Al12Co4: A Pioneering Heterometallic Aluminum-oxo Cluster with Surface-exposed Co Sites for Oxygen Evolution Reaction
Han, Er-Meng; Meng, Ru-Xin; Tian, Yi-Qi; Yan, Jun; Liu, Kaiyu; Liu, Chao; Chemical Communications  (2023) –; doi:10.1039/D3CC03672C

data_7132030
_publ_section_title
;
 Al12Co4: A Pioneering Heterometallic Aluminum-oxo Cluster with
 Surface-exposed Co Sites for Oxygen Evolution Reaction
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03672C
_journal_year                    2023
_chemical_formula_moiety
'C200 H268 Al12 Cl2 Co4 N8 O42, 14(C3 H7 N O), 4[C3H7ON], 0[C3H7ON]'
_chemical_formula_sum            'C254 H394 Al12 Cl2 Co4 N26 O60'
_chemical_formula_weight         5402.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-08-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-16 deposited with the CCDC.	2023-08-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.372(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   38.1054(16)
_cell_length_b                   23.6556(11)
_cell_length_c                   34.533(2)
_cell_measurement_reflns_used    9862
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      56.968
_cell_measurement_theta_min      2.525
_cell_volume                     28574(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1117
_diffrn_reflns_av_unetI/netI     0.1071
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            108187
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         57.091
_diffrn_reflns_theta_min         6.065
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.23
_diffrn_source_power             0.1557878
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.007
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.5214
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1567 before and 0.0675 after correction.
The Ratio of minimum to maximum transmission is 0.6941.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear orangish pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       prism
_exptl_crystal_F_000             11512
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.372
_refine_diff_density_min         -0.829
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1674
_refine_ls_number_reflns         29056
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.1287
_refine_ls_R_factor_gt           0.0744
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1228P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1905
_refine_ls_wR_factor_ref         0.2217
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16462
_reflns_number_total             29056
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03672c2.cif
_cod_data_source_block           Al12Co4
_cod_original_cell_volume        28574(3)
_cod_database_code               7132030
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.584
_shelx_estimated_absorpt_t_min   0.434
_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
 N3-C19 = N3-C3
 1.433 with sigma of 0.01
 N2-C14 = N2-C13
 1.433 with sigma of 0.01
 N4-C16 = N4-C17
 1.433 with sigma of 0.01
 C03S-C045 \\sim C03T-C0
 with sigma of 0.04
 C03Q-C03S \\sim C5-C03T
 with sigma of 0.04
 N02U-C03S \\sim N02V-C03T
 with sigma of 0.02
 N02U-C045 \\sim N02V-C0
 with sigma of 0.02
 C03Q-C045 \\sim C5-C0
 with sigma of 0.04
 O00S-C03Q \\sim O00S-C5
 with sigma of 0.02
 N02U-C03Q \\sim N02V-C5
 with sigma of 0.02
 O00S-N02U \\sim O00S-N02V
 with sigma of 0.04
 C02T-C8 \\sim C02T-C8A
 with sigma of 0.02
 C02T-C7 \\sim C02T-C7A
 with sigma of 0.02
 C02T-C6 \\sim C02T-C6A
 with sigma of 0.02
 C030-C9 \\sim C030-C9A
 with sigma of 0.04
 C030-C10 \\sim C030-C10A
