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_1564715
_publ_section_title
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 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         'C94 H124 Al2 Cu K N4 O2, 0.5(C6 H14)'
_chemical_formula_sum            'C97 H131 Al2 Cu K N4 O2'
_chemical_formula_weight         1541.65
_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
_audit_creation_date             2021-02-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
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2021-05-24 deposited with the CCDC.	2021-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                97.788(2)
_cell_angle_beta                 101.490(2)
_cell_angle_gamma                107.207(2)
_cell_formula_units_Z            2
_cell_length_a                   12.8390(3)
_cell_length_b                   18.1142(3)
_cell_length_c                   22.4774(5)
_cell_measurement_reflns_used    18606
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      76.1830
_cell_measurement_theta_min      3.7400
_cell_volume                     4786.76(19)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.4102
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            53406
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.147
_diffrn_reflns_theta_min         3.640
_exptl_absorpt_coefficient_mu    1.229
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93397
_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            yellow
_exptl_crystal_density_diffrn    1.070
_exptl_crystal_description       needle
_exptl_crystal_F_000             1662
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.398
_refine_diff_density_min         -0.463
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1147
_refine_ls_number_reflns         19763
_refine_ls_number_restraints     189
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0556
_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^)+(0.1098P)^2^+1.7085P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1600
_refine_ls_wR_factor_ref         0.1750
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15976
_reflns_number_total             19763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04676d2.cif
_cod_data_source_block           2
_cod_original_cell_volume        4786.76(18)
_cod_database_code               1564715
_publcif_datablock.id            {a5ad1bca-5f95-47d0-b18f-edeabdbe7297}
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.741
_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
 C14-C15 = C14-C16 = C14-C17
 1.53 with sigma of 0.008
 C14-C15A = C14-C16A = C14-C17A
 1.53 with sigma of 0.008
 C45-C46 = C45-C47
 1.53 with sigma of 0.008
 C45A-C46A = C45A-C47A
 1.53 with sigma of 0.008
 C67-C68 = C67-C69 = C67-C70
 1.53 with sigma of 0.008
 C67-C68A = C67-C69A = C67-C70A
 1.53 with sigma of 0.008
 C95-C96 = C96-C97 = C97-C98 = C98-C99 = C99-C100
 1.53 with sigma of 0.008
 C15-C16 = C16-C17 = C17-C15
 2.5 with sigma of 0.008
 C15A-C16A = C16A-C17A = C17A-C15A
 2.5 with sigma of 0.008
 C46-C47
 2.5 with sigma of 0.008
 C46A-C47A
 2.5 with sigma of 0.008
 C68-C69 = C69-C70 = C70-C68
 2.5 with sigma of 0.008
 C68A-C69A = C69A-C70A = C70A-C68A
 2.5 with sigma of 0.008
 C95-C97 = C96-C98 = C97-C99 = C98-C100
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C14 \\sim C15 \\sim C16 \\sim C17: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C14 \\sim C15A \\sim C16A \\sim C17A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
C45 \\sim C46 \\sim C47: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C45A \\sim C46A \\sim C47A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C67 \\sim C68 \\sim C69 \\sim C70: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C67 \\sim C68A \\sim C69A \\sim C70A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
C95 \\sim C96 \\sim C97 \\sim C98 \\sim C99 \\sim C100: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C79)
\\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
4. Others
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C32A)=
 Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(2)
 Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=FVAR(2)
 Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47A)=
 Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(3)
 Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47)=Sof(H47A)=
 Sof(H47B)=Sof(H47C)=FVAR(3)
 Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C69A)=Sof(H69D)=Sof(H69E)=
 Sof(H69F)=Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(4)
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=
 Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(4)
 Fixed Sof: C95(0.5) H95A(0.5) H95B(0.5) H95C(0.5) C96(0.5) H96A(0.5)
 H96B(0.5) C97(0.5) H97A(0.5) H97B(0.5) C98(0.5) H98A(0.5) H98B(0.5) C99(0.5)
 H99A(0.5) H99B(0.5) C100(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
5.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45), C77(H77), C80(H80), C89(H89),
 C92(H92), C30A(H30A), C45A(H45A)
5.b Secondary CH2 refined with riding coordinates:
 C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B), C99(H99A,H99B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40), C50(H50), C52(H52), C56(H56), C58(H58), C73(H73), C74(H74),
  C75(H75), C85(H85), C86(H86), C87(H87)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C78(H78A,H78B,H78C), C79(H79A,H79B,
 H79C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C90(H90A,H90B,H90C), C91(H91A,
 H91B,H91C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C),
 C100(H10A,H10B,H10C), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C17A(H17D,
 H17E,H17F), C31A(H31D,H31E,H31F), C32A(H32D,H32E,H32F), C46A(H46D,H46E,H46F),
 C47A(H47D,H47E,H47F), C68A(H68D,H68E,H68F), C69A(H69D,H69E,H69F), C70A(H70D,
 H70E,H70F)
;
_shelx_res_checksum              18183
_shelx_hkl_checksum              25435
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
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;