Chiral Eu(iii) tetrahedral cage: circularly polarized luminescence induced by an ancillary chiral terpyridyl ligand
Guo, Feng; Zhang, Xiao-Wei; Wu, Jin-Xiu; Liu, Zhao-Gang; New Journal of Chemistry 49 (2025) 12708–12715; doi:10.1039/D5NJ01193K

data_7063875
_publ_section_title
;
 Chiral Eu(iii) tetrahedral cage: circularly polarized luminescence
 induced by an ancillary chiral terpyridyl ligand
;
_journal_issue                   29
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              12708
_journal_page_last               12715
_journal_paper_doi               10.1039/D5NJ01193K
_journal_volume                  49
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C118 H91 Eu2 F18 N8 O12), C2 H2 O0.5'
_chemical_formula_sum            'C238 H184 Eu4 F36 N16 O24.5'
_chemical_formula_weight         4951.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2025-05-30 deposited with the CCDC.	2025-07-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.616(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   34.7416(15)
_cell_length_b                   29.0218(7)
_cell_length_c                   46.1827(17)
_cell_measurement_reflns_used    11612
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.5890
_cell_measurement_theta_min      3.6020
_cell_volume                     42665(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1787
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -20.00  55.00   0.30   20.39    --   17.35 -99.00 -90.00  250
  2  \w      3.00  75.00   0.30   20.39    --   17.35  57.00  90.00  240
  3  \w    -16.00  45.20   0.30   20.39    --   17.35 -19.00 -90.00  204
  4  \w     -8.00  18.10   0.30   20.39    --   17.35  77.00-180.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0144997000
_diffrn_orient_matrix_UB_12      -0.0185446000
_diffrn_orient_matrix_UB_13      -0.0042110000
_diffrn_orient_matrix_UB_21      -0.0168994000
_diffrn_orient_matrix_UB_22      0.0159284000
_diffrn_orient_matrix_UB_23      -0.0048314000
_diffrn_orient_matrix_UB_31      -0.0004359000
_diffrn_orient_matrix_UB_32      0.0000910000
_diffrn_orient_matrix_UB_33      -0.0154907000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0852
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            61811
_diffrn_reflns_point_group_measured_fraction_full 0.819
_diffrn_reflns_point_group_measured_fraction_max 0.819
_diffrn_reflns_theta_full        20.000
_diffrn_reflns_theta_max         20.000
_diffrn_reflns_theta_min         3.276
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.632
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.23919
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.771
_exptl_crystal_description       block
_exptl_crystal_F_000             9984
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.857
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.101
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2682
_refine_ls_number_reflns         32601
_refine_ls_number_restraints     7342
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.1266
_refine_ls_R_factor_gt           0.0902
_refine_ls_shift/su_max          2.110
_refine_ls_shift/su_mean         0.020
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1874P)^2^+27.5142P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2509
_refine_ls_wR_factor_ref         0.2888
_reflns_Friedel_coverage         0.605
_reflns_Friedel_fraction_full    0.634
_reflns_Friedel_fraction_max     0.634
_reflns_number_gt                22685
_reflns_number_total             32601
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj01193k2.cif
_cod_data_source_block           20210525-ldf-c6
_cod_depositor_comments          'Adding full bibliography for 7063875.cif.'
