The effect of terminal N-donor aromatic ligands on the sensitization and emission of lanthanide ions in Zn2Ln (Ln = Eu, Tb) complexes with 4-biphenylcarboxylate anions
Melnikov, Stanislav N.; Evstifeev, Igor S.; Nikolaveskii, Stanislav A.; Ananyev, Ivan V.; Varaksina, Evgenia A.; Taydakov, Ilya V.; Goloveshkin, Alexander S.; Sidorov, Aleksey A.; Kiskin, Mikhail A.; Eremenko, Igor L.; New Journal of Chemistry 45 (2021) 13349–13359; doi:10.1039/D0NJ05994C

data_7060753
_publ_section_title
;
 The effect of terminal N-donor aromatic ligands on the sensitization and
 emission of lanthanide ions in Zn2Ln (Ln = Eu, Tb) complexes with
 4-biphenylcarboxylate anions
;
_journal_issue                   30
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              13349
_journal_page_last               13359
_journal_paper_doi               10.1039/D0NJ05994C
_journal_volume                  45
_journal_year                    2021
_chemical_formula_moiety         'C92 H72 Eu N3 O15 Zn2, 3.25(C2 H3 N)'
_chemical_formula_sum            'C98.5 H81.75 Eu N6.25 O15 Zn2'
_chemical_formula_weight         1875.65
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-12-01 deposited with the CCDC.	2021-06-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.100(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.717(2)
_cell_length_b                   28.415(4)
_cell_length_c                   18.868(3)
_cell_measurement_reflns_used    3774
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      20.81
_cell_measurement_theta_min      2.35
_cell_volume                     9288(2)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1267
_diffrn_reflns_av_unetI/netI     0.1371
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            66712
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.373
_diffrn_reflns_theta_min         1.316
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.245
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.6151
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       prism
_exptl_crystal_F_000             3838
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.381
_refine_diff_density_min         -1.987
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1112
_refine_ls_number_reflns         18997
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1739
_refine_ls_R_factor_gt           0.0867
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0769P)^2^+75.5039P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2008
_refine_ls_wR_factor_ref         0.2409
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9445
_reflns_number_total             18997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj05994c2.cif
_cod_data_source_block           znn
_cod_depositor_comments
'Adding full bibliography for 7060753--7060757.cif.'
_cod_original_formula_sum        'C98.50 H81.75 Eu N6.25 O15 Zn2'
_cod_database_code               7060753
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.835
_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
 N1S-C1S = N2S_$1-C3S_$1 = N3S_$2-C5S_$2 = N4S_$3-C7S_$3
 1.2 with sigma of 0.01
 N95-C93
 0.001 with sigma of 2.63
 C1S-C2S = C3S_$1-C4S_$1 = C5S_$2-C6S_$2 = C7S_$3-C8S_$3
 1.4 with sigma of 0.01
 N2SA-C3SA
 1.2 with sigma of 0.01
 C3SA-C4SA
 1.4 with sigma of 0.01
 N1S-C2S = N2S_$1-C4S_$1 = N3S_$2-C6S_$2 = N4S_$3-C8S_$3
 2.6 with sigma of 0.02
 N2SA-C4SA
 2.6 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C72) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C77)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1S) \\sim Ueq, Uanis(C2S) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(N2SA)=Sof(C3SA)=Sof(C4SA)=Sof(H4SD)=Sof(H4SE)=Sof(H4SF)=0.5*(1-FVAR(2))
 Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=Sof(C3S)=Sof(N2S)=0.5*FVAR(2)
 Fixed Sof: N1S(0.75) C2S(0.75) H2SA(0.75) H2SB(0.75) H2SC(0.75) C1S(0.75)
 C7S(0.5) N4S(0.5) C8S(0.5) H8SA(0.5) H8SB(0.5) H8SC(0.5) C93(0.5) H93A(0.5)
 H93B(0.5) H93C(0.5) C94(0.5) N95(0.5)
5.a Me refined with riding coordinates:
 C2S(H2SA,H2SB,H2SC), C4SA(H4SD,H4SE,H4SF), C6S(H6SA,H6SB,H6SC), C8S(H8SA,H8SB,
 H8SC)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C29(H29), C30(H30), C32(H32), C33(H33), C35(H35),
 C36(H36), C37(H37), C38(H38), C39(H39), C42(H42), C43(H43), C45(H45), C46(H46),
  C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C55(H55), C56(H56),
 C58(H58), C59(H59), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C68(H68),
  C69(H69), C71(H71), C72(H72), C74(H74), C75(H75), C76(H76), C77(H77),
 C78(H78), C81(H81), C82(H82), C83(H83), C88(H88), C89(H89), C90(H90)
5.c Idealised Me refined as rotating group:
 C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C91(H91A,H91B,H91C), C92(H92A,H92B,
 H92C), C4S(H4SA,H4SB,H4SC), C93(H93A,H93B,H93C)
;
_olex2_submission_special_instructions 'No special instructions were received'