Achieving stable photoluminescence by double thiacalix[4]arene-capping: the lanthanide-oxo cluster core matters
Lu, Zixiu; Wang, Shujian; Zhuo, Zhu; Li, Guo-Ling; Zhu, Haomiao; Wang, Wei; Huang, You-Gui; Hong, Maochun; RSC Advances 12 (2022) 29151–29161; doi:10.1039/D2RA04942B

data_7245671
_publ_section_title
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 Achieving stable photoluminescence by double thiacalix[4]arene-capping:
 the lanthanide-oxo cluster core matters
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_journal_issue                   45
_journal_name_full               'RSC Advances'
_journal_page_first              29151
_journal_page_last               29161
_journal_paper_doi               10.1039/D2RA04942B
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety
'C49 H65 Cl N3 O7.5 S4 Tb2, C45 H56 Cl N O8.5 S4 Tb2, 2(C H4 O)'
_chemical_formula_sum            'C96 H129 Cl2 N4 O18 S8 Tb4'
_chemical_formula_weight         2590.08
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-06
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-07-11 deposited with the CCDC.	2022-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                69.3000(10)
_cell_angle_beta                 83.0000(10)
_cell_angle_gamma                86.5820(10)
_cell_formula_units_Z            2
_cell_length_a                   12.2571(3)
_cell_length_b                   20.9533(5)
_cell_length_c                   22.9088(6)
_cell_measurement_reflns_used    9430
_cell_measurement_temperature    200.00
_cell_measurement_theta_max      26.39
_cell_measurement_theta_min      2.64
_cell_volume                     5461.9(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      200.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            104934
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.374
_diffrn_reflns_theta_min         1.922
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.822
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6416
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0915 before and 0.0487 after correction.
The Ratio of minimum to maximum transmission is 0.8607.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.575
_exptl_crystal_description       block
_exptl_crystal_F_000             2598
_exptl_crystal_size_max          0.157
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.111
_refine_diff_density_max         1.726
_refine_diff_density_min         -1.143
_refine_diff_density_rms         0.247
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.177
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1230
_refine_ls_number_reflns         22162
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.179
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0351
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0531P)^2^+20.1793P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19893
_reflns_number_total             22162
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra04942b2.cif
_cod_data_source_block           eeee
_cod_database_code               7245671
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.745
_shelx_estimated_absorpt_t_min   0.666
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O19-H19
 0.87 with sigma of 0.01
 C75-H19
 1.907758 with sigma of 0.02
 Tb1-H19
 2.934366 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C18) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C51) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C95) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C86) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Riding coordinates:
 C18(H18A,H18B,H18C)
4.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C16(H16), C22(H22), C30(H30), C32(H32), C44(H44),
 C48(H48), C52(H52), C60(H60), C74(H74), C7(H7), C17(H17), C19(H19A), C35(H35),
 C37(H37), C53(H53), C61(H61), C67(H67), C71(H71), C81(H81)
4.c Tetrahedral OH refined with riding coordinates:
 O9(H9)
4.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C28(H28A,H28B,H28C), C54(H54A,H54B,H54C), C62(H62A,H62B,
 H62C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C70(H70A,H70B,H70C), C76(H76A,
 H76B,H76C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C84(H84A,H84B,H84C),
 C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C92(H92A,H92B,
 H92C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C11(H11A,H11B,H11C), C21(H21A,
 H21B,H21C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C43(H43A,H43B,H43C),
 C45(H45A,H45B,H45C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C75(H75A,H75B,
 H75C), C83(H83A,H83B,H83C), C85(H85A,H85B,H85C), C87(H87A,H87B,H87C), C89(H89A,
 H89B,H89C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C47(H47A,H47B,H47C),
 C95(H95A,H95B,H95C)
4.e Idealised tetrahedral OH refined as rotating group:
 O17(H17A)
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_smtbx_masks_special_details
;
A solvent mask was calculated and 16 electrons were 
found in a volume of 308\%A^3^ in 5 voids per unit cell. 
This is consistent with the presence of 
0.66[CH3OH], 0.22[CH3OH] per Asymmetric Unit 
which account for 16 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              94001
_shelx_fab_checksum              33553
_olex2_submission_special_instructions 'No special instructions were received'