_cod_original_formula_sum        'C238 H184 Eu4 F36 N16 O24.50'
_cod_database_code               7063875
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.922
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.99(2)
 0.01(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 F15-C160 = F17-C160 = F11-C160 = F1-C110 = F7-C110 = F16-C110 = F26-C165 = F8-
 C165 = F10-C165
 1.2 with sigma of 0.01
 C228-C194 = C227-C194 = C194-C191 = C211-C191 = C211-C173 = C194-C173
 1.5 with sigma of 0.01
 C224-C216 = C223-C216
 1.5 with sigma of 0.01
 F27-C169 = F33-C169
 1.2 with sigma of 0.01
 C224-C223
 2.5 with sigma of 0.01
 C217-C223 = C223-C214
 2.5 with sigma of 0.01
 F33-F27
 2.2 with sigma of 0.02
 F7-F16 = F17-F15
 2 with sigma of 0.02
 C175-F27
 2.2 with sigma of 0.01
 F18-C199 = F22-C199 = F25-C199
 1.2 with sigma of 0.01
 Eu4-C182
 3.5 with sigma of 0.01
 C170-C140 = C202-C170
 1.25 with sigma of 0.01
 C202-C201
 1.46 with sigma of 0.01
 F23-C201 = F29-C201 = F28-C201
 1.2 with sigma of 0.01
 F29-F28 = F29-F23
 2.2 with sigma of 0.01
 F25-F22 = F22-F18
 2.2 with sigma of 0.01
 F22-C172 = C172-F25
 2.2 with sigma of 0.02
 F18-C172
 2.2 with sigma of 0.02
 C199-C172
 1.46 with sigma of 0.01
 C165-C136
 1.46 with sigma of 0.01
 F28-C202 = C202-F23
 2.2 with sigma of 0.01
 C203-C182
 1.46 with sigma of 0.01
 F30-C203 = F32-C203 = F31-C203
 1.2 with sigma of 0.01
 F30-F32 = F32-F31
 2.2 with sigma of 0.01
 F25-F18 = F18-F22
 2.2 with sigma of 0.01
 F31-C182 = C182-F32
 2.2 with sigma of 0.01
 C215-C217 = C215-C214 = C214-C216 = C217-C216
 1.6 with sigma of 0.01
 C167-C163 = C179-C167 = C179-C174 = C174-C163
 1.5 with sigma of 0.01
 C217-C216 = C215-C217 = C215-C214 = C214-C216
 1.5 with sigma of 0.01
 C219-C197 = C197-C190 = C220-C190 = C220-C219
 1.5 with sigma of 0.01
 F30-F31
 2.2 with sigma of 0.01
 F32-C182 = C182-F30
 2.2 with sigma of 0.01
 C182-F31
 2.2 with sigma of 0.01
 F14-F4 = F14-F13
 2.2 with sigma of 0.02
 F13-C229 = F14-C229 = F4-C229
 1.2 with sigma of 0.02
 F2-C40 = F9-C40 = F6-C40
 1.2 with sigma of 0.01
 C175-C169
 1.46 with sigma of 0.01
 C229-C133
 1.46 with sigma of 0.01
 C31-C140
 1.46 with sigma of 0.01
 F14-C133 = C133-F4
 2.2 with sigma of 0.02
 C133-F13
 2.2 with sigma of 0.02
 C175-C134
 1.4 with sigma of 0.01
 C175-F33
 2.2 with sigma of 0.01
 C40-C19
 1.46 with sigma of 0.01
 F6-C19 = C19-F9
 2.2 with sigma of 0.01
 C19-F2
 2.2 with sigma of 0.01
 F3-F20 = F20-F12
 2.2 with sigma of 0.01
 C193-C166 = C193-C164 = C198-C193 = C200-C193 = C200-C176 = C198-C176
 1.5 with sigma of 0.01
 C222-C219 = C221-C219
 1.5 with sigma of 0.01
 C222-C197 = C197-C221
 2.5 with sigma of 0.01
 C222-C221
 2.5 with sigma of 0.01
 C217-C224 = C224-C214
 2.5 with sigma of 0.01
 C212-C196 = C213-C212 = C212-C187 = C212-C143 = C185-C143 = C187-C185
 1.5 with sigma of 0.01
 C225-C189 = C226-C225 = C225-C178 = C225-C195 = C195-C177 = C178-C177
 1.5 with sigma of 0.01
 C234-C233 = C233-C230 = C233-C181 = C233-C231 = C231-C192 = C192-C181
 1.5 with sigma of 0.01
 C210-C179 = C209-C179
 1.5 with sigma of 0.01
 C81-C161
 1.5 with sigma of 0.01
 F28-F23
 2.2 with sigma of 0.01
 C218-C214
 1.5 with sigma of 0.01
 C125-C186
 1.4 with sigma of 0.01
 C77-C220
 2.5 with sigma of 0.01
 C77-C0AA = C220-C0AA
 1.45 with sigma of 0.01
 C186-C191
 1.4 with sigma of 0.01
 C39-C117
 1.43 with sigma of 0.01
 C58-C90
 1.46 with sigma of 0.01
 C117-C
 1.45 with sigma of 0.01
 F237-C
 1.27 with sigma of 0.01
 F235-C
 1.27 with sigma of 0.01
 F238-C
 1.27 with sigma of 0.01
