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_4082802
_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 Hf N6'
_chemical_formula_sum            'C41 H50 Hf N6'
_chemical_formula_weight         805.36
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_psch20
_audit_creation_date
;
'Fri Jun 21 18:10:23 2013'
;
_audit_update_record             'Fri Jun 21 18:13:12 CEST 2013'
_cell_angle_alpha                90
_cell_angle_beta                 100.9538(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.29490(17)
_cell_length_b                   15.89343(12)
_cell_length_c                   24.70562(19)
_cell_measurement_reflns_used    29328
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      26.2170
_cell_measurement_theta_min      3.4170
_cell_volume                     7438.24(11)
_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
;
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  'SHELXL-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 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -50.00  -17.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.8347   79.0000   31.6504 66

  2 omega  -71.00  -32.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.8347  -57.0000  -60.0000 78

  3 omega  -47.00   50.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -79.0000  117.7157 194

  4 omega   23.00   50.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -80.0000  142.0656 54

  5 omega  -15.00   88.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347   77.0000   30.0000 206

  6 omega  -54.00  -10.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -38.0000 -120.0000 88

  7 omega    2.00   86.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347   57.0000  150.0000 168

  8 omega  -10.00   83.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347   77.0000 -120.0000 186

  9 omega  -52.00   37.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -57.0000    0.0000 178

 10 omega  -43.00   49.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -78.0000  -54.9421 184

 11 omega   19.00   50.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -80.0000   47.0564 62

 12 omega  -33.00   48.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -77.0000 -180.0000 162

 13 omega  -14.00   12.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -57.0000  -30.0000 52

 14 omega   16.00   50.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -79.0000 -131.3337 68

 15 omega  -38.00   52.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.8347   57.0000    0.0000 180

 16 omega  -11.00   89.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347   38.0000   30.0000 200

 17 omega  -54.00   48.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -77.0000  -90.0000 204

 18 omega   -5.00   86.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347   57.0000  120.0000 182

 19 omega  -46.00   23.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347  -80.0000  104.4969 138

 20 omega  -11.00   89.00   0.5000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       16.8347   38.0000  -90.0000 200

;
_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      0.0123807000
_diffrn_orient_matrix_UB_12      0.0160667000
_diffrn_orient_matrix_UB_13      0.0268838000
_diffrn_orient_matrix_UB_21      0.0345441000
_diffrn_orient_matrix_UB_22      -0.0141761000
_diffrn_orient_matrix_UB_23      -0.0011564000
_diffrn_orient_matrix_UB_31      0.0074283000
_diffrn_orient_matrix_UB_32      0.0391476000
_diffrn_orient_matrix_UB_33      -0.0114530000
_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  0.0887
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            184315
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.380
_diffrn_reflns_theta_min         3.175
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.842
_exptl_absorpt_correction_T_max  0.963
_exptl_absorpt_correction_T_min  0.767
_exptl_absorpt_correction_type   gaussian
_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)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            bronze
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3280
_exptl_crystal_size_max          0.1222
_exptl_crystal_size_mid          0.0965
_exptl_crystal_size_min          0.0135
_refine_diff_density_max         1.754
_refine_diff_density_min         -0.972
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     883
_refine_ls_number_reflns         15168
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0186P)^2^+10.3227P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0616
_refine_ls_wR_factor_ref         0.0656
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12690
_reflns_number_total             15168
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500087s_si_002.cif
_cod_data_source_block           complex_3b
_cod_depositor_comments          'Adding full bibliography for 4082802.cif.'
_cod_original_cell_volume        7438.24(10)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4082802
_audit_block_refno               1785
_audit_block_usercomment         'PD460_2, irregular, bronze'
_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 Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C1(H1A,H1B), C2(H2A,H2B),
 C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C56(H56), C58(H58), C60(H60), C64(H64), C65(H65), C66(H66), C67(H67),
 C68(H68), C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C85(H85), C86(H86),
  C88(H88), C89(H89), 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), C35(H35),
  C36(H36), C38(H38), C39(H39)
2.c Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C80(H80A,H80B,H80C), C81(H81A,H81B,
 H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C90(H90A,
 H90B,H90C), C91(H91A,H91B,H91C), 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), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.764
_shelx_hkl_checksum              55398
_cell_oxdiff_length_a            19.2957(2)
_cell_oxdiff_length_b            15.89371(15)
_cell_oxdiff_length_c            24.7031(3)
_cell_oxdiff_angle_alpha         89.9985(9)
_cell_oxdiff_angle_beta          100.9413(10)
_cell_oxdiff_angle_gamma         90.0008(9)
_cell_oxdiff_volume              7438.24(15)
_cell_oxdiff_measurement_reflns_used 29328
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_theta     24.97
_reflns_odcompleteness_iscentric 1