            15.94540(8)
_cell_oxdiff_length_c            24.69920(16)
_cell_oxdiff_angle_alpha         90.0050(5)
_cell_oxdiff_angle_beta          101.2697(6)
_cell_oxdiff_angle_gamma         89.9861(5)
_cell_oxdiff_volume              7470.47(8)
_cell_oxdiff_measurement_reflns_used 150362