Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium <i>tert</i>-Butoxy Halides, Cp <sub> <i>x</i> </sub> TiX <sub> <i>y</i> </sub> (O <sup> <i>t</i> </sup> Bu)<sub>4-(<i>x</i>+<i>y</i>)</sub> (<i>x</i>, <i>y</i> = 1, 2; X = Cl, Br).
Boyde, Nicholas C.; Steelman, Grant W.; Hanusa, Timothy P.; ACS omega 3 (2018) 8149–8159; doi:10.1021/acsomega.8b00943

data_4516070
_publ_section_title
;
 Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium
 <i>tert</i>-Butoxy Halides, Cp <sub> <i>x</i> </sub> TiX <sub> <i>y</i>
 </sub> (O <sup> <i>t</i> </sup> Bu)<sub>4-(<i>x</i>+<i>y</i>)</sub>
 (<i>x</i>, <i>y</i> = 1, 2; X = Cl, Br).
;
_journal_issue                   7
_journal_name_full               'ACS omega'
_journal_page_first              8149
_journal_page_last               8159
_journal_paper_doi               10.1021/acsomega.8b00943
_journal_volume                  3
_journal_year                    2018
_chemical_formula_moiety
'0.5(C14 H19 Br O Ti), 0.5(C14 H19 Br0.63 O Ti), 0.19(Br)'
_chemical_formula_sum            'C14 H19 Br O Ti'
_chemical_formula_weight         331.10
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.079(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.0669(4)
_cell_length_b                   12.2725(3)
_cell_length_c                   15.5128(4)
_cell_measurement_reflns_used    10874
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.4150
_cell_measurement_theta_min      3.7620
_cell_modulation_dimension       1
_cell_volume                     2868.45(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.3012
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.929
_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    -55.00  45.00   1.00   14.79    --   15.96 -19.00 120.00  100
  2  \w     -3.00  85.00   1.00   14.79    --   15.96  38.00   0.00   88
  3  \w    -52.00  37.00   1.00   14.79    --   15.96 -77.00  30.00   89
  4  \w     30.00  55.00   1.00   14.79    --   15.96 -99.00-180.00   25
  5  \w    -11.00  60.00   1.00   14.79    --   15.96  77.00 120.00   71
  6  \w     35.00  81.00   1.00   14.79    --   15.96 178.00   0.00   46
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0235249000
_diffrn_orient_matrix_UB_12      0.0448674000
_diffrn_orient_matrix_UB_13      -0.0175266000
_diffrn_orient_matrix_UB_21      -0.0096814000
_diffrn_orient_matrix_UB_22      0.0310670000
_diffrn_orient_matrix_UB_23      0.0374175000
_diffrn_orient_matrix_UB_31      0.0395936000
_diffrn_orient_matrix_UB_32      -0.0190379000
_diffrn_orient_matrix_UB_33      0.0196074000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26410
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.358
_diffrn_reflns_theta_min         3.004
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.365
_exptl_absorpt_correction_T_max  0.953
_exptl_absorpt_correction_T_min  0.910
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.533
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.179
_refine_diff_density_min         -0.865
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.986
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         6965
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0720P)^2^+2.0100P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1165
_refine_ls_wR_factor_ref         0.1285
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5885
_reflns_number_total             6965
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            Cp2TiBr(OtBu).cif
_cod_data_source_block           nb06
_cod_original_cell_volume        2868.44(12)
_cod_database_code               4516070
_chemical_oxdiff_formula         C14H19BrOTi
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.3296(12) 0.6704(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Ti1-Br1 \\sim Ti1-Br1B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C26 \\sim C26B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C28 \\sim C28B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C27 \\sim C27B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
Br1 \\sim Br1B: within 2.8A with sigma of 0.003 and sigma for terminal atoms of
0.006
5. Others
 Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=Sof(H27D)=Sof(H27E)=
 Sof(H27F)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(Br1B)=1-FVAR(2)
 Sof(Br1)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6),
 C7(H7), C8(H8), C9(H9), C10(H10)
6.b Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C26B(H26D,H26E,
 H26F), C27B(H27D,H27E,H27F), C28B(H28D,H28E,H28F), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              30125
_shelx_hkl_checksum              19987
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-07-19
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_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 1.443
_oxdiff_exptl_absorpt_empirical_full_min 0.626