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_7712492
_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_formula_moiety         'C48 H47 Al Cl2 N2 O, C6 H4 F2'
_chemical_formula_sum            'C54 H51 Al Cl2 F2 N2 O'
_chemical_formula_weight         879.85
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-10-12
_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                113.677(2)
_cell_angle_beta                 95.1890(10)
_cell_angle_gamma                102.2070(10)
_cell_formula_units_Z            1
_cell_length_a                   10.05910(10)
_cell_length_b                   10.2551(2)
_cell_length_c                   12.5367(2)
_cell_measurement_reflns_used    34343
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      79.4260
_cell_measurement_theta_min      3.9140
_cell_volume                     1135.18(4)
_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 1.000
_diffrn_measured_fraction_theta_max 0.978
_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 -27.00   0.50    0.15    --  -47.74 -72.00  49.00  184
  2  \w     27.00 120.00   0.50    0.15    --   47.74  72.00 179.00  186
  3  \w    -24.00  68.00   0.50    0.15    --   47.74 -72.00  49.00  184
  4  \w   -163.00 -71.00   0.50    0.60    --  -91.75 -72.00  49.00  184
  5  \w   -112.00 -19.00   0.50    0.60    --  -91.75  72.00 179.00  186
  6  \w     93.00 178.00   0.50    0.60    --  113.25  72.00 179.00  170
  7  \w     42.00 134.00   0.50    0.60    --  113.25 -72.00  49.00  184
  8  \w    -63.00 -32.00   0.50    0.15    --   10.00 164.00 114.36   62
  9  \w     -7.00  23.00   0.50    0.15    --   26.00  99.00 -87.20   60
 10  \w     -3.00  42.00   0.50    0.15    --   26.00  91.00  93.96   90
 11  \w      1.00  27.00   0.50    0.15    --   34.00  98.00-126.58   52
 12  \w     13.00  42.00   0.50    0.15    --   42.00  91.00 -66.43   58
 13  \w     17.00  43.00   0.50    0.15    --   46.00  90.00 176.05   52
 14  \w    -68.00  25.00   0.50    0.15    --  -47.74  72.00 179.00  186
 15  \w   -122.00 -35.00   0.50    0.15    --  -47.74 -19.00   0.00  174
 16  \w   -119.00 -25.00   0.50    0.15    --  -47.74 -77.00  60.00  188
 17  \w   -119.00 -25.00   0.50    0.15    --  -47.74 -77.00 -90.00  188
 18  \w    -86.00 -13.00   0.50    0.15    --  -47.74 125.00 150.00  146
 19  \w   -121.00 -35.00   0.50    0.15    --  -47.74 -38.00 -90.00  172
 20  \w     36.00 121.00   0.50    0.15    --   47.74  38.00  30.00  170
 21  \w     27.00 122.00   0.50    0.15    --   50.00  77.00  45.20  190
 22  \w     29.00 122.00   0.50    0.15    --   50.00  72.00 101.52  186
 23  \w     32.00 126.00   0.50    0.15    --   54.00  76.00 114.00  188
 24  \w     31.00 126.00   0.50    0.15    --   54.00  77.00 133.67  190
 25  \w     37.00 131.00   0.50    0.15    --   58.00  73.00 -43.25  188
 26  \w     35.00 131.00   0.50    0.15    --   58.00  77.00-123.89  192
 27  \w     37.00 131.00   0.50    0.15    --   58.00  73.00  20.97  188
 28  \w    -72.00 -42.00   0.50    0.15    --  -62.00 -71.00-146.02   60
 29  \w     40.00  66.00   0.50    0.15    --   62.00  75.00 -27.33   52
 30  \w     40.00  82.00   0.50    0.15    --   62.00  75.00-178.35   84
 31  \w    -72.00 -46.00   0.50    0.15    --  -66.00 -69.00   2.78   52
 32  \w    -73.00 -48.00   0.50    0.15    --  -66.00 -65.00  30.40   50
