Why europium acylpyrazolonates are bad phosphors: lessons learned from the study of ionic and polymer complexes [MLnQ<sub>4</sub>], M = NEt<sub>4</sub><sup>+</sup>, Ag<sup/>.
Belousov, Yuriy A.; Polikovsky, Trofim A.; Metlin, Mikhail T.; Shikin, Daniil D.; Gontcharenko, Victoria E.; Lyssenko, Konstanin A.; Drozdov, Andrey A.; Korshunov, Vladislav M.; Taydakov, Ilya V.; Marchetti, Fabio; Pettinari, Claudio; Dalton transactions (Cambridge, England : 2003) 55 (2026) 3087–3100; doi:10.1039/d5dt02746b

data_7720242
_publ_section_title
;
 Why europium acylpyrazolonates are bad phosphors: lessons learned from
 the study of ionic and polymer complexes [MLnQ<sub>4</sub>], M =
 NEt<sub>4</sub><sup>+</sup>, Ag<sup/>.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3087
_journal_page_last               3100
_journal_paper_doi               10.1039/d5dt02746b
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C68 H52 Ag Eu N8 O8, 1.75(C2 H3 N)'
_chemical_formula_sum            'C71.5 H57.25 Ag Eu N9.75 O8'
_chemical_formula_weight         1440.85
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-07-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-29 deposited with the CCDC.	2026-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.8130(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.0434(8)
_cell_length_b                   29.1528(16)
_cell_length_c                   16.7937(9)
_cell_measurement_reflns_used    10092
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.58
_cell_measurement_theta_min      2.48
_cell_volume                     6337.6(6)
_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_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'SMART APEX II area-detector diffractometer'
_diffrn_measurement_method       \"I?-scans
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0751
_diffrn_reflns_av_unetI/netI     0.0622
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            75904
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.999
_diffrn_reflns_theta_min         1.397
_exptl_absorpt_coefficient_mu    1.355
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5643
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1543 before and 0.0751 after correction.
The Ratio of minimum to maximum transmission is 0.8711.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.510
_exptl_crystal_description       block
_exptl_crystal_F_000             2914
_exptl_crystal_size_max          0.138
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.119
_refine_diff_density_max         1.418
_refine_diff_density_min         -1.213
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1005
_refine_ls_number_reflns         16834
_refine_ls_number_restraints     226
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0427
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0306P)^2^+8.8160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0841
_refine_ls_wR_factor_ref         0.0939
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12632
_reflns_number_total             16834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02746b2.cif
_cod_data_source_block           ag_eu
_cod_original_formula_sum        'C71.50 H57.25 Ag Eu N9.75 O8'
_cod_database_code               7720242
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2S-C3S
 1.14 with sigma of 0.02
 N2S-C3S = N2SA-C3SA
 1.15 with sigma of 0.002
 C4SA-C3SA
