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_1575589
_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         'C23 H26 Al Cl2 Li N2 O7, C2 H4 Cl2'
_chemical_formula_sum            'C25 H30 Al Cl4 Li N2 O7'
_chemical_formula_weight         646.23
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-12-16
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-22 deposited with the CCDC.	2025-08-21 downloaded from the CCDC.
;
_cell_angle_alpha                75.8345(18)
_cell_angle_beta                 72.468(2)
_cell_angle_gamma                71.7946(15)
_cell_formula_units_Z            4
_cell_length_a                   14.0391(2)
_cell_length_b                   14.1908(2)
_cell_length_c                   16.3182(4)
_cell_measurement_reflns_used    38646
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.7680
_cell_measurement_theta_min      2.8600
_cell_volume                     2903.83(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.978
_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    106.00 160.00   0.50    1.44    --  102.53  19.00  90.00  108
  2  \w    109.00 160.00   0.50    1.44    --  102.53  19.00   0.00  102
  3  \w    137.00 165.00   0.50    1.44    --  102.53  77.00 -30.00   56
  4  \w    118.00 158.00   0.50    1.44    --  102.53  77.00  90.00   80
  5  \w     38.00 101.00   0.50    1.44    --  102.53-125.00 -60.00  126
  6  \w     38.00  99.00   0.50    1.44    --  102.53-125.00  90.00  122
  7  \w     41.00  66.00   0.50    1.44    --  102.53 -99.00-120.00   50
  8  \w     50.00  77.00   0.50    1.44    --  102.53 -99.00-180.00   54
  9  \w     41.00  66.00   0.50    1.44    --  102.53 -99.00  30.00   50
 10  \w    107.00 132.00   0.50    1.44    --  102.53  77.00 -90.00   50
 11  \w    -93.00 -67.00   0.50    1.44    --  -95.50 101.00-142.20   52
 12  \w    -92.00 -38.00   0.50    1.44    --  -95.50  93.00  95.95  108
 13  \w    -61.00 -36.00   0.50    1.44    --  -95.50 101.00-142.20   50
 14  \w    -93.00 -68.00   0.50    1.44    --  -95.50  98.00   0.33   50
 15  \w    -97.00 -40.00   0.50    1.44    --  -95.50 115.00 107.65  114
 16  \w    -93.00 -55.00   0.50    1.44    --  -95.50  91.00 -54.41   76
 17  \w    -93.00 -67.00   0.50    1.44    --  -95.50  98.00  20.87   52
 18  \w    -92.00 -66.00   0.50    1.44    --  -95.50  93.00-111.50   52
 19  \w    -92.00 -39.00   0.50    1.44    --  -95.50  94.00 -36.87  106
 20  \w    -93.00 -66.00   0.50    1.44    --  -94.00  94.00-169.40   54
 21  \w    -93.00 -65.00   0.50    1.44    --  -94.00  94.00  56.08   56
 22  \w    -93.00 -35.00   0.50    1.44    --  -94.00  94.00  72.76  116
 23  \w    -63.00 -31.00   0.50    1.44    --  -94.00  94.00-169.40   64
 24  \w    -44.00 -19.00   0.50    1.44    --  -87.49  57.00  30.00   50
 25  \w    -58.00 -28.00   0.50    1.44    --  -87.49  77.00 -90.00   60
 26  \w    -44.00 -19.00   0.50    1.44    --  -87.49  57.00 -60.00   50
 27  \w    -43.00 -18.00   0.50    1.44    --  -87.49  57.00 120.00   50
 28  \w    -44.00 -19.00   0.50    1.44    --  -87.49  57.00 -30.00   50
 29  \w   -149.00-124.00   0.50    1.44    --  -87.49 -99.00 -90.00   50
 30  \w    -44.00 -18.00   0.50    1.44    --  -87.49  57.00   0.00   52
 31  \w   -152.00 -93.00   0.50    1.44    --  -87.49 -19.00-150.00  118
 32  \w   -152.00 -89.00   0.50    1.44    --  -87.49 -19.00 120.00  126
 33  \w    -20.00  10.00   0.50    0.36    --  -55.02  38.00 -90.00   60
 34  \w   -119.00 -57.00   0.50    0.36    --  -55.02 -19.00  60.00  124
 35  \w    -20.00  17.00   0.50    0.36    --  -55.02  38.00  60.00   74
 36  \w    -66.00   6.00   0.50    0.36    --  -55.02  77.00 150.00  144
 37  \w    -20.00  16.00   0.50    0.36    --  -55.02  38.00   0.00   72
