Highly heteroselective ring-opening polymerization of rac-lactide initiated by rare-earth alkoxides bearing chiral [NNOO]-type amine-bis(phenolate) ligands
Duan, Yu-Lai; Guo, Qian; Liu, Gui-Yang; Yi, Zhong-Zhou; Feng, Shao-Ping; Huang, Yong; Polymer Chemistry 13 (2022) 4249–4259; doi:10.1039/D2PY00455K

data_1567256
_publ_section_title
;
 Highly heteroselective ring-opening polymerization of rac-lactide
 initiated by rare-earth alkoxides bearing chiral [NNOO]-type
 amine-bis(phenolate) ligands
;
_journal_issue                   29
_journal_name_full               'Polymer Chemistry'
_journal_page_first              4249
_journal_page_last               4259
_journal_paper_doi               10.1039/D2PY00455K
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C46 H77 N2 O4 Y, 0.5(C6 H14), 0.25(C4 H8 O)'
_chemical_formula_sum            'C50 H86 N2 O4.25 Y'
_chemical_formula_weight         872.11
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-03-23 deposited with the CCDC.	2022-06-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.244(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.9272(8)
_cell_length_b                   11.1967(5)
_cell_length_c                   41.785(2)
_cell_measurement_reflns_used    4858
_cell_measurement_temperature    294.06(10)
_cell_measurement_theta_max      23.4630
_cell_measurement_theta_min      3.4970
_cell_volume                     10250.9(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      294.06(10)
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0724
_diffrn_reflns_av_unetI/netI     0.1503
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            20504
_diffrn_reflns_point_group_measured_fraction_full 0.800
_diffrn_reflns_point_group_measured_fraction_max 0.800
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         3.330
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.179
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91034
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.130
_exptl_crystal_description       plate
_exptl_crystal_F_000             3784
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.09
_refine_diff_density_max         2.311
_refine_diff_density_min         -1.397
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.023(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1271
_refine_ls_number_reflns         14494
_refine_ls_number_restraints     1100
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1342
_refine_ls_R_factor_gt           0.1046
_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^)+(0.1403P)^2^+25.5350P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2596
_refine_ls_wR_factor_ref         0.2917
_reflns_Friedel_coverage         0.519
_reflns_Friedel_fraction_full    0.579
_reflns_Friedel_fraction_max     0.579
_reflns_number_gt                10545
_reflns_number_total             14494
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2py00455k2.cif
_cod_data_source_block           a
_cod_depositor_comments
'Adding full bibliography for 1567255--1567256.cif.'
_cod_database_code               1567256
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.977(14)
 0.023(14)
2. 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
3. Restrained distances
 C98'-C99' = C99'-C1B
 1.54 with sigma of 0.02
 C97'-C98' = C98'-C99'
 1.54 with sigma of 0.02
 C96-O9 = O9-C93
 1.43 with sigma of 0.02
 C1B-C1A = C1A-C1C
 1.54 with sigma of 0.02
 C100-C101 = C101-C102
 1.54 with sigma of 0.02
 C99-C100 = C100-C101
 1.54 with sigma of 0.02
 C99'-C1B = C1B-C1A
 1.54 with sigma of 0.02
 C97-C98 = C98-C99
 1.54 with sigma of 0.02
 C98-C99 = C99-C100
 1.54 with sigma of 0.02
 C96-C95 = C95-C94
 1.54 with sigma of 0.02
 C97'-C99'
 2.515 with sigma of 0.04
 C1B-C1C
 2.515 with sigma of 0.04
 C99-C101
 2.515 with sigma of 0.04
 C100-C102
 2.515 with sigma of 0.04
