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_4086895
_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         'C64 H102 S2 Si4 Ti2'
_chemical_formula_sum            'C64 H102 S2 Si4 Ti2'
_chemical_formula_weight         1143.73
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                93.573(3)
_cell_angle_beta                 108.624(4)
_cell_angle_gamma                105.973(3)
_cell_formula_units_Z            2
_cell_length_a                   14.3166(6)
_cell_length_b                   15.1682(5)
_cell_length_c                   20.1061(9)
_cell_measurement_reflns_used    9698
_cell_measurement_temperature    173
_cell_measurement_theta_max      28.9260
_cell_measurement_theta_min      3.6330
_cell_volume                     3923.4(3)
_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    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_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 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega  -23.00   47.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -      -18.0128   57.0000   30.0000 70

  2 omega   27.00   52.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -      -18.0128   77.0000  120.0000 25

  3 omega  -18.00   22.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -       18.6378  102.0000  118.0000 40

  4 omega  -42.00   -3.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -      -18.0128   77.0000  120.0000 39

  5 omega  -62.00    9.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -      -18.0128   19.0000   30.0000 71

  6 omega  -39.00   45.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -      -18.0128   57.0000  -90.0000 84

  7 omega    1.00   61.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -       18.6378  -99.0000  -90.0000 60

  8 omega   19.00   61.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -       18.6378  -99.0000   30.0000 42

  9 omega  -94.00  -47.00   1.0000   80.1850
omega____ theta____ kappa____ phi______ frames
    -      -18.0128 -178.0000   60.0000 47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0543012000
_diffrn_orient_matrix_UB_12      0.0078502000
_diffrn_orient_matrix_UB_13      0.0141992000
_diffrn_orient_matrix_UB_21      -0.0039231000
_diffrn_orient_matrix_UB_22      -0.0098318000
_diffrn_orient_matrix_UB_23      0.0332137000
_diffrn_orient_matrix_UB_31      -0.0080079000
_diffrn_orient_matrix_UB_32      -0.0476832000
_diffrn_orient_matrix_UB_33      -0.0109461000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0538
_diffrn_reflns_av_unetI/netI     0.0687
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            30605
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.028
_diffrn_reflns_theta_max         25.028
_diffrn_reflns_theta_min         3.326
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.348
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70942
_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.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    0.968
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1236
_exptl_crystal_recrystallization_method 'From Et2O solution at -35 C'
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_platon_squeeze_details
;
Compound 5 contained disordered pentane molecules that could not 
be refined satisfactorily; for this reason, the program SQUEEZE 
was used to mathematically remove the effects of the solvent. 

;
_refine_diff_density_max         1.797
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     673
_refine_ls_number_reflns         13794
_refine_ls_number_restraints     867
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0896
_refine_ls_R_factor_gt           0.0728
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1022P)^2^+4.7564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1916
_refine_ls_wR_factor_ref         0.2015
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10926
_reflns_number_total             13794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00791_si_003.cif
_cod_data_source_block           Compound5
_cod_database_code               4086895
_chemical_oxdiff_formula         'C64 H102 S2 Si4 Ti2'
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.768
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Rigid body (RIGU) restrains
 C55, Ti1, C1, C27, C2, S1, C28, C31, C29, C5, C3, C30, C4, Ti2, Si1, Si3, H2,
 C53, H28, C32, H29, C6, H3, C34, C8, S2, C7, C33, C9, C12, C15, C41, C38, C35,
 C54, C58, H32, H6, Si4, Si2, C59, H7, H33, H9, C11, C10, H12, C14, C13, H15,
 C17, C16, H41, C43, C42, H38, C40, C39, H35, C37, C36, H54, H58, C57, C44, C47,
  C50, C21, C24, C18, C60, C64, H11A, H11B, H11C, H10A, H10B, H10C, H14A, H14B,
 H14C, H13A, H13B, H13C, H17A, H17B, H17C, H16A, H16B, H16C, H43A, H43B, H43C,
 H42A, H42B, H42C, H40A, H40B, H40C, H39A, H39B, H39C, H37A, H37B, H37C, H36A,
 H36B, H36C, H55, C56, H57, H44, C45, C46, C49, H47, C48, H50, C51, C52, H21,
 C23, C22, H24, C26, C25, H18, C20, C19, H60, C61, H64, C63, H56, H45A, H45B,
 H45C, H46A, H46B, H46C, H49A, H49B, H49C, H48A, H48B, H48C, H51A, H51B, H51C,
 H52A, H52B, H52C, H23A, H23B, H23C, H22A, H22B, H22C, H26A, H26B, H26C, H25A,
 H25B, H25C, H20A, H20B, H20C, H19A, H19B, H19C, H61, C62, H63, H62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C9(H9), C41(H41), C21(H21), C24(H24), C44(H44), C38(H38), C47(H47), C12(H12),
 C15(H15), C50(H50), C35(H35), C18(H18)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C28(H28), C7(H7), C33(H33), C29(H29), C32(H32), C3(H3), C2(H2),
 C54(H54), C58(H58), C57(H57), C60(H60), C55(H55), C56(H56), C64(H64), C61(H61),
  C62(H62), C63(H63)
3.c Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C43(H43A,H43B,H43C), C42(H42A,H42B,H42C), C26(H26A,H26B,
 H26C), C25(H25A,H25B,H25C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C40(H40A,
 H40B,H40C), C39(H39A,H39B,H39C), C51(H51A,H51B,H51C), C23(H23A,H23B,H23C),
 C13(H13A,H13B,H13C), C48(H48A,H48B,H48C), C45(H45A,H45B,H45C), C52(H52A,H52B,
 H52C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C19(H19A,H19B,H19C), C37(H37A,
 H37B,H37C), C10(H10A,H10B,H10C), C36(H36A,H36B,H36C), C17(H17A,H17B,H17C),
 C16(H16A,H16B,H16C), C46(H46A,H46B,H46C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'