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_4516072
_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         'C9 H14 Br2 O Ti'
_chemical_formula_sum            'C9 H14 Br2 O Ti'
_chemical_formula_weight         345.92
_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             2016-08-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.141(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.9173(2)
_cell_length_b                   16.12491(19)
_cell_length_c                   12.6854(2)
_cell_measurement_reflns_used    15071
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.0850
_cell_measurement_theta_min      3.6130
_cell_volume                     2464.41(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43g (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43g (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43g (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      air
_diffrn_ambient_temperature      100
_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 0.990
_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  33.00   1.00    1.00    --  -36.58  38.00 150.00   88
  2  \w    -53.00  31.00   1.00    1.00    --  -36.58  57.00  30.00   84
  3  \w    -53.00  31.00   1.00    1.00    --  -36.58  57.00 150.00   84
  4  \w     23.00  90.00   1.00    1.00    --   36.58-125.00 -30.00   67
  5  \w      1.00  76.00   1.00    1.00    --   36.58 -99.00  60.00   75
  6  \w     23.00  90.00   1.00    1.00    --   36.58-125.00 150.00   67
  7  \w     39.00 109.00   1.00    3.00    --  108.65 -94.00-120.00   70
  8  \w     42.00 127.00   1.00    3.00    --  108.65 -61.00 -60.00   85
  9  \w     91.00 177.00   1.00    3.00    --  108.65  45.00  90.00   86
 10  \w    100.00 178.00   1.00    3.00    --  108.65 111.00 -90.00   78
 11  \w     39.00 109.00   1.00    3.00    --  108.65 -94.00 -30.00   70
 12  \w     39.00 109.00   1.00    3.00    --  108.65 -94.00-180.00   70
 13  \w     39.00 130.00   1.00    3.00    --  108.65 -30.00   0.00   91
 14  \w     41.00 135.00   1.00    3.00    --  108.65 -77.00   0.00   94
 15  \w   -106.00  33.00   1.00    1.00    --  -36.58   0.00 -30.00  139
 16  \w   -104.00 -10.00   1.00    1.00    --  -36.58 -77.00 -60.00   94
 17  \w   -104.00 -10.00   1.00    1.00    --  -36.58 -77.00  60.00   94
 18  \w   -104.00 -10.00   1.00    1.00    --  -36.58 -77.00-180.00   94
 19  \w     87.00 178.00   1.00    3.00    --  108.65  30.00-180.00   91
 20  \w     82.00 176.00   1.00    3.00    --  108.65  77.00  30.00   94
 21  \w     91.00 177.00   1.00    3.00    --  108.65  45.00   0.00   86
 22  \w     91.00 177.00   1.00    3.00    --  108.65  45.00 120.00   86
 23  \w     91.00 153.00   1.00    3.00    --  108.65  45.00 -30.00   62
 24  \w     70.00 178.00   1.00    3.00    --  108.65  15.00 -60.00  108
;
_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      -0.1099480000
_diffrn_orient_matrix_UB_12      -0.0476828000
_diffrn_orient_matrix_UB_13      -0.0529864000
_diffrn_orient_matrix_UB_21      0.0645679000
_diffrn_orient_matrix_UB_22      -0.0767436000
_diffrn_orient_matrix_UB_23      -0.0145786000
_diffrn_orient_matrix_UB_31      0.0095975000
_diffrn_orient_matrix_UB_32      -0.0310428000
_diffrn_orient_matrix_UB_33      0.1180892000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            23134
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.238
_diffrn_reflns_theta_min         3.669
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.187
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.123
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43g (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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.865
_exptl_crystal_description       plate
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.322
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.034
_refine_diff_density_max         1.201
_refine_diff_density_min         -0.734
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         4810
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0312
_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^)+(0.0490P)^2^+1.1580P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0812
_refine_ls_wR_factor_ref         0.0824
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4620
_reflns_number_total             4810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CpTiBr2(OtBu).cif
_cod_data_source_block           nb07
_cod_original_cell_volume        2464.42(7)
_cod_database_code               4516072
_chemical_oxdiff_formula         C9H14Br2O1Ti1
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C1B(H1B), C2B(H2B), C3B(H3B),
 C4B(H4B), C5B(H5B)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C7B(H7BA,H7BB,H7BC),
 C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC)
;
_shelx_res_checksum              96619
_shelx_hkl_checksum              32782
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-08-10
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.645
_oxdiff_exptl_absorpt_empirical_full_min 0.363