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_1575592
_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 H24 Cl2 In Li N2 O6'
_chemical_formula_sum            'C23 H24 Cl2 In Li N2 O6'
_chemical_formula_weight         617.120
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_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                90
_cell_angle_beta                 96.153(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2410(1)
_cell_length_b                   19.9078(1)
_cell_length_c                   13.6849(1)
_cell_measurement_reflns_used    50765
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.8000
_cell_measurement_theta_min      3.9030
_cell_volume                     2503.08(4)
_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  'olex2.refine 1.5-beta (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(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 1.0000
_diffrn_measured_fraction_theta_max 0.9934
_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    102.00 167.00   0.50    0.06    --   96.20  38.00  30.00  130
  2  \w     43.00  90.00   0.50    0.06    --   96.20 -99.00 -30.00   94
  3  \w    107.00 159.00   0.50    0.06    --   96.20  77.00  90.00  104
  4  \w     35.00  70.00   0.50    0.06    --   96.20 -77.00-120.00   70
  5  \w   -147.00 -99.00   0.50    0.06    --  -87.45 -77.00   0.00   96
  6  \w    -44.00 -18.00   0.50    0.06    --  -87.45  57.00-120.00   52
  7  \w   -101.00 -40.00   0.50    0.06    --  -87.45 125.00-120.00  122
  8  \w    -67.00 -25.00   0.50    0.06    --  -87.45  77.00   0.00   84
  9  \w    -64.00 -25.00   0.50    0.06    --  -87.45  77.00 150.00   78
 10  \w    -43.00  12.00   0.50    0.06    --  -54.93  57.00-120.00  110
 11  \w    -19.00  17.00   0.50    0.06    --  -54.93  38.00  30.00   72
 12  \w    -17.00   9.00   0.50    0.06    --  -54.93  38.00   0.00   52
 13  \w    -18.00  17.00   0.50    0.06    --   51.93 -38.00  90.00   70
 14  \w     57.00  89.00   0.50    0.06    --   51.89  38.00  30.00   64
 15  \w    -45.00 -20.00   0.50    0.06    --    2.00 131.00  33.66   50
 16  \w     33.00  58.00   0.50    0.06    --   34.00  56.00  -7.26   50
 17  \w   -101.00 -75.00   0.50    0.06    --  -95.50 125.00-146.11   52
 18  \w     53.00  89.00   0.50    0.06    --  102.53 -95.00 -90.00   72
 19  \w     40.00  71.00   0.50    0.06    --  102.53 -77.00-150.00   62
 20  \w     42.00  92.00   0.50    0.06    --  102.53 -95.00 -60.00  100
 21  \w     42.00  69.00   0.50    0.06    --  102.53 -77.00  90.00   54
 22  \w     44.00  91.00   0.50    0.06    --  102.53 -95.00 -30.00   94
 23  \w    127.00 160.00   0.50    0.06    --  102.53  77.00 120.00   66
 24  \w    101.00 128.00   0.50    0.06    --  102.53  61.00   0.00   54
 25  \w    146.00 171.00   0.50    0.06    --  102.53  61.00   0.00   50
 26  \w    113.00 151.00   0.50    0.06    --  102.53  15.00  60.00   76
 27  \w     55.00  81.00   0.50    0.06    --  102.53 -95.00-150.00   52
 28  \w     41.00  68.00   0.50    0.06    --  102.53 -77.00 -60.00   54
 29  \w     97.00 123.00   0.50    0.06    --  102.53 125.00-120.00   52
 30  \w    131.00 157.00   0.50    0.06    --  102.53 125.00 150.00   52
 31  \w    130.00 164.00   0.50    0.06    --  102.53 125.00-120.00   68
 32  \w     41.00  73.00   0.50    0.06    --  102.53 -77.00 -90.00   64
 33  \w     40.00  65.00   0.50    0.06    --  102.53 -77.00 -30.00   50
 34  \w     44.00  70.00   0.50    0.06    --  102.53 -77.00   0.00   52
 35  \w    121.00 150.00   0.50    0.06    --  102.53  77.00-120.00   58
 36  \w    128.00 164.00   0.50    0.06    --  102.53 125.00  90.00   72
 37  \w    103.00 147.00   0.50    0.06    --  102.53  15.00 -90.00   88
 38  \w     49.00  76.00   0.50    0.06    --  102.53 -95.00 150.00   54
 39  \w     44.00  91.00   0.50    0.06    --  102.53 -95.00   0.00   94
