Photoabsorption of 1–2 nm molecular Ce-oxo nanoclusters versus ceria: intervalence charge transfer but no size effects
Brown, Stephen E.; Pike, Sebastian D.; Chemical Science 16 (2025) 11659–11668; doi:10.1039/D5SC00905G

data_1574749
_publ_section_title
;
 Photoabsorption of 1--2 nm molecular Ce-oxo nanoclusters versus ceria:
 intervalence charge transfer but no size effects
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              11659
_journal_page_last               11668
_journal_paper_doi               10.1039/D5SC00905G
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C400 H284 Ce24 N14 O96'
_chemical_formula_sum            'C400 H284 Ce24 N14 O96'
_chemical_formula_weight         10185.57
_chemical_melting_point          ?
_chemical_name_systematic        ' [Ce24O28(OH)8(OOCC10H7)30(py)4]'
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     other
_audit_creation_date             2025-01-21
_audit_creation_method           CRYSTALS_ver_14.61_build_6999
_audit_update_record
;
2025-01-21 deposited with the CCDC.	2025-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.0526(5)
_cell_length_b                   42.5286(7)
_cell_length_c                   35.9018(6)
_cell_measurement_reflns_used    25487
_cell_measurement_temperature    200
_cell_measurement_theta_max      26
_cell_measurement_theta_min      2
_cell_volume                     39778.5(12)
_computing_cell_refinement
; 
 CrysAlisPro (Rigaku Oxford Diffraction, 2017) 
;
_computing_data_collection       'SuperNova, (Oxford Diffraction, 2010)'
_computing_data_reduction
; 
 CrysAlisPro (Rigaku Oxford Diffraction, 2017) 
;
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_temperature      200
_diffrn_measured_fraction_theta_full 0.883
_diffrn_measured_fraction_theta_max 0.850
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction SuperNova'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  'focussing mirrors'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.075
_diffrn_reflns_av_unetI/netI     0.104
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            158450
_diffrn_reflns_theta_full        25.094
_diffrn_reflns_theta_max         26.415
_diffrn_reflns_theta_min         2.103
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.761
_exptl_absorpt_correction_T_max  0.86
_exptl_absorpt_correction_T_min  0.69
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
 CrysAlisPro (Rigaku Oxford Diffraction, 2017) 
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.701
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             19768
_exptl_crystal_size_max          0.108
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.053
_platon_squeeze_details
;
38 unresolved solvent pyridines 
is consistent with void volume and e density count
in 8 voids in unit cell 2 in assym unit
other solvent cannon be ruled out such as water acetone 
and pyridinium carboxylate etc however similar structures
only have pyridine in solvent volume recrystalised from pyridine
;
_refine_diff_density_max         7.03
_refine_diff_density_min         -4.13
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9920
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2406
_refine_ls_number_reflns         34778
_refine_ls_number_restraints     1724
_refine_ls_R_factor_all          0.1581
_refine_ls_R_factor_gt           0.0777
_refine_ls_shift/su_max          0.0920016
_refine_ls_shift/su_mean         0.0006077
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.07P)^2^ +*****P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.2566
_refine_ls_wR_factor_gt          0.1886
_refine_ls_wR_factor_ref         0.2566
_reflns_limit_h_max              30
_reflns_limit_h_min              0
_reflns_limit_k_max              51
_reflns_limit_k_min              0
_reflns_limit_l_max              44
_reflns_limit_l_min              0
_reflns_number_gt                17207
_reflns_number_total             34778
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.23
_oxford_diffrn_Wilson_scale      3143.78
_oxford_refine_ls_r_factor_ref   0.1581
_oxford_refine_ls_scale          0.0099803(3)
_oxford_reflns_number_all        34778
_oxford_structure_analysis_title '\Solve\SB3.75mo200k.cif_od At 10:28 on 1/ 9'
_cod_data_source_file            d5sc00905g2.cif
_cod_data_source_block           Ce24_2Nap
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1574748--1574755.cif.
;
_cod_original_sg_symbol_H-M      'P b c n '
_cod_database_code               1574749
_oxford_refine_reflns_threshold_expression_ref I>-10.0\s(I)
_platon_squeeze_void_probe_radius 1.20