Magnetic hysteresis in 1D organometallic lanthanide chain compounds containing 4,4'-bipyridine.
Castellanos, Ernesto; Benner, Florian; Deshapriya, Saroshan; Demir, Selvan; Chemical science 16 (2025) 18616–18631; doi:10.1039/d5sc05460e

data_1575900
_publ_section_title
;
 Magnetic hysteresis in 1D organometallic lanthanide chain compounds
 containing 4,4'-bipyridine.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              18616
_journal_page_last               18631
_journal_paper_doi               10.1039/d5sc05460e
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C30 H38 N2 Tb, C24 H20 B, 3(C2 H4 O0.50), 2(C2 H4 O0.50)'
_chemical_formula_sum            'C66 H82 B N2 O3 Tb'
_chemical_formula_weight         1121.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-21
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-07-21 deposited with the CCDC.	2025-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 120.680(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6459(6)
_cell_length_b                   21.3539(6)
_cell_length_c                   17.3232(7)
_cell_measurement_reflns_used    17547
_cell_measurement_temperature    99.8(9)
_cell_measurement_theta_max      25.2240
_cell_measurement_theta_min      2.9630
_cell_volume                     5613.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.8(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.986
_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    -24.00   3.00   0.50   45.33    --   -4.53 -95.00  75.00   54
  2  \w    -76.00 -16.00   0.50   45.33    --   -4.53 -73.00 -39.00  120
  3  \w    -34.00   5.00   0.50   45.33    --   -4.53 -37.00 150.00   78
  4  \w     13.00  38.00   0.50   45.33    --    5.31 -99.00  60.00   50
  5  \w     14.00  39.00   0.50   45.33    --    5.31 -99.00-180.00   50
  6  \w    -19.00   6.00   0.50   45.33    --   -4.56 -53.00 117.44   50
  7  \w    -73.00 -43.00   0.50   45.33    --   -4.56   0.00-150.00   60
  8  \w    -33.00  -7.00   0.50   45.33    --   -4.56 -37.00-180.00   52
  9  \w    -41.00   3.00   0.50   45.33    --   -4.56 -37.00  60.00   88
 10  \w     17.00  43.00   0.50   45.33    --   -4.56   0.00-150.00   52
 11  \w    -19.00  15.00   0.50   45.33    --   -4.56  57.00  90.00   68
 12  \w    -11.00  15.00   0.50   45.33    --   -4.56  57.00 -30.00   52
 13  \w    -20.00   7.00   0.50   45.33    --   -4.56  67.00-114.32   54
 14  \w    -19.00  15.00   0.50   45.33    --   -4.56  57.00-150.00   68
 15  \w    -16.00  15.00   0.50   45.33    --   -4.56  57.00 150.00   62
 16  \w      5.00  31.00   0.50   45.33    --   -4.56  37.00 -60.00   52
 17  \w     -5.00  28.00   0.50   45.33    --   -4.56  23.00  17.90   66
 18  \w     10.00  63.00   0.50   45.33    --   -4.56  19.00  30.00  106
 19  \w      1.00  26.00   0.50   45.33    --    5.57 -77.00-150.00   50
 20  \w     -7.00  22.00   0.50   45.33    --    5.57  50.00  11.88   58
 21  \w     -6.00  19.00   0.50   45.33    --    5.57  53.00 -85.62   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0230460000
_diffrn_orient_matrix_UB_12      -0.0204116000
_diffrn_orient_matrix_UB_13      0.0595998000
_diffrn_orient_matrix_UB_21      -0.0011619000
_diffrn_orient_matrix_UB_22      0.0231649000
_diffrn_orient_matrix_UB_23      0.0274852000
_diffrn_orient_matrix_UB_31      -0.0405546000
_diffrn_orient_matrix_UB_32      -0.0121851000
_diffrn_orient_matrix_UB_33      -0.0468700000
_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  0.0544
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            47856
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.387
_diffrn_reflns_theta_min         2.995
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.308
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.589
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             2344
_exptl_crystal_size_max          0.206
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.103
_refine_diff_density_max         2.471
_refine_diff_density_min         -1.417
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.185
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         5101
_refine_ls_number_restraints     721
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0592
_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^)+(0.0442P)^2^+47.8233P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1390
_refine_ls_wR_factor_ref         0.1412
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4773
_reflns_number_total             5101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05460e2.cif
_cod_data_source_block           ec-2-146tb
_cod_depositor_comments
'Adding full bibliography for 1575900--1575902.cif.'