 33  \w    -79.00 -47.00   0.50    0.15    --  -66.00 -70.00 -24.95   64
 34  \w    -72.00 -46.00   0.50    0.15    --  -66.00 -70.00-161.00   52
 35  \w    -77.00 -51.00   0.50    0.60    --  -74.00 -76.00 -64.44   52
 36  \w    -79.00 -54.00   0.50    0.60    --  -74.00 -69.00  83.37   50
 37  \w    -79.00 -54.00   0.50    0.60    --  -74.00 -69.00 -45.88   50
 38  \w    -79.00 -53.00   0.50    0.60    --  -74.00 -73.00 -88.52   52
 39  \w    -79.00 -54.00   0.50    0.60    --  -74.00 -71.00-155.83   50
 40  \w    -76.00 -51.00   0.50    0.60    --  -74.00 -76.00-120.67   50
 41  \w   -145.00-114.00   0.50    0.60    --  -74.00 -73.00 -88.52   62
 42  \w    -89.00 -54.00   0.50    0.60    --  -74.00 -72.00 141.80   70
 43  \w    -78.00 -52.00   0.50    0.60    --  -74.00 -75.00  47.16   52
 44  \w    -80.00 -52.00   0.50    0.60    --  -74.00 -75.00   8.44   56
 45  \w    -81.00 -54.00   0.50    0.60    --  -74.00 -71.00  69.11   54
 46  \w    -88.00 -60.00   0.50    0.60    --  -78.00 -66.00-120.93   56
 47  \w    -97.00 -61.00   0.50    0.60    --  -78.00 -65.00 114.16   72
 48  \w    -82.00 -56.00   0.50    0.60    --  -78.00 -74.00 165.00   52
 49  \w    -93.00 -61.00   0.50    0.60    --  -82.00 -72.00  26.35   64
 50  \w   -143.00-117.00   0.50    0.60    --  -82.00 -66.00 169.00   52
 51  \w    -89.00 -63.00   0.50    0.60    --  -82.00 -68.00 101.99   52
 52  \w    -98.00 -64.00   0.50    0.60    --  -82.00 -66.00 169.00   68
 53  \w    -86.00 -60.00   0.50    0.60    --  -82.00 -74.00  77.35   52
 54  \w   -107.00 -63.00   0.50    0.60    --  -82.00 -73.00 148.22   88
 55  \w    -87.00 -61.00   0.50    0.60    --  -82.00 -73.00-161.87   52
 56  \w    -95.00 -69.00   0.50    0.60    --  -90.00 -74.00-165.08   52
 57  \w    -93.00 -67.00   0.50    0.60    --  -90.00 -76.00 -98.30   52
 58  \w   -161.00-129.00   0.50    0.60    --  -90.00 -76.00 -98.30   64
 59  \w    -95.00 -69.00   0.50    0.60    --  -91.75 -77.00-120.00   52
 60  \w    -97.00 -71.00   0.50    0.60    --  -91.75 -77.00-150.00   52
 61  \w   -104.00 -73.00   0.50    0.60    --  -91.75 -66.00  30.38   62
 62  \w    -94.00 -69.00   0.50    0.60    --  -91.75 -77.00 150.00   50
 63  \w   -110.00 -75.00   0.50    0.60    --  -91.75 -68.00 -59.37   70
 64  \w   -158.00-124.00   0.50    0.60    --  -91.75 -77.00 150.00   68
 65  \w    -99.00 -73.00   0.50    0.60    --  -91.75 -66.00 -55.44   52
 66  \w    -96.00 -70.00   0.50    0.60    --  -91.75 -77.00  60.00   52
 67  \w   -114.00 -71.00   0.50    0.60    --  -91.75 -73.00 102.45   86
 68  \w   -163.00-117.00   0.50    0.60    --  -91.75 -66.00 -55.44   92
 69  \w    -97.00 -71.00   0.50    0.60    --  -91.75 -77.00 -30.00   52
 70  \w   -110.00 -75.00   0.50    0.60    --  -91.75 -67.00 155.02   70
 71  \w    -94.00 -69.00   0.50    0.60    --  -91.75 -77.00-180.00   50
 72  \w   -163.00-107.00   0.50    0.60    --  -91.75 -77.00-180.00  112
 73  \w    -96.00 -70.00   0.50    0.60    --  -91.75 -75.00-135.06   52
 74  \w    -95.00 -69.00   0.50    0.60    --  -91.75 -76.00 127.13   52
 75  \w    -99.00 -73.00   0.50    0.60    --  -91.75 -73.00 -21.92   52
 76  \w    -97.00 -72.00   0.50    0.60    --  -91.75 -69.00  67.46   50
 77  \w   -152.00-125.00   0.50    0.60    --  -91.75 -69.00  67.46   54
