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_4082804
_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         'C48 H64 N8 Zr'
_chemical_formula_sum            'C48 H64 N8 Zr'
_chemical_formula_weight         844.29
_chemical_properties_physical    air-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_psch28
_audit_creation_date
;
'Wed Oct 02 09:51:03 2013'
;
_audit_update_record             'Wed Oct  2 09:55:50 CEST 2013'
_cell_angle_alpha                80.1134(7)
_cell_angle_beta                 74.5705(7)
_cell_angle_gamma                67.8028(8)
_cell_formula_units_Z            2
_cell_length_a                   10.88743(8)
_cell_length_b                   13.16505(12)
_cell_length_c                   16.92306(14)
_cell_measurement_reflns_used    49416
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      34.0290
_cell_measurement_theta_min      3.6410
_cell_volume                     2158.03(3)
_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, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_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 0.9989
_diffrn_measured_fraction_theta_max 0.9618
_diffrn_measurement_details
;
  1 omega  -69.00   31.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064   19.0000 -120.0000 200

  2 omega  -27.00    0.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -78.0000   24.0134 54

  3 omega  -39.00    1.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -79.0000  108.4196 80

  4 omega    8.00   34.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064   77.0000   30.0000 52

  5 omega  -37.00   -1.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -77.0000 -150.0000 72

  6 omega  -25.00   30.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064   57.0000  -90.0000 110

  7 omega  -45.00    1.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -80.0000  -54.5670 92

  8 omega  -30.00   -5.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -77.0000 -180.0000 50

  9 omega   11.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000 -120.0000 178

 10 omega   11.00   91.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000   60.0000 160

 11 omega   28.00   66.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -80.0000  -92.8043 76

 12 omega    5.00   78.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   38.0000    0.0000 146

 13 omega   37.00   64.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -77.0000 -180.0000 54

 14 omega  -39.00   65.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -79.0000  114.9645 208

 15 omega    6.00   77.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   38.0000  150.0000 142

 16 omega   17.00   67.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   38.0000 -150.0000 100

 17 omega   55.00   81.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000  -90.0000 52

 18 omega   36.00   64.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -77.0000  150.0000 56

 19 omega  -36.00   64.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -77.0000  -30.0000 200

 20 omega  -39.00   66.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -80.0000   28.2627 210

 21 omega -101.00  -11.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -57.0000   30.0000 180

 22 omega  -54.00   37.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064   57.0000 -120.0000 182

 23 omega -103.00   -1.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -77.0000  -30.0000 204

 24 omega  -47.00  -11.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -79.0000  108.4196 72

 25 omega -101.00  -11.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -32.2064  -57.0000 -120.0000 180

 26 omega  -39.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -49.0000  -44.0000 190

 27 omega   11.00  101.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   57.0000 -150.0000 180

 28 omega  -39.00   64.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -77.0000    0.0000 206

 29 omega  -37.00   54.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -57.0000   90.0000 182

 30 omega    5.00  105.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845   38.0000  120.0000 200

 31 omega  -37.00   54.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       32.2845  -57.0000   30.0000 182

;
_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      0.0016696000
_diffrn_orient_matrix_UB_12      0.0397115000
_diffrn_orient_matrix_UB_13      0.0228241000
_diffrn_orient_matrix_UB_21      0.0581360000
_diffrn_orient_matrix_UB_22      -0.0391491000
_diffrn_orient_matrix_UB_23      0.0129778000
_diffrn_orient_matrix_UB_31      0.0426799000
_diffrn_orient_matrix_UB_32      0.0172656000
_diffrn_orient_matrix_UB_33      -0.0348321000
_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  0.0446
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            125250
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.253
_diffrn_reflns_theta_min         3.208
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.298
_exptl_absorpt_correction_T_max  0.970
_exptl_absorpt_correction_T_min  0.948
_exptl_absorpt_correction_type   analytical
_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)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'light bronze'
_exptl_crystal_density_diffrn    1.299
_exptl_crystal_description       irregular
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.2259
_exptl_crystal_size_mid          0.2167
_exptl_crystal_size_min          0.1245
_refine_diff_density_max         0.841
_refine_diff_density_min         -0.442
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     527
_refine_ls_number_reflns         17277
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0343
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0344P)^2^+0.8655P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0832
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15493
_reflns_number_total             17277
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500087s_si_002.cif
_cod_data_source_block           complex_7
_cod_depositor_comments          'Adding full bibliography for 4082804.cif.'
_cod_database_code               4082804
_audit_block_refno               1863
_audit_block_usercomment         'PD479_3_FILT, irregular, bronze'
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C48 H64 N8 Zr1'
_chemical_oxdiff_usercomment     'PD479_3_FILT, irregular, bronze'
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.971
_reflns_odcompleteness_completeness 99.89
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C10(H10), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
 C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C42(H42), C43(H43), C45(H45),
  C46(H46)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              7701
_cell_oxdiff_length_a            10.88743(8)
_cell_oxdiff_length_b            13.16505(12)
_cell_oxdiff_length_c            16.92306(14)
_cell_oxdiff_angle_alpha         80.1134(7)
_cell_oxdiff_angle_beta          74.5705(7)
_cell_oxdiff_angle_gamma         67.8028(8)
_cell_oxdiff_volume              2158.03(3)
_cell_oxdiff_measurement_reflns_used 49416