Synthesis, Characterisation and Reactivity studies of Chiral β-Diketiminate-like Supported Aluminium Lewis Acid Complexes Towards Difficult Diels Alder Cycloadditions
Dissanayake, Deepamali; Forsyth, Craig M.; Vidovic, Dragoslav; Dalton Transactions  (2023) –; doi:10.1039/D3DT00206C

data_7712496
_publ_section_title
;
 Synthesis, Characterisation and Reactivity studies of Chiral
 \b-Diketiminate-like Supported Aluminium Lewis Acid Complexes Towards
 Difficult Diels Alder Cycloadditions
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00206C
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H36 N2 O'
_chemical_formula_sum            'C34 H36 N2 O'
_chemical_formula_weight         488.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-08-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-01-18 deposited with the CCDC.	2023-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.015(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.9991(2)
_cell_length_b                   10.05330(10)
_cell_length_c                   19.1215(2)
_cell_measurement_reflns_used    26941
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      77.4960
_cell_measurement_theta_min      4.5650
_cell_volume                     2851.32(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_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   -119.00 -26.00   0.50    0.57    --  -47.86 -74.00 177.00  186
  2  \w    -69.00  25.00   0.50    0.57    --  -47.86  74.00 -53.00  188
  3  \w     27.00 121.00   0.50    0.57    --   47.86  74.00 -53.00  188
  4  \w    -24.00  69.00   0.50    0.57    --   47.86 -74.00 177.00  186
  5  \w   -163.00 -70.00   0.50    2.30    --  -91.75 -74.00 177.00  186
  6  \w   -113.00 -19.00   0.50    2.30    --  -91.75  74.00 -53.00  188
  7  \w     92.00 178.00   0.50    2.30    --  113.25  74.00 -53.00  172
  8  \w     42.00 135.00   0.50    2.30    --  113.25 -74.00 177.00  186
  9  \w   -119.00 -73.00   0.50    0.57    --  -47.86-125.00 -60.00   92
 10  \w   -119.00 -73.00   0.50    0.57    --  -47.86-125.00  60.00   92
 11  \w   -119.00 -73.00   0.50    0.57    --  -47.86-125.00-120.00   92
 12  \w    -26.00  61.00   0.50    0.57    --   47.86 -19.00-150.00  174
 13  \w    -25.00  61.00   0.50    0.57    --   47.86 -38.00-180.00  172
 14  \w   -163.00 -75.00   0.50    2.30    --  -91.75 -61.00  60.00  176
 15  \w    -68.00 -17.00   0.50    2.30    --  -91.75  30.00 150.00  102
 16  \w   -166.00 -78.00   0.50    2.30    --  -91.75 -15.00  60.00  176
 17  \w   -163.00 -79.00   0.50    2.30    --  -91.75 -45.00  60.00  168
 18  \w     42.00  76.00   0.50    2.30    --  113.25 -45.00 -60.00   68
 19  \w     42.00  76.00   0.50    2.30    --  113.25 -45.00  30.00   68
 20  \w     42.00 106.00   0.50    2.30    --  113.25 -94.00 -60.00  128
 21  \w     97.00 178.00   0.50    2.30    --  113.25  61.00  30.00  162
 22  \w     39.00  66.00   0.50    2.30    --  113.25 -30.00-150.00   54
 23  \w    100.00 178.00   0.50    2.30    --  113.25  15.00-120.00  156
 24  \w     42.00  76.00   0.50    2.30    --  113.25 -45.00  90.00   68
 25  \w     91.00 178.00   0.50    2.30    --  113.25  77.00 -30.00  174
 26  \w     42.00 106.00   0.50    2.30    --  113.25 -94.00-120.00  128
 27  \w     42.00  76.00   0.50    2.30    --  113.25 -45.00-180.00   68
 28  \w     42.00 130.00   0.50    2.30    --  113.25 -61.00-150.00  176
 29  \w     42.00 106.00   0.50    2.30    --  113.25 -94.00 150.00  128
 30  \w    101.00 178.00   0.50    2.30    --  113.25  45.00  60.00  154
 31  \w     42.00 111.00   0.50    2.30    --  113.25-125.00  30.00  138
 32  \w    101.00 178.00   0.50    2.30    --  113.25  45.00  30.00  154
 33  \w     42.00  76.00   0.50    2.30    --  113.25 -45.00   0.00   68
 34  \w     42.00  70.00   0.50    2.30    --  113.25 -94.00-150.00   56
 35  \w     74.00  99.00   0.50    2.30    --  113.25 -94.00-150.00   50
 36  \w    126.00 161.00   0.50    2.30    --  113.25  15.00  30.00   70
 37  \w     39.00  66.00   0.50    2.30    --  113.25 -30.00  90.00   54
 38  \w     94.00 120.00   0.50    2.30    --  113.25 -61.00 120.00   52
