Implementing magnetic properties on demand with a dynamic lanthanoid-organic framework.
Gómez-Muñoz, Iván; Hu, Ziqi; Vitórica-Yrezábal, Iñigo J; Coronado, Eugenio; Mínguez Espallargas, Guillermo; Chemical science 16 (2025) 2879–2885; doi:10.1039/d4sc07042a

data_1574051
_publ_section_title
;
 Implementing magnetic properties on demand with a dynamic
 lanthanoid-organic framework.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              2879
_journal_page_last               2885
_journal_paper_doi               10.1039/d4sc07042a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C28.304 H18.673 La N0.435 O6.75, [+ solvents]0.6[H2O]'
_chemical_formula_sum            'C28.32 H21.49 La N0.44 O8.15'
_chemical_formula_weight         637.17
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-16 deposited with the CCDC.	2025-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.546(4)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   15.4232(6)
_cell_length_b                   20.5544(9)
_cell_length_c                   32.2850(11)
_cell_measurement_reflns_used    8415
_cell_measurement_temperature    119.99(10)
_cell_measurement_theta_max      67.9010
_cell_measurement_theta_min      2.1500
_cell_volume                     10202.6(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.73a 64-bit (release 27-10-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      119.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_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    -80.00 -21.00   0.50    5.00    --  -45.87 110.00 156.00  118
  2  \w     13.00  43.00   0.50    5.00    --   45.87-110.00  61.00   60
  3  \w   -122.00 -94.00   0.50   20.00    -- -103.00-110.00  61.00   56
  4  \w    -95.00 -69.00   0.50   20.00    -- -103.00 110.00 156.00   52
  5  \w     88.00 117.00   0.50   20.00    --  105.57 110.00 156.00   58
  6  \w     55.00  82.00   0.50   20.00    --  105.57-110.00  61.00   54
  7  \w    -15.00  24.00   0.50    5.00    --  -45.87  19.00 -90.00   78
  8  \w   -118.00 -72.00   0.50    5.00    --  -45.87   0.00 -90.00   92
  9  \w     -7.00  30.00   0.50    5.00    --  -45.87  19.00-120.00   74
 10  \w    -15.00  27.00   0.50    5.00    --  -45.87  19.00-150.00   84
 11  \w     31.00 118.00   0.50    5.00    --   45.87  57.00 150.00  174
 12  \w   -133.00 -86.00   0.50   20.00    -- -103.00 -61.00   0.00   94
 13  \w    -59.00 -31.00   0.50   20.00    -- -103.00  61.00 150.00   56
 14  \w    -70.00 -31.00   0.50   20.00    -- -103.00  61.00-150.00   78
 15  \w   -173.00-132.00   0.50   20.00    -- -103.00 -95.00-180.00   82
 16  \w    -70.00 -30.00   0.50   20.00    -- -103.00  61.00 -90.00   80
 17  \w    -70.00 -45.00   0.50   20.00    -- -103.00  61.00 -60.00   50
 18  \w    -68.00 -33.00   0.50   20.00    -- -103.00  61.00-120.00   70
 19  \w     45.00  76.00   0.50   20.00    --  105.57 -61.00  90.00   62
 20  \w     94.00 175.00   0.50   20.00    --  105.57  45.00 -60.00  162
 21  \w    145.00 172.00   0.50   20.00    --  105.57   0.00 -60.00   54
 22  \w     48.00  75.00   0.50   20.00    --  105.57 -61.00-150.00   54
 23  \w     80.00 127.00   0.50   20.00    --  105.57 -77.00 150.00   94
 24  \w     36.00 101.00   0.50   20.00    --  105.57 -95.00-180.00  130
 25  \w    109.00 165.00   0.50   20.00    --  105.57   0.00   0.00  112
 26  \w     40.00  74.00   0.50   20.00    --  105.57 -77.00 150.00   68
 27  \w    110.00 176.00   0.50   20.00    --  105.57   0.00 -90.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0344075000
_diffrn_orient_matrix_UB_12      0.0668411000
_diffrn_orient_matrix_UB_13      0.0153394000
_diffrn_orient_matrix_UB_21      -0.0178830000
_diffrn_orient_matrix_UB_22      0.0277031000
_diffrn_orient_matrix_UB_23      -0.0441922000
_diffrn_orient_matrix_UB_31      -0.0924350000
_diffrn_orient_matrix_UB_32      0.0195108000
_diffrn_orient_matrix_UB_33      0.0101341000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0809
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            70344
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.740
_diffrn_reflns_theta_min         2.551
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.395
_exptl_absorpt_correction_T_max  0.702
_exptl_absorpt_correction_T_min  0.480
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.659
_exptl_crystal_description       needle
_exptl_crystal_F_000             5066
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.02
_refine_diff_density_max         7.248
_refine_diff_density_min         -2.295
