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_4516074
_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         'C12 H15 Cl O Ti'
_chemical_formula_sum            'C12 H15 Cl O Ti'
_chemical_formula_weight         258.59
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.444(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.9901(4)
_cell_length_b                   17.6571(9)
_cell_length_c                   7.9779(4)
_cell_measurement_reflns_used    7195
_cell_measurement_temperature    100.00(19)
_cell_measurement_theta_max      73.3500
_cell_measurement_theta_min      6.0620
_cell_volume                     1125.50(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(19)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.976
_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   -104.00 -20.00   1.00    1.00    --  -37.19 -57.00  90.00   84
  2  \w    -64.00  30.00   1.00    1.00    --  -37.19  77.00-120.00   94
  3  \w    -64.00  30.00   1.00    1.00    --  -37.19  77.00-150.00   94
  4  \w   -104.00 -20.00   1.00    1.00    --  -37.19 -57.00 150.00   84
  5  \w    -30.00  54.00   1.00    1.00    --   37.19 -57.00-180.00   84
  6  \w     18.00 106.00   1.00    1.00    --   37.19  38.00   0.00   88
  7  \w    -30.00  64.00   1.00    1.00    --   37.19 -77.00 -30.00   94
  8  \w     43.00 138.00   1.00    1.00    --  111.00 -77.00 -60.00   95
  9  \w     43.00 138.00   1.00    1.00    --  111.00 -77.00 120.00   95
 10  \w     84.00 178.00   1.00    1.00    --  111.00  77.00-150.00   94
 11  \w     93.00 178.00   1.00    1.00    --  111.00  61.00-120.00   85
 12  \w     44.00 129.00   1.00    1.00    --  111.00 -61.00  90.00   85
 13  \w     43.00 128.00   1.00    1.00    --  111.00 -45.00-180.00   85
 14  \w     94.00 178.00   1.00    1.00    --  111.00  45.00 150.00   84
 15  \w     94.00 178.00   1.00    1.00    --  111.00  45.00 -30.00   84
 16  \w   -105.00 -10.00   1.00    1.00    --  -37.19 -77.00-150.00   95
 17  \w   -105.00 -10.00   1.00    1.00    --  -37.19 -77.00  30.00   95
 18  \w   -104.00 -20.00   1.00    1.00    --  -37.19 -57.00-120.00   84
 19  \w    -64.00  30.00   1.00    1.00    --  -37.19  77.00 120.00   94
 20  \w   -105.00 -10.00   1.00    1.00    --  -37.19 -77.00 -30.00   95
 21  \w    -64.00  30.00   1.00    1.00    --  -37.19  77.00 -30.00   94
 22  \w    -30.00  54.00   1.00    1.00    --   37.19 -57.00  60.00   84
 23  \w     94.00 178.00   1.00    1.00    --  111.00  45.00-180.00   84
 24  \w     90.00 178.00   1.00    1.00    --  111.00  30.00 -60.00   88
 25  \w     73.00 178.00   1.00    1.00    --  111.00  15.00  90.00  105
;
_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      0.0781108000
_diffrn_orient_matrix_UB_12      -0.0796966000
_diffrn_orient_matrix_UB_13      -0.0097921000
_diffrn_orient_matrix_UB_21      0.0687846000
_diffrn_orient_matrix_UB_22      0.0089888000
_diffrn_orient_matrix_UB_23      0.1797056000
_diffrn_orient_matrix_UB_31      -0.1624865000
_diffrn_orient_matrix_UB_32      -0.0344144000
_diffrn_orient_matrix_UB_33      0.0694535000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0372
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            11079
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.309
_diffrn_reflns_theta_min         5.010
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.363
_exptl_absorpt_correction_T_max  0.764
_exptl_absorpt_correction_T_min  0.319
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.526
_exptl_crystal_description       block
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.098
_refine_diff_density_max         0.509
_refine_diff_density_min         -1.102
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.161
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     138
_refine_ls_number_reflns         2220
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0610P)^2^+2.6300P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1298
_refine_ls_wR_factor_ref         0.1304
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2179
_reflns_number_total             2220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            Cp2TiCl(OEt).cif
_cod_data_source_block           nb14
_cod_database_code               4516074
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C12H16ClOTi
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.809(2)
 0.191(2)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              12092
_shelx_hkl_checksum              81920
_olex2_date_sample_data_collection 2017-06-09
_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 1.377
_oxdiff_exptl_absorpt_empirical_full_min 0.775