Reactivity of a Dititanium Bis(pentalene) Complex toward Heteroallenes and Main-Group Element‒Element Bonds
Kilpatrick, Alexander F. R.; Green, Jennifer C.; Cloke, F. Geoffrey N.; Organometallics  (2016) –; doi:10.1021/acs.organomet.6b00791

data_4086892
_publ_section_title
;
 Reactivity of a Dititanium Bis(pentalene) Complex toward Heteroallenes
 and Main-Group Element--Element Bonds
;
_journal_name_full               Organometallics
_journal_paper_doi               10.1021/acs.organomet.6b00791
_journal_year                    2016
_chemical_formula_moiety         'C54 H95 N Si4 Ti2'
_chemical_formula_sum            'C54 H95 N Si4 Ti2'
_chemical_formula_weight         966.46
_chemical_name_common            'Compound 2'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-08-02
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.543(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9319(5)
_cell_length_b                   22.7725(11)
_cell_length_c                   18.9297(9)
_cell_measurement_reflns_used    6899
_cell_measurement_temperature    173
_cell_measurement_theta_max      70.7190
_cell_measurement_theta_min      4.1360
_cell_volume                     5572.6(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34i (release 04-08-2014 CrysAlis171 .NET)
(compiled Aug  4 2014,14:34:23)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34i (release 04-08-2014 CrysAlis171 .NET)
(compiled Aug  4 2014,14:34:23)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34i (release 04-08-2014 CrysAlis171 .NET)
(compiled Aug  4 2014,14:34:23)
;
_computing_molecular_graphics    'Ortep for Windows (Farrugia, 2012)'
_computing_publication_material
;
Olex2 (Dolomanov et al., 2009) and WinGX (Farrugia, 2012) publication routines 
;
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      173.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1033
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_details
;
  1 omega -109.00  -53.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -36.7513  178.0000  120.0000 56

  2 omega -105.00  -18.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      -36.7513  -38.0000 -120.0000 87

  3 omega    7.00  108.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7513   19.0000  150.0000 101

  4 omega   40.00   69.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000  120.0000 29

  5 omega   37.00   62.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000  150.0000 25

  6 omega   42.00   77.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000 -120.0000 35

  7 omega   41.00   74.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000 -150.0000 33

  8 omega   40.00   72.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000 -180.0000 32

  9 omega   45.00  162.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000    0.0000  120.0000 117

 10 omega  108.00  165.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000  -60.0000 57

 11 omega   42.00  140.00   1.0000  200.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -89.0000  160.2816 98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0316468000
_diffrn_orient_matrix_UB_12      0.0385709000
_diffrn_orient_matrix_UB_13      -0.0626881000
_diffrn_orient_matrix_UB_21      -0.0530080000
_diffrn_orient_matrix_UB_22      0.0532953000
_diffrn_orient_matrix_UB_23      0.0336847000
_diffrn_orient_matrix_UB_31      0.1019347000
_diffrn_orient_matrix_UB_32      0.0157620000
_diffrn_orient_matrix_UB_33      0.0395422000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0655
_diffrn_reflns_av_unetI/netI     0.0919
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            16451
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        66.995
_diffrn_reflns_theta_max         66.995
_diffrn_reflns_theta_min         3.932
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.501
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50514
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34i (release 04-08-2014 CrysAlis171 .NET)
(compiled Aug  4 2014,14:34:23)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.152
_exptl_crystal_description       block
_exptl_crystal_F_000             2104
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.131
_refine_diff_density_min         -0.612
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         9634
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1076
_refine_ls_R_factor_gt           0.0877
_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^)+(0.1924P)^2^+1.2596P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2455
_refine_ls_wR_factor_ref         0.2642
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7423
_reflns_number_total             9634
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00791_si_003.cif
_cod_data_source_block           Compound2
_cod_database_code               4086892
_chemical_oxdiff_formula         C53H95Si4Ti2N1
_shelx_estimated_absorpt_t_max   0.844
_shelx_estimated_absorpt_t_min   0.721
_reflns_odcompleteness_completeness 96.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C53B-N1B \\sim C53A-N1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1B \\sim C53A \\sim C53B \\sim N1A \\sim C54A \\sim C54B: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C53B) = Uanis(C53A)
Uanis(N1A) = Uanis(N1B)
4. Rigid body (RIGU) restrains
 N1B, C53A, C53B, N1A, C54A, C54B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C13, C14, C41, C43, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C53A)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(N1A)=1-FVAR(1)
 Sof(C53B)=Sof(C54B)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(N1B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12), C15(H15), C18(H18), C21(H21), C24(H24), C35(H35), C38(H38),
 C41(H41), C44(H44), C47(H47), C50(H50)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C28(H28), C29(H29), C32(H32), C33(H33)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,
 H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C),
 C26(H26A,H26B,H26C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,
 H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C),
 C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54B(H54A,H54B,H54C), C54A(H54D,H54E,
 H54F)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'