Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide
Aldridge, Simon; McManus, Caitilín; Hicks, Jamie; Goicoechea, Jose M.; Cui, Xianlu; Zhao, Lili; Frenking, Gernot; Chemical Science  (2021) –; doi:10.1039/D1SC04676D

data_1564721
_publ_section_title
;
 Coinage metal aluminyl complexes: probing regiochemistry and mechanism in
 the insertion and reduction of carbon dioxide
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04676D
_journal_year                    2021
_chemical_formula_moiety         'C60 H89 Ag Al N2 O4 P, 2.5(C6 H6)'
_chemical_formula_sum            'C75 H104 Ag Al N2 O4 P'
_chemical_formula_weight         1263.42
_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             2021-02-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-05-24 deposited with the CCDC.	2021-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                113.433(4)
_cell_angle_beta                 99.104(3)
_cell_angle_gamma                91.609(3)
_cell_formula_units_Z            2
_cell_length_a                   13.0018(4)
_cell_length_b                   15.7611(7)
_cell_length_c                   19.2597(10)
_cell_measurement_reflns_used    5270
_cell_measurement_temperature    150.0(3)
_cell_measurement_theta_max      73.9120
_cell_measurement_theta_min      4.6330
_cell_volume                     3557.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -44.00  28.00   1.00   10.00    --  -42.53  38.00  30.00   72
  2  \w    -42.00 -17.00   1.00   10.00    --  -42.53  38.00 -90.00   25
  3  \w   -113.00 -23.00   1.00   10.00    --  -42.53 -57.00 120.00   90
  4  \w    -82.00 -55.00   1.00   10.00    --  -42.53-155.00 -95.00   27
  5  \w      3.00  28.00   1.00   10.00    --  -42.53  57.00 -90.00   25
  6  \w    -69.00  -9.00   1.00   10.00    --  -42.53  57.00 -90.00   60
  7  \w     -1.00  26.00   1.00   10.00    --  -42.53  38.00 -90.00   27
  8  \w     58.00 117.00   1.00   10.00    --   42.53 178.00-180.00   59
  9  \w     88.00 129.00   1.00   10.00    --   42.53 178.00  90.00   41
 10  \w     95.00 149.00   1.00   32.00    --  111.00 125.00   0.00   54
 11  \w     85.00 118.00   1.00   32.00    --  111.00-125.00 -30.00   33
 12  \w     91.00 155.00   1.00   32.00    --  111.00 -15.00-150.00   64
 13  \w     51.00 136.00   1.00   32.00    --  111.00 -61.00-180.00   85
 14  \w     51.00  89.00   1.00   32.00    --  111.00 -30.00  60.00   38
 15  \w     40.00  96.00   1.00   32.00    --  111.00 -45.00 -60.00   56
 16  \w     81.00 164.00   1.00   32.00    --  111.00  15.00 150.00   83
 17  \w     65.00  97.00   1.00   32.00    --  111.00 -45.00  30.00   32
 18  \w     71.00 117.00   1.00   32.00    --  111.00-125.00-120.00   46
 19  \w     42.00  72.00   1.00   32.00    --  111.00-125.00 -60.00   30
 20  \w     70.00  96.00   1.00   32.00    --  111.00 -45.00 -30.00   26
 21  \w     37.00  83.00   1.00   32.00    --  111.00 -95.00 -30.00   46
 22  \w     32.00  75.00   1.00   32.00    --  111.00 -15.00-150.00   43
 23  \w     76.00 118.00   1.00   32.00    --  111.00-125.00  60.00   42
 24  \w     79.00 140.00   1.00   32.00    --  111.00 -77.00   0.00   61
 25  \w     42.00  80.00   1.00   32.00    --  111.00-125.00 120.00   38
 26  \w     91.00 116.00   1.00   32.00    --  111.00-125.00 120.00   25
 27  \w     45.00  70.00   1.00   32.00    --  111.00 -95.00 150.00   25
 28  \w     53.00  91.00   1.00   32.00    --  111.00 -30.00 120.00   38
 29  \w     59.00  86.00   1.00   32.00    --  111.00 -77.00  60.00   27
 30  \w     86.00 113.00   1.00   32.00    --  111.00  15.00-120.00   27
 31  \w    103.00 156.00   1.00   32.00    --  111.00  30.00  30.00   53
 32  \w     74.00 116.00   1.00   32.00    --  111.00-125.00  30.00   42
 33  \w    120.00 175.00   1.00   32.00    --  111.00  15.00-120.00   55
 34  \w     89.00 142.00   1.00   32.00    --  111.00 -77.00  60.00   53
 35  \w     44.00  69.00   1.00   32.00    --  111.00-125.00 -90.00   25
 36  \w     80.00 105.00   1.00   32.00    --  111.00-125.00 -90.00   25
 37  \w     51.00  76.00   1.00   32.00    --  111.00 -30.00-150.00   25
 38  \w    139.00 178.00   1.00   32.00    --  111.00  61.00  90.00   39
 39  \w     55.00  91.00   1.00   32.00    --  111.00 -30.00 -30.00   36
 40  \w    104.00 129.00   1.00   32.00    --  111.00-142.00-135.48   25
