It's not just the size that matters: crystal engineering of lanthanide-based coordination polymers.
Hauser, Adrian; Münzfeld, Luca; Uhlmann, Cedric; Lebedkin, Sergei; Schlittenhardt, Sören; Ruan, Ting-Ting; Kappes, Manfred M.; Ruben, Mario; Roesky, Peter W.; Chemical science 15 (2024) 1338–1347; doi:10.1039/d3sc03746k

data_1570581
_publ_section_title
;
 It's not just the size that matters: crystal engineering of
 lanthanide-based coordination polymers.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              1338
_journal_page_last               1347
_journal_paper_doi               10.1039/d3sc03746k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C104 H192.001 K2 Pr2 Si8, 2(C7 H8)'
_chemical_formula_sum            'C118 H208 K2 Pr2 Si8'
_chemical_formula_weight         2211.57
_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             2022-09-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-07-19 deposited with the CCDC.	2023-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.638(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8875(3)
_cell_length_b                   33.4663(9)
_cell_length_c                   26.0210(6)
_cell_measurement_reflns_used    46710
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.01
_cell_measurement_theta_min      1.68
_cell_volume                     12080.8(5)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)
;
_computing_data_reduction
;
X-Area Integrate 2.5.3.0 (STOE, 2021)
X-Area LANA 2.7.5.0 (STOE, 2022)
;
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.1, Darmstadt 2022
;
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.882
_diffrn_measurement_details
;
 466 frames, detector distance = 80 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0459
_diffrn_reflns_av_unetI/netI     0.0878
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.882
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            65016
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.535
_diffrn_reflns_theta_min         1.681
_diffrn_source                   'Mo Genix 3D HF'
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.989
_exptl_absorpt_correction_T_max  0.9184
_exptl_absorpt_correction_T_min  0.7972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       fragment
_exptl_crystal_F_000             4736
_exptl_crystal_size_max          0.229
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.984
_refine_diff_density_min         -0.943
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1539
_refine_ls_number_reflns         29803
_refine_ls_number_restraints     424
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1331
_refine_ls_R_factor_gt           0.0695
_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^)+(0.0411P)^2^+35.7449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1323
_refine_ls_wR_factor_ref         0.1549
_reflns_d_resolution_high        0.721
_reflns_d_resolution_low         12.115
_reflns_Friedel_coverage         0.000
_reflns_limit_h_max              18
_reflns_limit_h_min              -16
_reflns_limit_k_max              46
_reflns_limit_k_min              -45
_reflns_limit_l_max              29
_reflns_limit_l_min              -34
_reflns_number_gt                17854
_reflns_number_total             29803
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03746k2.cif
_cod_data_source_block           ah146
_cod_depositor_comments
