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_4129067
_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         'C44 H64 Al Li N4 O4'
_chemical_formula_sum            'C44 H64 Al Li N4 O4'
_chemical_formula_weight         746.91
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                gr_fe2
_audit_creation_date             2019-02-12
_audit_creation_method
;
Olex2 1.2
(compiled May 29 2018 13:30:08 for OlexSys, GUI svn.r5506)
;
_audit_update_record
'10.07.2019 18:21:15 CEST UTC+02:00  encif 1.93'
_cell_angle_alpha                90
_cell_angle_beta                 100.411(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5770(3)
_cell_length_b                   15.5510(4)
_cell_length_c                   22.4542(6)
_cell_measurement_reflns_used    12875
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      26.8250
_cell_measurement_theta_min      2.6150
_cell_volume                     3975.97(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_publication_material
'encif (Wadepohl, 2009-19); encifer 1.7.x (CCDC, 2018)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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      6.00 104.00   0.50   20.00    --   31.15  38.00   0.00  196
  2  \w    -20.00  73.00   0.50   20.00    --   31.15 -99.00 150.00  186
  3  \w    -38.00  53.00   0.50   20.00    --   31.15 -57.00  30.00  182
  4  \w    -38.00  53.00   0.50   20.00    --   31.15 -57.00-150.00  182
  5  \w      1.00 101.00   0.50   20.00    --   31.15  77.00 150.00  200
  6  \w      1.00 101.00   0.50   20.00    --   31.15  77.00   0.00  200
  7  \w      1.00 101.00   0.50   20.00    --   31.15  77.00-120.00  200
  8  \w      1.00 101.00   0.50   20.00    --   31.15  77.00  60.00  200
  9  \w    -39.00  61.00   0.50   20.00    --   31.15 -77.00 -60.00  200
 10  \w    -20.00   5.00   0.50   20.00    --   31.15 -99.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0471906000
_diffrn_orient_matrix_UB_12      -0.0295816000
_diffrn_orient_matrix_UB_13      0.0021394000
_diffrn_orient_matrix_UB_21      -0.0101842000
_diffrn_orient_matrix_UB_22      -0.0134435000
_diffrn_orient_matrix_UB_23      0.0287839000
_diffrn_orient_matrix_UB_31      -0.0394058000
_diffrn_orient_matrix_UB_32      -0.0319878000
_diffrn_orient_matrix_UB_33      -0.0140927000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0683
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            85681
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.545
_diffrn_reflns_theta_min         2.217
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.717
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
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    1.248
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.141
_exptl_crystal_size_min          0.139
_refine_diff_density_max         1.271
_refine_diff_density_min         -0.651
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     578
_refine_ls_number_reflns         12157
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1380
_refine_ls_R_factor_gt           0.0950
_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^)+(0.1697P)^2^+2.9357P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2694
_refine_ls_wR_factor_ref         0.3094
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7692
_reflns_number_total             12157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10628_si_007.cif
_cod_data_source_block           gr_fe2