 78  \w    -95.00 -69.00   0.50    0.60    --  -91.75 -77.00 -69.59   52
 79  \w    -99.00 -70.00   0.50    0.60    --  -91.75 -77.00   0.00   58
 80  \w    -95.00 -69.00   0.50    0.60    --  -91.75 -76.00  15.27   52
 81  \w   -145.00-119.00   0.50    0.60    --  -91.75 -77.00   0.00   52
 82  \w   -160.00-124.00   0.50    0.60    --  -91.75 -75.00-135.06   72
 83  \w     59.00 100.00   0.50    0.60    --  113.25 -94.00  90.00   82
 84  \w    147.00 175.00   0.50    0.60    --  113.25  45.00 120.00   56
 85  \w    108.00 140.00   0.50    0.60    --  113.25  45.00 120.00   64
 86  \w    132.00 167.00   0.50    0.60    --  113.25  77.00  60.00   70
 87  \w     96.00 125.00   0.50    0.60    --  113.25  77.00  60.00   58
 88  \w     91.00 124.00   0.50    0.60    --  113.25  77.00  30.00   66
 89  \w     92.00 119.00   0.50    0.60    --  113.25  77.00   0.00   54
 90  \w     91.00 175.00   0.50    0.60    --  113.25  77.00 -30.00  168
 91  \w     39.00  65.00   0.50    0.60    --  113.25 -30.00 -60.00   52
 92  \w     98.00 177.00   0.50    0.60    --  113.25  61.00 -90.00  158
 93  \w    105.00 130.00   0.50    0.60    --  113.25 -61.00 -90.00   50
 94  \w    147.00 177.00   0.50    0.60    --  113.25  77.00-150.00   60
 95  \w     42.00 106.00   0.50    0.60    --  113.25 -94.00 120.00  128
 96  \w     90.00 115.00   0.50    0.60    --  113.25 -77.00 150.00   50
 97  \w     45.00  77.00   0.50    0.60    --  113.25 -61.00 -90.00   64
 98  \w     45.00  85.00   0.50    0.60    --  113.25 -77.00 150.00   80
 99  \w     91.00 130.00   0.50    0.60    --  113.25  77.00-150.00   78
100  \w     42.00  68.00   0.50    0.60    --  113.25 -45.00 150.00   52
101  \w     42.00  68.00   0.50    0.60    --  113.25 -45.00-120.00   52
102  \w     74.00 106.00   0.50    0.60    --  113.25 -94.00  30.00   64
103  \w    134.00 173.00   0.50    0.60    --  113.25  77.00-120.00   78
104  \w    106.00 133.00   0.50    0.60    --  113.25  30.00-180.00   54
105  \w     99.00 138.00   0.50    0.60    --  113.25  61.00 -60.00   78
106  \w     97.00 129.00   0.50    0.60    --  113.25  77.00-120.00   64
107  \w     91.00 138.00   0.50    0.60    --  113.25  77.00 -60.00   94
108  \w    145.00 177.00   0.50    0.60    --  113.25  77.00 -60.00   64
109  \w    136.00 161.00   0.50    0.60    --  113.25  77.00 120.00   50
110  \w    146.00 178.00   0.50    0.60    --  113.25  77.00   0.00   64
111  \w     91.00 126.00   0.50    0.60    --  113.25  77.00 120.00   70
112  \w    145.00 173.00   0.50    0.60    --  113.25  77.00  30.00   56
113  \w    147.00 177.00   0.50    0.60    --  113.25  77.00-180.00   60
114  \w     91.00 140.00   0.50    0.60    --  113.25  77.00-180.00   98
115  \w     97.00 155.00   0.50    0.60    --  113.25  61.00  90.00  116
116  \w     75.00 104.00   0.50    0.60    --  113.25 -94.00-120.00   58
117  \w     43.00  88.00   0.50    0.60    --  113.25 -94.00  60.00   90
118  \w    104.00 153.00   0.50    0.60    --  113.25  61.00  60.00   98
119  \w     98.00 150.00   0.50    0.60    --  113.25  61.00-120.00  104
120  \w     47.00 104.00   0.50    0.60    --  113.25 -94.00   0.00  114
121  \w     45.00  75.00   0.50    0.60    --  113.25 -45.00  90.00   60
122  \w     48.00  74.00   0.50    0.60    --  113.25 -45.00 -90.00   52
