Improvement of Catalytic Activity of Aluminum Complexes for the Ring-Opening Polymerization of ε‑Caprolactone: Aluminum Thioamidate and Thioureidate Systems
Chen, Hsuan-Ying; Ganta, Prasanna Kumar; Teja, Mallemadugula Ravi; Chang, Chun-Juei; Anandan, Sambandam; Kamaraj, Rajiv; Chu, Yu-Ting; Ding, Shangwu; Chen, Hsing-Yin; Dalton Transactions  (2023) –; doi:10.1039/D3DT03198E

data_7714313
_publ_section_title
;
 Improvement of Catalytic Activity of Aluminum Complexes for the
 Ring-Opening Polymerization of \e&#x2011;Caprolactone: Aluminum
 Thioamidate and Thioureidate Systems
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT03198E
_journal_year                    2023
_chemical_formula_moiety         'C38 H48 Al2 N2 O2'
_chemical_formula_sum            'C38 H48 Al2 N2 O2'
_chemical_formula_weight         618.74
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-23 deposited with the CCDC.	2023-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                100.483(2)
_cell_angle_beta                 98.099(2)
_cell_angle_gamma                90.645(2)
_cell_formula_units_Z            1
_cell_length_a                   8.8582(2)
_cell_length_b                   9.1762(2)
_cell_length_c                   12.8820(2)
_cell_measurement_reflns_used    16087
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.9190
_cell_measurement_theta_min      1.6990
_cell_volume                     1018.63(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      113(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -17.00 100.00   0.50    7.34    --   10.60  82.00 -90.00  234
  2  \w    -20.00 100.00   0.50    7.34    --   10.60  57.00-120.00  240
  3  \w    -17.00 100.00   0.50    7.34    --   10.60  82.00 -60.00  234
  4  \w    -17.00 100.00   0.50    7.34    --   10.60  82.00 150.00  234
  5  \w    -79.00  48.00   0.50    7.34    --   10.60 -38.00  60.00  254
  6  \w    -79.00  41.00   0.50    7.34    --   10.60 -57.00 -30.00  240
  7  \w    -79.00  48.00   0.50    7.34    --   10.60 -38.00  30.00  254
  8  \w    -17.00 100.00   0.50    7.34    --   10.60  82.00   0.00  234
  9  \w    -17.00 100.00   0.50    7.34    --   10.60  82.00-150.00  234
 10  \w    -41.00  79.00   0.50    7.34    --  -10.90  57.00  90.00  240
 11  \w   -100.00  17.00   0.50    7.34    --  -10.90 -82.00 -60.00  234
 12  \w   -100.00  17.00   0.50    7.34    --  -10.90 -82.00   0.00  234
 13  \w    -41.00  76.00   0.50    7.34    --  -10.90  57.00-120.00  234
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0121538000
_diffrn_orient_matrix_UB_12      -0.0242394000
_diffrn_orient_matrix_UB_13      -0.0535818000
_diffrn_orient_matrix_UB_21      -0.0375823000
_diffrn_orient_matrix_UB_22      0.0626613000
_diffrn_orient_matrix_UB_23      -0.0146423000
_diffrn_orient_matrix_UB_31      0.0706455000
_diffrn_orient_matrix_UB_32      0.0409203000
_diffrn_orient_matrix_UB_33      0.0108545000
_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  0.0454
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            25684
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.259
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.101
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25168
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
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    1.009
_exptl_crystal_description       block
_exptl_crystal_F_000             332
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         3589
_refine_ls_number_restraints     660
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0660
_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^)+(0.0549P)^2^+2.1733P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1704
_refine_ls_wR_factor_ref         0.1745
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3246
_reflns_number_total             3589
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03198e3.cif
_cod_data_source_block           k11104-hyc-b_autored
_cod_database_code               7714313
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C38 H48 Al2 N2 O2'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim N1 \\sim O1 \\sim Al1: within
3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
3. Others
 Fixed Sof: C6(0.5) H6(0.5) C7(0.5) H7(0.5) C20(0.5) H20(0.5) C21(0.5) H21(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C13(H13), C20(H20), C21(H21)
4.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              79777
_shelx_fab_checksum              85460
_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 3.588
_oxdiff_exptl_absorpt_empirical_full_min 0.568