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_7714312
_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         'C14 H23 Al N2 O2'
_chemical_formula_sum            'C14 H23 Al N2 O2'
_chemical_formula_weight         278.32
_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             2020-08-28
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.07.16 svn.r6f6c53a7 for OlexSys, GUI svn.r6139)
;
_audit_update_record
;
2023-03-23 deposited with the CCDC.	2023-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                74.366(2)
_cell_angle_beta                 70.847(2)
_cell_angle_gamma                82.515(2)
_cell_formula_units_Z            2
_cell_length_a                   9.12550(10)
_cell_length_b                   9.5913(2)
_cell_length_c                   9.7627(2)
_cell_measurement_reflns_used    14749
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.7090
_cell_measurement_theta_min      2.2040
_cell_volume                     776.50(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (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 0.959
_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    -79.00  38.00   0.50    1.72    --   10.60 -82.00-180.00  234
  2  \w    -17.00 100.00   0.50    1.72    --   10.60  82.00 -90.00  234
  3  \w    -17.00 100.00   0.50    1.72    --   10.60  82.00  30.00  234
  4  \w    -20.00 100.00   0.50    1.72    --   10.60  57.00-150.00  240
  5  \w    -79.00  36.00   0.50    1.72    --   10.60 -77.00 -60.00  230
  6  \w    -17.00 100.00   0.50    1.72    --   10.60  82.00 120.00  234
  7  \w    -17.00 100.00   0.50    1.72    --   10.60  82.00   0.00  234
  8  \w    -27.00 100.00   0.50    1.72    --   10.60  38.00-120.00  254
  9  \w    -17.00 100.00   0.50    1.72    --   10.60  82.00  90.00  234
 10  \w   -100.00  17.00   0.50    1.72    --  -10.90 -82.00  90.00  234
 11  \w   -100.00  17.00   0.50    1.72    --  -10.90 -82.00  30.00  234
 12  \w    -79.00  41.00   0.50    1.72    --   10.60 -57.00  30.00  240
 13  \w    -79.00  38.00   0.50    1.72    --   10.60 -82.00-120.00  234
 14  \w    -79.00  36.00   0.50    1.72    --   10.60 -77.00   0.00  230
 15  \w    -79.00  38.00   0.50    1.72    --   10.60 -82.00 120.00  234
 16  \w    -38.00  28.00   0.50    1.72    --  -10.90  82.00  18.99  132
;
_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      0.0809343000
_diffrn_orient_matrix_UB_12      0.0107232000
_diffrn_orient_matrix_UB_13      -0.0290027000
_diffrn_orient_matrix_UB_21      -0.0126020000
_diffrn_orient_matrix_UB_22      0.0666972000
_diffrn_orient_matrix_UB_23      0.0213841000
_diffrn_orient_matrix_UB_31      0.0086857000
_diffrn_orient_matrix_UB_32      -0.0366907000
_diffrn_orient_matrix_UB_33      0.0706064000
_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  0.0458
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            24693
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.044
_diffrn_reflns_theta_min         2.207
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.131
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50596
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.56a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.190
_exptl_crystal_description       block
_exptl_crystal_F_000             300
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.5
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         3266
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0502P)^2^+0.2176P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0962
_refine_ls_wR_factor_ref         0.0989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2914
_reflns_number_total             3266
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03198e3.cif
_cod_data_source_block           k10908-hyc-a
_cod_database_code               7714312
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H23 Al N2 O2'
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              26221
_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 1.875
_oxdiff_exptl_absorpt_empirical_full_min 0.674