Synthesis and Reactivity of Group 4 Metal Benzyl Complexes Supported by Carbazolide-Based PNP Pincer Ligands.
Plundrich, Gudrun T.; Wadepohl, Hubert; Gade, Lutz H.; Inorganic chemistry 55 (2015) 353–; doi:10.1021/acs.inorgchem.5b02498

data_4344798
_publ_section_title
;
 Synthesis and Reactivity of Group 4 Metal Benzyl Complexes Supported by
 Carbazolide-Based PNP Pincer Ligands.
;
_journal_issue                   1
_journal_name_full               'Inorganic chemistry'
_journal_page_first              353
_journal_paper_doi               10.1021/acs.inorgchem.5b02498
_journal_volume                  55
_journal_year                    2015
_chemical_formula_moiety         'C48 H67 N P2 Zr, C3.5 H3.5'
_chemical_formula_sum            'C51.5 H71 N P2 Zr'
_chemical_formula_weight         857.25
_chemical_properties_physical    'air-sensitive, moisture-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     direct
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_gp35
_audit_creation_date             2015-10-21
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'21.10.2015 18:08:25 CEST UTC+02:00  encif 1.36'
_cell_angle_alpha                99.162(7)
_cell_angle_beta                 91.086(6)
_cell_angle_gamma                96.061(10)
_cell_formula_units_Z            2
_cell_length_a                   9.824(5)
_cell_length_b                   12.521(6)
_cell_length_c                   20.151(8)
_cell_measurement_reflns_used    8035
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.10
_cell_measurement_theta_min      2.29
_cell_volume                     2432(2)
_computing_cell_refinement
;
SAINT (see _computing_data_reduction). 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 (Bruker AXS, 1997-2013),SADABS-2014_5 (Sheldrick and Bruker AXS, 1997-2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2014 (Giacovazzo et al., 2014)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            63462
_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         32.535
_diffrn_reflns_theta_min         1.024
_diffrn_source                   'sealed X-Ray tube (Mo)'
_diffrn_source_type              'fine focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.325
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6970
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (see _computing_data_reduction)
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.171
_exptl_crystal_description       block
_exptl_crystal_F_000             914
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.782
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     541
_refine_ls_number_reflns         16440
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0320
_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^)+(0.0448P)^2^+0.8687P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0806
_refine_ls_wR_factor_ref         0.0882
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14135
_reflns_number_total             16440
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02498_si_002.cif
_cod_data_source_block           ga_gp35_sq
_cod_original_cell_volume        2431.8(18)
_cod_original_formula_sum        'C51.50 H71 N P2 Zr'
_cod_database_code               4344798
_audit_block_refno               2453
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.968
_shelxl_version_number           2014/7
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 P1-C27A \\sim P1-C27B
 with sigma of 0.02
 C27A-C29A \\sim C27B-C29B \\sim C27A-C28 \\sim C27B-C28
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C28, C27A, C29A, C27B, C29B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C27B)=Sof(H27B)=Sof(C29B)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=1-FVAR(1)
 Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C27A)=Sof(H27A)=Sof(C29A)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=FVAR(1)
 Fixed Sof: C87(0.5) H87A(0.5) H87B(0.5) H87C(0.5)
5.a Ternary CH refined with riding coordinates:
 C24(H24), C30(H30), C33(H33), C27A(H27A), C27B(H27B)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C48(H48A,H48B), C55(H55A,H55B)
5.c Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C28(H28D,H28E,H28F), C87(H87A,H87B,H87C)
5.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C50(H50), C51(H51), C52(H52), C53(H53),
 C54(H54), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C82(H82), C83(H83)
5.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C29A(H29A,H29B,H29C), C29B(H29D,H29E,H29F)
;
_shelx_res_checksum              82045
_olex2_submission_special_instructions 'No special instructions were received'
_platon_squeeze_void_probe_radius 1.20