Extending Chain Growth Beyond C1 → C4 in CO Homologation: Aluminyl Promoted Formation of the [C5O5]5– Ligand
Evans, Matthew J.; Gardiner, Michael; Anker, Mathew David; Coles, Martyn P.; Chemical Communications  (2022) –; doi:10.1039/D2CC01554D

data_7129956
_publ_section_title
;
 Extending Chain Growth Beyond C1 \\rightarrow C4 in CO Homologation:
 Aluminyl Promoted Formation of the [C5O5]5-- Ligand
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01554D
_journal_year                    2022
_chemical_formula_moiety
'C72 H124 Al2 K2 N8 O6 Si3.826, 0.288(Si1), 2(C6 H14)'
_chemical_formula_sum            'C84 H152 Al2 K2 N8 O6 Si4'
_chemical_formula_weight         1614.65
_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             2022-03-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-17 deposited with the CCDC.	2022-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                115.548(6)
_cell_angle_beta                 108.416(5)
_cell_angle_gamma                97.403(4)
_cell_formula_units_Z            4
_cell_length_a                   19.3051(7)
_cell_length_b                   24.5006(10)
_cell_length_c                   24.9778(13)
_cell_measurement_reflns_used    14960
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.0210
_cell_measurement_theta_min      4.2400
_cell_volume                     9616.0(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0856
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_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    -54.00  18.00   1.00    6.00    --  -37.38  57.00 -60.00   72
  2  \w    -60.00   8.00   1.00    6.00    --  -37.38  77.00 120.00   68
  3  \w    -65.00  17.00   1.00    6.00    --  -37.38  19.00 150.00   82
  4  \w    -82.00 -21.00   1.00    6.00    --  -37.38 125.00 150.00   61
  5  \w    -86.00 -34.00   1.00    6.00    --  -37.38 125.00 -60.00   52
  6  \w   -102.00  26.00   1.00    6.00    --  -37.38   0.00 -90.00  128
  7  \w     46.00  87.00   1.00    6.00    --   37.38-125.00-180.00   41
  8  \w      9.00  61.00   1.00    6.00    --   37.38 -99.00  30.00   52
  9  \w     66.00  91.00   1.00    6.00    --   37.38-125.00  30.00   25
 10  \w     81.00 109.00   1.00   23.00    --  111.00-111.00 150.00   28
 11  \w     42.00 107.00   1.00   23.00    --  111.00-111.00 120.00   65
 12  \w     83.00 115.00   1.00   23.00    --  111.00 -45.00 150.00   32
 13  \w     43.00 130.00   1.00   23.00    --  111.00 -30.00 -90.00   87
 14  \w     68.00 109.00   1.00   23.00    --  111.00-111.00-180.00   41
 15  \w     93.00 120.00   1.00   23.00    --  111.00  30.00-120.00   27
 16  \w     70.00 100.00   1.00   23.00    --  111.00 -15.00-150.00   30
 17  \w     45.00  78.00   1.00   23.00    --  111.00 -45.00 150.00   33
 18  \w     69.00 121.00   1.00   23.00    --  111.00 -61.00 150.00   52
 19  \w    136.00 178.00   1.00   23.00    --  111.00  45.00 -30.00   42
 20  \w     74.00 103.00   1.00   23.00    --  111.00-111.00 -30.00   29
 21  \w     81.00 109.00   1.00   23.00    --  111.00-111.00  30.00   28
 22  \w     96.00 141.00   1.00   23.00    --  111.00  45.00 -90.00   45
