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_7714310
_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         'C17 H20 Al N O2'
_chemical_formula_sum            'C17 H20 Al N O2'
_chemical_formula_weight         297.32
_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             2021-05-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-03-23 deposited with the CCDC.	2023-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                75.009(2)
_cell_angle_beta                 80.544(2)
_cell_angle_gamma                72.856(2)
_cell_formula_units_Z            2
_cell_length_a                   7.9077(2)
_cell_length_b                   9.9326(2)
_cell_length_c                   11.2085(3)
_cell_measurement_reflns_used    31095
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      27.0050
_cell_measurement_theta_min      1.8860
_cell_volume                     808.91(4)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      113(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.968
_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    2.60    --   10.60  82.00 120.00  234
  2  \w    -20.00 100.00   0.50    2.60    --   10.60  57.00  60.00  240
  3  \w    -79.00  36.00   0.50    2.60    --   10.60 -77.00 150.00  230
  4  \w    -17.00 100.00   0.50    2.60    --   10.60  82.00-120.00  234
  5  \w    -79.00  36.00   0.50    2.60    --   10.60 -77.00 -60.00  230
  6  \w    -17.00 100.00   0.50    2.60    --   10.60  82.00  30.00  234
  7  \w    -17.00 100.00   0.50    2.60    --   10.60  82.00 150.00  234
  8  \w    -15.00 100.00   0.50    2.60    --   10.60  77.00   0.00  230
  9  \w    -17.00 100.00   0.50    2.60    --   10.60  82.00 -30.00  234
 10  \w    -20.00 100.00   0.50    2.60    --   10.60  57.00-150.00  240
 11  \w   -100.00  15.00   0.50    2.60    --  -10.90 -77.00-120.00  230
 12  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00  30.00  234
 13  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00   0.00  234
 14  \w    -79.00  41.00   0.50    2.60    --   10.60 -57.00  30.00  240
 15  \w    -79.00  36.00   0.50    2.60    --   10.60 -76.00-172.60  230
 16  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00-180.00  234
 17  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00  60.00  234
 18  \w    -79.00  36.00   0.50    2.60    --   10.60 -77.00  90.00  230
 19  \w    -79.00  37.00   0.50    2.60    --   10.60 -80.00-134.73  232
 20  \w    -79.00  36.00   0.50    2.60    --   10.60 -77.00 120.00  230
 21  \w    -36.00  79.00   0.50    2.60    --  -10.90  77.00 -90.00  230
 22  \w    -38.00  79.00   0.50    2.60    --  -10.90  82.00 -30.00  234
 23  \w    -41.00  79.00   0.50    2.60    --  -10.90  57.00 -90.00  240
 24  \w    -79.00 -45.00   0.50    2.60    --   10.60 -82.00 120.00   68
 25  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00 -30.00  234
 26  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00 150.00  234
 27  \w    -79.00  36.00   0.50    2.60    --   10.60 -77.00-120.00  230
 28  \w    -79.00  38.00   0.50    2.60    --   10.60 -81.00  77.90  234
 29  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00-150.00  234
 30  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00  90.00  234
 31  \w    -79.00  38.00   0.50    2.60    --   10.60 -82.00 -60.00  234
 32  \w    -41.00  79.00   0.50    2.60    --  -10.90  57.00  90.00  240
 33  \w    -38.00  79.00   0.50    2.60    --  -10.90  82.00 120.00  234
 34  \w    -36.00  79.00   0.50    2.60    --  -10.90  77.00-120.00  230
;
_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      0.0476735000
_diffrn_orient_matrix_UB_12      -0.0458244000
_diffrn_orient_matrix_UB_13      0.0503036000
_diffrn_orient_matrix_UB_21      0.0401752000
_diffrn_orient_matrix_UB_22      -0.0517240000
_diffrn_orient_matrix_UB_23      -0.0365967000
_diffrn_orient_matrix_UB_31      0.0707485000
_diffrn_orient_matrix_UB_32      0.0331968000
_diffrn_orient_matrix_UB_33      -0.0214819000
_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  0.0528
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            54747
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.098
_diffrn_reflns_theta_min         2.201
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.129
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27197
_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    1.221
_exptl_crystal_description       block
_exptl_crystal_F_000             316
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.331
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     194
_refine_ls_number_reflns         3458
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0514P)^2^+0.3207P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1016
_refine_ls_wR_factor_ref         0.1043
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3147
_reflns_number_total             3458
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03198e3.cif
_cod_data_source_block           k11005-hyc-h
_cod_database_code               7714310
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.975
_diffrn_oxdiff_digest_frames
;
012906203a29fbf3740197fbbd90464da3000255787
;
_diffrn_oxdiff_digest_hkl
;
019ff641b8981f0ae3df0a9a1633158bee3694
;
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14)
2.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              993
_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 2.280
_oxdiff_exptl_absorpt_empirical_full_min 0.579