Cyclometalated titanium and zirconium complexes stabilised by a new silylmethylene-linked tetradentate triamidophosphine.
Sietzen, M.; Federmann, P.; Sonnenschein, C.; Wadepohl, H.; Ballmann, J.; Dalton transactions (Cambridge, England : 2003) 45 (2016) 3013–3023; doi:10.1039/c5dt04561d

data_7037958
_publ_section_title
;
 Cyclometalated titanium and zirconium complexes stabilised by a new
 silylmethylene-linked tetradentate triamidophosphine.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3013
_journal_page_last               3023
_journal_paper_doi               10.1039/c5dt04561d
_journal_volume                  45
_journal_year                    2016
_chemical_formula_moiety         'C27 H39 Cl N3 P Si3 Ti, 0.5(C7 H8)'
_chemical_formula_sum            'C30.5 H43 Cl N3 P Si3 Ti'
_chemical_formula_weight         650.27
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ba_jb1
_audit_creation_date
;
'Tue Jun 12 14:54:34 2012'
;
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-12-14 deposited with the CCDC.
2015-12-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.8442(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.90658(10)
_cell_length_b                   18.00949(16)
_cell_length_c                   17.67069(16)
_cell_measurement_reflns_used    20759
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      28.9533
_cell_measurement_theta_min      3.2597
_cell_volume                     3397.01(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-14); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      110(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9241
_diffrn_detector_type            'Agilent EOS'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.928
_diffrn_measurement_details
;
  1 omega  -10.00   81.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036   77.0000  150.0000 91

  2 omega  -12.00   60.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036  -99.0000 -150.0000 72

  3 omega    6.00   87.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036   57.0000   60.0000 81

  4 omega   21.00   67.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036   57.0000 -120.0000 46

  5 omega  -50.00   40.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036  -57.0000  -90.0000 90

  6 omega  -50.00   25.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036  -55.0000  142.0000 75

  7 omega  -48.00   39.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036  -57.0000    0.0000 87

  8 omega   -3.00   84.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -       18.3036   77.0000  -60.0000 87

  9 omega   -2.00   53.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.7723   38.0000   90.0000 55

 10 omega  -72.00  -29.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.7723  118.0000   25.0000 43

;
_diffrn_measurement_device       '\k-geometry 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      -0.0453877000
_diffrn_orient_matrix_UB_12      -0.0214386000
_diffrn_orient_matrix_UB_13      -0.0252920000
_diffrn_orient_matrix_UB_21      0.0213429000
_diffrn_orient_matrix_UB_22      0.0147650000
_diffrn_orient_matrix_UB_23      -0.0322057000
_diffrn_orient_matrix_UB_31      0.0435834000
_diffrn_orient_matrix_UB_32      -0.0295579000
_diffrn_orient_matrix_UB_33      0.0022535000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            49411
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.017
_diffrn_reflns_theta_min         3.266
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.508
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             1372
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_refine_diff_density_max         2.073
_refine_diff_density_min         -0.999
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         8403
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.251
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0397P)^2^+3.6197P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0914
_refine_ls_wR_factor_ref         0.0973
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7135
_reflns_number_total             8403
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5dt04561d2.cif
_cod_data_source_block           ba_jb1
_cod_depositor_comments
'Adding full bibliography for 7037956--7037963.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_original_formula_sum        'C30.50 H43 Cl N3 P Si3 Ti'
_cod_database_code               7037958
_audit_block_refno               1515
_audit_block_usercomment         'jbo 52_Ti, red, block'
_chemical_oxdiff_formula         'C30 H42 Cl1 N3 P1 Si3 Ti1'
_chemical_oxdiff_usercomment     'jbo 52_Ti, red, block'
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.951
_reflns_odcompleteness_completeness 99.76
_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
 C97-C94 \\sim C97-C96
 with sigma of 0.02
3. Restrained atomic chiral volume
 C95
 fixed at 0 with sigma of 0.1
4. Rigid body (RIGU) restrains
 C91, C92, C93, C94, C95
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C91(0.5) H91(0.5) C92(0.5) H92(0.5) C93(0.5) H93(0.5) C95(0.5)
 C94(0.5) H94(0.5) C96(0.5) H96(0.5) C97(0.5) H97A(0.5) H97B(0.5) H97C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C91(H91),
  C92(H92), C93(H93), C94(H94), C96(H96)
6.c Fitted hexagon refined as free rotating group:
 C91(C92,C93,C95,C94,C96)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C97(H97A,H97B,H97C)
;
_shelx_res_checksum              60573
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            10.9066(2)
_cell_oxdiff_length_b            18.0088(4)
_cell_oxdiff_length_c            17.6705(4)
_cell_oxdiff_angle_alpha         90.0039(18)
_cell_oxdiff_angle_beta          101.8328(19)
_cell_oxdiff_angle_gamma         89.9979(17)
_cell_oxdiff_volume              3396.99(13)
_cell_oxdiff_measurement_reflns_used 20759