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_1564720
_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         'C66 H103 Ag Al N4 O P, 1(C5 H12)'
_chemical_formula_sum            'C71 H115 Ag Al N4 O P'
_chemical_formula_weight         1206.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.30440(10)
_cell_length_b                   18.14880(10)
_cell_length_c                   22.24090(10)
_cell_measurement_reflns_used    43835
_cell_measurement_temperature    150.01(11)
_cell_measurement_theta_max      76.0910
_cell_measurement_theta_min      3.9460
_cell_volume                     6984.85(6)
_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      150.01(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_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    -34.00  29.00   1.00    1.00    --  -42.66  38.00-150.00   63
  2  \w    -49.00   4.00   1.00    1.00    --  -42.66  38.00-180.00   53
  3  \w     61.00 129.00   1.00    1.00    --   42.66 178.00-150.00   68
  4  \w     60.00  90.00   1.00    7.00    --  111.00 -30.00 -60.00   30
  5  \w     71.00 170.00   1.00    7.00    --  111.00  15.00-150.00   99
  6  \w     41.00  79.00   1.00    7.00    --  111.00 -45.00  30.00   38
  7  \w     89.00 114.00   1.00    7.00    --  111.00  30.00 -90.00   25
  8  \w     51.00  93.00   1.00    7.00    --  111.00 -45.00 120.00   42
  9  \w     36.00  61.00   1.00    7.00    --  111.00 -30.00   0.00   25
 10  \w    132.00 174.00   1.00    7.00    --  111.00  30.00 -90.00   42
 11  \w     83.00 108.00   1.00    7.00    --  111.00  15.00 120.00   25
 12  \w    139.00 165.00   1.00    7.00    --  111.00  15.00 120.00   26
 13  \w     86.00 118.00   1.00    7.00    --  111.00 -77.00 120.00   32
 14  \w    -47.00 -21.00   1.00    1.00    --  -42.66  38.00 -90.00   26
 15  \w    -43.00  29.00   1.00    1.00    --  -42.66  38.00  60.00   72
 16  \w    -35.00  10.00   1.00    1.00    --  -42.66  38.00   0.00   45
 17  \w    -21.00  23.00   1.00    1.00    --  -42.66  38.00 -60.00   44
 18  \w    -14.00  19.00   1.00    1.00    --  -42.66  38.00 -90.00   33
 19  \w     86.00 128.00   1.00    1.00    --   42.66 178.00  30.00   42
 20  \w     96.00 123.00   1.00    7.00    --  111.00 -77.00  30.00   27
 21  \w     45.00  74.00   1.00    7.00    --  111.00 -77.00  30.00   29
 22  \w     72.00 118.00   1.00    7.00    --  111.00-125.00  30.00   46
 23  \w     45.00  90.00   1.00    7.00    --  111.00 -30.00 -90.00   45
 24  \w     41.00  96.00   1.00    7.00    --  111.00-125.00 150.00   55
 25  \w     30.00  86.00   1.00    7.00    --  111.00 -95.00-120.00   56
 26  \w     30.00  61.00   1.00    7.00    --  111.00 -95.00 150.00   31
 27  \w     80.00 106.00   1.00    7.00    --  111.00 -77.00 -90.00   26
 28  \w     68.00 111.00   1.00    7.00    --  111.00-125.00 -60.00   43
 29  \w     48.00  96.00   1.00    7.00    --  111.00 -45.00-120.00   48
 30  \w     67.00 100.00   1.00    7.00    --  111.00-125.00  60.00   33
 31  \w     51.00  77.00   1.00    7.00    --  111.00 -30.00-120.00   26
 32  \w     60.00  91.00   1.00    7.00    --  111.00 -30.00-180.00   31
 33  \w     48.00  87.00   1.00    7.00    --  111.00 -15.00 -90.00   39
 34  \w     96.00 136.00   1.00    7.00    --  111.00 -15.00 -90.00   40
 35  \w     91.00 117.00   1.00    7.00    --  111.00-125.00-120.00   26
 36  \w     45.00 117.00   1.00    7.00    --  111.00-125.00 120.00   72
 37  \w     75.00 118.00   1.00    7.00    --  111.00-125.00-180.00   43
 38  \w    133.00 172.00   1.00    7.00    --  111.00  30.00-120.00   39
 39  \w     40.00 118.00   1.00    7.00    --  111.00-125.00 -30.00   78
 40  \w     58.00  88.00   1.00    7.00    --  111.00 -30.00  30.00   30
 41  \w     63.00 114.00   1.00    7.00    --  111.00-125.00  90.00   51
 42  \w     84.00 109.00   1.00    7.00    --  111.00  77.00 -30.00   25
 43  \w    153.00 178.00   1.00    7.00    --  111.00  77.00 -30.00   25
 44  \w    116.00 142.00   1.00    7.00    --  111.00 -77.00 150.00   26
