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_1574752
_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_compound_source        'MASB 4.14 UoW'
_chemical_formula_moiety         'C300 H230 Ce24 N18 O96'
_chemical_formula_sum            'C300 H230 Ce24 N18 O96'
_chemical_formula_weight         8985.95
_chemical_melting_point          ?
_chemical_name_systematic        '[Ce24O28(OH)8(OOCPh)30(Py)4](Py)14'
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     other
_audit_creation_date             2025-01-14
_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                 90.7010(18)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   21.834400(17)
_cell_length_b                   26.493099(17)
_cell_length_c                   25.106501(14)
_cell_measurement_reflns_used    97063
_cell_measurement_temperature    100
_cell_measurement_theta_max      30
_cell_measurement_theta_min      2
_cell_volume                     14522.043(18)
_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    'USER DEFINED STRUCTURE SOLUTION'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.862
_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  0.051
_diffrn_reflns_av_unetI/netI     0.067
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            327519
_diffrn_reflns_theta_full        25.077
_diffrn_reflns_theta_max         30.582
_diffrn_reflns_theta_min         2.166
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.762
_exptl_absorpt_correction_T_max  0.75
_exptl_absorpt_correction_T_min  0.16
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
 CrysAlisPro (Rigaku Oxford Diffraction, 2017) 
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.986
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             8324
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: pyridine'
_exptl_crystal_size_max          0.324
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.076
_platon_squeeze_details
;
60 electrons and 218 A3 corresponds to approximately 2 pyridines C5H5N
in the solvent accesible volume per void/assymetric unit 
implying 8 missing pyridines in the unit cell
;
_refine_diff_density_max         4.97
_refine_diff_density_min         -1.66
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9989
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1919
_refine_ls_number_reflns         38438
_refine_ls_number_restraints     584
_refine_ls_R_factor_all          0.0794
_refine_ls_R_factor_gt           0.0541
_refine_ls_shift/su_max          0.0443679
_refine_ls_shift/su_mean         0.0004566
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.09P)^2^ +*****P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1689
_refine_ls_wR_factor_gt          0.1479
_refine_ls_wR_factor_ref         0.1684
_reflns_limit_h_max              29
_reflns_limit_h_min              -30
_reflns_limit_k_max              36
_reflns_limit_k_min              0
_reflns_limit_l_max              34
_reflns_limit_l_min              0
_reflns_number_gt                28035
_reflns_number_total             38462
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   1.91
_oxford_diffrn_Wilson_scale      179.01
_oxford_refine_ls_r_factor_ref   0.0794
_oxford_refine_ls_scale          0.078894(12)
_oxford_reflns_number_all        38439
_oxford_structure_analysis_title 'eint_fr30_re30_sb_7.cif_od At 8:54 on 7/10'
_cod_data_source_file            d5sc00905g2.cif
_cod_data_source_block           3Ce24Ph
_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 1 21/n 1 '
_cod_database_code               1574752
_oxford_refine_reflns_threshold_expression_ref I>-3.0\s(I)
_platon_squeeze_void_probe_radius 1.20