 38  \w    -20.00  13.00   0.50    0.36    --  -55.02  38.00-150.00   66
 39  \w     16.00  41.00   0.50    0.36    --   22.00  69.00-179.35   50
 40  \w    -93.00 -67.00   0.50    1.44    --  -94.00  94.00 -52.74   52
 41  \w    -99.00 -73.00   0.50    1.44    --  -95.50 123.00-130.87   52
 42  \w    -92.00 -66.00   0.50    1.44    --  -95.50  95.00-150.25   52
 43  \w    -93.00 -67.00   0.50    1.44    --  -95.50 101.00  60.87   52
 44  \w    -93.00 -67.00   0.50    1.44    --  -95.50 101.00 -60.52   52
 45  \w     40.00  65.00   0.50    1.44    --  102.53 -77.00-180.00   50
 46  \w     55.00 100.00   0.50    1.44    --  102.53-125.00-120.00   90
 47  \w     58.00  84.00   0.50    1.44    --  102.53-125.00-180.00   52
 48  \w     40.00  65.00   0.50    1.44    --  102.53 -77.00 -90.00   50
 49  \w     63.00  89.00   0.50    1.44    --  102.53 -95.00 150.00   52
 50  \w    128.00 154.00   0.50    1.44    --  102.53 125.00   0.00   52
 51  \w     42.00  92.00   0.50    1.44    --  102.53 -95.00 120.00  100
 52  \w     44.00  91.00   0.50    1.44    --  102.53 -95.00 -60.00   94
 53  \w     45.00  71.00   0.50    1.44    --  102.53 -77.00  60.00   52
 54  \w    119.00 157.00   0.50    1.44    --  102.53  77.00   0.00   76
 55  \w     40.00  65.00   0.50    1.44    --  102.53 -77.00  30.00   50
 56  \w    110.00 157.00   0.50    1.44    --  102.53  77.00 150.00   94
 57  \w     66.00  92.00   0.50    1.44    --  102.53 -95.00 -30.00   52
 58  \w    104.00 131.00   0.50    1.44    --  102.53  30.00 -60.00   54
 59  \w    149.00 174.00   0.50    1.44    --  102.53  30.00 -60.00   50
 60  \w     40.00  84.00   0.50    1.44    --  102.53-125.00 -90.00   88
 61  \w     73.00  99.00   0.50    1.44    --  102.53-125.00  60.00   52
 62  \w    120.00 166.00   0.50    1.44    --  102.53 125.00 -30.00   92
 63  \w     40.00  66.00   0.50    1.44    --  102.53 -77.00 -30.00   52
 64  \w     40.00  66.00   0.50    1.44    --  102.53 -77.00 150.00   52
 65  \w    101.00 132.00   0.50    1.44    --  102.53  61.00 120.00   62
 66  \w     53.00  92.00   0.50    1.44    --  102.53 -95.00 -90.00   78
 67  \w     64.00  90.00   0.50    1.44    --  102.53 -95.00  30.00   52
 68  \w     57.00  88.00   0.50    1.44    --  102.53 -95.00  90.00   62
 69  \w     44.00  90.00   0.50    1.44    --  102.53 -95.00   0.00   92
 70  \w    108.00 133.00   0.50    1.44    --  102.53  30.00 -30.00   50
 71  \w     64.00  90.00   0.50    1.44    --  102.53 -95.00  60.00   52
 72  \w     40.00  65.00   0.50    1.44    --  102.53 -77.00   0.00   50
 73  \w     65.00  91.00   0.50    1.44    --  102.53 -95.00-180.00   52
 74  \w    116.00 142.00   0.50    1.44    --  102.53  45.00   0.00   52
 75  \w    143.00 169.00   0.50    1.44    --  102.53  45.00  30.00   52
 76  \w    137.00 163.00   0.50    1.44    --  102.53  77.00-120.00   52
 77  \w    112.00 138.00   0.50    1.44    --  102.53  77.00 120.00   52
 78  \w     75.00 101.00   0.50    1.44    --  102.53-125.00  30.00   52
 79  \w    138.00 166.00   0.50    1.44    --  102.53 125.00-180.00   56
 80  \w    122.00 148.00   0.50    1.44    --  102.53  15.00-150.00   52
 81  \w     57.00  83.00   0.50    1.44    --  102.53 -95.00-120.00   52
 82  \w    122.00 155.00   0.50    1.44    --  102.53  77.00-150.00   66
 83  \w    105.00 152.00   0.50    1.44    --  102.53  45.00  90.00   94
 84  \w     58.00  94.00   0.50    1.44    --  102.53-125.00   0.00   72
 85  \w     41.00  69.00   0.50    1.44    --  102.53 -77.00 -60.00   56
 86  \w     75.00 101.00   0.50    1.44    --  102.53-125.00  90.00   52
 87  \w    113.00 139.00   0.50    1.44    --  102.53  30.00   0.00   52
 88  \w    114.00 140.00   0.50    1.44    --  102.53  61.00-180.00   52
 89  \w    100.00 126.00   0.50    1.44    --  102.53  61.00  30.00   52
