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_1564718
_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         'C120 H178 Al2 Cu2 N4 O8 P2, 5(C6 H6)'
_chemical_formula_sum            'C150 H208 Al2 Cu2 N4 O8 P2'
_chemical_formula_weight         2438.17
_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             2021-02-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-05-24 deposited with the CCDC.	2021-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                112.876(4)
_cell_angle_beta                 98.299(3)
_cell_angle_gamma                92.821(3)
_cell_formula_units_Z            1
_cell_length_a                   13.0313(4)
_cell_length_b                   15.8057(7)
_cell_length_c                   18.8852(9)
_cell_measurement_reflns_used    6233
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      67.6340
_cell_measurement_theta_min      4.2740
_cell_volume                     3522.6(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 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      150.00(10)
_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 0.982
_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    -69.00  28.00   1.00    5.00    --  -42.28  57.00-180.00   97
  2  \w    -91.00 -64.00   1.00    5.00    --  -42.28 178.00-180.00   27
  3  \w   -111.00 -16.00   1.00    5.00    --  -42.28 -57.00  30.00   95
  4  \w   -128.00 -37.00   1.00    5.00    --  -42.28-178.00 150.00   91
  5  \w    102.00 127.00   1.00    5.00    --   42.28-178.00-180.00   25
  6  \w    -28.00  58.00   1.00    5.00    --   42.28 -38.00 -90.00   86
  7  \w     31.00  96.00   1.00   27.50    --  111.00 -95.00-120.00   65
  8  \w     73.00 100.00   1.00   27.50    --  111.00 -77.00 150.00   27
  9  \w     32.00  57.00   1.00   27.50    --  111.00 -95.00   0.00   25
 10  \w     49.00  90.00   1.00   27.50    --  111.00 -30.00  90.00   41
 11  \w     71.00  98.00   1.00   27.50    --  111.00 -45.00 -30.00   27
 12  \w     67.00  94.00   1.00   27.50    --  111.00-125.00 120.00   27
 13  \w     63.00  93.00   1.00   27.50    --  111.00-125.00   0.00   30
 14  \w     43.00 107.00   1.00   27.50    --  111.00-125.00 150.00   64
 15  \w     48.00  91.00   1.00   27.50    --  111.00 -30.00-120.00   43
 16  \w     45.00  72.00   1.00   27.50    --  111.00 -77.00 150.00   27
 17  \w     74.00 101.00   1.00   27.50    --  111.00 -95.00 150.00   27
 18  \w     30.00  64.00   1.00   27.50    --  111.00 -95.00 150.00   34
 19  \w     36.00  64.00   1.00   27.50    --  111.00 -30.00 150.00   28
 20  \w     62.00  91.00   1.00   27.50    --  111.00 -30.00 -60.00   29
 21  \w     89.00 132.00   1.00   27.50    --  111.00  45.00 120.00   43
 22  \w    145.00 175.00   1.00   27.50    --  111.00  45.00 120.00   30
 23  \w     76.00 118.00   1.00   27.50    --  111.00-125.00-120.00   42
 24  \w     40.00  65.00   1.00   27.50    --  111.00-125.00 120.00   25
 25  \w     42.00  97.00   1.00   27.50    --  111.00 -45.00  30.00   55
 26  \w     86.00 118.00   1.00   27.50    --  111.00-125.00  90.00   32
 27  \w     75.00 118.00   1.00   27.50    --  111.00-125.00-180.00   43
 28  \w     40.00  90.00   1.00   27.50    --  111.00 -30.00-180.00   50
 29  \w     43.00 118.00   1.00   27.50    --  111.00 -61.00 -30.00   75
 30  \w    100.00 169.00   1.00   27.50    --  111.00  45.00  60.00   69
 31  \w     30.00  76.00   1.00   27.50    --  111.00 -95.00 -60.00   46
 32  \w     80.00 107.00   1.00   27.50    --  111.00 -95.00   0.00   27
 33  \w     42.00  75.00   1.00   27.50    --  111.00 -45.00 150.00   33
 34  \w     54.00  81.00   1.00   27.50    --  111.00 -77.00-120.00   27
 35  \w     83.00 118.00   1.00   27.50    --  111.00-125.00 -90.00   35
 36  \w    106.00 177.00   1.00   27.50    --  111.00  30.00 -30.00   71
 37  \w     87.00 114.00   1.00   27.50    --  111.00  30.00  30.00   27
 38  \w    130.00 178.00   1.00   27.50    --  111.00  30.00  30.00   48
 39  \w    123.00 177.00   1.00   27.50    --  111.00   0.00 -60.00   54
 40  \w     85.00 118.00   1.00   27.50    --  111.00-125.00 -30.00   33
 41  \w     73.00 116.00   1.00   27.50    --  111.00-125.00  30.00   43
 42  \w     41.00  69.00   1.00   27.50    --  111.00   0.00 -60.00   28
;
_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      -0.0031875000
_diffrn_orient_matrix_UB_12      0.0628559000
_diffrn_orient_matrix_UB_13      -0.0452597000
_diffrn_orient_matrix_UB_21      0.0543979000
_diffrn_orient_matrix_UB_22      -0.0693317000
_diffrn_orient_matrix_UB_23      -0.0613869000
_diffrn_orient_matrix_UB_31      -0.1072247000
_diffrn_orient_matrix_UB_32      -0.0508443000
_diffrn_orient_matrix_UB_33      -0.0477266000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0684
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            14058
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.491
_diffrn_reflns_theta_min         3.451
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.132
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86360