 45  \w     39.00  81.00   1.00    7.00    --  111.00 -77.00 150.00   42
;
_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      0.0621756000
_diffrn_orient_matrix_UB_12      -0.0371736000
_diffrn_orient_matrix_UB_13      0.0392141000
_diffrn_orient_matrix_UB_21      -0.0621233000
_diffrn_orient_matrix_UB_22      -0.0502420000
_diffrn_orient_matrix_UB_23      0.0279502000
_diffrn_orient_matrix_UB_31      0.0142584000
_diffrn_orient_matrix_UB_32      -0.0573285000
_diffrn_orient_matrix_UB_33      -0.0498583000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            83407
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.303
_diffrn_reflns_theta_min         3.529
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.964
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93917
_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    1.147
_exptl_crystal_description       block
_exptl_crystal_F_000             2608
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.638
_refine_diff_density_min         -0.404
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 6152 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0225(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     791
_refine_ls_number_reflns         14559
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0308
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0468P)^2^+2.4328P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0813
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                14111
_reflns_number_total             14559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04676d2.cif
_cod_data_source_block           5-Ag
_cod_database_code               1564720
_publcif_datablock.id            {8c32765d-aadc-428f-ae6e-ec600f50f0eb}
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 O2 N4 Ag1 Al1 P1'
_shelx_estimated_absorpt_t_max   0.756
_shelx_estimated_absorpt_t_min   0.470
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C68A-C67A = C69A-C68A = C70A-C69A = C68-C67 = C69-C68 = C70-C69 = C71A-C70A =
 C71-C70
 1.53 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C71A \\sim C64 \\sim C63 \\sim C65 \\sim C66: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
4. Others
 Sof(C68A)=Sof(H68c)=Sof(H68d)=Sof(C70A)=Sof(H70c)=Sof(H70d)=Sof(C69A)=
 Sof(H69c)=Sof(H69d)=Sof(C67A)=Sof(H67d)=Sof(H67e)=Sof(H67f)=Sof(C71A)=
 Sof(H71d)=Sof(H71e)=Sof(H71f)=1-FVAR(1)
 Sof(C69)=Sof(H69a)=Sof(H69b)=Sof(C67)=Sof(H67a)=Sof(H67b)=Sof(H67c)=Sof(C71)=
 Sof(H71a)=Sof(H71b)=Sof(H71c)=Sof(C68)=Sof(H68a)=Sof(H68b)=Sof(C70)=Sof(H70a)=
 Sof(H70b)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C52(H52), C49(H49), C45(H45), C31(H31), C42(H42), C33(H33)
5.b Secondary CH2 refined with riding coordinates:
 C69(H69a,H69b), C68(H68a,H68b), C70(H70a,H70b), C68A(H68c,H68d), C70A(H70c,
 H70d), C69A(H69c,H69d)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C38(H38), C8(H8), C19(H19), C39(H39), C17(H17), C40(H40), C26(H26),
 C27(H27), C28(H28)
5.d Idealised Me refined as rotating group:
 C12(H12a,H12b,H12c), C30(H30a,H30b,H30c), C5(H5a,H5b,H5c), C51(H51a,H51b,
 H51c), C6(H6a,H6b,H6c), C13(H13a,H13b,H13c), C22(H22a,H22b,H22c), C7(H7a,H7b,
 H7c), C53(H53a,H53b,H53c), C46(H46a,H46b,H46c), C47(H47a,H47b,H47c), C50(H50a,
 H50b,H50c), C1AA(H1Aa,H1Ab,H1Ac), C44(H44a,H44b,H44c), C23(H23a,H23b,H23c),
 C54(H54a,H54b,H54c), C43(H43a,H43b,H43c), C34(H34a,H34b,H34c), C32(H32a,H32b,
 H32c), C21(H21a,H21b,H21c), C60(H60a,H60b,H60c), C3AA(H3Aa,H3Ab,H3Ac),
 C65(H65a,H65b,H65c), C62(H62a,H62b,H62c), C64(H64a,H64b,H64c), C35(H35a,H35b,
 H35c), C2AA(H2Aa,H2Ab,H2Ac), C67(H67a,H67b,H67c), C66(H66a,H66b,H66c),
 C61(H61a,H61b,H61c), C71(H71a,H71b,H71c), C67A(H67d,H67e,H67f), C71A(H71d,H71e,
 H71f)
;
_shelx_res_checksum              66029
_shelx_hkl_checksum              3945
_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 1.088
_oxdiff_exptl_absorpt_empirical_full_min 0.886
_publcif_funding_html
;
;