 23  \w    149.00 176.00   1.00   23.00    --  111.00  45.00 -90.00   27
 24  \w    123.00 165.00   1.00   23.00    --  111.00 111.00-180.00   42
 25  \w     70.00 109.00   1.00   23.00    --  111.00-111.00   0.00   39
 26  \w     47.00  72.00   1.00   23.00    --  111.00-111.00 150.00   25
 27  \w     62.00 118.00   1.00   23.00    --  111.00 -30.00  60.00   56
 28  \w     56.00 106.00   1.00   23.00    --  111.00 -94.00 -30.00   50
 29  \w    127.00 158.00   1.00   23.00    --  111.00 111.00 -30.00   31
 30  \w     82.00 109.00   1.00   23.00    --  111.00-111.00-120.00   27
 31  \w    106.00 131.00   1.00   23.00    --  111.00 -77.00 -30.00   25
 32  \w    149.00 177.00   1.00   23.00    --  111.00  77.00-150.00   28
 33  \w     83.00 108.00   1.00   23.00    --  111.00-111.00  90.00   25
 34  \w    108.00 135.00   1.00   23.00    --  111.00 -77.00 120.00   27
 35  \w    153.00 178.00   1.00   23.00    --  111.00  61.00-120.00   25
 36  \w     83.00 109.00   1.00   23.00    --  111.00-111.00 -60.00   26
 37  \w    114.00 141.00   1.00   23.00    --  111.00  61.00-120.00   27
 38  \w     45.00  76.00   1.00   23.00    --  111.00 -94.00 150.00   31
 39  \w     71.00  98.00   1.00   23.00    --  111.00 -61.00-120.00   27
 40  \w     66.00  91.00   1.00   23.00    --  111.00 178.00  30.00   25
 41  \w    105.00 132.00   1.00   23.00    --  111.00 178.00  30.00   27
 42  \w     62.00 124.00   1.00   23.00    --  111.00 -61.00 -60.00   62
 43  \w     77.00 103.00   1.00   23.00    --  111.00 178.00 150.00   26
 44  \w     60.00 109.00   1.00   23.00    --  111.00-111.00-150.00   49
 45  \w     63.00 109.00   1.00   23.00    --  111.00-111.00 -90.00   46
 46  \w    113.00 140.00   1.00   23.00    --  111.00 111.00-150.00   27
 47  \w     45.00  77.00   1.00   23.00    --  111.00-111.00 -60.00   32
 48  \w    134.00 166.00   1.00   23.00    --  111.00  45.00   0.00   32
 49  \w     44.00  73.00   1.00   23.00    --  111.00 -45.00 -90.00   29
 50  \w     98.00 125.00   1.00   23.00    --  111.00 -45.00 -90.00   27
 51  \w    153.00 178.00   1.00   23.00    --  111.00  45.00 -60.00   25
 52  \w     97.00 176.00   1.00   23.00    --  111.00  45.00-120.00   79
 53  \w    101.00 144.00   1.00   23.00    --  111.00  45.00  60.00   43
 54  \w    145.00 172.00   1.00   23.00    --  111.00  30.00 -60.00   27
 55  \w    134.00 176.00   1.00   23.00    --  111.00  77.00  60.00   42
 56  \w    124.00 151.00   1.00   23.00    --  111.00 111.00 -60.00   27
 57  \w     65.00  92.00   1.00   23.00    --  111.00 -77.00 -90.00   27
 58  \w    104.00 131.00   1.00   23.00    --  111.00 -77.00 -90.00   27
 59  \w     68.00  95.00   1.00   23.00    --  111.00 -94.00 -90.00   27
 60  \w     70.00  97.00   1.00   23.00    --  111.00 -94.00  60.00   27
 61  \w     44.00  69.00   1.00   23.00    --  111.00 -94.00  90.00   25
 62  \w    108.00 147.00   1.00   23.00    --  111.00 111.00-120.00   39
 63  \w     94.00 124.00   1.00   23.00    --  111.00  45.00 -60.00   30
 64  \w     83.00 108.00   1.00   23.00    --  111.00-111.00  60.00   25
