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_4082803
_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         'C40 H58 Hf Li N5 Si2'
_chemical_formula_sum            'C40 H58 Hf Li N5 Si2'
_chemical_formula_weight         850.52
_chemical_properties_physical    air-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      15
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_psch32
_audit_creation_date
;
'Fri Nov 08 10:36:18 2013'
;
_audit_update_record             'Fri Nov  8 11:46:22 CET 2013'
_cell_angle_alpha                90
_cell_angle_beta                 99.1198(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   36.53978(11)
_cell_length_b                   10.09021(3)
_cell_length_c                   22.10604(8)
_cell_measurement_reflns_used    140709
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      34.1380
_cell_measurement_theta_min      3.5520
_cell_volume                     8047.34(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
'encif (Wadepohl, 2009-13); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'SHELX-2013 (Sheldrick 2013)'
_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 0.9985
_diffrn_measured_fraction_theta_max 0.9805
_diffrn_measurement_details
;
  1 omega -110.00  -85.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  178.0000   90.0000 50

  2 omega -104.00  -58.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  178.0000  -60.0000 92

  3 omega  -74.00  -40.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  103.0000  100.0000 68

  4 omega  -54.00   27.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502   38.0000 -120.0000 162

  5 omega  -16.00   76.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -99.0000  -60.0000 184

  6 omega    1.00   64.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   77.0000  150.0000 126

  7 omega    1.00   96.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   77.0000 -120.0000 190

  8 omega    1.00  103.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   77.0000   60.0000 204

  9 omega  -40.00   57.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -38.0000   60.0000 194

 10 omega    1.00   56.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   77.0000  -30.0000 110

 11 omega   -8.00  106.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845    0.0000 -120.0000 228

 12 omega  -16.00  106.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   19.0000   30.0000 244

 13 omega  -54.00   37.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502   57.0000  120.0000 182

 14 omega -110.00  -57.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502 -178.0000  120.0000 106

 15 omega -110.00  -55.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  178.0000   60.0000 110

 16 omega   11.00  101.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000  -30.0000 180

 17 omega   11.00  101.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000   90.0000 180

 18 omega  -20.00   76.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -99.0000   30.0000 192

 19 omega    5.00  105.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   38.0000 -120.0000 200

 20 omega   35.00  110.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  178.0000    0.0000 150

 21 omega   11.00  101.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000   30.0000 180

 22 omega  -37.00   54.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -57.0000  -60.0000 182

 23 omega -106.00   42.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502    0.0000 -120.0000 296

 24 omega -106.00   42.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502    0.0000 -180.0000 296

 25 omega -103.00    0.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  -77.0000  -90.0000 206

 26 omega -105.00   -5.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  -38.0000  150.0000 200

 27 omega -101.00  -10.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502  -57.0000 -180.0000 182

 28 omega -106.00   42.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502    0.0000 -150.0000 296

 29 omega    1.00  103.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   77.0000 -150.0000 204

 30 omega  -40.00   60.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -38.0000  150.0000 200

 31 omega  -20.00   76.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -99.0000   60.0000 192

 32 omega    1.00  103.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   77.0000   90.0000 204

 33 omega -106.00   35.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502    0.0000  -60.0000 282

 34 omega -106.00   42.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.0502    0.0000  -90.0000 296

;
_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      -0.0122744000
_diffrn_orient_matrix_UB_12      0.0344484000
_diffrn_orient_matrix_UB_13      0.0162971000
_diffrn_orient_matrix_UB_21      -0.0143431000
_diffrn_orient_matrix_UB_22      -0.0452624000
_diffrn_orient_matrix_UB_23      -0.0111533000
_diffrn_orient_matrix_UB_31      0.0054867000
_diffrn_orient_matrix_UB_32      -0.0413051000
_diffrn_orient_matrix_UB_33      0.0258133000
_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  0.0437
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       57
_diffrn_reflns_limit_h_min       -57
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            339925
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.217
_diffrn_reflns_theta_min         3.381
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.686
_exptl_absorpt_correction_T_max  0.814
_exptl_absorpt_correction_T_min  0.635
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3488
_exptl_crystal_size_max          0.2187
_exptl_crystal_size_mid          0.1937
_exptl_crystal_size_min          0.1004
_refine_diff_density_max         1.148
_refine_diff_density_min         -0.498
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         16373
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0220
_refine_ls_R_factor_gt           0.0187
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0173P)^2^+8.7568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0421
_refine_ls_wR_factor_ref         0.0431
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15068
_reflns_number_total             16373
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500087s_si_002.cif
_cod_data_source_block           complex_4
_cod_depositor_comments          'Adding full bibliography for 4082803.cif.'
_cod_original_cell_volume        8047.33(4)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               4082803
_audit_block_refno               1901
_audit_block_usercomment         'PD541_1, block, light yellow'
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C34 H40 N4 Hf'
_chemical_oxdiff_usercomment     'PD541_1, block, light yellow'
_shelx_estimated_absorpt_t_max   0.775
_shelx_estimated_absorpt_t_min   0.775
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.50
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1A-C2A \\sim C1B-C2B \\sim C3-C2A \\sim C3-C2B
 with sigma of 0.02
 N1-C1A \\sim N1-C1B
 with sigma of 0.01
3. Rigid bond restraints
 C1A, C1B, C2A, C2B, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C2A \\sim C2B: within 1A with sigma of 0.02 and sigma for
terminal atoms of 0.02
5. Others
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H3BC)=Sof(H3BD)=
 1-FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H3AA)=Sof(H3AB)=
 FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C2A(H2AA,H2AB), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C3(H3AA,H3AB),
  C3(H3BC,H3BD)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C10(H10), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
6.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              7083
_cell_oxdiff_length_a            36.54423(16)
_cell_oxdiff_length_b            10.09023(4)
_cell_oxdiff_length_c            22.10495(10)
_cell_oxdiff_angle_alpha         90.0021(4)
_cell_oxdiff_angle_beta          99.1465(4)
_cell_oxdiff_angle_gamma         89.9891(3)
_cell_oxdiff_volume              8047.33(6)
_cell_oxdiff_measurement_reflns_used 140709