 40  \w     43.00  69.00   0.50    0.06    --  102.53 -77.00-180.00   52
 41  \w    118.00 143.00   0.50    0.06    --  102.53  15.00-120.00   50
 42  \w    105.00 131.00   0.50    0.06    --  102.53  15.00  30.00   52
 43  \w    109.00 135.00   0.50    0.06    --  102.53  77.00  90.00   52
 44  \w     43.00  69.00   0.50    0.06    --  102.53-125.00-120.00   52
 45  \w    139.00 169.00   0.50    0.06    --  102.53  61.00  60.00   60
 46  \w    102.00 134.00   0.50    0.06    --  102.53  61.00  60.00   64
 47  \w     18.00  43.00   0.50    0.06    --   51.89-105.00-114.00   50
 48  \w     43.00  69.00   0.50    0.06    --  102.53 -77.00  90.00   52
 49  \w     65.00  91.00   0.50    0.06    --  102.53 -95.00 -30.00   52
 50  \w    123.00 149.00   0.50    0.06    --  102.53  61.00 -90.00   52
 51  \w    142.00 167.00   0.50    0.06    --  102.53 125.00  90.00   50
 52  \w    131.00 157.00   0.50    0.06    --  102.53 125.00 150.00   52
 53  \w     57.00  88.00   0.50    0.06    --  102.53-125.00-180.00   62
 54  \w   -149.00-124.00   0.50    0.06    --  -87.49-105.00-114.00   50
 55  \w     43.00  69.00   0.50    0.06    --  102.53 -77.00 120.00   52
 56  \w     65.00  91.00   0.50    0.06    --  102.53 -95.00 -30.00   52
 57  \w    131.00 157.00   0.50    0.06    --  102.53 125.00 150.00   52
 58  \w     43.00  69.00   0.50    0.06    --  102.53 -77.00  90.00   52
 59  \w    -65.00 -40.00   0.50    0.06    --  -55.02 105.00 -14.00   50
 60  \w     65.00  91.00   0.50    0.06    --  102.53 -95.00 -30.00   52
 61  \w    131.00 157.00   0.50    0.06    --  102.53 125.00 150.00   52
 62  \w     43.00  69.00   0.50    0.06    --  102.53 -77.00  90.00   52
 63  \w     26.00  54.00   0.50    0.06    --   30.00  64.00 -41.07   56
 64  \w     33.00  59.00   0.50    0.06    --   34.00  58.00  32.44   52
 65  \w     33.00  59.00   0.50    0.06    --   34.00  57.00-140.40   52
 66  \w     33.00  59.00   0.50    0.06    --   34.00  56.00 168.22   52
 67  \w     32.00  59.00   0.50    0.06    --   34.00  60.00 102.37   54
 68  \w     53.00 122.00   0.50    0.06    --   51.89  50.00-135.86  138
 69  \w   -139.00 -69.00   0.50    0.06    --  -70.00 -55.00 147.82  140
 70  \w   -147.00 -80.00   0.50    0.06    --  -78.00 -56.00-138.00  134
 71  \w   -147.00 -77.00   0.50    0.06    --  -78.00 -55.00 -54.74  140
 72  \w   -147.00 -78.00   0.50    0.06    --  -78.00 -54.00 105.61  138
 73  \w   -147.00 -77.00   0.50    0.06    --  -78.00 -55.00  74.66  140
 74  \w   -148.00 -79.00   0.50    0.06    --  -78.00 -48.00 -36.80  138
 75  \w   -147.00 -77.00   0.50    0.06    --  -78.00 -55.00 179.19  140
 76  \w   -151.00 -82.00   0.50    0.06    --  -82.00 -54.00  39.66  138
 77  \w   -151.00 -82.00   0.50    0.06    --  -82.00 -54.00  -0.47  138
 78  \w   -151.00 -81.00   0.50    0.06    --  -82.00 -55.00 -91.85  140
 79  \w   -150.00 -80.00   0.50    0.06    --  -82.00 -61.00 133.12  140
 80  \w   -151.00 -81.00   0.50    0.06    --  -82.00 -56.00 -70.27  140
 81  \w   -152.00 -82.00   0.50    0.06    --  -82.00 -51.00  55.88  140
 82  \w   -152.00 -82.00   0.50    0.06    --  -82.00 -51.00-164.83  140
 83  \w   -160.00 -89.00   0.50    0.06    --  -94.00 -67.00 -94.98  142
 84  \w    -92.00 -34.00   0.50    0.06    --  -95.50  97.00-152.25  116
 85  \w   -162.00 -91.00   0.50    0.06    --  -95.50 -65.00  41.99  142
 86  \w   -163.00 -92.00   0.50    0.06    --  -95.50 -63.00  94.82  142
 87  \w   -162.00 -91.00   0.50    0.06    --  -95.50 -66.00 -40.25  142
 88  \w    -97.00 -32.00   0.50    0.06    --  -95.50 115.00  30.47  130
 89  \w     38.00 101.00   0.50    0.06    --  102.53-125.00  90.00  126
 90  \w    100.00 171.00   0.50    0.06    --  102.53  61.00 150.00  142
 91  \w     38.00 101.00   0.50    0.06    --  102.53-125.00-150.00  126
 92  \w    100.00 171.00   0.50    0.06    --  102.53  61.00-150.00  142