_cod_database_code               1575900
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C54H58TbBN2
_chemical_oxdiff_usercomment     Cp*2Tb(bipy)(BPh4)
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.774
_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
 C3-C2 = C3-C4 = C2-C22 = C22-C5 = C5-C4
 1.42 with sigma of 0.02
 C3-C8 = C4-C9
 1.5 with sigma of 0.02
 C2-C7 = C22-C6 = C5-C10
 1.51 with sigma of 0.02
 C15-C11 = C15-C14 = C11-C12 = C12-C13 = C13-C14
 1.42 with sigma of 0.02
 C15-C20 = C14-C19
 1.5 with sigma of 0.02
 C11-C16 = C12-C17 = C13-C18
 1.51 with sigma of 0.02
 C1A-C1B = C1D-C1E
 1.38 with sigma of 0.02
 C1-O1I = C1-C1L
 1.44 with sigma of 0.02
 C1J-C1K
 1.54 with sigma of 0.02
 O1I-C1J = C1K-C1L
 1.53 with sigma of 0.02
 O3-C1Q = O3-C1T
 1.44 with sigma of 0.02
 C1R-C1S
 1.54 with sigma of 0.02
 C1Q-C1R = C1S-C1T
 1.53 with sigma of 0.02
 C1N-C1O
 1.54 with sigma of 0.02
 C1M-C1N = C1O-C1P
 1.53 with sigma of 0.02
 O2-C1M = O2-C1P
 1.44 with sigma of 0.02
 C3-C7 = C3-C9 = C2-C6
 2.6 with sigma of 0.04
 C3-C22 = C3-C5
 2.29 with sigma of 0.04
 C22-C10 = C5-C9
 2.61 with sigma of 0.04
 C2-C5 = C22-C4
 2.3 with sigma of 0.04
 C11-C13 = C12-C14
 2.3 with sigma of 0.04
 C15-C12 = C15-C13
 2.29 with sigma of 0.04
 C15-C16 = C15-C19 = C11-C17
 2.6 with sigma of 0.04
 C12-C18 = C13-C19
 2.61 with sigma of 0.04
 C1B-C1D
 2.35 with sigma of 0.04
 C1-C1J = C1-C1K = O1I-C1K = C1J-C1L
 2.38 with sigma of 0.04
 O3-C1R = O3-C1S = C1Q-C1S = C1R-C1T
 2.38 with sigma of 0.04
 O2-C1N = O2-C1O = C1M-C1O = C1N-C1P
 2.38 with sigma of 0.04
 C8-C2 \\sim C8-C4 \\sim C7-C3 \\sim C7-C22 \\sim C6-C2 \\sim C6-C5 \\sim
C10-C22 \\sim C10-C4 \\sim C9-C5 ~
 C9-C3
 with sigma of 0.04
 C3-C8 \\sim C2-C7 \\sim C22-C6 \\sim C5-C10 \\sim C4-C9
 with sigma of 0.02
 C3-C2 \\sim C2-C22 \\sim C22-C5 \\sim C5-C4 \\sim C4-C3
 with sigma of 0.02
 C3-C22 \\sim C2-C5 \\sim C22-C4 \\sim C4-C2 \\sim C3-C5
 with sigma of 0.04
 C15-C20 \\sim C11-C16 \\sim C12-C17 \\sim C13-C18 \\sim C14-C19
 with sigma of 0.02
 C20-C11 \\sim C20-C14 \\sim C16-C15 \\sim C16-C12 \\sim C17-C11 \\sim C17-C13
\\sim C18-C12 \\sim C18-C14
 \\sim C19-C13 \\sim C19-C15
 with sigma of 0.04
 C15-C11 \\sim C11-C12 \\sim C12-C13 \\sim C13-C14 \\sim C14-C15
 with sigma of 0.02
 C15-C12 \\sim C11-C13 \\sim C12-C14 \\sim C14-C11 \\sim C15-C13
 with sigma of 0.04
 C1D-C1B \\sim C1E-C1A
 with sigma of 0.04
 C1A-C1B \\sim C1D-C1E
 with sigma of 0.02
 C1J-C1L \\sim O1I-C1K
 with sigma of 0.04
 C1-C1J \\sim C1-C1K
 with sigma of 0.04
 O1I-C1J \\sim C1J-C1K \\sim C1K-C1L
 with sigma of 0.02
 C1-O1I \\sim C1-C1L
 with sigma of 0.02
 C1R-C1T \\sim C1Q-C1S
 with sigma of 0.04
 O3-C1Q \\sim O3-C1T
 with sigma of 0.02
 O3-C1R \\sim O3-C1S
 with sigma of 0.04
 C1Q-C1R \\sim C1R-C1S \\sim C1S-C1T
 with sigma of 0.02
 O2-C1N \\sim O2-C1O
 with sigma of 0.04
 C1M-C1N \\sim C1N-C1O \\sim C1O-C1P
 with sigma of 0.02
 C1N-C1P \\sim C1M-C1O
 with sigma of 0.04
 O2-C1M \\sim O2-C1P
 with sigma of 0.02
3. Restrained planarity
 C3, C2, C22, C5, C4, C9, C10, C6, C7, C8