 65  \w     51.00  76.00   1.00   23.00    --  111.00 -45.00   0.00   25
 66  \w     66.00  93.00   1.00   23.00    --  111.00 -61.00-180.00   27
 67  \w     92.00 120.00   1.00   23.00    --  111.00 -45.00  60.00   28
 68  \w    127.00 152.00   1.00   23.00    --  111.00  30.00 -30.00   25
 69  \w     94.00 172.00   1.00   23.00    --  111.00  30.00  30.00   78
 70  \w    117.00 144.00   1.00   23.00    --  111.00 -15.00-150.00   27
 71  \w    101.00 131.00   1.00   23.00    --  111.00 -83.00 150.10   30
 72  \w     55.00  80.00   1.00   23.00    --  111.00 -83.00 150.10   25
;
_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      0.0167653000
_diffrn_orient_matrix_UB_12      0.0615672000
_diffrn_orient_matrix_UB_13      0.0633148000
_diffrn_orient_matrix_UB_21      -0.0855103000
_diffrn_orient_matrix_UB_22      -0.0178273000
_diffrn_orient_matrix_UB_23      -0.0130367000
_diffrn_orient_matrix_UB_31      0.0152615000
_diffrn_orient_matrix_UB_32      -0.0355705000
_diffrn_orient_matrix_UB_33      0.0383508000
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.0659
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            114242
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.250
_diffrn_reflns_theta_min         3.639
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.913
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92705
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.115
_exptl_crystal_description       plate
_exptl_crystal_F_000             3520
_exptl_crystal_size_max          0.221
_exptl_crystal_size_mid          0.132
_exptl_crystal_size_min          0.111
_refine_diff_density_max         1.039
_refine_diff_density_min         -0.495
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1937
_refine_ls_number_reflns         35070
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.1356
_refine_ls_R_factor_gt           0.0935
_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^)+(0.1654P)^2^+9.8363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2444
_refine_ls_wR_factor_ref         0.2916
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23048
_reflns_number_total             35070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01554d2.cif
_cod_data_source_block           compound-3
_cod_original_cell_volume        9616.1(9)
_cod_database_code               7129956
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C42 H74 Al2 K2 N8 O6 Si4'
_chemical_oxdiff_usercomment     'bifringent yellow-red crystals'
_reflns_odcompleteness_completeness 96.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9296(8)
 0.0704(8)
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
 C14S-C13S = C17S-C18S = C16S-C17S = C14S-C15S = C15S-C15S_$1
 1.5 with sigma of 0.01
 C12S-C11S = C11S-C10S = C10S-C9S = C9S-C8S = C8S-C7S
 1.5 with sigma of 0.01
 C18S-C18S_$2
 1.5 with sigma of 0.01
 C12S-C10S = C11S-C9S
 2.6 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C7S) \\sim Ueq, Uanis(C11S) \\sim Ueq, Uanis(C12S) \\sim Ueq, Uanis(C10S)