 C98-C100
 2.515 with sigma of 0.04
 C98'-C1B
 2.515 with sigma of 0.04
 C99'-C1A
 2.515 with sigma of 0.04
 C97-C99
 2.515 with sigma of 0.04
 C96-C94
 2.515 with sigma of 0.04
 C83-C82 \\sim C85-C82 \\sim C84-C82 \\sim C80-C78 \\sim C79-C78 \\sim C81-C78
\\sim C71-C70 \\sim C72-C70
 \\sim C73-C70
 with sigma of 0.02
 C32-C34 \\sim C32-C33 \\sim C32-C35 \\sim C32-C35' \\sim C32-C34' \\sim
C32-C33'
 with sigma of 0.02
 C34-C33 \\sim C34-C35 \\sim C33-C35 \\sim C35'-C34' \\sim C35'-C33' \\sim
C34'-C33'
 with sigma of 0.04
 C74-C77 \\sim C74-C76 \\sim C74-C75 \\sim C74-C75' \\sim C74-C77' \\sim
C74-C76'
 with sigma of 0.02
 C77-C76 \\sim C77-C75 \\sim C76-C75 \\sim C75'-C77' \\sim C75'-C76' \\sim
C77'-C76'
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C101 \\sim C100 \\sim C99 \\sim C98 \\sim C97 \\sim C102 \\sim C1A \\sim C1B
\\sim C99' \\sim C98' \\sim C97' \\sim C1C: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C40 \\sim C41' \\sim C42 \\sim O3' \\sim C41 \\sim C42' \\sim O3: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C30 \\sim C29 \\sim C31 \\sim C30' \\sim C29' \\sim C31': within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C20 \\sim C21 \\sim C22 \\sim C23 \\sim C21' \\sim C22' \\sim C23': within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C50 \\sim C74 \\sim C77 \\sim C76 \\sim C75 \\sim C75' \\sim C77' \\sim C76':
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C95 \\sim C94 \\sim C93 \\sim C96 \\sim O9: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C32 \\sim C34 \\sim C33 \\sim C35 \\sim C35' \\sim C34' \\sim C33': within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C89 \\sim C90 \\sim C91 \\sim C92 \\sim C89' \\sim C90' \\sim C91' \\sim C92':
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C40) \\sim Ueq, Uanis(O3') \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C101) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C98)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C1A) \\sim Ueq,
Uanis(C1B) \\sim Ueq, Uanis(C99') \\sim Ueq, Uanis(C98') \\sim Ueq, Uanis(C97')
\\sim Ueq, Uanis(C1C) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C84) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C86) \\sim Ueq,
Uanis(C57) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C85)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C95) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C96)
\\sim Ueq, Uanis(O9) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms
of 0.04
Uanis(O5) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C50) \\sim
Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O7) \\sim Ueq, Uanis(C56) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
5. Rigid body (RIGU) restrains
 C101, C100, C99, C98, C97, C102, C1A, C1B, C99', C98', C97', C1C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C40, Y1, C41', C42, O3', C41, C42', O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C20, C21, C21', C22, C22', C23, C23'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O8, C89, C90, C91, C92, C89', C90', C91', C92'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Same fragment restrains
{C30, C29, C31} sigma for 1-2: 0.01, 1-3: 0.02
as
{C30', C29', C31'}
{C89, C90, C91, C92} sigma for 1-2: 0.01, 1-3: 0.02
as
{C89', C90', C91', C92'}
7. Others
 Sof(H40A)=Sof(C30')=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C29')=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C31')=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C41)=Sof(H41D)=
 Sof(H41E)=Sof(H41F)=Sof(C42')=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(O3)=1-FVAR(1)
 Sof(H40)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C41')=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(O3')=FVAR(1)
 Sof(C75')=Sof(H75D)=Sof(H75E)=Sof(H75F)=Sof(C77')=Sof(H77D)=Sof(H77E)=
 Sof(H77F)=Sof(C76')=Sof(H76D)=Sof(H76E)=Sof(H76F)=1-FVAR(2)
 Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(2)
 Sof(C35')=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C34')=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=Sof(C33')=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(3)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(3)
 Sof(C89')=Sof(H89C)=Sof(H89D)=Sof(C90')=Sof(H90C)=Sof(H90D)=Sof(C91')=
 Sof(H91C)=Sof(H91D)=Sof(C92')=Sof(H92C)=Sof(H92D)=1-FVAR(4)
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(C91)=Sof(H91A)=
 Sof(H91B)=Sof(C92)=Sof(H92A)=Sof(H92B)=FVAR(4)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C99')=Sof(H99C)=
 Sof(H99D)=Sof(C98')=Sof(H98C)=Sof(H98D)=Sof(C97')=Sof(H97D)=Sof(H97E)=
 Sof(H97F)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=1-FVAR(5)
 Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(C100)=Sof(H10C)=Sof(H10D)=Sof(C99)=
 Sof(H99A)=Sof(H99B)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(C97)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=Sof(C102)=Sof(H10E)=Sof(H10F)=Sof(H10G)=FVAR(5)
 Sof(H20C)=Sof(H20D)=Sof(C21')=Sof(H21C)=Sof(H21D)=Sof(C22')=Sof(H22C)=
 Sof(H22D)=Sof(C23')=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(6)
 Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(6)
 Fixed Sof: C95(0.5) H95A(0.5) H95B(0.5) C94(0.5) H94A(0.5) H94B(0.5) C93(0.5)
 H93A(0.5) H93B(0.5) C96(0.5) H96A(0.5) H96B(0.5) O9(0.5)
 Fixed U11: O3'(0.009999) O3(0.010281)
 Fixed U22: O3'(0.01) O3(0.01104)
 Fixed U33: O3'(0.01) O3(0.01038)
 Fixed X: O9(0.5068)
 Fixed Y: C97'(-0.1543)
 Fixed Z: C21'(0.32059)
8.a Riding coordinates:
 C29'(H29D,H29E,H29F), C33'(H33D,H33E,H33F), C97'(H97D,H97E,H97F), C1C(H1CA,
 H1CB,H1CC)
8.b Ternary CH refined with riding coordinates:
 C16(H16), C40(H40A), C40(H40), C62(H62), C86(H86)
8.c Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B), C20(H20C,H20D), C43(H43A,H43B), C44(H44A,H44B),
  C45(H45A,H45B), C46(H46A,H46B), C54(H54A,H54B), C53(H53A,H53B), C61(H61A,
 H61B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B),
 C67(H67A,H67B), C68(H68A,H68B), C21(H21A,H21B), C22(H22A,H22B), C89(H89A,H89B),
  C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B), C101(H10A,H10B), C100(H10C,
 H10D), C99(H99A,H99B), C98(H98A,H98B), C21'(H21C,H21D), C22'(H22C,H22D),
 C89'(H89C,H89D), C90'(H90C,H90D), C91'(H91C,H91D), C92'(H92C,H92D), C1A(H1AA,
 H1AB), C1B(H1BA,H1BB), C99'(H99C,H99D), C98'(H98C,H98D), C95(H95A,H95B),
 C94(H94A,H94B), C93(H93A,H93B), C96(H96A,H96B)
8.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C10(H10), C12(H12), C58(H58), C56(H56), C51(H51), C49(H49)
8.e Fitted hexagon refined as free rotating group:
 C5(C4,C3,C2,C1,C6), C11(C10,C9,C14,C13,C12), C57(C58,C59,C60,C55,C56),
 C51(C52,C47,C48,C49,C50)
8.f Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C39(H39A,H39B,
 H39C), C38(H38A,H38B,H38C), C37(H37A,H37B,H37C), C84(H84A,H84B,H84C), C83(H83A,
 H83B,H83C), C85(H85A,H85B,H85C), C79(H79A,H79B,H79C), C81(H81A,H81B,H81C),
 C80(H80A,H80B,H80C), C73(H73A,H73B,H73C), C72(H72A,H72B,H72C), C71(H71A,H71B,
 H71C), C69(H69A,H69B,H69C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C30(H30A,
 H30B,H30C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C34(H34A,H34B,H34C),
 C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C23(H23A,H23B,H23C), C41'(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C77(H77A,H77B,H77C), C76(H76A,H76B,H76C), C75(H75A,
 H75B,H75C), C97(H97A,H97B,H97C), C102(H10E,H10F,H10G), C30'(H30D,H30E,H30F),
 C31'(H31D,H31E,H31F), C35'(H35D,H35E,H35F), C34'(H34D,H34E,H34F), C23'(H23D,
 H23E,H23F), C41(H41D,H41E,H41F), C42'(H42D,H42E,H42F), C75'(H75D,H75E,H75F),
 C77'(H77D,H77E,H77F), C76'(H76D,H76E,H76F)
;
_shelx_res_checksum              28891
_shelx_hkl_checksum              2566
_olex2_submission_special_instructions 'No special instructions were received'