Tandem templating strategies facilitate the assembly of calix[8]arene-supported Ln<sub>18</sub> clusters.
Jiao, Yushu; Sanz, Sergio; van Leusen, Jan; Gracia, David; Canaj, Angelos B.; Evangelisti, Marco; Brechin, Euan K.; Dalgarno, Scott J.; Kögerler, Paul; Dalton transactions (Cambridge, England : 2003) 53 (2024) 4624–4630; doi:10.1039/d4dt00280f

data_7715114
_publ_section_title
;
 Tandem templating strategies facilitate the assembly of
 calix[8]arene-supported Ln<sub>18</sub> clusters.
;
_journal_issue                   10
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4624
_journal_page_last               4630
_journal_paper_doi               10.1039/d4dt00280f
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'C320 H420 Cl6 La18 N18 O69, Cl, 2(O), 12[C3H7NO]'
_chemical_formula_sum            'C356 H549 Cl7 La18 N30 O83'
_chemical_formula_weight         9325.75
_chemical_name_systematic        La18
_space_group_crystal_system      trigonal
_space_group_IT_number           163
_space_group_name_Hall           '-P 3 2c'
_space_group_name_H-M_alt        'P -3 1 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-10-03 deposited with the CCDC.	2024-02-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   32.5846(4)
_cell_length_b                   32.5846(4)
_cell_length_c                   34.4461(6)
_cell_measurement_reflns_used    9488
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      60.84
_cell_measurement_theta_min      3.13
_cell_volume                     31673.5(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1166
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            458160
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        65.344
_diffrn_reflns_theta_max         65.344
_diffrn_reflns_theta_min         3.132
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.799
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.3649
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1293 before and 0.0611 after correction.
The Ratio of minimum to maximum transmission is 0.4855.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    0.978
_exptl_crystal_description       block
_exptl_crystal_F_000             9408
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.055
_refine_diff_density_min         -1.125
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         18091
_refine_ls_number_restraints     470
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.1262
_refine_ls_R_factor_gt           0.0832
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2445
_refine_ls_wR_factor_ref         0.3071
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8434
_reflns_number_total             18091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00280f2.cif
_cod_data_source_block           la18
_cod_depositor_comments          'Adding full bibliography for 7715114.cif.'
_cod_original_cell_volume        31673.5(10)
_cod_database_code               7715114
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.508
_shelx_estimated_absorpt_t_min   0.111
_olex2_refinement_description
;
1. 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
2. Restrained distances
 O9-C90 = O9-C93 = O12-C80 = O12-C83
 1.2 with sigma of 0.02
 N1-C93 = N1-C90 = N1-C94 = N1-C91 = N1-C95 = N1-C92
 1.45 with sigma of 0.02
 N4-C83 = N4-C81 = N4-C84 = N4-C82 = N4-C85 = N4-C80
 1.45 with sigma of 0.02
 C53-C50 = C56-C50 = C55-C50 = C52-C50 = C54-C50 = C51-C50
 1.54 with sigma of 0.02
 O8-C59 = O8-C58
 1.2 with sigma of 0.02
 N2-C57 = N2-C63 = N2-C58 = N7-C59 = N7-C62 = N7-C61
 1.45 with sigma of 0.02
 C58-C57
 2.5 with sigma of 0.04
 C57-C63
 2.5 with sigma of 0.04
 C63-C58
 2.5 with sigma of 0.04
 C59-C62
 2.5 with sigma of 0.04
 C62-C61
 2.5 with sigma of 0.04
 C61-C59
 2.5 with sigma of 0.04
 C54-C56
 2.54 with sigma of 0.04
 C54-C55
 2.54 with sigma of 0.04
 C56-C55
 2.54 with sigma of 0.04
 C36-C39 \\sim C36-C37 \\sim C36-C38 \\sim C36-C41 \\sim C36-C40 \\sim C36-C42
\\sim C36-C11
 with sigma of 0.02
 C93-C94 \\sim C94-C95 \\sim C91-C92
 with sigma of 0.04
 N1-C93 \\sim N1-C94 \\sim N1-C95 \\sim N1-C90 \\sim N1-C91 \\sim N1-C92
 with sigma of 0.02
 C29-C4 \\sim C29-C30 \\sim C29-C31 \\sim C29-C32 \\sim C29-C33 \\sim C29-C34
