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_4082806
_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         'C46 H62 N6 Si2 Zr, 0.5(C7 H8)'
_chemical_formula_sum            'C49.5 H66 N6 Si2 Zr'
_chemical_formula_weight         892.48
_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   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_psch31a
_audit_creation_date             2013-11-01
_audit_update_record             'Fri Nov  1 14:04:40 CET 2013'
_cell_angle_alpha                79.350(8)
_cell_angle_beta                 78.097(12)
_cell_angle_gamma                68.934(14)
_cell_formula_units_Z            2
_cell_length_a                   11.135(7)
_cell_length_b                   11.859(7)
_cell_length_c                   19.746(10)
_cell_measurement_reflns_used    8160
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.83
_cell_measurement_theta_min      2.22
_cell_volume                     2363(2)
_computing_cell_refinement
;
SAINT 8.x (Bruker AXS, 1997-2012). Includes estimated systematic errors
 of the unit cell constants from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction        'SAINT 8.x (Bruker AXS, 1997-2011)'
_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_environment      'perfluoro polyether oil'
_diffrn_ambient_temperature      100(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.931
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0711
_diffrn_reflns_av_unetI/netI     0.0801
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            59967
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.541
_diffrn_reflns_theta_min         1.062
_diffrn_source                   'sealed X-Ray tube (Mo)'
_diffrn_source_type              'fine focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.323
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (Sheldrick & Bruker AXS, 2004-2008)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       block
_exptl_crystal_F_000             946
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.766
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     562
_refine_ls_number_reflns         15970
_refine_ls_number_restraints     59
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.0779
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0340P)^2^+1.2384P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11622
_reflns_number_total             15970
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500087s_si_002.cif
_cod_data_source_block           complex_13
_cod_depositor_comments          'Adding full bibliography for 4082806.cif.'
_cod_original_formula_sum        'C49.50 H66 N6 Si2 Zr'
_cod_database_code               4082806
_audit_block_refno               1897
_audit_block_usercomment         PD518
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.965
_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. Restrained distances
 C97-C92 \\sim C97-C96
 with sigma of 0.02
3. Restrained atomic chiral volume
 C91
 fixed at 0 with sigma of 0.1
4. Rigid bond restraints
 C91, C92, C93, C94, C95, C96, C97
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97: within 1.7A
with sigma of 1 and sigma for terminal atoms of 2
6. Others
 Fixed Sof: C91(0.5) C92(0.5) H92(0.5) C93(0.5) H93(0.5) C94(0.5) H94(0.5)
 C95(0.5) H95(0.5) C96(0.5) H96(0.5) C97(0.5) H97A(0.5) H97B(0.5) H97C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B)
7.b Me refined with riding coordinates:
 C97(H97A,H97B,H97C)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C24(H24), C25(H25), C26(H26), C27(H27),
 C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37),
  C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45),
 C46(H46), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96)
7.d Fitted hexagon refined as free rotating group:
 C91(C92,C93,C94,C95,C96)
7.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,
 H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              91867