_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            colourless
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       block
_exptl_crystal_F_000             1314
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.332
_refine_diff_density_min         -0.468
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     835
_refine_ls_number_reflns         14058
_refine_ls_number_restraints     372
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.1519
_refine_ls_R_factor_gt           0.0973
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2453
_refine_ls_wR_factor_ref         0.3017
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7805
_reflns_number_total             14058
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 1.4272\% 
 around [-0.91 -0.24 0.34] (reciprocal) or [-0.98 -0.21 0.01] (direct)
;
_cod_data_source_file            d1sc04676d2.cif
_cod_data_source_block           6-Cu
_cod_database_code               1564718
_publcif_datablock.id            {a0496cf9-2cda-49d9-92d4-1d2268384caa}
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 O2 N2 P1 Cu1 Al1'
_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
 C72-C71 \\sim C71-C70 \\sim C70-C69 \\sim C69-C68 \\sim C68-C67 \\sim C67-C72
 with sigma of 0.02
 C72-C68 \\sim C72-C68 \\sim C69-C71 \\sim C69-C67 \\sim C67-C71 \\sim C68-C70
 with sigma of 0.04
 C78-C77 \\sim C77-C76 \\sim C76-C75 \\sim C75-C74 \\sim C74-C73 \\sim C73-C78
 with sigma of 0.02
 C78-C74 \\sim C78-C74 \\sim C75-C77 \\sim C75-C73 \\sim C73-C77 \\sim C74-C76
 with sigma of 0.04
 C15-C17 \\sim C17-C16
 with sigma of 0.02
 C15A-C16A \\sim C16A-C17A
 with sigma of 0.02
 C81-C80 \\sim C80-C79 \\sim C79-C84 \\sim C84-C83 \\sim C83-C82 \\sim C82-C81
 with sigma of 0.02
 C81-C83 \\sim C81-C83 \\sim C84-C80 \\sim C84-C82 \\sim C82-C80 \\sim C83-C79
 with sigma of 0.04
 C62-C61 \\sim C61-C66 \\sim C66-C65 \\sim C65-C64 \\sim C64-C63 \\sim C63-C62
 with sigma of 0.02
 C62-C64 \\sim C62-C64 \\sim C65-C61 \\sim C65-C63 \\sim C63-C61 \\sim C64-C66
 with sigma of 0.04
3. Restrained planarity
 C72, C71, C70, C69, C68, C67
 with sigma of 0.1
 C78, C77, C76, C75, C74, C73
 with sigma of 0.1
 C81, C80, C79, C84, C83, C82
 with sigma of 0.1
 C62, C61, C66, C65, C64, C63
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C72 \\sim C71 \\sim C70 \\sim C69 \\sim C68 \\sim C67: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C78 \\sim C77 \\sim C76 \\sim C75 \\sim C74 \\sim C73: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C81 \\sim C80 \\sim C79 \\sim C84 \\sim C83 \\sim C82: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C62 \\sim C61 \\sim C66 \\sim C65 \\sim C64 \\sim C63: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uiso(C80) = Uiso(C79) = Uiso(C84) = Uiso(C83) = Uiso(C82) = Uiso(C81)
5. Rigid body (RIGU) restrains
 C72, C71, C70, C69, C68, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C78, C77, C76, C75, C74, C73
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C16, C17, C15, C15A, C17A, C16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C81, C80, C79, C84, C83, C82
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62, C61, C66, C65, C64, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Fixed Sof: C78(0.5) H78(0.5) C77(0.5) H77(0.5) C76(0.5) H76(0.5) C75(0.5)
 H75(0.5) C74(0.5) H74(0.5) C73(0.5) H73(0.5) C84(0.5) H84(0.5) C83(0.5)
 H83(0.5) C82(0.5) H82(0.5) C81(0.5) H81(0.5) C80(0.5) H80(0.5) C79(0.5)
 H79(0.5) C62(0.5) H62(0.5) C61(0.5) H61(0.5) C66(0.5) H66(0.5) C65(0.5)
 H65(0.5) C64(0.5) H64(0.5) C63(0.5) H63(0.5)
7.a Ternary CH refined with riding coordinates:
 C45(H45), C42(H42), C30(H30), C33(H33)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C9(H9), C28(H28), C11(H11), C27(H27), C26(H26), C39(H39),
 C38(H38), C40(H40), C72(H72), C71(H71), C70(H70), C69(H69), C68(H68), C67(H67),
  C78(H78), C77(H77), C76(H76), C75(H75), C74(H74), C73(H73), C84(H84),
 C83(H83), C82(H82), C81(H81), C80(H80), C79(H79), C62(H62), C61(H61), C66(H66),
  C65(H65), C64(H64), C63(H63)
7.c Fitted hexagon refined as free rotating group:
 C72(C71,C70,C69,C68,C67), C84(C83,C82,C81,C80,C79)
7.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C), C51(H51A,H51B,H51C), C47(H47A,H47B,
 H47C), C60(H60A,H60B,H60C), C46(H46A,H46B,H46C), C22(H22A,H22B,H22C), C52(H52A,
 H52B,H52C), C21(H21A,H21B,H21C), C55(H55A,H55B,H55C), C50(H50A,H50B,H50C),
 C31(H31A,H31B,H31C), C44(H44A,H44B,H44C), C32(H32A,H32B,H32C), C54(H54A,H54B,
 H54C), C56(H56A,H56B,H56C), C23(H23A,H23B,H23C), C34(H34A,H34B,H34C), C59(H59A,
 H59B,H59C), C43(H43A,H43B,H43C), C35(H35A,H35B,H35C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C58(H58A,H58B,H58C), C15(H15A,H15B,H15C), C15A(H15D,H15E,
 H15F), C17A(H17D,H17E,H17F), C16A(H16D,H16E,H16F)
;
_shelx_res_checksum              72361
_shelx_hkl_checksum              59426
_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 1.521
_oxdiff_exptl_absorpt_empirical_full_min 0.578
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_publcif_funding_html
;
;