'Adding full bibliography for 1570572--1570581.cif.'
_cod_database_code               1570581
_shelx_shelxl_version_number     2018/3
_audit_contact_author
;
      Prof. Dr. Peter W. Roesky
      Karlsruher Institut fuer Technologie (KIT), CS
      Institut fuer Anorganische Chemie (AOC)
      Lehrstuhl fuer Anorganische Funktionsmaterialien
      Engesserstr. 15, Geb. 30.45
      76131 Karlsruhe 
      Bundesrepublik Deutschland
;
_audit_contact_letter
;

;
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C33A-C35A = C33A-C34A = C33B-C34B = C33B-C35B = C38-C36B = C38-C36A = C37B-
 C36B = C37A-C36A = C41A-C39A = C41B-C39B = C40B-C39B = C40A-C39A
 1.53 with sigma of 0.02
 C63B-C64B = C65A-C63A = C65B-C63B = C64A-C63A = C60A-C61A = C60A-C62A = C60B-
 C62B = C61B-C60B = C66A-C68 = C66B-C68 = C67B-C66B = C67A-C66A
 1.53 with sigma of 0.02
 C94A-C93A = C94B-C93B = C95B-C93B = C93A-C95A
 1.53 with sigma of 0.02
 C102-C103 = C1E-C1D = C104-C1E = C102-C1F
 1.53 with sigma of 0.02
 Si2B-C36B \\sim Si2A-C36A \\sim Si2B-C39B \\sim Si2A-C39A \\sim Si2B-C33B
\\sim Si2A-C33A
 with sigma of 0.02
 Si3B-C60B \\sim Si3A-C60A \\sim Si3A-C63A \\sim Si3A-C66A \\sim Si3B-C66B
\\sim Si3B-C63B
 with sigma of 0.02
 Si7-C93A \\sim Si7-C93B
 with sigma of 0.02
 Si8-C102 \\sim Si8-C1E
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C125 \\sim C123 \\sim C124 \\sim C119 \\sim C120 \\sim C121 \\sim C122: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C132 \\sim C129 \\sim C128 \\sim C127 \\sim C126 \\sim C131 \\sim C130: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C35A \\sim C33A \\sim C34A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C41A \\sim C39A \\sim C40A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C35B \\sim C33B \\sim C34B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C37A \\sim C36A \\sim C38: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C111 \\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C38 \\sim C36B \\sim C37B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C40B \\sim C39B \\sim C41B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C35B \\sim C33B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C36B \\sim Si2B \\sim C39B \\sim C33B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Si2A \\sim C33A \\sim C36A \\sim C39A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Si3B \\sim C63B \\sim C66B \\sim C60B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C66A \\sim Si3A \\sim C60A \\sim C63A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C67B \\sim C66B \\sim C68: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C62B \\sim C60B \\sim C61B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C65B \\sim C63B \\sim C64B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C94A \\sim C93A \\sim C95A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C103 \\sim C102 \\sim C1F: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C1D \\sim C1E \\sim C104: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C94B \\sim C93B \\sim C95B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C132) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Others
 Fixed Sof: Si2B(0.7) Si3B(0.33333) C66B(0.33333) H66B(0.33333) H68D(0.33333)
 H68E(0.33333) H68F(0.33333) H68A(0.6667) H68B(0.6667) H68C(0.6667)
 C94A(0.3333) H94A(0.3333) H94B(0.3333) H94C(0.3333) C63B(0.33333)
 H63B(0.33333) C67B(0.33333) H67A(0.33333) H67B(0.33333) H67C(0.33333)