123  \w     44.00  70.00   0.50    0.60    --  113.25 -94.00-120.00   52
124  \w     68.00 104.00   0.50    0.60    --  113.25 -94.00 -30.00   72
125  \w    131.00 175.00   0.50    0.60    --  113.25  45.00  30.00   88
126  \w     72.00 105.00   0.50    0.60    --  113.25 -94.00-180.00   66
127  \w    130.00 178.00   0.50    0.60    --  113.25  77.00 150.00   96
128  \w    100.00 127.00   0.50    0.60    --  113.25  77.00 150.00   54
129  \w    104.00 159.00   0.50    0.60    --  113.25  61.00   0.00  110
130  \w    136.00 177.00   0.50    0.60    --  113.25  45.00-150.00   82
131  \w    101.00 152.00   0.50    0.60    --  113.25  45.00 -30.00  102
132  \w     42.00 105.00   0.50    0.60    --  113.25 -94.00 -90.00  126
;
_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      0.0044521000
_diffrn_orient_matrix_UB_12      -0.1180498000
_diffrn_orient_matrix_UB_13      0.0457805000
_diffrn_orient_matrix_UB_21      0.0732492000
_diffrn_orient_matrix_UB_22      -0.0772121000
_diffrn_orient_matrix_UB_23      -0.1006043000
_diffrn_orient_matrix_UB_31      0.1419424000
_diffrn_orient_matrix_UB_32      0.0956695000
_diffrn_orient_matrix_UB_33      0.0806560000
_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  0.0388
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            45509
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.947
_diffrn_reflns_theta_min         3.926
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.871
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92488
_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    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             462
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 4132 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.014(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     564
_refine_ls_number_reflns         9189
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0428P)^2^+0.2478P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0793
_refine_ls_wR_factor_ref         0.0799
_reflns_Friedel_coverage         0.899
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                8983
_reflns_number_total             9189
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00206c2.cif
_cod_data_source_block           dd_tbutipralcl2_auto
_cod_original_cell_volume        1135.18(3)
_cod_database_code               7712492
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Cl'
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.400
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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 Ternary CH refined with riding coordinates:
 C36(H36), C10(H10), C23(H23), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C31(H31), C17(H17), C5(H5), C42(H42), C4(H4), C2(H2), C34(H34),
 C35(H35), C3(H3), C33(H33), C44(H44), C29(H29), C46(H46), C38(H38), C45(H45),
 C32(H32), C48(H48), C39(H39), C41(H41), C40(H40), C47(H47), C28(H28), C25(H25),
  C50(H50), C53(H53), C27(H27), C52(H52), C26(H26), C51(H51)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C8(H8A,H8B,
 H8C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              59479
_shelx_hkl_checksum              19682
_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 1.272
_oxdiff_exptl_absorpt_empirical_full_min 0.874