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_4344803
_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         'C65 H61 I N P3 Zr'
_chemical_formula_sum            'C67 H66 I N O0.5 P3 Zr'
_chemical_formula_weight         1204.23
_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'
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'Mon Oct 12 14:56:20 2015'
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Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
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'23.10.2015 18:40:08 CEST UTC+02:00  encif 1.36'
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_cell_formula_units_Z            2
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_cell_measurement_reflns_used    20929
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
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'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
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_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
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_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.916
_diffrn_measurement_details
;
  1 omega  -20.00   61.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -99.0000   60.0000 162

  2 omega  -46.00   36.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -57.0000 -180.0000 164

  3 omega    1.00   83.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000   90.0000 164

  4 omega    1.00   83.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   38.0000    0.0000 164

  5 omega    1.00   83.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000 -120.0000 164

  6 omega  -44.00   39.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -77.0000  -60.0000 166

  7 omega  -50.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -57.0000   90.0000 180

  8 omega  -11.00   89.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   77.0000   60.0000 200

  9 omega  -20.00   61.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -99.0000  -60.0000 162

 10 omega  -11.00   89.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   77.0000  -90.0000 200

 11 omega   -3.00   87.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000 -180.0000 180

 12 omega  -20.00   61.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -99.0000  150.0000 162

 13 omega   -3.00   47.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161   57.0000  -30.0000 100

 14 omega  -50.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6161  -57.0000    0.0000 180

;
_diffrn_measurement_device       'four-circle 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      0.0347343000
_diffrn_orient_matrix_UB_12      -0.0088243000
_diffrn_orient_matrix_UB_13      -0.0303832000
_diffrn_orient_matrix_UB_21      -0.0539722000
_diffrn_orient_matrix_UB_22      0.0428953000
_diffrn_orient_matrix_UB_23      -0.0119439000
_diffrn_orient_matrix_UB_31      0.0193981000
_diffrn_orient_matrix_UB_32      0.0469501000
_diffrn_orient_matrix_UB_33      0.0028223000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0546
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            67397
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.916
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.988
_diffrn_reflns_theta_min         3.227
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    0.872
_exptl_absorpt_correction_T_max  0.976
_exptl_absorpt_correction_T_min  0.958
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
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_exptl_crystal_description       irregular
_exptl_crystal_F_000             1234
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.092
_refine_diff_density_max         1.291
_refine_diff_density_min         -2.212
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     674
_refine_ls_number_reflns         13722
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0657
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0486P)^2^+10.7312P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1245
_refine_ls_wR_factor_ref         0.1335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11171
_reflns_number_total             13722
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b02498_si_002.cif
_cod_data_source_block           ga_gp42_sq
_cod_original_formula_sum        'C67 H66 I N O0.50 P3 Zr'
_cod_database_code               4344803
_audit_block_refno               2548
_audit_block_usercomment         'gp768, red irregular'
_chemical_oxdiff_formula         'C56 H61 N P3 Zr (C4H10O)0.5'
_chemical_oxdiff_usercomment     'gp768, red irregular'
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.918
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2. Restrained distances
 C20-C21A \\sim C20-C22A \\sim C20-C23A \\sim C20-C21B \\sim C20-C22B \\sim
C20-C23B
 with sigma of 0.02
 C21A-C22A \\sim C21A-C23A \\sim C22A-C23A \\sim C21B-C22B \\sim C21B-C23B
\\sim C22B-C23B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C21A \\sim C22A \\sim C23A \\sim C21B \\sim C22B \\sim C23B: within 1.6A with
sigma of 0.02 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C20, C21A, C22A, C23A, C21B, C22B, C23B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C48(H48A,H48B)
6.b Me refined with riding coordinates:
 C21A(H21A,H21B,H21C), C22A(H22A,H22B,H22C), C23A(H23A,H23B,H23C), C21B(H21D,
 H21E,H21F), C22B(H22D,H22E,H22F), C23B(H23D,H23E,H23F)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38),
  C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C46(H46),
 C47(H47), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58),
  C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66)
6.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              80403
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            11.76549(16)
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_cell_oxdiff_length_c            22.1227(3)
_cell_oxdiff_angle_alpha         82.5449(13)
_cell_oxdiff_angle_beta          78.4729(12)
_cell_oxdiff_angle_gamma         65.6661(14)
_cell_oxdiff_volume              2817.51(7)
_cell_oxdiff_measurement_reflns_used 20929
_platon_squeeze_void_probe_radius 1.20