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_1554178
_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         'C49 H74 N O4 Ti'
_chemical_formula_sum            'C49 H74 N O4 Ti'
_chemical_formula_weight         788.99
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                91.943(2)
_cell_angle_beta                 100.093(2)
_cell_angle_gamma                96.4710(10)
_cell_formula_units_Z            2
_cell_length_a                   10.3781(2)
_cell_length_b                   11.0454(2)
_cell_length_c                   20.6189(5)
_cell_measurement_reflns_used    15282
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      75.7420
_cell_measurement_theta_min      4.4500
_cell_volume                     2308.67(8)
_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 0.980
_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    -68.00  29.00   1.00   10.00    --  -41.42  57.00 -30.00   97
  2  \w    -68.00  29.00   1.00   10.00    --  -41.42  57.00-180.00   97
  3  \w   -112.00 -15.00   1.00   10.00    --  -41.42 -57.00  30.00   97
  4  \w    -32.00  73.00   1.00   10.00    --   41.42 -77.00 -90.00  105
  5  \w    -32.00  73.00   1.00   10.00    --   41.42 -77.00 150.00  105
  6  \w     57.00 128.00   1.00   10.00    --   41.42 178.00  60.00   71
  7  \w     30.00 109.00   1.00   30.00    --  111.00 -94.00 -90.00   79
  8  \w     87.00 178.00   1.00   30.00    --  111.00  45.00 -60.00   91
  9  \w     94.00 178.00   1.00   30.00    --  111.00 125.00 120.00   84
 10  \w     39.00 121.00   1.00   30.00    --  111.00-125.00 150.00   82
 11  \w     37.00 142.00   1.00   30.00    --  111.00 -77.00 -60.00  105
 12  \w     87.00 178.00   1.00   30.00    --  111.00  45.00  90.00   91
 13  \w     94.00 178.00   1.00   30.00    --  111.00 125.00 -30.00   84
 14  \w     83.00 178.00   1.00   30.00    --  111.00  61.00 120.00   95
 15  \w     87.00 178.00   1.00   30.00    --  111.00  30.00-180.00   91
 16  \w     41.00 139.00   1.00   30.00    --  111.00 -61.00  60.00   98
 17  \w     39.00 121.00   1.00   30.00    --  111.00-125.00  60.00   82
 18  \w     30.00 109.00   1.00   30.00    --  111.00 -94.00-180.00   79
 19  \w     80.00 178.00   1.00   30.00    --  111.00  77.00  30.00   98
 20  \w   -128.00 -35.00   1.00   10.00    --  -41.42-178.00 -90.00   93
 21  \w   -112.00 -65.00   1.00   10.00    --  -41.42-137.00 -47.00   47
 22  \w   -115.00 -10.00   1.00   10.00    --  -41.42 -77.00-120.00  105
 23  \w   -112.00 -15.00   1.00   10.00    --  -41.42 -57.00 -60.00   97
 24  \w   -112.00 -15.00   1.00   10.00    --  -41.42 -57.00 120.00   97
 25  \w     87.00 178.00   1.00   30.00    --  111.00  45.00   0.00   91
 26  \w     83.00 178.00   1.00   30.00    --  111.00  61.00  90.00   95
 27  \w     87.00 178.00   1.00   30.00    --  111.00  45.00-120.00   91
 28  \w     80.00 178.00   1.00   30.00    --  111.00  77.00   0.00   98
 29  \w     87.00 178.00   1.00   30.00    --  111.00  45.00 -30.00   91
 30  \w     87.00 178.00   1.00   30.00    --  111.00  45.00 -90.00   91
 31  \w     83.00 178.00   1.00   30.00    --  111.00  61.00  60.00   95
 32  \w     83.00 178.00   1.00   30.00    --  111.00  61.00-150.00   95
 33  \w     83.00 178.00   1.00   30.00    --  111.00  61.00-180.00   95
 34  \w     80.00 178.00   1.00   30.00    --  111.00  77.00-180.00   98
 35  \w   -115.00 -10.00   1.00   10.00    --  -41.42 -77.00 150.00  105
;
_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      0.0327150000
_diffrn_orient_matrix_UB_12      -0.0295478000
_diffrn_orient_matrix_UB_13      0.0731130000
_diffrn_orient_matrix_UB_21      0.0227813000
_diffrn_orient_matrix_UB_22      -0.1300788000
_diffrn_orient_matrix_UB_23      -0.0207362000
_diffrn_orient_matrix_UB_31      0.1465595000
_diffrn_orient_matrix_UB_32      0.0443812000
_diffrn_orient_matrix_UB_33      0.0011057000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0703
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            44555
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.395
_diffrn_reflns_theta_min         4.034
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.884
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.653
_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    1.135
_exptl_crystal_description       plate
_exptl_crystal_F_000             858
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.755
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     711
_refine_ls_number_reflns         9466
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0680
_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^)+(0.0958P)^2^+1.5545P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1763
_refine_ls_wR_factor_ref         0.1830
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8262
_reflns_number_total             9466
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ma9b00182_si_006.cif
_cod_data_source_block           Complex6
_cod_database_code               1554178
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C50 H75 N1 O3 Ti1'
_chemical_oxdiff_usercomment     '@ 120 K BRML425'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C2-C1 \\sim C2A-C1A
 with sigma of 0.02
 C3-C2A \\sim C3-C2
 with sigma of 0.02
 C5A-C4A \\sim C5-C4
 with sigma of 0.02
 C4A-C3 \\sim C4-C3
 with sigma of 0.02
 C4-C11 \\sim C4A-C11
 with sigma of 0.02
 C7-C2A \\sim C7-C2
 with sigma of 0.02
 C35-C34 \\sim C35A-C34A
 with sigma of 0.02
 C34A-C33 \\sim C34-C33
 with sigma of 0.02
 C41-C34 \\sim C41-C34A
 with sigma of 0.02
 C32-C31A \\sim C32-C31
 with sigma of 0.02
 C20-C19 \\sim C20A-C19A
 with sigma of 0.02
 C19-C18 \\sim C19A-C18
 with sigma of 0.02
 C26-C19 \\sim C26-C19A
 with sigma of 0.02
 C17-C16 \\sim C17-C16A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19) = Uanis(C19A)
4. Others
 Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C1A)=Sof(C2A)=Sof(H3B)=Sof(C4A)=Sof(C5A)=
 Sof(H5A)=Sof(C6A)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H18A)=Sof(C19A)=
 Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=
 Sof(H33A)=Sof(C34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(C45A)=Sof(H45C)=
 Sof(H45D)=1-FVAR(1)
 Sof(O1)=Sof(O2)=Sof(O3)=Sof(C1)=Sof(C2)=Sof(H3A)=Sof(C4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H18)=Sof(C19)=Sof(C20)=
 Sof(H20)=Sof(C21)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H33)=Sof(C34)=
 Sof(C35)=Sof(H35)=Sof(C36)=Sof(C45)=Sof(H45A)=Sof(H45B)=FVAR(1)
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(2)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C15A(H15C,H15D), C30(H30A,H30B), C30A(H30C,H30D), C45(H45A,
 H45B), C45A(H45C,H45D), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B),
 C49(H49A,H49B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3A), C3(H3B), C5(H5), C5A(H5A), C18(H18), C18(H18A), C20(H20), C20A(H20A),
  C33(H33), C33(H33A), C35(H35), C35A(H35A)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C12A(H12D,H12E,H12F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,
 H14C), C14A(H14D,H14E,H14F), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C)
;
_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 1.270
_oxdiff_exptl_absorpt_empirical_full_min 0.815