Heterometallic Li/Zn, Li/Al and Li/In catalysts for <i>rac</i>-lactide ring-opening polymerisation: "ate" or "non-ate" pathways?
Piyawongsiri, Thitirat; Gaston, Anand J.; Abdul Rahman, Maisarah; Hughes, Jack W. J.; Rudman, George E.; Lowy, Phoebe A.; Nichol, Gary S.; Morrison, Carole A.; Phomphrai, Khamphee; Garden, Jennifer A.; Catalysis science & technology 15 (2025) 6113–6121; doi:10.1039/d5cy00872g

data_1575591
_publ_section_title
;
 Heterometallic Li/Zn, Li/Al and Li/In catalysts for <i>rac</i>-lactide
 ring-opening polymerisation: "ate" or "non-ate" pathways?
;
_journal_issue                   20
_journal_name_full               'Catalysis science &amp; technology'
_journal_page_first              6113
_journal_page_last               6121
_journal_paper_doi               10.1039/d5cy00872g
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety
'2(C H2 Cl2), 2(C46 H48 Li4 N4 O12), 3[CH2Cl2], 0.5[], 1[], 1[]'
_chemical_formula_sum            'C97 H106 Cl10 Li8 N8 O24'
_chemical_formula_weight         2178.00
_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             2020-11-02
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2025-04-22 deposited with the CCDC.	2025-08-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.824(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.8774(4)
_cell_length_b                   19.3305(2)
_cell_length_c                   26.1585(4)
_cell_measurement_reflns_used    33385
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      76.1000
_cell_measurement_theta_min      4.0810
_cell_volume                     10412.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(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 0.993
_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   -113.00 -56.00   1.00   12.00    --  -40.50-156.00 -45.00   57
  2  \w   -108.00 -22.00   1.00   12.00    --  -40.50 156.00  -8.00   86
  3  \w    -85.00  -1.00   1.00   12.00    --  -40.50 119.00-164.00   84
  4  \w     22.00  94.00   1.00   12.00    --   42.22-119.00 110.00   72
  5  \w     44.00 118.00   1.00   12.00    --   42.22-156.00 -45.00   74
  6  \w     44.00 133.00   1.00   27.00    --  111.00-156.00 -45.00   89
  7  \w    100.00 178.00   1.00   27.00    --  111.00 119.00-164.00   78
  8  \w     78.00 161.00   1.00   27.00    --  111.00 156.00  -8.00   83
  9  \w     38.00 110.00   1.00   27.00    --  111.00-119.00 110.00   72
 10  \w   -113.00 -18.00   1.00   12.00    --  -40.50 -38.00 -60.00   95
 11  \w   -111.00 -14.00   1.00   12.00    --  -40.50 -57.00-150.00   97
 12  \w     11.00  42.00   1.00   12.00    --   42.22  78.00-141.48   31
 13  \w     10.00  42.00   1.00   12.00    --   42.22  79.00 166.20   32
 14  \w     20.00 115.00   1.00   12.00    --   42.22  38.00  90.00   95
 15  \w     11.00  42.00   1.00   12.00    --   42.22  78.00-160.75   31
 16  \w    103.00 178.00   1.00   27.00    --  111.00  77.00 -90.00   75
 17  \w     39.00 112.00   1.00   27.00    --  111.00-125.00-120.00   73
 18  \w     40.00 135.00   1.00   27.00    --  111.00 -45.00  90.00   95
 19  \w    103.00 178.00   1.00   27.00    --  111.00  77.00 150.00   75
 20  \w     86.00 178.00   1.00   27.00    --  111.00  50.00 -30.80   92
 21  \w     97.00 178.00   1.00   27.00    --  111.00 125.00  30.00   81
 22  \w    103.00 178.00   1.00   27.00    --  111.00  77.00  60.00   75
 23  \w     30.00 107.00   1.00   27.00    --  111.00 -94.00 120.00   77
 24  \w     87.00 178.00   1.00   27.00    --  111.00  30.00  60.00   91
 25  \w     97.00 178.00   1.00   27.00    --  111.00 125.00  90.00   81
 26  \w     39.00 112.00   1.00   27.00    --  111.00-125.00 -30.00   73
 27  \w     39.00 112.00   1.00   27.00    --  111.00-125.00-150.00   73
 28  \w     66.00 178.00   1.00   27.00    --  111.00  15.00 -90.00  112
 29  \w     30.00 107.00   1.00   27.00    --  111.00 -94.00  90.00   77
 30  \w     39.00 112.00   1.00   27.00    --  111.00-125.00  90.00   73
 31  \w     34.00 108.00   1.00   27.00    --  111.00-104.00-162.35   74
 32  \w     32.00 107.00   1.00   27.00    --  111.00-101.00 -30.03   75
 33  \w     39.00 112.00   1.00   27.00    --  111.00-125.00 -90.00   73
 34  \w     41.00 139.00   1.00   27.00    --  111.00 -61.00  30.00   98
 35  \w     41.00 139.00   1.00   27.00    --  111.00 -61.00 -30.00   98
 36  \w     30.00 107.00   1.00   27.00    --  111.00 -94.00   0.00   77
 37  \w     97.00 178.00   1.00   27.00    --  111.00 125.00 150.00   81
 38  \w     41.00  93.00   1.00   27.00    --  111.00-125.00  30.00   52
 39  \w     42.00 112.00   1.00   27.00    --  111.00-125.00 -60.00   70
 40  \w     44.00  71.00   1.00   27.00    --  111.00-125.00 150.00   27
 41  \w    134.00 161.00   1.00   27.00    --  111.00  49.00 126.24   27
 42  \w     86.00 116.00   1.00   27.00    --  111.00  49.00 126.24   30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0601878000
_diffrn_orient_matrix_UB_12      -0.0002037000
_diffrn_orient_matrix_UB_13      0.0579222000
_diffrn_orient_matrix_UB_21      0.0428037000
_diffrn_orient_matrix_UB_22      0.0214626000
