Carbon dioxide reduction by an Al-O-P frustrated Lewis pair.
Wickemeyer, Lucas; Aders, Niklas; Mix, Andreas; Neumann, Beate; Stammler, Hans-Georg; Cabrera-Trujillo, Jorge J; Fernández, Israel; Mitzel, Norbert W.; Chemical science 13 (2022) 8088–8094; doi:10.1039/d2sc01870e

data_1567185
_publ_section_title
;
 Carbon dioxide reduction by an Al-O-P frustrated Lewis pair.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              8088
_journal_page_last               8094
_journal_paper_doi               10.1039/d2sc01870e
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C23 H55 Al O3 P Si4'
_chemical_formula_sum            'C23 H55 Al O3 P Si4'
_chemical_formula_weight         549.98
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-02-14 deposited with the CCDC.	2022-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.12(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.738(2)
_cell_length_b                   28.6426(13)
_cell_length_c                   11.8207(18)
_cell_measurement_reflns_used    15683
_cell_measurement_temperature    220.0(1)
_cell_measurement_theta_max      27.8210
_cell_measurement_theta_min      3.4300
_cell_volume                     3471.9(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      220.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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   -134.00 -61.00   1.00   16.00    --  -29.96-178.00-180.00   73
  2  \w   -104.00 -74.00   1.00   16.00    --  -29.96-178.00  90.00   30
  3  \w     -5.00  30.00   1.00   16.00    --  -29.96-112.00  91.96   35
  4  \w    -40.00  14.00   1.00   16.00    --  -29.96 -77.00-150.00   54
  5  \w   -106.00 -58.00   1.00   16.00    --  -29.96 178.00   0.00   48
  6  \w    -22.00 124.00   1.00   16.00    --   29.96  38.00-120.00  146
  7  \w     -5.00 122.00   1.00   16.00    --   29.96  57.00  90.00  127
  8  \w    -32.00  80.00   1.00   16.00    --   29.96 -38.00 -60.00  112
  9  \w    -55.00 121.00   1.00   16.00    --   29.96 -19.00  90.00  176
 10  \w     -4.00  73.00   1.00   16.00    --   29.96  57.00   0.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0670504000
_diffrn_orient_matrix_UB_12      0.0044750000
_diffrn_orient_matrix_UB_13      -0.0425194000
_diffrn_orient_matrix_UB_21      -0.0081737000
_diffrn_orient_matrix_UB_22      0.0065441000
_diffrn_orient_matrix_UB_23      0.0535151000
_diffrn_orient_matrix_UB_31      0.0150503000
_diffrn_orient_matrix_UB_32      0.0235032000
_diffrn_orient_matrix_UB_33      -0.0067982000
_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  0.0418
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            64458
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.026
_diffrn_reflns_theta_min         2.432
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.262
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.563
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.052
_exptl_crystal_description       block
_exptl_crystal_F_000             1204
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.298
_exptl_crystal_size_min          0.197
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.519
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         10143
_refine_ls_number_restraints     858
_refine_ls_restrained_S_all      1.168
_refine_ls_R_factor_all          0.0936
_refine_ls_R_factor_gt           0.0657
_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^)+(0.1135P)^2^+1.3608P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1914
_refine_ls_wR_factor_ref         0.2165
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7019
_reflns_number_total             10143
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01870e2.cif
_cod_data_source_block           compound5
_cod_depositor_comments
'Adding full bibliography for 1567184--1567187.cif.'
_cod_original_cell_volume        3471.9(10)
_cod_database_code               1567185
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H55AlO3PSi4
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si2-C15 \\sim Si2B-C15B \\sim Si2B-C16B \\sim Si2B-C14B \\sim Si2-C14 \\sim
Si2-C16 \\sim Si1-C11 ~
 Si1B-C11B \\sim Si1-C13 \\sim Si1-C12 \\sim Si1B-C12B \\sim Si1B-C13B \\sim
Si4-C22 \\sim Si4-C21 ~
 Si4-C23 \\sim Si4B-C22B \\sim Si4B-C21B \\sim Si4B-C23B \\sim Si3-C19 \\sim
Si3-C20 \\sim Si3B-C19B ~
 Si3B-C20B \\sim Si3B-C18B \\sim Si3-C18
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si1 \\sim Si1B \\sim Si2 \\sim Si2B \\sim Si3 \\sim Si3B \\sim Si4 \\sim Si4B
\\sim C11 \\sim C11B \\sim C12 \\sim C12B \\sim C13 \\sim C13B \\sim C14 \\sim
C14B \\sim C15 \\sim C15B \\sim C16 \\sim C16B \\sim C17 \\sim C17B \\sim C18
\\sim C18B \\sim C19 \\sim C19B \\sim C20 \\sim C20B \\sim C21 \\sim C21B \\sim
C22 \\sim C22B \\sim C23 \\sim C23B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(Si1) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C18B) \\sim Ueq, Uanis(Si3B)
\\sim Ueq, Uanis(C20B) \\sim Ueq, Uanis(Si2B) \\sim Ueq, Uanis(C13B) \\sim Ueq,
Uanis(Si2) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(Si4) \\sim Ueq, Uanis(C23B) \\sim Ueq, Uanis(C16B) \\sim Ueq,
Uanis(C21) \\sim Ueq, Uanis(C22B) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C17B)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C21B) \\sim Ueq,
Uanis(Si3) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(Si4B) \\sim Ueq, Uanis(C15B)
\\sim Ueq, Uanis(C19B) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C14B) \\sim Ueq, Uanis(Si1B) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(Si1B)=Sof(Si2B)=Sof(Si3B)=Sof(Si4B)=Sof(H10)=Sof(C11B)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=Sof(C12B)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13B)=
 Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14B)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15B)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16B)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17B)=Sof(C18B)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19B)=
 Sof(H19C)=Sof(H19A)=Sof(H19B)=Sof(C20B)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(Si1)=Sof(Si2)=Sof(Si3)=Sof(Si4)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13)=Sof(H13D)=Sof(H13E)=Sof(H13F)=
 Sof(C14)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20)=Sof(H20D)=
 Sof(H20E)=Sof(H20F)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C17(H17)
5.b Me refined with riding coordinates:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C11B(H11D,H11E,H11F), C12(H12D,
 H12E,H12F), C12B(H12A,H12B,H12C), C13(H13D,H13E,H13F), C13B(H13A,H13B,H13C),
 C14(H14D,H14E,H14F), C14B(H14A,H14B,H14C), C15(H15A,H15B,H15C), C15B(H15D,H15E,
 H15F), C16(H16A,H16B,H16C), C16B(H16D,H16E,H16F), C18(H18A,H18B,H18C),
 C18B(H18D,H18E,H18F), C19(H19D,H19E,H19F), C19B(H19A,H19B,H19C), C20(H20D,H20E,
 H20F), C20B(H20A,H20B,H20C), C21(H21A,H21B,H21C), C21B(H21D,H21E,H21F),
 C22(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C23(H23A,H23B,H23C), C23B(H23D,H23E,
 H23F)
;
_shelx_res_checksum              57314
_shelx_hkl_checksum              12596
_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 1.275
_oxdiff_exptl_absorpt_empirical_full_min 0.859