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_7712497
_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         'C46 H43 Al Cl2 N2 O'
_chemical_formula_sum            'C46 H43 Al Cl2 N2 O'
_chemical_formula_weight         737.70
_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   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                90
_cell_angle_beta                 105.529(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.2370(2)
_cell_length_b                   17.2186(2)
_cell_length_c                   15.4659(2)
_cell_measurement_reflns_used    56318
_cell_measurement_temperature    122.99(10)
_cell_measurement_theta_max      31.0320
_cell_measurement_theta_min      3.5420
_cell_volume                     3909.51(9)
_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      122.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.865
_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     14.00  41.00   0.50    4.35    --    5.25  71.00 133.00   54
  2  \w    -61.00 -27.00   0.50    4.35    --    5.25 -71.00   2.00   68
  3  \w    -22.00  18.00   0.50    4.35    --   -5.09 -99.00 -90.00   80
  4  \w    -71.00   8.00   0.50    4.35    --   -5.09 -38.00 -60.00  158
  5  \w    -23.00   2.00   0.50    4.35    --   -5.09 -99.00-180.00   50
  6  \w    -42.00 -16.00   0.50    4.35    --   -5.09 -38.00  60.00   52
  7  \w    -77.00 -26.00   0.50    4.35    --   -5.09 -57.00  30.00  102
  8  \w    -17.00   9.00   0.50    4.35    --   -5.09 -57.00  30.00   52
  9  \w    -77.00   8.00   0.50    4.35    --   -5.09 -38.00-150.00  170
 10  \w    -12.00  23.00   0.50    4.35    --    5.25 -99.00   0.00   70
 11  \w     41.00  66.00   0.50    4.35    --    5.25  77.00  30.00   50
 12  \w    -15.00  16.00   0.50    4.35    --    5.25  77.00  30.00   62
 13  \w    -14.00  38.00   0.50    4.35    --    5.25 -99.00 150.00  104
 14  \w     16.00  81.00   0.50    4.35    --    5.25  19.00 120.00  130
;
_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      0.0397346000
_diffrn_orient_matrix_UB_12      -0.0122508000
_diffrn_orient_matrix_UB_13      -0.0117625000
_diffrn_orient_matrix_UB_21      -0.0251650000
_diffrn_orient_matrix_UB_22      -0.0303972000
_diffrn_orient_matrix_UB_23      -0.0263388000
_diffrn_orient_matrix_UB_31      -0.0111031000
_diffrn_orient_matrix_UB_32      0.0249521000
_diffrn_orient_matrix_UB_33      -0.0378544000
_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  0.0328
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.865
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            80470
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.817
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.013
_diffrn_reflns_theta_min         3.334
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.226
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77843
_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 yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 7676 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     964
_refine_ls_number_reflns         20379
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0382
_refine_ls_R_factor_gt           0.0325
_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^)+(0.0412P)^2^+0.4475P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0812
_refine_ls_wR_factor_ref         0.0832
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.766
_reflns_number_gt                18179
_reflns_number_total             20379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00206c2.cif
_cod_data_source_block           dd_cla15alcl2_auto
_cod_database_code               7712497
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C44H75N2OAlCl2
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.840
_reflns_odcompleteness_completeness 99.73
_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. Restrained distances
 O1A-C7 \\sim O1-C7
 with sigma of 0.02
 O1-C8 \\sim O1A-C8A
 with sigma of 0.02
 C9-C8 \\sim C9-C8A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C7 \\sim O1 \\sim C8 \\sim C9: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C7 \\sim O1A \\sim C8A \\sim C9: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 C7, O1A, C8A, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, O1, C8, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H9B)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(O1A)=1-FVAR(1)
 Sof(O1)=Sof(H9A)=Sof(C8)=Sof(H8A)=Sof(H8B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C68(H68), C42(H42), C57(H57), C83(H83), C9(H9B), C9(H9A)
6.b Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C8A(H8AA,H8AB), C8(H8A,H8B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C16(H16), C40(H40), C32(H32), C85(H85), C79(H79), C89(H89), C24(H24),
 C25(H25), C18(H18), C50(H50), C76(H76), C80(H80), C66(H66), C51(H51), C64(H64),
  C95(H95), C38(H38), C23(H23), C39(H39), C4(H4), C92(H92), C70(H70), C71(H71),
 C30(H30), C87(H87), C29(H29), C27(H27), C2(H2), C33(H33), C44(H44), C36(H36),
 C48(H48), C88(H88), C45(H45), C91(H91), C46(H46), C3(H3), C94(H94), C31(H31),
 C77(H77), C52(H52), C53(H53), C74(H74), C78(H78), C73(H73), C37(H37), C26(H26),
  C86(H86), C72(H72), C47(H47), C93(H93)
6.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C13(H13A,H13B,H13C), C60(H60A,H60B,H60C), C81(H81A,H81B,
 H81C), C12(H12A,H12B,H12C), C61(H61A,H61B,H61C), C11(H11A,H11B,H11C), C58(H58A,
 H58B,H58C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              70355
_shelx_hkl_checksum              63990
_shelx_fab_checksum              8371
_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 1.219
_oxdiff_exptl_absorpt_empirical_full_min 0.666