_cod_original_cell_volume        3975.96(17)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4129067
_audit_block_refno               3275
_audit_block_usercomment         'FE_401, irregular, colourless'
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.981
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_shelxl_version_number           2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O41-C41 \\sim O41-C44A \\sim O41-C44B
 with sigma of 0.02
 C41-C42 \\sim C42-C43 \\sim C43-C44A \\sim C43-C44B
 with sigma of 0.02
 O41-C42 \\sim O41-C43
 with sigma of 0.04
 C41-C43 \\sim C42-C44A \\sim C42-C44B
 with sigma of 0.04
 C61-C62A \\sim C61-C62B \\sim C62A-C63A \\sim C62B-C63B \\sim C63A-C64 \\sim
C63B-C64
 with sigma of 0.02
 O61-C61 \\sim O61-C64
 with sigma of 0.02
 C61-C63A \\sim C61-C63B \\sim C64-C62A \\sim C64-C62B
 with sigma of 0.04
 O61-C62A \\sim O61-C62B \\sim O61-C63A \\sim O61-C63B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
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 C41
\\sim C42 \\sim C43 \\sim C44A \\sim C44B \\sim C51A \\sim C52A \\sim C53A
\\sim C54A \\sim C51B \\sim C52B \\sim C53B \\sim C54B \\sim C61 \\sim C62A
\\sim C63A \\sim C62B \\sim C63B \\sim C64 \\sim O31 \\sim O41 \\sim O51A \\sim
O51B \\sim O61: within 1A with sigma of 0.001 and sigma for terminal atoms of
0.001
4. Rigid body (RIGU) restrains
 Li, O41, C41, C42, C43, C44A, C44B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Li, O51A, C51A, C52A, C53A, C54A, O51B, C51B, C52B, C53B, C54B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Li, O61, C61, C62A, C63A, C62B, C63B, C64
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{O51A, C54A, C53A, C52A, C51A} sigma for 1-2: 0.02, 1-3: 0.04
as
{O51A, C51A, C52A, C53A, C54A}
{O51B, C54B, C53B, C52B, C51B} sigma for 1-2: 0.02, 1-3: 0.04
as
{O51B, C51B, C52B, C53B, C54B}
6. Others
 Sof(O51B)=Sof(C51B)=Sof(H51C)=Sof(H51D)=Sof(C52B)=Sof(H52C)=Sof(H52D)=
 Sof(C53B)=Sof(H53C)=Sof(H53D)=Sof(C54B)=Sof(H54C)=Sof(H54D)=1-FVAR(1)
 Sof(O51A)=Sof(C51A)=Sof(H51A)=Sof(H51B)=Sof(C52A)=Sof(H52A)=Sof(H52B)=
 Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(C54A)=Sof(H54A)=Sof(H54B)=FVAR(1)
 Sof(H61C)=Sof(H61D)=Sof(C62B)=Sof(H62C)=Sof(H62D)=Sof(C63B)=Sof(H63C)=
 Sof(H63D)=Sof(H64C)=Sof(H64D)=1-FVAR(2)
 Sof(H61A)=Sof(H61B)=Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(C63A)=Sof(H63A)=
 Sof(H63B)=Sof(H64A)=Sof(H64B)=FVAR(2)
 Sof(H43C)=Sof(H43D)=Sof(C44B)=Sof(H44C)=Sof(H44D)=1-FVAR(3)
 Sof(H43A)=Sof(H43B)=Sof(C44A)=Sof(H44A)=Sof(H44B)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C41(H41A,
 H41B), C42(H42A,H42B), C43(H43A,H43B), C43(H43C,H43D), C44A(H44A,H44B),
 C44B(H44C,H44D), C51A(H51A,H51B), C52A(H52A,H52B), C53A(H53A,H53B), C54A(H54A,
 H54B), C51B(H51C,H51D), C52B(H52C,H52D), C53B(H53C,H53D), C54B(H54C,H54D),
 C61(H61A,H61B), C61(H61C,H61D), C62A(H62A,H62B), C63A(H63A,H63B), C62B(H62C,
 H62D), C63B(H63C,H63D), C64(H64A,H64B), C64(H64C,H64D)
7.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18)
7.c 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)
;
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.095
_oxdiff_exptl_absorpt_empirical_full_min 0.949
_shelx_res_checksum              59469
_cell_oxdiff_length_a            11.5741(5)
_cell_oxdiff_length_b            15.5561(6)
_cell_oxdiff_length_c            22.4555(6)
_cell_oxdiff_angle_alpha         90.017(3)
_cell_oxdiff_angle_beta          100.453(3)
_cell_oxdiff_angle_gamma         90.026(3)
_cell_oxdiff_volume              3976.0(2)
_cell_oxdiff_measurement_reflns_used 12875