 1.45 with sigma of 0.002
 C3S-N2S
 1.137 with sigma of 0.01
 N2SA-C3SA
 1.15 with sigma of 0.002
 C3S-C4S
 1.456 with sigma of 0.01
 C4S-N2S
 2.593 with sigma of 0.02
 N7A-N8A
 1.4 with sigma of 0.02
 N8A-C52A
 1.38 with sigma of 0.02
 C52A-C53A
 1.43 with sigma of 0.02
 C54A-C53A
 1.43 with sigma of 0.02
 N7A-C54A
 1.31 with sigma of 0.02
 C54A-C55A
 1.51 with sigma of 0.02
 N2S-C4S
 2.6 with sigma of 0.02
 C4SA-N2SA
 2.61 with sigma of 0.002
 N2SA-C4SA
 2.6 with sigma of 0.002
 N2S-C4S
 2.59 with sigma of 0.04
 N2SA-C4SA
 2.59 with sigma of 0.04
 O8A-C56A \\sim O8-C56 \\sim O7A-C52A \\sim O7-C52
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N2S \\sim C3S \\sim C4S: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C4SA) \\sim Ueq, Uanis(N2SA) \\sim Ueq, Uanis(C3SA) \\sim Ueq, Uanis(C4S)
\\sim Ueq, Uanis(N2S) \\sim Ueq, Uanis(C3S) \\sim Ueq: with sigma of 0.003 and
sigma for terminal atoms of 0.006
Uanis(O8A) \\sim Ueq, Uanis(C58A) \\sim Ueq, Uanis(O7A) \\sim Ueq, Uanis(N8A)
\\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C56A) \\sim Ueq, Uanis(C60A) \\sim Ueq,
Uanis(N7A) \\sim Ueq, Uanis(C62A) \\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C55A)
\\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C65A) \\sim Ueq,
Uanis(C59A) \\sim Ueq, Uanis(C66A) \\sim Ueq, Uanis(C57A) \\sim Ueq,
Uanis(C67A) \\sim Ueq, Uanis(C61A) \\sim Ueq, Uanis(C68A) \\sim Ueq,
Uanis(C63A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C44) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C42) \\sim Ueq: with sigma of
0.006 and sigma for terminal atoms of 0.012
Uanis(C67A) = Uanis(C68A) = Uanis(C66A)
Uanis(C4SA) = Uanis(C4S)
Uanis(C3SA) = Uanis(C3S)
4. Rigid body (RIGU) restrains
 N2S, C3S, C4S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O7(0.8) O8(0.8) N8(0.8) N7(0.8) C52(0.8) C53(0.8) C54(0.8)
 C56(0.8) C58(0.8) H58(0.8) C59(0.8) H59(0.8) C60(0.8) H60(0.8) C61(0.8)
 H61(0.8) C62(0.8) H62(0.8) C63(0.8) C64(0.8) H64(0.8) C65(0.8) H65(0.8)
 C66(0.8) H66(0.8) C67(0.8) H67(0.8) C68(0.8) H68(0.8) C55(0.8) H55A(0.8)
 H55B(0.8) H55C(0.8) N2S(0.5) C3S(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5)
 O8A(0.2) N8A(0.2) C56A(0.2) N7A(0.2) C52A(0.2) C57(0.8) C64A(0.2) H64A(0.2)
 C65A(0.2) H65A(0.2) C66A(0.2) H66A(0.2) C67A(0.2) H67A(0.2) C68A(0.2)
 H68A(0.2) C63A(0.2) C55A(0.2) H55D(0.2) H55E(0.2) H55F(0.2) O7A(0.2) C53A(0.2)
 C60A(0.2) H60A(0.2) C59A(0.2) H59A(0.2) C58A(0.2) H58A(0.2) C57A(0.2)
 C62A(0.2) H62A(0.2) C61A(0.2) H61A(0.2) C54A(0.2) N2SA(0.25) C3SA(0.25)
 C4SA(0.25) H4SD(0.25) H4SE(0.25) H4SF(0.25)
6.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64),
  C65(H65), C66(H66), C67(H67), C68(H68), C41(H41), C42(H42), C43(H43),
 C44(H44), C45(H45), C51(H51), C50(H50), C49(H49), C48(H48), C47(H47), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32),
 C33(H33), C34(H34), C64A(H64A), C65A(H65A), C66A(H66A), C67A(H67A), C68A(H68A),
  C60A(H60A), C59A(H59A), C58A(H58A), C62A(H62A), C61A(H61A)
6.b Fitted hexagon refined as free rotating group:
 C64A(C65A,C66A,C67A,C68A,C63A), C60A(C59A,C58A,C57A,C62A,C61A)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C55(H55A,H55B,H55C), C38(H38A,H38B,H38C), C21(H21A,H21B,
 H21C), C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C55A(H55D,H55E,H55F),
 C4SA(H4SD,H4SE,H4SF)
;
_shelx_res_checksum              41146
_olex2_submission_special_instructions 'No special instructions were received'