N-Aryloxide-Amidinate Group 4 Metal Complexes
Xu, Hanhua; Lv, Ze-Jie; Wei, Junnian; Xi, Zhenfeng; Dalton Transactions  (2023) –; doi:10.1039/D3DT01767B

data_7713565
_publ_section_title
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 N-Aryloxide-Amidinate Group 4 Metal Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01767B
_journal_year                    2023
_chemical_formula_moiety         'C24 H31 Cl4 Hf2 N8 O2, C16 H32 Li O4'
_chemical_formula_sum            'C40 H63 Cl4 Hf2 Li N8 O6'
_chemical_formula_weight         1256.709
_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_Int_Tables_number      2
_audit_creation_date             2023-03-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-03-16 deposited with the CCDC.	2023-07-25 downloaded from the CCDC.
;
_cell_angle_alpha                89.129(1)
_cell_angle_beta                 71.984(1)
_cell_angle_gamma                72.209(1)
_cell_formula_units_Z            2
_cell_length_a                   12.5852(2)
_cell_length_b                   12.8869(2)
_cell_length_c                   17.0743(2)
_cell_measurement_reflns_used    25481
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      30.7120
_cell_measurement_theta_min      2.5830
_cell_volume                     2497.84(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.9988
_diffrn_measured_fraction_theta_max 0.9989
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -10.00  15.00   0.50    0.62    --   -1.70 -38.00 -30.00   50
  2  \w    -90.00 -26.00   0.50    0.62    --   -1.70 -38.00 -30.00  128
  3  \w    -91.00 -23.00   0.50    0.62    --   -1.70 -57.00 120.00  136
  4  \w    -44.00  31.00   0.50    0.62    --   -1.70 -82.00 150.00  150
  5  \w    -35.00 -10.00   0.50    0.62    --   -1.70 -38.00-150.00   50
  6  \w    -21.00  40.00   0.50    0.62    --   -1.70  38.00 -60.00  122
  7  \w     50.00  86.00   0.50    0.62    --   -1.70  38.00 -60.00   72
  8  \w    -87.00 -50.00   0.50    0.62    --   -1.70 -38.00 -60.00   74
  9  \w    -59.00 -27.00   0.50    0.62    --    1.70 -57.00  30.00   64
 10  \w    -88.00   0.00   0.50    0.62    --    1.70 -57.00  60.00  176
 11  \w     43.00  68.00   0.50    0.62    --    1.70  38.00  30.00   50
 12  \w     57.00  82.00   0.50    0.62    --    1.70  38.00-180.00   50
 13  \w     16.00  41.00   0.50    0.62    --    1.70  38.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0330824000
_diffrn_orient_matrix_UB_12      0.0519668000
_diffrn_orient_matrix_UB_13      0.0219601000
_diffrn_orient_matrix_UB_21      -0.0223611000
_diffrn_orient_matrix_UB_22      0.0167088000
_diffrn_orient_matrix_UB_23      -0.0331223000
_diffrn_orient_matrix_UB_31      -0.0480481000
_diffrn_orient_matrix_UB_32      -0.0196849000
_diffrn_orient_matrix_UB_33      0.0185386000
_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  0.0522
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.9988
_diffrn_reflns_Laue_measured_fraction_max 0.9989
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            60063
_diffrn_reflns_point_group_measured_fraction_full 0.9988
_diffrn_reflns_point_group_measured_fraction_max 0.9989
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         2.52
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.417
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75336
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.671
_exptl_crystal_description       block
_exptl_crystal_F_000             1243.080
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.7688
_refine_diff_density_min         -0.9497
_refine_diff_density_rms         0.1097
_refine_ls_d_res_high            0.8100
_refine_ls_d_res_low             8.0874
_refine_ls_goodness_of_fit_ref   1.0515
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    107
_refine_ls_number_parameters     603
_refine_ls_number_reflns         9843
_refine_ls_number_restraints     142
_refine_ls_restrained_S_all      1.0435
_refine_ls_R_factor_all          0.0281
_refine_ls_R_factor_gt           0.0231
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0120P)^2^+3.6203P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0538
_refine_ls_wR_factor_ref         0.0568
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -14
_reflns_limit_k_max              15
_reflns_limit_k_min              -15
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                8772
_reflns_number_total             9843
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3dt01767b2.cif
_cod_data_source_block           exp_11297
_cod_database_code               7713565
_chemical_oxdiff_formula         'Hf C H O N  K Li'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H3ab of C3a, H15 of C15, H29 of C29, H30 of C30, H16 of
  C16, H14 of C14, H28 of C28
 At 1.5 times of:
  All C(H,H,H) groups, H3aa of C3a
2. Restrained distances
 O1a-C3a = O1a-C2a
 1.43 with sigma of 0.01
 C5a-C3a = C5a-C4a = C4a-C2a = C4-C2 = C5-C4 = C5-C3
 1.54 with sigma of 0.01
 O1-C3 = O1-C2
 1.43 with sigma of 0.01
 C3a-C2a
 2.336 with sigma of 0.01
 C2a-C5a = C4a-C3a
 2.515 with sigma of 0.02
 C2-C3
 2.336 with sigma of 0.02
 C2-C5 = C4-C3
 2.515 with sigma of 0.02
 O1a-C4a
 2.426 with sigma of 0.02
 O1a-C5a
 2.426 with sigma of 0.02
 O1-C4
 2.426 with sigma of 0.02
 O1-C5
 2.426 with sigma of 0.02
 O1a-Li61 \\sim O1-Li61
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O1a \\sim C2a \\sim C4a \\sim C5a \\sim C3a: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O1 \\sim C2 \\sim C4 \\sim C5 \\sim C3: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 O1a, C3a, C5a, C4a, C2a
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, C2, C4, C5, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(O1a)=Sof(C2a)=Sof(H2aa)=Sof(H2ab)=Sof(C4a)=Sof(H4aa)=Sof(H4ab)=Sof(C5a)=
 Sof(H5aa)=Sof(H5ab)=Sof(C3a)=Sof(H3aa)=Sof(H3ab)=1-FVAR(1)
 Sof(C2)=Sof(H2a)=Sof(H2b)=Sof(C3)=Sof(H3a)=Sof(H3b)=Sof(O1)=Sof(C4)=Sof(H4a)=
 Sof(H4b)=Sof(C5)=Sof(H5a)=Sof(H5b)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C23(H23a,H23b), C41(H41a,H41b), C42(H42a,H42b), C43(H43a,
 H43b), C52(H52a,H52b), C55(H55a,H55b), C45(H45a,H45b), C57(H57a,H57b),
 C58(H58a,H58b), C60(H60a,H60b), C53(H53a,H53b), C54(H54a,H54b), C59(H59a,H59b),
  C2(H2a,H2b), C3(H3a,H3b), C4(H4a,H4b), C5(H5a,H5b), C2a(H2aa,H2ab), C4a(H4aa,
 H4ab), C5a(H5aa,H5ab), C3a(H3aa,H3ab)
6.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C14(H14), C15(H15), C30(H30), C28(H28), C29(H29)
6.c Idealised Me refined as rotating group:
 C24(H24a,H24b,H24c), C38(H38a,H38b,H38c), C39(H39a,H39b,H39c), C33(H33a,H33b,
 H33c), C40(H40a,H40b,H40c), C34(H34a,H34b,H34c), C35(H35a,H35b,H35c)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.703
_oxdiff_exptl_absorpt_empirical_full_min 0.515