\\sim Ueq, Uanis(C9S) \\sim Ueq, Uanis(C8S) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C14S) \\sim Ueq, Uanis(C15S) \\sim Ueq, Uanis(C13S) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C17S) \\sim Ueq, Uanis(C18S) \\sim Ueq, Uanis(C16S) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
5. Others
 Sof(Si6C)=Sof(Si5C)=1-FVAR(1)
 Sof(Si2C)=Sof(Si28)=FVAR(1)
 Sof(Si8C)=Sof(Si7C)=1-FVAR(2)
 Sof(Si3C)=Sof(Si4C)=FVAR(2)
 Sof(Si3A)=Sof(Si4A)=1-FVAR(3)
 Sof(Si1A)=Sof(Si2A)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C9A(H9A), C12A(H12D), C25A(H25A), C28A(H28D), C9B(H9B), C12B(H12E),
 C25B(H25B), C28B(H28E), C11C(H11C), C14C(H14C), C27C(H27C), C30C(H30C),
 C39C(H39C), C42C(H42C), C51C(H51C), C54C(H54C)
6.b Secondary CH2 refined with riding coordinates:
 C33A(H33A,H33B), C34A(H34A,H34B), C33B(H33C,H33D), C34B(H34C,H34D), C63C(H63A,
 H63B), C64C(H64A,H64B), C69C(H69A,H69B), C70C(H70A,H70B), C2S(H2SA,H2SB),
 C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,H5SB), C04N(H04A,H04B), C04Z(H04C,
 H04D), C8S(H8SA,H8SB), C9S(H9SA,H9SB), C10S(H10G,H10H), C11S(H11H,H11I),
 C14S(H14H,H14I), C15S(H15J,H15K), C17S(H17J,H17K), C18S(H18J,H18K), C19S(H19D,
 H19E), C20S(H20D,H20E)
6.c Aromatic/amide H refined with riding coordinates:
 C5A(H5A), C6A(H6A), C7A(H7A), C21A(H21A), C22A(H22A), C23A(H23A), C5B(H5B),
 C6B(H6B), C7B(H7B), C21B(H21B), C22B(H22B), C23B(H23B), C7C(H7C), C8C(H8C),
 C9C(H9C), C23C(H23C), C24C(H24C), C25C(H25C), C35C(H35C), C36C(H36C),
 C37C(H37C), C47C(H47C), C48C(H48C), C49C(H49C)
6.d Idealised Me refined with riding coordinates:
 C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11D), C13A(H13D,H13E,H13F), C14A(H14A,
 H14B,H14D), C15A(H15D,H15E,H15F), C18A(H18D,H18E,H18F), C26A(H26A,H26B,H26C),
 C27A(H27A,H27B,H27D), C29A(H29D,H29E,H29F), C30A(H30A,H30B,H30D), C31A(H31D,
 H31E,H31F), C32A(H32D,H32E,H32F), C35A(H35A,H35B,H35D), C36A(H36A,H36B,H36D),
 C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C10B(H10D,H10E,H10F), C11B(H11E,
 H11F,H11G), C13B(H13G,H13H,H13I), C14B(H14E,H14F,H14G), C15B(H15G,H15H,H15I),
 C16B(H16G,H16H,H16I), C17B(H17G,H17H,H17I), C18B(H18G,H18H,H18I), C26B(H26D,
 H26E,H26F), C27B(H27E,H27F,H27G), C29B(H29G,H29H,H29I), C30B(H30E,H30F,H30G),
 C31B(H31G,H31H,H31I), C32B(H32G,H32H,H32I), C35B(H35E,H35F,H35G), C36B(H36E,
 H36F,H36G), C12C(H12A,H12B,H12C), C13C(H13A,H13B,H13C), C15C(H15A,H15B,H15C),
 C16C(H16A,H16B,H16C), C18C(H18A,H18B,H18C), C28C(H28A,H28B,H28C), C29C(H29A,
 H29B,H29C), C31C(H31A,H31B,H31C), C32C(H32A,H32B,H32C), C40C(H40A,H40B,H40C),
 C41C(H41A,H41B,H41C), C43C(H43A,H43B,H43C), C44C(H44A,H44B,H44C), C52C(H52A,
 H52B,H52C), C53C(H53A,H53B,H53C), C55C(H55A,H55B,H55C), C56C(H56A,H56B,H56C),
 C58C(H58A,H58B,H58C), C61C(H61A,H61B,H61C), C62C(H62A,H62B,H62C), C65C(H65A,
 H65B,H65C), C66C(H66A,H66B,H66C), C67C(H67A,H67B,H67C), C68C(H68A,H68B,H68C),
 C71C(H71A,H71B,H71C), C72C(H72A,H72B,H72C), C17C(H17A,H17B,H17C), C19C(H19A,
 H19B,H19C), C20C(H20A,H20B,H20C), C57C(H57A,H57B,H57C), C59C(H59A,H59B,H59C),
 C60C(H60A,H60B,H60C), C1S(H1SA,H1SB,H1SC), C6S(H6SA,H6SB,H6SC), C05L(H05A,H05B,
 H05C), C7S(H7SA,H7SB,H7SC), C12S(H12F,H12G,H12H), C13S(H13J,H13K,H13L),
 C16S(H16J,H16K,H16L), C21S(H21C,H21D,H21E)
;