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_1564716
_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         'C72 H111 Al Cu N4 O P, C6 H6'
_chemical_formula_sum            'C78 H117 Al Cu N4 O P'
_chemical_formula_weight         1248.24
_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             2019-08-26
_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                 98.787(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6572(4)
_cell_length_b                   19.3809(6)
_cell_length_c                   30.2695(12)
_cell_measurement_reflns_used    6251
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      75.8600
_cell_measurement_theta_min      3.6120
_cell_volume                     7338.2(4)
_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(2)
_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    -65.00  36.00   1.00   25.00    --  -42.66  19.00  60.00  101
  2  \w   -128.00 -84.00   1.00   25.00    --  -42.66 178.00-120.00   44
  3  \w    -36.00 -10.00   1.00   25.00    --  -42.66  38.00-180.00   26
  4  \w    -43.00  30.00   1.00   25.00    --  -42.66  38.00 120.00   73
  5  \w     56.00  93.00   1.00   55.00    --  111.00 -61.00 -30.00   37
  6  \w     32.00  57.00   1.00   55.00    --  111.00 -15.00 -90.00   25
  7  \w     47.00  90.00   1.00   55.00    --  111.00 -30.00 -30.00   43
  8  \w     34.00 110.00   1.00   55.00    --  111.00 -95.00 150.00   76
  9  \w     50.00 118.00   1.00   55.00    --  111.00-125.00 -30.00   68
 10  \w     92.00 143.00   1.00   55.00    --  111.00  45.00  90.00   51
 11  \w     41.00  70.00   1.00   55.00    --  111.00 -45.00-180.00   29
 12  \w     98.00 135.00   1.00   55.00    --  111.00 -61.00 -30.00   37
 13  \w    142.00 172.00   1.00   55.00    --  111.00  30.00 -30.00   30
 14  \w     92.00 153.00   1.00   55.00    --  111.00  45.00 120.00   61
 15  \w     94.00 121.00   1.00   55.00    --  111.00-133.00 -60.00   27
 16  \w     80.00 135.00   1.00   55.00    --  111.00 -15.00 -90.00   55
 17  \w     38.00  75.00   1.00   55.00    --  111.00 -30.00 120.00   37
 18  \w     40.00 138.00   1.00   55.00    --  111.00 -77.00 150.00   98
;
_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      -0.0720484000
_diffrn_orient_matrix_UB_12      -0.0015465000
_diffrn_orient_matrix_UB_13      -0.0458523000
_diffrn_orient_matrix_UB_21      -0.0996761000
_diffrn_orient_matrix_UB_22      -0.0039270000
_diffrn_orient_matrix_UB_23      0.0234499000
_diffrn_orient_matrix_UB_31      -0.0062236000
_diffrn_orient_matrix_UB_32      0.0793735000
_diffrn_orient_matrix_UB_33      0.0002621000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0779
_diffrn_reflns_av_unetI/netI     0.0921
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            41242
_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         76.407
_diffrn_reflns_theta_min         3.616
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.071
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86629
_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_colour_primary    colourless
_exptl_crystal_density_diffrn    1.130
_exptl_crystal_description       plank
_exptl_crystal_F_000             2712
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.802
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     949
_refine_ls_number_reflns         15157
_refine_ls_number_restraints     372
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.1236
_refine_ls_R_factor_gt           0.0790
_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^)+(0.0657P)^2^+9.9856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1856
_refine_ls_wR_factor_ref         0.2153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9591
_reflns_number_total             15157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04676d2.cif
_cod_data_source_block           5-Cu
_cod_database_code               1564716
_publcif_datablock.id            {8611d99c-9c01-4445-b9e7-6b3c1792dddd}
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H40 N2 O2 Cu1 P1 Al1'
