Aluminyl derived ethene functionalization with heteroallenes, leading to an intramolecular ligand rearrangement.
O'Reilly, Andrea; Gardiner, Michael G.; McMullin, Claire L.; Fulton, J. Robin; Coles, Martyn P.; Chemical communications (Cambridge, England) 60 (2024) 881–884; doi:10.1039/d3cc05785b

data_7132539
_publ_section_title
;
 Aluminyl derived ethene functionalization with heteroallenes, leading to
 an intramolecular ligand rearrangement.
;
_journal_issue                   7
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              881
_journal_page_last               884
_journal_paper_doi               10.1039/d3cc05785b
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C78 H140 Al2 K2 N4 O10 Si4'
_chemical_formula_sum            'C78 H140 Al2 K2 N4 O10 Si4'
_chemical_formula_weight         1538.45
_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     dual
_audit_creation_date             2022-12-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-11-26 deposited with the CCDC.	2023-12-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.397(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.7613(2)
_cell_length_b                   13.63024(18)
_cell_length_c                   21.2238(18)
_cell_measurement_reflns_used    48991
_cell_measurement_temperature    119.99(10)
_cell_measurement_theta_max      72.6260
_cell_measurement_theta_min      4.9350
_cell_volume                     4559.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      119.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0856
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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   -110.00 -39.00   1.00    1.00    --  -37.60-178.00 -60.00   71
  2  \w   -105.00 -21.00   1.00    1.00    --  -37.60 -57.00-150.00   84
  3  \w   -105.00 -21.00   1.00    1.00    --  -37.60 -57.00 -60.00   84
  4  \w    -54.00  30.00   1.00    1.00    --  -37.60  57.00   0.00   84
  5  \w      5.00  31.00   1.00    1.00    --   37.60  87.00 141.30   26
  6  \w      8.00 109.00   1.00    1.00    --   37.60  19.00 -90.00  101
  7  \w      6.00  32.00   1.00    1.00    --   37.60  85.00 -57.34   26
  8  \w      8.00  34.00   1.00    1.00    --   37.60  83.00 103.92   26
  9  \w      6.00  77.00   1.00    1.00    --   37.60 -99.00   0.00   71
 10  \w    -34.00  67.00   1.00    1.00    --   37.60 -19.00  60.00  101
 11  \w      6.00  32.00   1.00    1.00    --   37.60  85.00-140.25   26
 12  \w      5.00  31.00   1.00    1.00    --   37.60  87.00-178.98   26
 13  \w     41.00 136.00   1.00    3.18    --  109.00 -77.00  60.00   95
 14  \w     39.00 130.00   1.00    3.18    --  109.00 -30.00 -90.00   91
 15  \w     42.00 127.00   1.00    3.18    --  109.00 -61.00-150.00   85
 16  \w     71.00 178.00   1.00    3.18    --  109.00  15.00  60.00  107
 17  \w     92.00 177.00   1.00    3.18    --  109.00  45.00 120.00   85
 18  \w     39.00 109.00   1.00    3.18    --  109.00-111.00 150.00   70
 19  \w     88.00 178.00   1.00    3.18    --  109.00  30.00-180.00   90
 20  \w    103.00 177.00   1.00    3.18    --  109.00  77.00-180.00   74
 21  \w     41.00 136.00   1.00    3.18    --  109.00 -77.00 -90.00   95
 22  \w     39.00 130.00   1.00    3.18    --  109.00 -30.00 150.00   91
 23  \w     39.00 109.00   1.00    3.18    --  109.00-111.00 -60.00   70
 24  \w     40.00 106.00   1.00    3.18    --  109.00 -94.00-150.00   66
 25  \w     40.00 106.00   1.00    3.18    --  109.00 -94.00-180.00   66
 26  \w     39.00 109.00   1.00    3.18    --  109.00-111.00  60.00   70
 27  \w     40.00 106.00   1.00    3.18    --  109.00 -94.00 -90.00   66
 28  \w     39.00 109.00   1.00    3.18    --  109.00-111.00 -90.00   70
 29  \w     39.00 109.00   1.00    3.18    --  109.00-111.00  30.00   70
 30  \w     88.00 178.00   1.00    3.18    --  109.00  30.00 -90.00   90
 31  \w     39.00 109.00   1.00    3.18    --  109.00-111.00-180.00   70
 32  \w     39.00 109.00   1.00    3.18    --  109.00-111.00  90.00   70
 33  \w     41.00 126.00   1.00    3.18    --  109.00 -45.00  30.00   85
 34  \w     39.00 109.00   1.00    3.18    --  109.00-111.00 -30.00   70
 35  \w     88.00 178.00   1.00    3.18    --  109.00  30.00 150.00   90
 36  \w     39.00 130.00   1.00    3.18    --  109.00 -30.00-120.00   91
 37  \w     42.00 127.00   1.00    3.18    --  109.00 -61.00 -60.00   85
 38  \w     71.00 178.00   1.00    3.18    --  109.00  15.00 -90.00  107
 39  \w     71.00 178.00   1.00    3.18    --  109.00  15.00  90.00  107
 40  \w     39.00 130.00   1.00    3.18    --  109.00 -30.00  90.00   91
 41  \w     41.00 126.00   1.00    3.18    --  109.00 -45.00  90.00   85
 42  \w     77.00 108.00   1.00    3.18    --  109.00-111.00   0.00   31
 43  \w     67.00  92.00   1.00    3.18    --  109.00 -15.00 -30.00   25
 44  \w    100.00 147.00   1.00    3.18    --  109.00 -15.00 -30.00   47
 45  \w     67.00 126.00   1.00    3.18    --  109.00 -61.00  30.00   59
 46  \w    110.00 137.00   1.00    3.18    --  109.00  30.00  60.00   27
 47  \w     89.00 126.00   1.00    3.18    --  109.00  30.00 -30.00   37