 93  \w     40.00  92.00   0.50    0.06    --  102.53 -95.00  90.00  104
 94  \w    102.00 151.00   0.50    0.06    --  102.53  15.00 -30.00   98
 95  \w    100.00 171.00   0.50    0.06    --  102.53  61.00  90.00  142
 96  \w    100.00 171.00   0.50    0.06    --  102.53  61.00-180.00  142
 97  \w    105.00 173.00   0.50    0.06    --  102.53  45.00 -30.00  136
 98  \w     38.00 101.00   0.50    0.06    --  102.53-125.00-180.00  126
 99  \w    104.00 174.00   0.50    0.06    --  102.53  30.00 150.00  140
100  \w    100.00 160.00   0.50    0.06    --  102.53  61.00-120.00  120
101  \w    102.00 151.00   0.50    0.06    --  102.53  15.00-150.00   98
;
_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      0.0704067000
_diffrn_orient_matrix_UB_12      -0.0324013000
_diffrn_orient_matrix_UB_13      0.0957333000
_diffrn_orient_matrix_UB_21      0.0740381000
_diffrn_orient_matrix_UB_22      0.0672947000
_diffrn_orient_matrix_UB_23      0.0303222000
_diffrn_orient_matrix_UB_31      -0.1331140000
_diffrn_orient_matrix_UB_32      0.0202894000
_diffrn_orient_matrix_UB_33      0.0521032000
_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  0.0397
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9934
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            87855
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9934
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         77.17
_diffrn_reflns_theta_min         3.94
_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    9.865
_exptl_absorpt_correction_T_max  0.830
_exptl_absorpt_correction_T_min  0.313
_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    1.638
_exptl_crystal_description       rod
_exptl_crystal_F_000             1247.898
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of benzene, 1,2-dichloroethane and hexane  by vapour diffusion'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_exptl_crystal_size_rad          0.051
_refine_diff_density_max         1.3598
_refine_diff_density_min         -0.6364
_refine_diff_density_rms         0.0635
_refine_ls_d_res_high            0.7906
_refine_ls_d_res_low             11.2331
_refine_ls_goodness_of_fit_ref   1.0525
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     532
_refine_ls_number_reflns         5281
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.0495
_refine_ls_R_factor_all          0.0216
_refine_ls_R_factor_gt           0.0206
_refine_ls_shift/su_max          0.0004
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0273P)^2^+1.8623P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0528
_refine_ls_wR_factor_ref         0.0533
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              25
_reflns_limit_k_min              0
_reflns_limit_l_max              17
_reflns_limit_l_min              0
_reflns_number_gt                5042
_reflns_number_total             5281
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cy00872g2.cif
_cod_data_source_block           JG24021
_cod_depositor_comments
'Adding full bibliography for 1575589--1575592.cif.'
_cod_database_code               1575592
_chemical_oxdiff_formula         C23H24Cl2InLiN2O6
_chemical_oxdiff_usercomment     '@ 100 K  L2-In/Li'
_olex2_refinement_description
;
1. Rigid body (RIGU) restrains
 C22, H22a, H22b
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, H23b, H23a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, H21a, H21b
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         R2SCAN
   BASIS SET:      x2c-TZVP
   CHARGE:         0
   MULTIPLICITY:   1
   RELATIVISTIC:   DKH2
   DATE:           2024-12-16_12-28-16
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 1000'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id L2-In/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 1.140
_oxdiff_exptl_absorpt_empirical_full_min 0.848