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

data_7713561
_publ_section_title
;
 N-Aryloxide-Amidinate Group 4 Metal Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01767B
_journal_year                    2023
_chemical_formula_moiety
'2(C24 H31 Cl N2 O2 Ti), 0.5(C6 H6), 0.5(C4 H10 O), 0.5(C4 H8 O)'
_chemical_formula_sum            'C55 H74 Cl2 N4 O5 Ti2'
_chemical_formula_weight         1037.88
_space_group_crystal_system      orthorhombic
_space_group_IT_number           54
_space_group_name_Hall           '-P 2a 2ac'
_space_group_name_H-M_alt        'P c c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-06-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-25 deposited with the CCDC.	2023-07-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.7408(8)
_cell_length_b                   16.6115(4)
_cell_length_c                   24.3585(7)
_cell_measurement_reflns_used    16116
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      29.4420
_cell_measurement_theta_min      2.2270
_cell_volume                     11224.8(5)
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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    -28.00   2.00   0.50    3.65    --  -15.70  57.00  30.00   60
  2  \w      7.00  57.00   0.50    3.65    --  -15.70  57.00 120.00  100
  3  \w     31.00  74.00   0.50    3.65    --  -15.70  57.00  30.00   86
  4  \w    -15.00  85.00   0.50    3.65    --   15.80  82.00 -30.00  200
;
_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      -0.0052274000
_diffrn_orient_matrix_UB_12      0.0257465000
_diffrn_orient_matrix_UB_13      -0.0224648000
_diffrn_orient_matrix_UB_21      0.0057695000
_diffrn_orient_matrix_UB_22      -0.0314971000
_diffrn_orient_matrix_UB_23      -0.0185454000
_diffrn_orient_matrix_UB_31      -0.0243372000
_diffrn_orient_matrix_UB_32      -0.0129945000
_diffrn_orient_matrix_UB_33      0.0004677000
_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  0.0289
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            49340
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         2.088
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.427
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72007
_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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description       block
_exptl_crystal_F_000             4400
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.877
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     689
_refine_ls_number_reflns         12844
_refine_ls_number_restraints     275
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0657
_refine_ls_R_factor_gt           0.0520
_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^)+(0.0795P)^2^+11.7322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1479
_refine_ls_wR_factor_ref         0.1560
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10330
_reflns_number_total             12844
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01767b2.cif
_cod_data_source_block           exp_9319
_cod_database_code               7713561
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Ti Cl'
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.919
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 C62-C56 = C56-O23 = O23-C12 = C42-C12
 1.54 with sigma of 0.01
 O57-C63 = O57-C51 = C51-C23 = C66-C23 = C66-C63
 1.54 with sigma of 0.01
 O23-C42
 2.5 with sigma of 0.01
 C62-O23
 2.5 with sigma of 0.01
 C56-C12
 2.5 with sigma of 0.01
 C23-C63
 2.5 with sigma of 0.01
 C63-C51
 2.5 with sigma of 0.01
 C66-O57
 2.5 with sigma of 0.01
 O57-C23
 2.5 with sigma of 0.01
 C51-C66
 2.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C40 \\sim C28 \\sim C14 \\sim C2 \\sim C3: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
C62 \\sim C56 \\sim O23 \\sim C12 \\sim C42: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
C23 \\sim C66 \\sim C63 \\sim O57 \\sim C51: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
Uanis(C14) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O57) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C63) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C23) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(O57) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Fixed Sof: C3(0.5) H3(0.5) C1(0.5) H1(0.5) C40(0.5) H40(0.5) C28(0.5)
 H28(0.5) C14(0.5) H14(0.5) C2(0.5) H2(0.5) C12(0.5) H12A(0.5) H12B(0.5)
 C56(0.5) H56A(0.5) H56B(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5) C62(0.5)
 H62A(0.5) H62B(0.5) H62C(0.5) O23(0.5) C63(0.5) H63A(0.5) H63B(0.5) C23(0.5)
 H23A(0.5) H23B(0.5) O57(0.5) C66(0.5) H66A(0.5) H66B(0.5) C51(0.5) H51A(0.5)
 H51B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C15(H15A,H15B), C39(H39A,H39B), C43(H43A,H43B), C12(H12A,
 H12B), C56(H56A,H56B), C63(H63A,H63B), C23(H23A,H23B), C66(H66A,H66B),
 C51(H51A,H51B)
5.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C9(H9), C36(H36), C34(H34), C50(H50), C8(H8), C35(H35), C49(H49),
 C48(H48), C22(H22), C21(H21), C20(H20), C3(H3), C1(H1), C40(H40), C28(H28),
 C14(H14), C2(H2)
5.c Fitted hexagon refined as free rotating group:
 C3(C1,C40,C28,C14,C2)
5.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C30(H30A,H30B,
 H30C), C60(H60A,H60B,H60C), C31(H31A,H31B,H31C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C32(H32A,H32B,H32C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C42(H42A,H42B,H42C), C62(H62A,H62B,
 H62C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              50854
_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 1.232
_oxdiff_exptl_absorpt_empirical_full_min 0.811