 C33A(0.3) H33A(0.3) C103(0.3333) H10D(0.3333) H10E(0.3333) H10F(0.3333)
 C60A(0.6667) H60A(0.6667) C35A(0.3) H35A(0.3) H35B(0.3) H35C(0.3)
 C65B(0.33333) H65A(0.33333) H65B(0.33333) H65C(0.33333) C39B(0.7) H39B(0.7)
 C65A(0.6667) H65D(0.6667) H65E(0.6667) H65F(0.6667) C93A(0.3333) H93A(0.3333)
 C102(0.3333) H102(0.3333) C60B(0.33333) H60B(0.33333) C64B(0.33333)
 H64A(0.33333) H64B(0.33333) H64C(0.33333) C41B(0.7) H41A(0.7) H41B(0.7)
 H41C(0.7) C40B(0.7) H40A(0.7) H40B(0.7) H40C(0.7) C95B(0.6667) H95A(0.6667)
 H95B(0.6667) H95C(0.6667) C104(0.6667) H10J(0.6667) H10K(0.6667) H10L(0.6667)
 C34A(0.3) H34A(0.3) H34B(0.3) H34C(0.3) C113(0.5) H113(0.5) C114(0.5)
 C115(0.5) H115(0.5) C116(0.5) H116(0.5) C117(0.5) H117(0.5) C112(0.5)
 H112(0.5) C118(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C109(0.5) H109(0.5)
 C110(0.5) H110(0.5) C105(0.5) C111(0.5) H11D(0.5) H11E(0.5) H11F(0.5)
 C107(0.5) H107(0.5) C106(0.5) H106(0.5) C108(0.5) H108(0.5) C120(0.5)
 H120(0.5) C119(0.5) H119(0.5) C124(0.5) H124(0.5) C123(0.5) C122(0.5)
 H122(0.5) C121(0.5) H121(0.5) C130(0.5) H130(0.5) C129(0.5) C128(0.5)
 H128(0.5) C127(0.5) H127(0.5) C126(0.5) H126(0.5) C131(0.5) H131(0.5)
 C132(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C125(0.5) H12A(0.5) H12B(0.5)
 H12C(0.5) C36B(0.7) H36B(0.7) C37B(0.7) H37A(0.7) H37B(0.7) H37C(0.7)
 H38A(0.7) H38B(0.7) H38C(0.7) H38D(0.3) H38E(0.3) H38F(0.3) C35B(0.7)
 H35D(0.7) H35E(0.7) H35F(0.7) C34B(0.7) H34D(0.7) H34E(0.7) H34F(0.7)
 C39A(0.3) H39A(0.3) C40A(0.3) H40D(0.3) H40E(0.3) H40F(0.3) C41A(0.3)
 H41D(0.3) H41E(0.3) H41F(0.3) C36A(0.3) H36A(0.3) C37A(0.3) H37D(0.3)
 H37E(0.3) H37F(0.3) C33B(0.7) H33B(0.7) Si2A(0.3) C62A(0.6667) H62A(0.6667)
 H62B(0.6667) H62C(0.6667) C62B(0.33333) H62D(0.33333) H62E(0.33333)
 H62F(0.33333) C61A(0.6667) H61A(0.6667) H61B(0.6667) H61C(0.6667) C63A(0.6667)
 H63A(0.6667) C64A(0.6667) H64D(0.6667) H64E(0.6667) H64F(0.6667) Si3A(0.6667)
 C61B(0.33333) H61D(0.33333) H61E(0.33333) H61F(0.33333) C66A(0.6667)
 H66A(0.6667) C67A(0.6667) H67D(0.6667) H67E(0.6667) H67F(0.6667) C95A(0.3333)
 H95D(0.3333) H95E(0.3333) H95F(0.3333) C1D(0.6667) H1DA(0.6667) H1DB(0.6667)
 H1DC(0.6667) C1E(0.6667) H1E(0.6667) C1F(0.3333) H1FA(0.3333) H1FB(0.3333)
 H1FC(0.3333) C93B(0.6667) H93B(0.6667) C94B(0.6667) H94D(0.6667) H94E(0.6667)
 H94F(0.6667)
5.a Ternary CH refined with riding coordinates:
 C54(H54), C84(H84), C72(H72), C51(H51), C81(H81), C57(H57), C45(H45),
 C78(H78), C48(H48), C66B(H66B), C42(H42), C75(H75), C90(H90), C96(H96),
 C69(H69), C99(H99), C87(H87), C63B(H63B), C33A(H33A), C60A(H60A), C39B(H39B),
 C93A(H93A), C102(H102), C60B(H60B), C36B(H36B), C39A(H39A), C36A(H36A),
 C33B(H33B), C63A(H63A), C66A(H66A), C1E(H1E), C93B(H93B)
5.b Me refined with riding coordinates:
 C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C68(H68D,H68E,H68F), C68(H68A,H68B,
 H68C), C38(H38A,H38B,H38C), C38(H38D,H38E,H38F)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C5(H5), C20(H20), C21(H21), C18(H18), C15(H15), C2(H2), C23(H23),
 C14(H14), C4(H4), C11(H11), C25(H25), C17(H17), C24(H24), C7(H7), C9(H9),
 C10(H10), C29(H29), C32(H32), C8(H8), C27(H27), C30(H30), C1(H1), C26(H26),
 C113(H113), C115(H115), C116(H116), C117(H117), C112(H112), C109(H109),
 C110(H110), C107(H107), C106(H106), C108(H108), C120(H120), C119(H119),
 C124(H124), C122(H122), C121(H121), C130(H130), C128(H128), C127(H127),
 C126(H126), C131(H131)