 F19-C169
 1.22 with sigma of 0.01
 F19-C169 \\sim F27A-C169 \\sim F27-C169 \\sim F33-C169 \\sim F33A-C169 \\sim
F19A-C169
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.1 and sigma
for terminal atoms of 0.2
Uanis(C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.001
Uanis(C23) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F27) \\sim Ueq, Uanis(F33) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.001
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C169, F19A, F27A, F33A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C169, F27, F33, F19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(F19A)=Sof(F27A)=Sof(F33A)=1-FVAR(1)
 Sof(F27)=Sof(F33)=Sof(F19)=FVAR(1)
 Fixed X: Eu3(0.508121)
 Fixed Y: Eu3(0.561851)
 Fixed Z: Eu3(0.664221)
7.a Riding coordinates:
 C223(H22P,H22Q,H22R), C227(H22D,H22E,H22F)
7.b Ternary CH refined with riding coordinates:
 C143(H143), C167(H167), C173(H173), C174(H174), C178(H178), C181(H181),
 C187(H187), C191(H191), C195(H195), C197(H197), C198(H198), C200(H200),
 C214(H214), C217(H217), C220(H220), C231(H231)
7.c Secondary CH2 refined with riding coordinates:
 C163(H16C,H16D), C168(H16A,H16B), C176(H17C,H17D), C177(H17A,H17B), C180(H18H,
 H18I), C184(H18A,H18B), C185(H18C,H18D), C188(H18J,H18K), C190(H19F,H19G),
 C192(H19A,H19B), C211(H21A,H21B), C215(H21I,H21J), C218(H21K,H21L), C232(H23D,
 H23E)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C42(H42), C84(H84), C89(H89), C80(H80), C7(H7), C22(H22),
 C146(H146), C145(H145), C9(H9), C10(H10), C11(H11), C13(H13), C15(H15),
 C16(H16), C17(H17), C21(H21), C235(H235), C27(H27), C29(H29), C30(H30),
 C34(H34), C116(H116), C171(H171), C142(H142), C64(H64), C67(H67), C139(H139),
 C122(H122), C37(H37), C38(H38), C39(H39), C44(H44), C45(H45), C47(H47),
 C48(H48), C51(H51), C53(H53), C54(H54), C55(H55), C60(H60), C63(H63), C66(H66),
  C68(H68), C71(H71), C74(H74), C76(H76), C79(H79), C83(H83), C85(H85),
 C86(H86), C91(H91), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96), C99(H99),
  C101(H101), C102(H102), C103(H103), C105(H105), C106(H106), C108(H108),
 C112(H112), C115(H115), C118(H118), C121(H121), C124(H124), C127(H127),
 C128(H128), C131(H131), C132(H132), C134(H134), C137(H137), C141(H141),
 C148(H148), C152(H152), C153(H153), C154(H154), C157(H157), C158(H158),
 C159(H159), C170(H170), C183(H183), C186(H186), C204(H204), C207(H207),
 C0AA(H0AA), C23(H23), C25(H25)
7.e Fitted hexagon refined as free rotating group:
 N3(C1,C238,C3,C4,C5), C6(C42,C84,C81,C89,C80), C7(C22,C24,C146,C145,C32),
 C8(C9,C10,C11,C12,N4), N5(C14,C15,C16,C17,C18), C235(C27,C28,C29,C30,C31),
 C34(C116,C149,C171,C142,C82), C35(C64,C67,C43,C139,C122), C44(C45,C46,C47,C48,
 C49), N7(C52,C53,C54,C55,C56), N8(C59,C60,C61,C62,C63), N9(C70,C71,C72,C73,
 C74), N10(C75,C76,C77,C78,C79), N11(C96,C97,C98,C99,C100), C103(C104,C105,C106,
 C107,C108), C111(N12,C112,C113,C114,C115), N13(C123,C124,C125,C126,C127),
 N15(C151,C152,C153,C154,C155), N16(C204,C205,C206,C207,C208)
7.f Idealised Me refined as rotating group:
 C164(H16E,H16F,H16G), C166(H16H,H16I,H16J), C189(H18E,H18F,H18G), C196(H19C,
 H19D,H19E), C209(H20A,H20B,H20C), C210(H21F,H21G,H21H), C213(H21C,H21D,H21E),
 C221(H22J,H22K,H22L), C222(H22M,H22N,H22O), C224(H22S,H22T,H22U), C226(H22A,
 H22B,H22C), C228(H22G,H22H,H22I), C230(H23A,H23B,H23C), C234(H23F,H23G,H23H)
;
_shelx_res_checksum              83534
_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 2.097
_oxdiff_exptl_absorpt_empirical_full_min 0.605