\\sim C29-C35
 with sigma of 0.02
 C30-C31 \\sim C30-C32 \\sim C31-C32 \\sim C33-C34 \\sim C33-C35 \\sim C34-C35
 with sigma of 0.04
 C29-C30 \\sim C29-C33
 with sigma of 0.02
 C29-C31 \\sim C29-C34
 with sigma of 0.02
 C29-C32 \\sim C29-C35
 with sigma of 0.02
 N4-C80 \\sim N4-C81 \\sim N4-C85 \\sim N4-C84 \\sim N4-C83 \\sim N4-C82
 with sigma of 0.02
 C43-C46 \\sim C43-C47
 with sigma of 0.02
 C43-C44 \\sim C43-C45 \\sim C43-C46 \\sim C43-C47 \\sim C43-C48 \\sim C43-C49
\\sim C43-C18
 with sigma of 0.02
 C43-C44 \\sim C43-C48
 with sigma of 0.02
 C43-C45 \\sim C43-C49
 with sigma of 0.02
 C50-C53 \\sim C50-C56
 with sigma of 0.02
 C50-C52 \\sim C50-C55
 with sigma of 0.02
 C50-C52 \\sim C50-C54 \\sim C50-C55 \\sim C50-C51 \\sim C50-C56 \\sim C50-C53
\\sim C50-C25
 with sigma of 0.02
 C50-C51 \\sim C50-C54
 with sigma of 0.02
3. Restrained planarity
 C58, N2, C63, C57
 with sigma of 0.1
 C62, C61, N7, C59
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(O5) = Uanis(O28)
5. Rigid body (RIGU) restrains
 C36, C37, C38, C39, C40, C41, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O9, N1, C93, C94, C95, C90, C91, C92
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, C30, C31, C32, C33, C34, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O12, N4, C80, C81, C85, C84, C83, C82
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O11, C60
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C43, C44, C45, C46, C47, C48, C49
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O8, C58, N2, N7, C59, C61, C57, C62, C63
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C58(0.5) H58(0.5) N2(0.5) N7(0.5) C59(0.5) H59(0.5) C44(0.5)
 H44A(0.5) H44B(0.5) H44C(0.5) C45(0.5) H45A(0.5) H45B(0.5) H45C(0.5) C46(0.5)
 H46A(0.5) H46B(0.5) H46C(0.5) C61(0.5) H61A(0.5) H61B(0.5) H61C(0.5) C57(0.5)
 H57A(0.5) H57B(0.5) H57C(0.5) C51(0.75) H51A(0.75) H51B(0.75) H51C(0.75)
 C52(0.75) H52A(0.75) H52B(0.75) H52C(0.75) C53(0.75) H53A(0.75) H53B(0.75)
 H53C(0.75) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5) C31(0.5) H31A(0.5) H31B(0.5)
 H31C(0.5) C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5) C37(0.5) H37A(0.5) H37B(0.5)
 H37C(0.5) C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5) C39(0.5) H39A(0.5) H39B(0.5)
 H39C(0.5) C80(0.5) H80(0.5) C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) C85(0.5)
 H85A(0.5) H85B(0.5) H85C(0.5) C93(0.5) H93(0.5) C94(0.5) H94A(0.5) H94B(0.5)
 H94C(0.5) C95(0.5) H95A(0.5) H95B(0.5) H95C(0.5) C40(0.5) H40A(0.5) H40B(0.5)
 H40C(0.5) C41(0.5) H41A(0.5) H41B(0.5) H41C(0.5) C42(0.5) H42A(0.5) H42B(0.5)
 H42C(0.5) C84(0.5) H84A(0.5) H84B(0.5) H84C(0.5) C83(0.5) H83(0.5) C90(0.5)
 H90(0.5) C91(0.5) H91A(0.5) H91B(0.5) H91C(0.5) C92(0.5) H92A(0.5) H92B(0.5)
 H92C(0.5) O5(0.166667) C33(0.5) H33A(0.5) H33B(0.5) H33C(0.5) C34(0.5)
 H34A(0.5) H34B(0.5) H34C(0.5) C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5) C82(0.5)
 H82A(0.5) H82B(0.5) H82C(0.5) C62(0.25) O28(0.166667) C47(0.5) H47A(0.5)
 H47B(0.5) H47C(0.5) C48(0.5) H48A(0.5) H48B(0.5) H48C(0.5) C49(0.5) H49A(0.5)
 H49B(0.5) H49C(0.5) C54(0.25) H54A(0.25) H54B(0.25) H54C(0.25) C55(0.25)
 H55A(0.25) H55B(0.25) H55C(0.25) C56(0.25) H56A(0.25) H56B(0.25) H56C(0.25)
 C63(0.75)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C15(H15A,H15B), C22(H22A,H22B)
7.b Me refined with riding coordinates:
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C61(H61A,H61B,
 H61C), C57(H57A,H57B,H57C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C81(H81A,H81B,
 H81C), C85(H85A,H85B,H85C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C40(H40A,
 H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C84(H84A,H84B,H84C),
 C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C82(H82A,H82B,H82C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C),
 C56(H56A,H56B,H56C)
7.c Aromatic/amide H refined with riding coordinates:
 C58(H58), C3(H3), C5(H5), C10(H10), C12(H12), C17(H17), C19(H19), C24(H24),
 C26(H26), C59(H59), C80(H80), C93(H93), C83(H83), C90(H90)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              14218
_shelx_fab_checksum              88290
_olex2_submission_special_instructions 'No special instructions were received'