Radically Initiated Group Transfer Polymerization of Methacrylates by Titanium Amino-Phenolate Complexes
Coward, Daniel L.; Lake, Benjamin R. M.; Poli, Rinaldo; Shaver, Michael P.; Macromolecules 52 (2019) 3252–; doi:10.1021/acs.macromol.9b00182

data_1554177
_publ_section_title
;
 Radically Initiated Group Transfer Polymerization of Methacrylates by
 Titanium Amino-Phenolate Complexes
;
_journal_issue                   9
_journal_name_full               Macromolecules
_journal_page_first              3252
_journal_paper_doi               10.1021/acs.macromol.9b00182
_journal_volume                  52
_journal_year                    2019
_chemical_formula_moiety         '2(C39 H61 Cl N O4 Ti), C7 H8'
_chemical_formula_sum            'C85 H130 Cl2 N2 O8 Ti2'
_chemical_formula_weight         1474.60
_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     dual
_audit_creation_date             2017-05-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.834(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.7740(4)
_cell_length_b                   20.1276(6)
_cell_length_c                   16.5375(4)
_cell_measurement_reflns_used    9895
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      75.9070
_cell_measurement_theta_min      4.0850
_cell_volume                     4236.8(2)
_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      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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   -115.00 -19.00   1.00    5.00    --  -41.92 -38.00 150.00   96
  2  \w    -69.00  28.00   1.00    5.00    --  -41.92  57.00 -60.00   97
  3  \w     55.00 128.00   1.00    5.00    --   41.92-178.00 120.00   73
  4  \w     57.00 129.00   1.00    5.00    --   41.92 178.00-150.00   72
  5  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00  90.00   79
  6  \w     87.00 178.00   1.00   20.00    --  111.00  30.00 -60.00   91
  7  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00  30.00   79
  8  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00   0.00   95
  9  \w     36.00 135.00   1.00   20.00    --  111.00 -30.00 120.00   99
 10  \w     39.00 121.00   1.00   20.00    --  111.00-125.00  60.00   82
 11  \w     36.00 135.00   1.00   20.00    --  111.00 -30.00-150.00   99
 12  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -60.00   84
 13  \w     40.00 123.00   1.00   20.00    --  111.00 -45.00-150.00   83
 14  \w     69.00 112.00   1.00   20.00    --  111.00 -61.00 -30.00   43
 15  \w     63.00 103.00   1.00   20.00    --  111.00 -94.00 120.00   40
 16  \w     41.00  92.00   1.00   20.00    --  111.00-125.00-120.00   51
 17  \w    110.00 155.00   1.00   20.00    --  111.00 125.00 -30.00   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1202525000
_diffrn_orient_matrix_UB_12      -0.0085558000
_diffrn_orient_matrix_UB_13      -0.0056861000
_diffrn_orient_matrix_UB_21      0.0137822000
_diffrn_orient_matrix_UB_22      -0.0753986000
_diffrn_orient_matrix_UB_23      0.0127628000
_diffrn_orient_matrix_UB_31      0.0009890000
_diffrn_orient_matrix_UB_32      0.0098616000
_diffrn_orient_matrix_UB_33      0.0924511000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0855
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            34874
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.105
_diffrn_reflns_theta_min         3.466
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.586
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.348
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.156
_exptl_crystal_description       plate
_exptl_crystal_F_000             1592
_exptl_crystal_size_max          0.661
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.466
_refine_diff_density_min         -0.721
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         8785
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0567
_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^)+(0.0914P)^2^+0.5587P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1549
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7216
_reflns_number_total             8785
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ma9b00182_si_005.cif
_cod_data_source_block           Complex4
_cod_database_code               1554177
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C39 H61 Cl N O4 Ti'
_chemical_oxdiff_usercomment     '@ 120 K BRML404'
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C35-C34B \\sim C35-C34A
 with sigma of 0.02
 C34B-C33B \\sim C34A-C33A
 with sigma of 0.02
 C33A-C32A \\sim C33B-C32B
 with sigma of 0.02
 C32A-C31 \\sim C32B-C31
 with sigma of 0.02
3. Others
 Sof(H31C)=Sof(H31D)=Sof(H35C)=Sof(H35D)=Sof(C32B)=Sof(H32B)=Sof(C34B)=
 Sof(H34C)=Sof(H34D)=Sof(C33B)=Sof(H33C)=Sof(H33D)=1-FVAR(1)
 Sof(H31A)=Sof(H31B)=Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H35A)=Sof(H35B)=
 Sof(C32A)=Sof(H32A)=Sof(C34A)=Sof(H34A)=Sof(H34B)=FVAR(1)
 Fixed Sof: C41(0.5) C46(0.5) H46(0.5) C44(0.5) H44(0.5) C43(0.5) H43(0.5)
 C40(0.5) H40A(0.5) H40B(0.5) H40C(0.5) C42(0.5) H42(0.5) C45(0.5) H45(0.5)
4.a Ternary CH refined with riding coordinates:
 C32A(H32A), C32B(H32B)
4.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C31(H31A,H31B), C31(H31C,H31D), C39(H39A,
 H39B), C33A(H33A,H33B), C38(H38A,H38B), C37(H37A,H37B), C36(H36A,H36B),
 C35(H35A,H35B), C35(H35C,H35D), C34A(H34A,H34B), C34B(H34C,H34D), C33B(H33C,
 H33D)
4.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C3(H3), C5(H5), C20(H20), C46(H46), C44(H44), C43(H43), C42(H42),
 C45(H45)
4.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C25(H25A,H25B,
 H25C), C14(H14A,H14B,H14C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C26(H26A,
 H26B,H26C), C13(H13A,H13B,H13C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C28(H28A,H28B,H28C), C40(H40A,H40B,H40C)
;
_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 1.383
_oxdiff_exptl_absorpt_empirical_full_min 0.787