 39  \w    146.00 176.00   0.50    2.30    --  113.25  30.00  90.00   60
 40  \w     60.00  88.00   0.50    2.30    --  113.25 -61.00 120.00   56
 41  \w    101.00 140.00   0.50    2.30    --  113.25  45.00  90.00   78
 42  \w     43.00  69.00   0.50    2.30    --  113.25 -45.00 -90.00   52
 43  \w     42.00  67.00   0.50    2.30    --  113.25-125.00 150.00   50
 44  \w     86.00 111.00   0.50    2.30    --  113.25-125.00 150.00   50
 45  \w    153.00 178.00   0.50    2.30    --  113.25  45.00-120.00   50
 46  \w    104.00 178.00   0.50    2.30    --  113.25  45.00 -90.00  148
 47  \w     39.00  65.00   0.50    2.30    --  113.25 -30.00-180.00   52
 48  \w     47.00  74.00   0.50    2.30    --  113.25 -45.00-120.00   54
 49  \w    114.00 142.00   0.50    2.30    --  113.25  45.00-120.00   56
 50  \w     80.00 106.00   0.50    2.30    --  113.25 -94.00-180.00   52
 51  \w     99.00 125.00   0.50    2.30    --  113.25   0.00 120.00   52
 52  \w    146.00 176.00   0.50    2.30    --  113.25   0.00 120.00   60
 53  \w     98.00 133.00   0.50    2.30    --  113.25  61.00-120.00   70
 54  \w    112.00 137.00   0.50    2.30    --  113.25  30.00  90.00   50
 55  \w     42.00  71.00   0.50    2.30    --  113.25 -45.00  60.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0942193000
_diffrn_orient_matrix_UB_12      -0.0592641000
_diffrn_orient_matrix_UB_13      0.0162481000
_diffrn_orient_matrix_UB_21      -0.0192890000
_diffrn_orient_matrix_UB_22      -0.1104492000
_diffrn_orient_matrix_UB_23      0.0478466000
_diffrn_orient_matrix_UB_31      -0.0392529000
_diffrn_orient_matrix_UB_32      -0.0881417000
_diffrn_orient_matrix_UB_33      -0.0706930000
_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  0.0690
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            59697
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.007
_diffrn_reflns_theta_min         4.548
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.523
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63449
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       block
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.457
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 4903 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     683
_refine_ls_number_reflns         12188
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0529
_refine_ls_R_factor_gt           0.0498
_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^)+(0.0868P)^2^+0.3973P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1340
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.865
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                11370
_reflns_number_total             12188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00206c2.cif
_cod_data_source_block           cla18h_auto
_cod_depositor_comments
;

2024-10-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C68 H72 N4 O2'
_cod_original_formula_weight         977.29
_cod_original_formula_moiety         '2(C34 H36 N2 O)'
_cod_original_formula_units_Z            2
_cod_database_code               7712496
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.780
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C10(H10), C9(H9), C32(H32), C72(H72), C25(H25), C69(H69), C51(H51), C56(H56)
1.b Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C8(H8A,H8B)
1.c Aromatic/amide H refined with riding coordinates:
 C46(H46), C14(H14), C49(H49), C48(H48), C47(H47), C16(H16), C18(H18),
 C12(H12), C2(H2), C62(H62), C5(H5), C30(H30), C15(H15), C42(H42), C3(H3),
 C13(H13), C29(H29), C68(H68), C58(H58), C21(H21), C60(H60), C20(H20), C67(H67),
  C61(H61), C22(H22), C4(H4), C40(H40), C59(H59), C41(H41), C19(H19), C28(H28),
 C64(H64), C66(H66), C65(H65)
1.d Idealised Me refined as rotating group:
 C74(H74A,H74B,H74C), C26(H26A,H26B,H26C), C71(H71A,H71B,H71C), C34(H34A,H34B,
 H34C), C33(H33A,H33B,H33C), C73(H73A,H73B,H73C), C70(H70A,H70B,H70C), C27(H27A,
 H27B,H27C)
;
_shelx_res_checksum              60404
_shelx_hkl_checksum              2987
_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 1.882
_oxdiff_exptl_absorpt_empirical_full_min 0.737