 with sigma of 0.1
 C15, C11, C12, C13, C14, C19, C18, C17, C16, C20
 with sigma of 0.1
 C1A, C1B, C1D, C1E
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C3 \\sim C2 \\sim C22 \\sim C5 \\sim C4 \\sim C9 \\sim C10 \\sim C6 \\sim C7
\\sim C8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C15 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C19 \\sim C18 \\sim C17 \\sim
C16 \\sim C20: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C1A \\sim C1B \\sim C1D \\sim C1E: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C1 \\sim O1I \\sim C1J \\sim C1K \\sim C1L: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O3 \\sim C1Q \\sim C1R \\sim C1S \\sim C1T: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O2 \\sim C1M \\sim C1N \\sim C1O \\sim C1P: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C3) = Uanis(C11)
Uanis(C14) = Uanis(C5)
Uanis(C9) = Uanis(C20)
Uanis(C19) = Uanis(C10)
Uanis(C7) = Uanis(C17)
Uanis(C13) = Uanis(C22)
Uanis(C18) = Uanis(C6)
Uanis(C4) = Uanis(C15)
Uanis(C2) = Uanis(C12)
Uanis(C8) = Uanis(C16)
5. Rigid body (RIGU) restrains
 C3, C2, C22, C5, C4, C9, C10, C6, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15, C11, C12, C13, C14, C19, C18, C17, C16, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C1D, C1E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, O1I, C1J, C1K, C1L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C1Q, C1R, C1S, C1T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C1M, C1N, C1O, C1P
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C22(0.5) C2(0.5) C3(0.5) C4(0.5) C5(0.5) C6(0.5) H6A(0.5) H6B(0.5)
 H6C(0.5) C7(0.5) H7A(0.5) H7B(0.5) H7C(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5)
 C9(0.5) H9A(0.5) H9B(0.5) H9C(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
 C11(0.5) C12(0.5) C13(0.5) C14(0.5) C15(0.5) C16(0.5) H16A(0.5) H16B(0.5)
 H16C(0.5) C17(0.5) H17A(0.5) H17B(0.5) H17C(0.5) C18(0.5) H18A(0.5) H18B(0.5)
 H18C(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C20(0.5) H20A(0.5) H20B(0.5)
 H20C(0.5) C1(0.5) H1C(0.5) H1F(0.5) O1I(0.5) C1J(0.5) H1JA(0.5) H1JB(0.5)
 C1K(0.5) H1KA(0.5) H1KB(0.5) C1L(0.5) H1LA(0.5) H1LB(0.5) O3(0.5) C1Q(0.5)
 H1QA(0.5) H1QB(0.5) C1R(0.5) H1RA(0.5) H1RB(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5)
 C1T(0.5) H1TA(0.5) H1TB(0.5) O2(0.5) C1M(0.5) H1MA(0.5) H1MB(0.5) C1N(0.5)
 H1NA(0.5) H1NB(0.5) C1O(0.5) H1OA(0.5) H1OB(0.5) C1P(0.5) H1PA(0.5) H1PB(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1C,H1F), C1J(H1JA,H1JB), C1K(H1KA,H1KB), C1L(H1LA,H1LB), C1Q(H1QA,H1QB),
 C1R(H1RA,H1RB), C1S(H1SA,H1SB), C1T(H1TA,H1TB), C1M(H1MA,H1MB), C1N(H1NA,H1NB),
  C1O(H1OA,H1OB), C1P(H1PA,H1PB)
7.b Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1B(H1B), C1D(H1D), C1E(H1E), C27(H27), C28(H28), C29(H29),
 C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37)
7.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              26454
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.473
_oxdiff_exptl_absorpt_empirical_full_min 0.739