Calix[4]pyrrole aluminate: a planar tetracoordinate aluminum(III) anion and its unusual Lewis acidity.
Ebner, Fabian; Wadepohl, Hubert; Greb, Lutz; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b10628

data_4129072
_publ_section_title
;
 Calix[4]pyrrole aluminate: a planar tetracoordinate aluminum(III) anion
 and its unusual Lewis acidity.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b10628
_journal_year                    2019
_chemical_formula_moiety
'C28 H33.58 Al N4, 1.5(C12 H30 Li O6), 0.5(C8 H20 Li O4)'
_chemical_formula_sum            'C50 H89 Al Li2 N4 O11'
_chemical_formula_weight         963.11
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-07-15
_audit_creation_method
;
Olex2 1.2
(compiled May 29 2018 13:30:08 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.21(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.157(2)
_cell_length_b                   23.544(5)
_cell_length_c                   39.927(8)
_cell_measurement_reflns_used    4748
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      40.0
_cell_measurement_theta_min      1.5
_cell_volume                     11311(4)
_computing_cell_refinement       'DENZO (Otwinowski & Minor, 1997)'
_computing_data_collection       'HKL-2000 (Otwinowski & Minor, 2000)'
_computing_data_reduction        'DENZO (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120(1)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'NONIUS Kappa CCD'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1265
_diffrn_reflns_av_unetI/netI     0.1727
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            39042
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.123
_diffrn_reflns_theta_max         25.123
_diffrn_reflns_theta_min         1.805
_diffrn_source                   'sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.092
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.131
_exptl_crystal_description       block
_exptl_crystal_F_000             4192
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.792
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1344
_refine_ls_number_reflns         20194
_refine_ls_number_restraints     1417
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.2215
_refine_ls_R_factor_gt           0.0875
_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^)+(0.1186P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2015
_refine_ls_wR_factor_ref         0.2570
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8504
_reflns_number_total             20194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10628_si_005.cif
_cod_data_source_block           fe478
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4129072
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.951
_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
 Al1-HA \\sim Al3-HB
 with sigma of 0.02
 Li81-O85A \\sim Li81-O85B \\sim Li81-O86A \\sim Li81-O86B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O61 \\sim O62 \\sim O63 \\sim O64 \\sim O65 \\sim O66 \\sim O81 \\sim O82 \\sim
O83 \\sim O84 \\sim O85A \\sim O86A \\sim O85B \\sim O86B \\sim O101 \\sim O102
\\sim O103 \\sim O104 \\sim O105 \\sim O106 \\sim O121 \\sim O122 \\sim O123
\\sim O124 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim
C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim
C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim
C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C31 \\sim C32 \\sim C33 \\sim
C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim
C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim
C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim
C58 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim
C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C81 \\sim C82 \\sim C83 \\sim
C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89A \\sim C90A \\sim C91A
\\sim C92A \\sim C89B \\sim C90B \\sim C91B \\sim C92B \\sim C101 \\sim C102
\\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109
\\sim C110 \\sim C111 \\sim C112 \\sim C121 \\sim C122 \\sim C123 \\sim C124
\\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim Li61 \\sim Li81 \\sim Li11
\\sim Li12: within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 Li61, Li81, Li11, Li12, O61, O62, O63, O64, O65, O66, O81, O82, O83, O84,
 O85A, O86A, O85B, O86B, O101, O102, O103, O104, O105, O106, O121, O122, O123,
 O124, C61, C62, C63, C64, O63, O64, C65, C66, C67, C68, O65, O66, C69, C70,
 C71, C72, Li61, O81, O82, C81, C82, C83, C84, O83, O84, C85, C86, C87, C88,
 O85A, O86A, C89A, C90A, C91A, C92A, O85B, O86B, C89B, C90B, C91B, C92B, Li81,
 O101, O102, C101, C102, C103, C104, O103, O104, C105, C106, C107, C108, O105,
 O106, C109, C110, C111, C112, Li11, O121, O122, C121, C122, C123, C124, O123,
 O124, C125, C126, C127, C128
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O63, O64, C65, C66, C67, C68}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O65, O66, C69, C70, C71, C72}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O81, O82, C81, C82, C83, C84}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O83, O84, C85, C86, C87, C88}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O85A, O86A, C89A, C90A, C91A, C92A}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O85B, O86B, C89B, C90B, C91B, C92B}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O101, O102, C101, C102, C103, C104}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O103, O104, C105, C106, C107, C108}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O105, O106, C109, C110, C111, C112}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O121, O122, C121, C122, C123, C124}
{O61, O62, C61, C62, C63, C64} sigma for 1-2: 0.02, 1-3: 0.04
as
{O123, O124, C125, C126, C127, C128}
6. Others
 Sof(Al2)=1-FVAR(1)
 Sof(Al1)=Sof(HA)=FVAR(1)
 Sof(Al4)=1-FVAR(2)
 Sof(Al3)=Sof(HB)=FVAR(2)
 Sof(O85B)=Sof(O86B)=Sof(C89B)=Sof(H89C)=Sof(H89D)=Sof(C90B)=Sof(H90C)=
 Sof(H90D)=Sof(C91B)=Sof(H91D)=Sof(H91E)=Sof(H91F)=Sof(C92B)=Sof(H92D)=
 Sof(H92E)=Sof(H92F)=1-FVAR(3)
 Sof(O85A)=Sof(O86A)=Sof(C89A)=Sof(H89A)=Sof(H89B)=Sof(C90A)=Sof(H90A)=
 Sof(H90B)=Sof(C91A)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C92A)=Sof(H92A)=
 Sof(H92B)=Sof(H92C)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C38(H38A,H38B), C61(H61A,H61B), C62(H62A,H62B), C65(H65A,H65B),
 C66(H66A,H66B), C69(H69A,H69B), C70(H70A,H70B), C81(H81A,H81B), C82(H82A,H82B),
  C85(H85A,H85B), C86(H86A,H86B), C89A(H89A,H89B), C90A(H90A,H90B), C89B(H89C,
 H89D), C90B(H90C,H90D), C101(H10A,H10B), C102(H10C,H10D), C105(H10K,H10L),
 C106(H10M,H10N), C109(H10U,H10V), C110(H11A,H11B), C121(H12A,H12B), C122(H12C,
 H12D), C125(H12K,H12L), C126(H12M,H12N)
7.b Me refined with riding coordinates:
 C91A(H91A,H91B,H91C), C92A(H92A,H92B,H92C), C91B(H91D,H91E,H91F), C92B(H92D,
 H92E,H92F)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18), C32(H32),
 C33(H33), C37(H37), C42(H42), C43(H43), C47(H47), C48(H48)
7.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C67(H67A,
 H67B,H67C), C68(H68A,H68B,H68C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C),
 C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C87(H87A,H87B,H87C), C88(H88A,H88B,
 H88C), C103(H10E,H10F,H10G), C104(H10H,H10I,H10J), C107(H10O,H10P,H10Q),
 C108(H10R,H10S,H10T), C111(H11C,H11D,H11E), C112(H11F,H11G,H11H), C123(H12E,
 H12F,H12G), C124(H12H,H12I,H12J), C127(H12O,H12P,H12Q), C128(H12R,H12S,H12T)
;
_shelx_res_checksum              48392
_shelx_hkl_checksum              67899
_olex2_submission_special_instructions 'No special instructions were received'