_refine_diff_density_rms         0.243
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.216
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1381
_refine_ls_number_reflns         18640
_refine_ls_number_restraints     303
_refine_ls_restrained_S_all      1.207
_refine_ls_R_factor_all          0.1360
_refine_ls_R_factor_gt           0.1061
_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          0.2785
_refine_ls_wR_factor_ref         0.3143
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13010
_reflns_number_total             18640
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07042a2.cif
_cod_data_source_block           sx1075
_cod_database_code               1574051
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         C28.2H19.8LaN0.4O7.3
_shelx_estimated_absorpt_t_max   0.775
_shelx_estimated_absorpt_t_min   0.454
_olex2_refinement_description
;
1. Restrained distances
 N4-C122 \\sim N4-C121
 with sigma of 0.02
 C104-C105 \\sim C104-C108
 with sigma of 0.02
 C101-C106 \\sim C101-C107
 with sigma of 0.02
 C106-C105 \\sim C107-C108
 with sigma of 0.02
 C55-C62 \\sim C61-C56
 with sigma of 0.02
 C55-C67 \\sim C61-C67
 with sigma of 0.02
 C55-C60 \\sim C61-C66
 with sigma of 0.02
 C62-C63 \\sim C56-C57
 with sigma of 0.02
 C60-C59 \\sim C66-C65
 with sigma of 0.02
 C104-C106 \\sim C104-C107
 with sigma of 0.04
 C101-C105 \\sim C101-C108
 with sigma of 0.04
 C68-C63 \\sim C68-C57
 with sigma of 0.04
 C68-C59 \\sim C68-C65
 with sigma of 0.04
 C55-C63 \\sim C61-C57
 with sigma of 0.04
 C55-C59 \\sim C61-C65
 with sigma of 0.04
 C62-C67 \\sim C56-C67
 with sigma of 0.04
 C62-C60 \\sim C56-C66
 with sigma of 0.04
 C63-C59 \\sim C57-C65
 with sigma of 0.04
 C67-C60 \\sim C67-C66
 with sigma of 0.04
2. Restrained planarity
 C120, O26, N4, C122, C121
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C104 \\sim C106 \\sim C105 \\sim C58 \\sim C55 \\sim C62 \\sim C63 \\sim C60
\\sim C59 \\sim C107 \\sim C108 \\sim C64 \\sim C61 \\sim C56 \\sim C57 \\sim
C66 \\sim C65: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O26 \\sim O27: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C120 \\sim O26 \\sim N4 \\sim C122 \\sim C121: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C120 \\sim N4 \\sim C122 \\sim C121 \\sim O26: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C58) = Uanis(C64)
4. Rigid body (RIGU) restrains
 C120, O26, N4, C122, C121
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O27)=Sof(H27A)=Sof(H27B)=1-FVAR(1)
 Sof(C120)=Sof(H120)=Sof(O26)=Sof(N4)=Sof(C122)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C121)=Sof(H12D)=Sof(H12E)=Sof(H12F)=FVAR(1)
 Sof(C107)=Sof(H107)=Sof(C108)=Sof(H108)=Sof(C64)=Sof(C61)=Sof(C56)=Sof(H56)=
 Sof(C57)=Sof(H57)=Sof(C66)=Sof(H66)=Sof(C65)=Sof(H65)=1-FVAR(2)
 Sof(C106)=Sof(H106)=Sof(C105)=Sof(H105)=Sof(C55)=Sof(C60)=Sof(H60)=Sof(C59)=
 Sof(H59)=Sof(C58)=Sof(C63)=Sof(H63)=Sof(C62)=Sof(H62)=FVAR(2)
6.a Riding coordinates:
 O27(H27A,H27B)
6.b Free rotating group:
 C120(O26,N4,C122,C121)
6.c Rotating group:
 O25(H25A,H25B)
6.d Me refined with riding coordinates:
 C119(H11A,H11B,H11C), C118(H11D,H11E,H11F), C122(H12A,H12B,H12C), C121(H12D,
 H12E,H12F)
6.e Aromatic/amide H refined with riding coordinates:
 C36(H36), C50(H50), C102(H102), C103(H103), C49(H49), C100(H100), C38(H38),
 C98(H98), C86(H86), C40(H40), C85(H85), C9(H9), C73(H73), C96(H96), C19(H19),
 C11(H11), C106(H106), C105(H105), C18(H18), C15(H15), C13(H13), C52(H52),
 C53(H53), C69(H69), C115(H115), C71(H71), C91(H91), C6(H6), C3(H3), C23(H23),
 C7(H7), C83(H83), C75(H75), C82(H82), C31(H31), C43(H43), C76(H76), C93(H93),
 C46(H46), C4(H4), C34(H34), C79(H79), C30(H30), C78(H78), C114(H114), C26(H26),
  C16(H16), C42(H42), C45(H45), C111(H111), C33(H33), C60(H60), C59(H59),
 C63(H63), C62(H62), C25(H25), C90(H90), C94(H94), C22(H22), C112(H112),
 C117(H117), C120(H120), C107(H107), C108(H108), C56(H56), C57(H57), C66(H66),
 C65(H65)
6.f Fitted hexagon refined as free rotating group:
 C55(C60,C59,C58,C63,C62)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 142 electrons were 
found in a volume of 1044\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
[+ solvents]0.6[H2O] per formula unit 
which account for 96 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              21210
_shelx_hkl_checksum              90405
_shelx_fab_checksum              22130
_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 2.082
_oxdiff_exptl_absorpt_empirical_full_min 0.545