 with sigma of 0.02
 C030-C11 \\sim C030-C11A
 with sigma of 0.02
 C9-C11 \\sim C9A-C11A
 with sigma of 0.04
3. Rigid bond restraints
 C02T, C7, C6, C8
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C030, C10, C11, C9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C13, N2, C14, C15, O12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C16, N4, C17, C18, O2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C02T \\sim C7 \\sim C6 \\sim C8: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C030 \\sim C10 \\sim C11 \\sim C9: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C3 \\sim N3 \\sim C19 \\sim C12 \\sim O1: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C13 \\sim N2 \\sim C14 \\sim C15 \\sim O12: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
O2 \\sim C18 \\sim N4 \\sim C17 \\sim C16: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
Uanis(C11) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 O00S, C5, N02V, C0, C03T
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C02T, C7A, C8A, C6A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C10A, C11A, C030, C9A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C5)=Sof(H03Z)=Sof(N02V)=Sof(C03T)=Sof(H11)=Sof(H21)=Sof(H22)=Sof(C0)=
 Sof(H0A)=Sof(H0B)=Sof(H0C)=1-FVAR(1)
 Sof(N02U)=Sof(C03Q)=Sof(H5)=Sof(C03S)=Sof(H7)=Sof(HT)=Sof(HU)=Sof(C045)=
 Sof(H04G)=Sof(H04H)=Sof(H04I)=FVAR(1)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=1-FVAR(2)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(2)
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(H9AC)=Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(3)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(3)
7.a Riding coordinates:
 C03O(H3,HN,HO), C03S(H7,HT,HU), C0(H0A,H0B,H0C)
7.b Secondary CH2 refined with riding coordinates:
 C011(H01A,H01B), C01D(H01C,H01D), C01M(H01E,H01F), C01O(H01G,H01H), C01P(H01I,
 H01J), C01Q(H01K,H01M), C023(H02A,H02B), C02A(H02C,H02D)
7.c Aromatic/amide H refined with riding coordinates:
 C01L(H01L), C01N(H01N), C01S(H01S), C01T(H01T), C01V(H01V), C01W(H01W),
 C01Y(H01Y), C024(H024), C025(H025), C026(H026), C02D(H02E), C02F(H02F),
 C02H(H02H), C02I(H02I), C02L(H02L), C02N(H02N), C02R(H02R), C02V(H02V),
 C02W(H02W), C037(H037), C03H(H03Y), C03Q(H5), C4(H4A), C040(H040), C12(H12A),
 C15(H15A), C18(H18), C5(H03Z)
7.d Idealised Me refined as rotating group:
 C02Q(H02G,H02J,H02K), C2(H2A,H2B,H2C), C02Y(H02M,H02O,H02P), C033(H03A,H03B,
 H03C), C034(H12,H,HA), C035(H03D,H03E,H03F), C036(H03G,H03H,H03I), C038(H03J,
 H03K,H03L), C03A(H16,HB,HC), C1(H1A,H1B,H1C), C03C(H03M,H03N,H03O), C03D(H03P,
 H03Q,H03R), C03E(H03S,H03T,H03U), C03G(H03V,H03W,H03X), C03I(H03,HD,HE),
 C03J(H1,HF,HG), C03K(H14,HH,HI), C03L(H13,HJ,HK), C03N(H2,HL,HM), C03P(H4,HP,
 HQ), C03R(H6,HR,HS), C03U(H8,HV,HW), C03W(H9,HX,HY), C03Y(H15,HZ,H17),
 C03Z(H10,H19,H20), C041(H04A,H04B,H04C), C044(H04D,H04E,H04F), C045(H04G,H04H,
 H04I), C10(H10A,H10B,H10C), C048(H04J,H04K,H04L), C049(H04M,H04N,H04O),
 C04A(H04P,H04Q,H04R), C7(H7A,H7B,H7C), C04D(H04S,H04T,H04U), C6(H6A,H6B,H6C),
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C19(H19A,H19B,H19C),
 C3(H3A,H3B,H3C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C),
  C16(H16A,H16B,H16C), C03T(H11,H21,H22), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,
 H8AC), C7A(H7AA,H7AB,H7AC), C10A(H10D,H10E,H10F), C9A(H9AA,H9AB,H9AC),
 C11A(H11D,H11E,H11F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              18678
_shelx_hkl_checksum              44157
_shelx_fab_checksum              76179
_olex2_submission_special_instructions 'No special instructions were received'