Sensitive detection of formaldehyde <i>via</i> a luminescent distorted Eu<sub>4</sub>L<sub>4</sub> tetrahedral cage.
Li, Ran; Deng, Xuan; Yin, Fan; Duan, Xiao-Fang; Zhou, Li-Peng; Zhou, Yang; Guo, Xiao-Qing; Sun, Qing-Fu; Chemical communications (Cambridge, England) 61 (2025) 2135–2138; doi:10.1039/d4cc05823b

data_7134112
_publ_section_title
;
 Sensitive detection of formaldehyde <i>via</i> a luminescent distorted
 Eu<sub>4</sub>L<sub>4</sub> tetrahedral cage.
;
_journal_issue                   10
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2135
_journal_page_last               2138
_journal_paper_doi               10.1039/d4cc05823b
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C348 H260 Eu4 N48 O44 P4'
_chemical_formula_sum            'C348 H260 Eu4 N48 O44 P4'
_chemical_formula_weight         6549.74
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-09-04
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-10-08 deposited with the CCDC.	2025-01-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.1287(5)
_cell_length_b                   30.1287(5)
_cell_length_c                   64.0464(16)
_cell_measurement_reflns_used    8897
_cell_measurement_temperature    100.0(4)
_cell_measurement_theta_max      33.4820
_cell_measurement_theta_min      2.1670
_cell_volume                     58137(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_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    -54.00  24.00   0.10    7.00    --  -25.30  94.00 140.00  780
  2  \w    -54.00 -28.00   0.10    7.00    --  -25.30  81.00  42.00  260
  3  \w     45.00 100.00   0.10    7.00    --   23.82 179.00  60.00  550
  4  \w    -21.00  32.00   0.10    7.00    --  -25.30  57.00 -60.00  530
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0203279000
_diffrn_orient_matrix_UB_12      -0.0154565000
_diffrn_orient_matrix_UB_13      -0.0170669000
_diffrn_orient_matrix_UB_21      0.0374757000
_diffrn_orient_matrix_UB_22      0.0207403000
_diffrn_orient_matrix_UB_23      0.0056743000
_diffrn_orient_matrix_UB_31      0.0127045000
_diffrn_orient_matrix_UB_32      -0.0361479000
_diffrn_orient_matrix_UB_33      0.0106307000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0717
_diffrn_reflns_av_unetI/netI     0.0652
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            30314
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        33.952
_diffrn_reflns_theta_max         33.952
_diffrn_reflns_theta_min         2.166
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    2.515
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53941
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    0.748
_exptl_crystal_description       block
_exptl_crystal_F_000             13392
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.832
_refine_diff_density_min         -0.447
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.198
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     916
_refine_ls_number_reflns         8638
_refine_ls_number_restraints     1872
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.1401
_refine_ls_R_factor_gt           0.1087
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2875
_refine_ls_wR_factor_ref         0.3126
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5341
_reflns_number_total             8638
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05823b2.cif
_cod_data_source_block           179-2_auto_sq
_cod_depositor_comments
'Adding full bibliography for 7134111--7134112.cif.'
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               7134112
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N P Eu S F'
_shelx_estimated_absorpt_t_max   0.633
_shelx_estimated_absorpt_t_min   0.473
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C29-C28 = C30-C28
 1.45 with sigma of 0.02
 C15_4-C14_4
 1.45 with sigma of 0.02
 C20_4-C18_4 = C19_4-C18_4
 1.45 with sigma of 0.02
 C15_4-O16_4
 1.3 with sigma of 0.02
 C15_4-N17_4
 1.4 with sigma of 0.02
 N17_4-C18_4
 1.4 with sigma of 0.02
 C3_1-C023 = C25-C27
 1.5 with sigma of 0.02
 C18_4-C19_4
 1.5 with sigma of 0.02
 C1_1-N7_1
 1.45 with sigma of 0.02
 N7_1-C8_1
 1.45 with sigma of 0.02
 C8_1-O15_1
 1.3 with sigma of 0.02
 C29-C30
 2.5 with sigma of 0.02
 N1_4-C8_1 = C8_1-C3_4 = O3-C14_3
 2.35 with sigma of 0.02
 N7_1-N1_4
 2.84 with sigma of 0.02
 O15_1-C3_4
 2.36 with sigma of 0.02
 N17_4-O16_4
 2.33 with sigma of 0.04
 C19_4-C20_4
 2.5 with sigma of 0.04
 O16_4-C14_4
 2.36 with sigma of 0.04
 N17_4-C20_4 = C19_4-N17_4
 2.3 with sigma of 0.02
 C26-C27
 2.5 with sigma of 0.02
 N7_1-C6_1
 2.45 with sigma of 0.02
 O15_1-C1_1
 2.84 with sigma of 0.02
3. Restrained planarity
 N7_1, C8_1, O15_1, C3_4
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2.5A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2.5A
5. Same fragment restrains
{N1_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, N2_2, C8_2, C9_2, C10_2,
C11_2, C12_2} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C8_3, N9_3, C10_3, C11_3, C12_3,
C13_3, C14_3}
{N1_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, N2_2, C8_2, C9_2, C10_2,
C11_2, C12_2} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C8_4, N9_4, C10_4, C11_4, C12_4,
C13_4, C14_4}
6.a Riding coordinates:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C)
6.b Rotating group:
 O4(H4A,H4B)
6.c Ternary CH refined with riding coordinates:
 C25(H25), C28(H28), C18(H18)
6.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C5(H5), C4(H4), N6(H6), N7(H7), N8(H8), C10(H10), C11(H11), C17(H17),
 C13(H13), C15(H15), C16(H16), C20(H20), C19(H19), C01V(H01V), C01U(H01U),
 C022(H022), C01P(H01P), C2(H2), C6(H6), C5(H5), C4(H4), N7(H7), C2(H2), C3(H3),
  C6(H6), C7(H7), C10(H10), C11(H11), C3(H3), C4(H4), C7(H7), C8(H8), C12(H12),
 C13(H13), C3(H3), C4(H4), C7(H7), C8(H8), C12(H12), C13(H13), N17(H17)
6.e Fitted hexagon refined as free rotating group:
 C3(C2,C1,C01S,C5,C4), C10(C9,C8,C7,C6,C11), C17(C12,C13,C14,C15,C16), C20(C18,
 C19,C01V,C01U,C21), C022(C023,C01R,C22,C23,C01P), C2(C1,C6,C5,C4,C3), N1(C1,C2,
 C3,C4,C5), N2(C8,C9,C10,C11,C12)
6.f Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              74997
_shelx_hkl_checksum              60519
_shelx_fab_checksum              53807
_platon_squeeze_void_probe_radius 1.20
_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 3.083
_oxdiff_exptl_absorpt_empirical_full_min 0.315