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.814
_reflns_odcompleteness_completeness 99.66
_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-C65A = C67A-C65A = C66A-C65A = C63A-C61A = C64A-C61A = C62A-C61A = C72A-
 C69A = C71A-C69A = C70A-C69A
 1.53 with sigma of 0.008
 C61-C63
 1.53 with sigma of 0.008
 C61-C64
 1.53 with sigma of 0.008
 C62-C61
 1.53 with sigma of 0.008
 C66-C65 = C67-C65 = C68-C65
 1.53 with sigma of 0.008
 C68A-C66A
 2.5 with sigma of 0.008
 C66A-C67A
 2.5 with sigma of 0.008
 C67A-C68A
 2.5 with sigma of 0.008
 C64A-C63A
 2.5 with sigma of 0.008
 C63A-C62A
 2.5 with sigma of 0.008
 C62A-C64A
 2.5 with sigma of 0.008
 C72A-C71A
 2.5 with sigma of 0.008
 C71A-C70A
 2.5 with sigma of 0.008
 C70A-C72A
 2.5 with sigma of 0.008
 C63-C62
 2.5 with sigma of 0.008
 C62-C64
 2.5 with sigma of 0.008
 C64-C63
 2.5 with sigma of 0.008
 C66-C67
 2.5 with sigma of 0.008
 C67-C68
 2.5 with sigma of 0.008
 C68-C66
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C23A \\sim C21A \\sim C22A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C63A \\sim C61A \\sim C64A \\sim C62A \\sim C69A \\sim C72A \\sim C70A \\sim
C71A \\sim C66A \\sim C65A \\sim C68A \\sim C67A: within 4A with sigma of 0.005
and sigma for terminal atoms of 0.01
C21 \\sim C20 \\sim C22 \\sim C23: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C69 \\sim C70 \\sim C71 \\sim C72: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C68 \\sim C65 \\sim C66 \\sim C67: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C20 \\sim C23A \\sim C21A \\sim C22A: within 3A with sigma of 0.005 and sigma
for terminal atoms of 0.01
4. Others
 Sof(C63A)=Sof(H63D)=Sof(H63E)=Sof(H63F)=Sof(C61A)=Sof(C64A)=Sof(H64D)=
 Sof(H64E)=Sof(H64F)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C69A)=
 Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C70A)=Sof(H70D)=Sof(H70E)=
 Sof(H70F)=Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C66A)=Sof(H66D)=
 Sof(H66E)=Sof(H66F)=Sof(C65A)=Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=
 Sof(C67A)=Sof(H67D)=Sof(H67E)=Sof(H67F)=1-FVAR(1)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C61)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C68)=Sof(H68A)=Sof(H68B)=
 Sof(H68C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C70)=Sof(H70A)=Sof(H70B)=
 Sof(H70C)=Sof(C69)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C66)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=Sof(C65)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=FVAR(1)
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(2)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C55(H55), C49(H49), C30(H30), C33(H33), C42(H42), C45(H45)
5.b Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C60(H60A,H60B), C58(H58A,H58B), C59(H59A,H59B), C57(H57A,
 H57B), C54(H54A,H54B), C52(H52A,H52B), C50(H50A,H50B), C51(H51A,H51B),
 C53(H53A,H53B)
5.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C3(H3), C5(H5), C19(H19), C26(H26), C28(H28), C27(H27), C38(H38),
 C40(H40), C39(H39), C202(H202), C201(H201), C203(H203), C200(H200), C204(H204),
  C205(H205)
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C47(H47A,H47B,H47C), C44(H44A,H44B,H44C), C43(H43A,H43B,H43C), C35(H35A,
 H35B,H35C), C8(H8A,H8B,H8C), C64(H64A,H64B,H64C), C62(H62A,H62B,H62C),
 C46(H46A,H46B,H46C), C34(H34A,H34B,H34C), C10(H10A,H10B,H10C), C67(H67A,H67B,
 H67C), C22(H22A,H22B,H22C), C9(H9A,H9B,H9C), C68(H68A,H68B,H68C), C71(H71A,
 H71B,H71C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C70(H70A,H70B,H70C),
 C72(H72A,H72B,H72C), C66(H66A,H66B,H66C), C63(H63A,H63B,H63C), C22A(H22D,H22E,
 H22F), C23A(H23D,H23E,H23F), C21A(H21D,H21E,H21F), C63A(H63D,H63E,H63F),
 C64A(H64D,H64E,H64F), C62A(H62D,H62E,H62F), C72A(H72D,H72E,H72F), C70A(H70D,
 H70E,H70F), C71A(H71D,H71E,H71F), C66A(H66D,H66E,H66F), C68A(H68D,H68E,H68F),
 C67A(H67D,H67E,H67F)
;
_shelx_res_checksum              1113
_shelx_hkl_checksum              71651
_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 1.237
_oxdiff_exptl_absorpt_empirical_full_min 0.754
_publcif_funding_html
;
;