 48  \w     86.00 134.00   1.00    3.18    --  109.00  15.00 -30.00   48
 49  \w     96.00 123.00   1.00    3.18    --  109.00 -77.00 120.00   27
 50  \w     39.00  66.00   1.00    3.18    --  109.00-111.00   0.00   27
 51  \w     79.00 104.00   1.00    3.18    --  109.00 -94.00 -60.00   25
 52  \w     93.00 118.00   1.00    3.18    --  109.00  45.00-150.00   25
 53  \w     76.00 103.00   1.00    3.18    --  109.00 -61.00 -30.00   27
 54  \w     82.00 109.00   1.00    3.18    --  109.00-111.00-150.00   27
 55  \w     57.00  92.00   1.00    3.18    --  109.00 -45.00 -60.00   35
 56  \w     40.00  65.00   1.00    3.18    --  109.00 -30.00  30.00   25
 57  \w     90.00 130.00   1.00    3.18    --  109.00 -30.00  30.00   40
 58  \w     80.00 106.00   1.00    3.18    --  109.00 -94.00  60.00   26
 59  \w     98.00 125.00   1.00    3.18    --  109.00 -15.00 -60.00   27
 60  \w     54.00  92.00   1.00    3.18    --  109.00 -77.00-150.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0752710000
_diffrn_orient_matrix_UB_12      -0.0020312000
_diffrn_orient_matrix_UB_13      0.0468279000
_diffrn_orient_matrix_UB_21      0.0318476000
_diffrn_orient_matrix_UB_22      0.0982519000
_diffrn_orient_matrix_UB_23      -0.0267004000
_diffrn_orient_matrix_UB_31      -0.0534541000
_diffrn_orient_matrix_UB_32      0.0558882000
_diffrn_orient_matrix_UB_33      0.0486566000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24344
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.245
_diffrn_reflns_theta_min         3.475
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.016
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98827
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.121
_exptl_crystal_description       block
_exptl_crystal_F_000             1672
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.247
_exptl_crystal_size_min          0.223
_refine_diff_density_max         0.146
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 7409 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     954
_refine_ls_number_reflns         24344
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0281
_refine_ls_R_factor_gt           0.0269
_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^)+(0.0419P)^2^+0.4864P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0741
_refine_ls_wR_factor_ref         0.0745
_reflns_Friedel_coverage         0.878
_reflns_Friedel_fraction_full    0.961
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                23544
_reflns_number_total             24344
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9996\% 
 around [-0.00 -0.00 1.00] (reciprocal) or [0.01 -0.00 1.00] (direct)
;
_cod_data_source_file            d3cc05785b2.cif
_cod_data_source_block           Compound1-Et2O
_cod_depositor_comments
'Adding full bibliography for 7132539--7132541.cif.'
_cod_database_code               7132539
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C78 H140 N4 O10 Al2 K2 Si4'
_shelx_estimated_absorpt_t_max   0.662
_shelx_estimated_absorpt_t_min   0.542
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5100(7)
 0.4900(7)
2. 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
3. Restrained distances
 O5-C38A \\sim O5-C38B
 with sigma of 0.02
 C39A-C38A \\sim C39A-C38B
 with sigma of 0.02
 C38A-C39B \\sim C38B-C39B
 with sigma of 0.02
4. Others
 Sof(C39B)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C38B)=Sof(H38C)=Sof(H38D)=1-FVAR(1)
 Sof(C39A)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C38A)=Sof(H38A)=Sof(H38B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C49(H49), C46(H46), C7(H7), C23(H23), C62(H62), C65(H65), C26(H26), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C013(H01A,H01B), C30(H30A,H30B), C01I(H01C,H01D), C29(H29A,H29B), C68(H68A,
 H68B), C024(H02A,H02B), C36(H36A,H36B), C029(H02C,H02D), C69(H69A,H69B),
 C32(H32A,H32B), C34(H34A,H34B), C38A(H38A,H38B), C38B(H38C,H38D)
5.c Aromatic/amide H refined with riding coordinates:
 C42(H42), C60(H60), C43(H43), C59(H59), C58(H58), C19(H19), C21(H21),
 C44(H44), C5(H5), C4(H4), C20(H20), C3(H3)
5.d Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C8(H8A,H8B,H8C), C55(H55A,H55B,H55C), C63(H63A,H63B,
 H63C), C11(H11A,H11B,H11C), C25(H25A,H25B,H25C), C33(H33A,H33B,H33C), C50(H50A,
 H50B,H50C), C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C01M(H01E,H01F,H01G),
 C28(H28A,H28B,H28C), C66(H66A,H66B,H66C), C9(H9A,H9B,H9C), C01W(H01H,H01I,
 H01J), C54(H54A,H54B,H54C), C01Z(H01K,H01L,H01M), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C53(H53A,H53B,H53C), C02B(H02E,H02F,H02G), C64(H64A,H64B,
 H64C), C16(H16A,H16B,H16C), C37(H37A,H37B,H37C), C12(H12A,H12B,H12C), C24(H24A,
 H24B,H24C), C15(H15A,H15B,H15C), C51(H51A,H51B,H51C), C67(H67A,H67B,H67C),
 C35(H35A,H35B,H35C), C27(H27A,H27B,H27C), C39A(H39A,H39B,H39C), C39B(H39D,H39E,
 H39F)
;
_shelx_res_checksum              48898
_shelx_hkl_checksum              62750
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_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 1.298
_oxdiff_exptl_absorpt_empirical_full_min 0.932
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2