_diffrn_orient_matrix_UB_23      -0.0293023000
_diffrn_orient_matrix_UB_31      -0.0118549000
_diffrn_orient_matrix_UB_32      0.0767547000
_diffrn_orient_matrix_UB_33      0.0083099000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1241
_diffrn_reflns_av_unetI/netI     0.0579
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            210539
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.416
_diffrn_reflns_theta_min         3.754
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.070
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47612
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.389
_exptl_crystal_description       needle
_exptl_crystal_F_000             4520
_exptl_crystal_recrystallization_method
'The material was recrystallised from dichloromethane by slow evaporation'
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.064
_refine_diff_density_max         2.464
_refine_diff_density_min         -1.266
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1403
_refine_ls_number_reflns         22026
_refine_ls_number_restraints     142
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0998
_refine_ls_R_factor_gt           0.0872
_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^)+(0.1784P)^2^+7.4193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2358
_refine_ls_wR_factor_ref         0.2514
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18666
_reflns_number_total             22026
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00872g2.cif
_cod_data_source_block           jg20014
_cod_depositor_comments
'Adding full bibliography for 1575589--1575592.cif.'
_cod_database_code               1575591
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H24Li2ClN2O6
_chemical_oxdiff_usercomment     '@120 K AJG214-Li'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6784(14)
 0.3216(14)
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. Shared sites
{C105, Cl0A}
{Cl9, C15A}
4. Rigid bond restraints
 Cl7A, Cl8A, C14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl7B, Cl8B, C14B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl7, Cl8, C104
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl5, Cl6, C103
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Cl7 \\sim Cl8 \\sim C104: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl7A \\sim Cl8A \\sim C14A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl7B \\sim Cl8B \\sim C14B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl5 \\sim Cl6 \\sim C103: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C105) = Uanis(Cl0A)
Uanis(Cl9) = Uanis(C15A)
6. Rigid body (RIGU) restrains
 Cl5, Cl6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl7, Cl8, C104
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl7B, Cl8B, C14B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl7A, Cl8A, C14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl5, Cl6, C103
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{Cl1, Cl2, C101} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cl0A, Cl9A, C15A}
{Cl1, Cl2, C101} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cl5, Cl6, C103}
{Cl1, Cl2, C101} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cl7, Cl8, C104}
{Cl1, Cl2, C101} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cl7A, Cl8A, C14A}
{Cl1, Cl2, C101} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cl7B, Cl8B, C14B}
{Cl1, Cl2, C101} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Cl9, Cl10, C105}
8. Others
 1*[Sof(Cl7)+Sof(Cl8)+Sof(C104)+Sof(H10G)+Sof(H10H)]+1*[Sof(Cl7A)+Sof(Cl8A)+
 Sof(C14A)+Sof(H14A)+Sof(H14B)]+1*[Sof(Cl7B)+Sof(Cl8B)+Sof(C14B)+Sof(H14C)+
 Sof(H14D)]=1 with esd of 0.001
 Sof(Cl7)=Sof(Cl8)=Sof(C104)=Sof(H10G)=Sof(H10H)=FVAR(1)
 Sof(Cl7A)=Sof(Cl8A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=FVAR(2)
 Sof(Cl7B)=Sof(Cl8B)=Sof(C14B)=Sof(H14C)=Sof(H14D)=FVAR(3)
 Sof(Cl0A)=Sof(Cl9A)=Sof(C15A)=Sof(H15A)=Sof(H15B)=1-FVAR(4)
 Sof(Cl9)=Sof(Cl10)=Sof(C105)=Sof(H10I)=Sof(H10J)=FVAR(4)
9.a Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C15A(H15A,H15B), C102(H10C,H10D), C103(H10E,H10F), C104(H10G,
 H10H), C14A(H14A,H14B), C14B(H14C,H14D), C105(H10I,H10J), C1(H1A,H1B), C2(H2A,
 H2B), C3(H3A,H3B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C74(H74A,H74B), C75(H75A,H75B),
 C76(H76A,H76B)
9.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C11(H11), C16(H16), C18(H18), C21(H21), C27(H27), C29(H29),
 C31(H31), C39(H39), C41(H41), C44(H44), C56(H56), C58(H58), C61(H61), C66(H66),
  C68(H68), C71(H71), C79(H79), C81(H81), C84(H84), C89(H89), C91(H91), C94(H94)
9.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C72(H72A,H72B,H72C),
 C73(H73A,H73B,H73C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C95(H95A,H95B,
 H95C), C96(H96A,H96B,H96C)
;
_shelx_res_checksum              89275
_platon_squeeze_void_probe_radius 1.20
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id AJG214-Li
_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 2.930
_oxdiff_exptl_absorpt_empirical_full_min 0.703