 41  \w     89.00 118.00   1.00   32.00    --  111.00-125.00 -60.00   29
 42  \w     47.00  88.00   1.00   32.00    --  111.00-142.00-135.48   41
;
_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      0.0655025000
_diffrn_orient_matrix_UB_12      0.0922952000
_diffrn_orient_matrix_UB_13      0.0197932000
_diffrn_orient_matrix_UB_21      -0.0202560000
_diffrn_orient_matrix_UB_22      -0.0174137000
_diffrn_orient_matrix_UB_23      -0.0858079000
_diffrn_orient_matrix_UB_31      -0.0992262000
_diffrn_orient_matrix_UB_32      0.0514083000
_diffrn_orient_matrix_UB_33      0.0106691000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1058
_diffrn_reflns_av_unetI/netI     0.1125
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            40430
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.403
_diffrn_reflns_theta_min         3.899
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.961
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74787
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.179
_exptl_crystal_description       plate
_exptl_crystal_F_000             1350
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.067
_refine_diff_density_min         -1.167
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     813
_refine_ls_number_reflns         14719
_refine_ls_number_restraints     41
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1077
_refine_ls_R_factor_gt           0.0615
_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^)+(0.0695P)^2^+0.3758P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1427
_refine_ls_wR_factor_ref         0.1768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9470
_reflns_number_total             14719
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04676d2.cif
_cod_data_source_block           6-Ag
_cod_database_code               1564721
_publcif_datablock.id            {3c09b2b0-5199-44b2-88d2-aa117959fec7}
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C70 H70 Al1 Ag1 N2 O4 P1'
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.665
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C76-C75 = C75-C74
 1.4 with sigma of 0.008
 C74_$1-C76
 1.4 with sigma of 0.008
 C69-C68 = C68_$2-C70 = C69_$2-C70_$2
 1.4 with sigma of 0.008
 C71-C72 = C72-C73
 1.4 with sigma of 0.008
 C74_$1-C75
 2.4 with sigma of 0.008
 C76-C74
 2.4 with sigma of 0.008
 C75-C76_$1
 2.4 with sigma of 0.008
 C69-C68_$2
 2.4 with sigma of 0.008
 C70-C69_$2
 2.4 with sigma of 0.008
 C68_$2-C70_$2
 2.4 with sigma of 0.008
 C71-C73
 2.4 with sigma of 0.008
 C72-C71_$3
 2.4 with sigma of 0.008
 C73_$3-C72
 2.4 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C76 \\sim C75 \\sim C74: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C69 \\sim C68 \\sim C70 \\sim C69 \\sim C70 \\sim C68: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(C9A)=Sof(H9Aa)=Sof(H9Ab)=Sof(H9Ac)=Sof(C8A)=Sof(H8Aa)=Sof(H8Ab)=Sof(H8Ac)=
 Sof(C10A)=Sof(H10d)=Sof(H10e)=Sof(H10f)=1-FVAR(1)
 Sof(C8)=Sof(H8a)=Sof(H8b)=Sof(H8c)=Sof(C9)=Sof(H9a)=Sof(H9b)=Sof(H9c)=
 Sof(C10)=Sof(H10a)=Sof(H10b)=Sof(H10c)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C34(H34), C46(H46), C31(H31), C43(H43)
5.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C5(H5), C3(H3), C18(H18), C39(H39), C41(H41), C29(H29), C40(H40),
 C28(H28), C27(H27), C67(H67), C64(H64), C66(H66), C65(H65), C63(H63), C72(H72),
  C71(H71), C68(H68), C73(H73), C62(H62), C76(H76), C70(H70), C74(H74),
 C75(H75), C69(H69)
5.c Idealised Me refined as rotating group:
 C14(H14a,H14b,H14c), C13(H13a,H13b,H13c), C32(H32a,H32b,H32c), C47(H47a,H47b,
 H47c), C0AA(H0Aa,H0Ab,H0Ac), C60(H60a,H60b,H60c), C35(H35a,H35b,H35c),
 C33(H33a,H33b,H33c), C51(H51a,H51b,H51c), C36(H36a,H36b,H36c), C22(H22a,H22b,
 H22c), C55(H55a,H55b,H55c), C45(H45a,H45b,H45c), C23(H23a,H23b,H23c), C58(H58a,
 H58b,H58c), C50(H50a,H50b,H50c), C44(H44a,H44b,H44c), C54(H54a,H54b,H54c),
 C24(H24a,H24b,H24c), C59(H59a,H59b,H59c), C52(H52a,H52b,H52c), C56(H56a,H56b,
 H56c), C8(H8a,H8b,H8c), C9(H9a,H9b,H9c), C10(H10a,H10b,H10c), C9A(H9Aa,H9Ab,
 H9Ac), C8A(H8Aa,H8Ab,H8Ac), C10A(H10d,H10e,H10f)
;
_shelx_res_checksum              66980
_shelx_hkl_checksum              1221
_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 1.421
_oxdiff_exptl_absorpt_empirical_full_min 0.827
_publcif_funding_html
;
;