 90  \w    116.00 142.00   0.50    1.44    --  102.53  61.00 150.00   52
 91  \w    131.00 157.00   0.50    1.44    --  102.53 125.00 -60.00   52
 92  \w    113.00 139.00   0.50    1.44    --  102.53 125.00  60.00   52
 93  \w    132.00 158.00   0.50    1.44    --  102.53 125.00-150.00   52
 94  \w     21.00  48.00   0.50    0.36    --   26.00  67.00  38.16   54
 95  \w     31.00  59.00   0.50    0.36    --   34.00  61.00 -20.12   56
 96  \w   -132.00 -62.00   0.50    0.36    --  -62.00 -51.00 -88.31  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0304411000
_diffrn_orient_matrix_UB_12      -0.0047383000
_diffrn_orient_matrix_UB_13      -0.0981209000
_diffrn_orient_matrix_UB_21      -0.1118244000
_diffrn_orient_matrix_UB_22      0.0020829000
_diffrn_orient_matrix_UB_23      0.0045134000
_diffrn_orient_matrix_UB_31      -0.0275274000
_diffrn_orient_matrix_UB_32      0.1157790000
_diffrn_orient_matrix_UB_33      -0.0208074000
_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  0.0476
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            75069
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.555
_diffrn_reflns_theta_min         2.880
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    4.398
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.819
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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            'clear colourless'
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_description       lath
_exptl_crystal_F_000             1336
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of hexane and 1,2-dichloroethane  by vapour diffusion'
_exptl_crystal_size_max          0.111
_exptl_crystal_size_mid          0.038
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.989
_refine_diff_density_min         -0.752
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     752
_refine_ls_number_reflns         12077
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0529P)^2^+1.8176P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1014
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10576
_reflns_number_total             12077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00872g2.cif
_cod_data_source_block           jg24020b
_cod_depositor_comments
'Adding full bibliography for 1575589--1575592.cif.'
_cod_original_cell_volume        2903.82(11)
_cod_database_code               1575589
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C50  H60  Al2  Cl8  Li2  N4  O14  '
_chemical_oxdiff_usercomment     '@ 100 K L2-Al/Li'
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.641
_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
 Cl74-C75A \\sim Cl74-C75
 with sigma of 0.02
 C75A-C74A \\sim C75-C74
 with sigma of 0.02
 Cl73-C74A \\sim Cl73-C74
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C74A) = Uanis(C74)
Uanis(C75) = Uanis(C75A)
4. Others
 Sof(C74A)=Sof(H74C)=Sof(H74D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=1-FVAR(1)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=Sof(H75B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C26(H26A,H26B), C71(H71A,H71B), C72(H72A,H72B), C74(H74A,H74B),
 C74A(H74C,H74D), C75(H75A,H75B), C75A(H75C,H75D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C13(H13), C15(H15), C17(H17), C53(H53), C55(H55),
 C57(H57), C63(H63), C65(H65), C67(H67)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C)
;
_shelx_res_checksum              95128
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 1000'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mitegen tip in Paratone oil'
_olex2_submission_original_sample_id L2-Al/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 1.214
_oxdiff_exptl_absorpt_empirical_full_min 0.823