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_1575590
_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(C23 H24 Cl Li N2 O6 Zn), 4.44(C H2 Cl2)'
_chemical_formula_sum            'C50.44 H56.88 Cl10.88 Li2 N4 O12 Zn2'
_chemical_formula_weight         1441.47
_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             2020-10-21
_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                 99.907(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.9150(3)
_cell_length_b                   24.9116(4)
_cell_length_c                   16.1264(3)
_cell_measurement_reflns_used    34829
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      28.7740
_cell_measurement_theta_min      3.6730
_cell_volume                     6298.3(2)
_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      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.981
_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      2.00  63.00   1.00    7.50    --   10.76-121.00 175.00   61
  2  \w     20.00  83.00   1.00    7.50    --   10.76-152.00  16.00   63
  3  \w    -36.00  61.00   1.00    7.50    --   -9.35  57.00   0.00   97
  4  \w    -80.00  17.00   1.00    7.50    --   -9.35 -57.00-150.00   97
  5  \w    -15.00  31.00   1.00    7.50    --   -9.35 -99.00 -30.00   46
  6  \w    -42.00  42.00   1.00    7.50    --   10.76 -77.00 120.00   84
  7  \w    -15.00  51.00   1.00    7.50    --   10.76 -99.00  60.00   66
  8  \w    -41.00  21.00   1.00    7.50    --   -9.35  77.00-150.00   62
  9  \w    -42.00  22.00   1.00    7.50    --   -9.35 -77.00 -60.00   64
 10  \w    -82.00 -57.00   1.00    7.50    --   -9.35 -38.00  60.00   25
 11  \w    -12.00  83.00   1.00    7.50    --   10.76  38.00 120.00   95
;
_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      0.0227813000
_diffrn_orient_matrix_UB_12      -0.0226216000
_diffrn_orient_matrix_UB_13      -0.0110555000
_diffrn_orient_matrix_UB_21      -0.0251755000
_diffrn_orient_matrix_UB_22      -0.0170556000
_diffrn_orient_matrix_UB_23      0.0210579000
_diffrn_orient_matrix_UB_31      -0.0299029000
_diffrn_orient_matrix_UB_32      -0.0028739000
_diffrn_orient_matrix_UB_33      -0.0377817000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            136091
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.280
_diffrn_reflns_theta_min         3.322
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.282
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6321
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1111 before and 0.0567 after correction.
The Ratio of minimum to maximum transmission is 0.8474.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'pale green'
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       prism
_exptl_crystal_F_000             2938
_exptl_crystal_recrystallization_method
'The material was recrystallised from dichloromethane by slow cooling'
_exptl_crystal_size_max          0.457
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.146
_refine_diff_density_max         2.381
_refine_diff_density_min         -1.730
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     785
_refine_ls_number_reflns         15347
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0564
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0687P)^2^+18.2225P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1428
_refine_ls_wR_factor_ref         0.1500
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12382
_reflns_number_total             15347
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00872g2.cif
_cod_data_source_block           jg20012
_cod_depositor_comments
'Adding full bibliography for 1575589--1575592.cif.'
_cod_database_code               1575590
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         ' C50 H56 Cl10 Li2 N4 O12 Zn2'
_chemical_oxdiff_usercomment     '@ 120 K  AJG212-ZnLi'
_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
 Cl10-Cl9 \\sim Cl10-Cl9A
 with sigma of 0.02
 C84-Cl9 \\sim C84-Cl9A
 with sigma of 0.02
 Cl7A-C83 \\sim Cl5A-C83
 with sigma of 0.02
 Cl5A-C83A \\sim Cl7A-C83
 with sigma of 0.02
 Cl6-Cl5A \\sim Cl6-Cl7A
 with sigma of 0.02
 Cl9A-C84 \\sim Cl9-C84
 with sigma of 0.02
3. Others
 Sof(Cl9A)=Sof(H84C)=Sof(H84D)=Sof(Cl10)=Sof(Cl11)=Sof(C85)=Sof(H85A)=
 Sof(H85B)=1-FVAR(1)
 Sof(Cl9)=Sof(H84A)=Sof(H84B)=FVAR(1)
 Sof(Cl5A)=Sof(C83A)=Sof(H83C)=Sof(H83D)=1-FVAR(2)
 Sof(Cl7A)=Sof(C83)=Sof(H83A)=Sof(H83B)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C61(H61A,H61B), C62(H62A,
 H62B), C63(H63A,H63B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
 C83A(H83C,H83D), C84(H84A,H84B), C84(H84C,H84D), C85(H85A,H85B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C16(H16), C18(H18), C20(H20), C53(H53), C55(H55),
 C57(H57), C66(H66), C68(H68), C70(H70)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C72(H72A,H72B,H72C), C73(H73A,
 H73B,H73C)
;
_shelx_res_checksum              807
_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 AJG212_Li
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 2.684
_oxdiff_exptl_absorpt_empirical_full_min 0.508