5.d Fitted hexagon refined as free rotating group:
 C113(C114,C115,C116,C117,C112), C120(C119,C124,C123,C122,C121), C130(C129,
 C128,C127,C126,C131)
5.e Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C73(H73A,H73B,
 H73C), C71(H71A,H71B,H71C), C74(H74A,H74B,H74C), C58(H58A,H58B,H58C), C79(H79A,
 H79B,H79C), C85(H85A,H85B,H85C), C56(H56A,H56B,H56C), C59(H59A,H59B,H59C),
 C80(H80A,H80B,H80C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C76(H76A,H76B,
 H76C), C46(H46A,H46B,H46C), C97(H97A,H97B,H97C), C77(H77A,H77B,H77C), C49(H49A,
 H49B,H49C), C91(H91A,H91B,H91C), C100(H10A,H10B,H10C), C70(H70A,H70B,H70C),
 C43(H43A,H43B,H43C), C94A(H94A,H94B,H94C), C44(H44A,H44B,H44C), C98(H98A,H98B,
 H98C), C47(H47A,H47B,H47C), C67B(H67A,H67B,H67C), C103(H10D,H10E,H10F),
 C101(H10G,H10H,H10I), C88(H88A,H88B,H88C), C35A(H35A,H35B,H35C), C65B(H65A,
 H65B,H65C), C89(H89A,H89B,H89C), C65A(H65D,H65E,H65F), C92(H92A,H92B,H92C),
 C64B(H64A,H64B,H64C), C41B(H41A,H41B,H41C), C40B(H40A,H40B,H40C), C95B(H95A,
 H95B,H95C), C104(H10J,H10K,H10L), C34A(H34A,H34B,H34C), C118(H11A,H11B,H11C),
 C111(H11D,H11E,H11F), C132(H13A,H13B,H13C), C125(H12A,H12B,H12C), C37B(H37A,
 H37B,H37C), C35B(H35D,H35E,H35F), C34B(H34D,H34E,H34F), C40A(H40D,H40E,H40F),
 C41A(H41D,H41E,H41F), C37A(H37D,H37E,H37F), C62A(H62A,H62B,H62C), C62B(H62D,
 H62E,H62F), C61A(H61A,H61B,H61C), C64A(H64D,H64E,H64F), C61B(H61D,H61E,H61F),
 C67A(H67D,H67E,H67F), C95A(H95D,H95E,H95F), C1D(H1DA,H1DB,H1DC), C1F(H1FA,H1FB,
 H1FC), C94B(H94D,H94E,H94F)
;
_shelx_res_checksum              35273
_shelx_hkl_checksum              73301
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '80.0 mm'
_stoe_detector_pixelsize_x       '0.172 mm'
_stoe_detector_pixelsize_y       '0.172 mm'
_stoe_detector_size_x            '7.0 cm'
_stoe_detector_size_y            '8.4 cm'
_stoe_evaluation_integration_a   6.1
_stoe_evaluation_integration_b   -2.0
_stoe_evaluation_integration_ems 0.014
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 88.1
_stoe_evaluation_lana_dxs_max_order 1
_stoe_evaluation_lana_dys_max_order 1
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 59.1
_stoe_evaluation_lana_max_2theta_desired 59.1
_stoe_evaluation_lana_mean_redundancy 2.2
_stoe_evaluation_lana_number_refls_after_or 65016
_stoe_evaluation_lana_number_refls_outliers 9986
_stoe_evaluation_lana_number_refls_total 75002
_stoe_evaluation_lana_number_refls_unique 29803
_stoe_evaluation_lana_number_refls_written 65016
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group 2/m
_stoe_evaluation_lana_table
;
2Theta           5.6   12.0   18.4   24.8   31.2   37.6   44.0   50.4   56.8
<Resolution>    5.80   3.17   2.18   1.64   1.33   1.10   0.95   0.83   0.77
N(total)         142   1729   4899   8967  10076  12845  15067  14648   6629
<Redundancy>     1.5    2.7    3.2    3.3    2.5    2.4    2.2    1.8    1.5
Complet. [%%]    72.3   98.1  100.0  100.0   98.6   99.4   99.7   96.9   54.3
<I/sigma>      123.2   60.0   42.5   20.4   14.3    6.9    3.7    2.1    1.0
R(int)         0.045  0.015  0.016  0.023  0.032  0.063  0.115  0.205  0.364
;
_stoe_measurement_identifier     AH146
_stoe_measurement_max_exposure_per_frame '500.0 s'
_stoe_measurement_mean_exposure_per_frame '500.0 s'
_stoe_measurement_min_exposure_per_frame '500.0 s'
_stoe_measurement_total_exposure_time '64.7 h'
_stoe_measurement_total_frame_number 466
_stoe_measurement_total_run_number 9
_stoe_measurement_tube_power     '50.0 W'