4f-intermediate valence in an ytterbium-bipyridine coordination solid.
Luneva, Evgeniia; Dunstan, Maja A.; Aribot, Frédéric; Yutronkie, Nathan J.; McPeak, Joseph E.; Rogalev, Andrei; Nocton, Grégory; Pedersen, Kasper S.; Chemical communications (Cambridge, England) 61 (2025) 14999–15002; doi:10.1039/d5cc04048e

data_1575484
_publ_section_title
;
 4f-intermediate valence in an ytterbium-bipyridine coordination solid.
;
_journal_issue                   77
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14999
_journal_page_last               15002
_journal_paper_doi               10.1039/d5cc04048e
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C60 H76 N4 Yb2'
_chemical_formula_sum            'C60 H76 N4 Yb2'
_chemical_formula_weight         1199.32
_chemical_name_systematic
catena-[bis(pentamethylcyclopentadienyl)ytterbium(4,4'-bipyridine)]
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-27
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-07-16 deposited with the CCDC.	2025-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.901(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.704(2)
_cell_length_b                   17.589(4)
_cell_length_c                   17.835(4)
_cell_measurement_reflns_used    986
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      71.8880
_cell_measurement_theta_min      4.9460
_cell_volume                     5227.9(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3073
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.981
_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   -114.00 -27.00   1.00   50.00    --  -40.81 -46.00 -92.00   87
  2  \w    -61.00  30.00   1.00   50.00    --  -40.81  46.00  56.00   91
  3  \w     -7.00  18.00   1.00   50.00    --   40.81 -46.00 -92.00   25
  4  \w     81.00 108.00   1.00   50.00    --   40.81  46.00  56.00   27
  5  \w     89.00 137.00   1.00  250.00    --  112.00  46.00  56.00   48
  6  \w     46.00 115.00   1.00  250.00    --  112.00 -46.00 -92.00   69
  7  \w    -34.00  -8.00   1.00   50.00    --  -40.81 125.00  60.00   26
  8  \w     59.00  90.00   1.00   50.00    --   40.81-125.00   0.00   31
  9  \w     12.00  81.00   1.00   50.00    --   40.81 -99.00 120.00   69
 10  \w    107.00 134.00   1.00  250.00    --  112.00 111.00 -90.00   27
 11  \w     98.00 132.00   1.00  250.00    --  112.00 -30.00  30.00   34
 12  \w    104.00 178.00   1.00  250.00    --  112.00  77.00  60.00   74
 13  \w    108.00 178.00   1.00  250.00    --  112.00 111.00 -60.00   70
 14  \w    104.00 174.00   1.00  250.00    --  112.00  77.00 -30.00   70
 15  \w    109.00 155.00   1.00  250.00    --  112.00 111.00-120.00   46
 16  \w     44.00  74.00   1.00  250.00    --  112.00 -30.00  30.00   30
 17  \w    104.00 177.00   1.00  250.00    --  112.00  77.00   0.00   73
 18  \w     58.00 101.00   1.00  250.00    --  112.00-111.00 -30.00   43
 19  \w     53.00  87.00   1.00  250.00    --  112.00-111.00  90.00   34
 20  \w     61.00 109.00   1.00  250.00    --  112.00 -61.00 -60.00   48
 21  \w     38.00  63.00   1.00  250.00    --  112.00 -94.00-180.00   25
 22  \w     75.00 103.00   1.00  250.00    --  112.00 -94.00-180.00   28
 23  \w     61.00 136.00   1.00  250.00    --  112.00-178.00-150.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0255143000
_diffrn_orient_matrix_UB_12      -0.0474474000
_diffrn_orient_matrix_UB_13      -0.0670355000
_diffrn_orient_matrix_UB_21      -0.0820232000
_diffrn_orient_matrix_UB_22      0.0150124000
_diffrn_orient_matrix_UB_23      -0.0420278000
_diffrn_orient_matrix_UB_31      0.0342063000
_diffrn_orient_matrix_UB_32      0.0720747000
_diffrn_orient_matrix_UB_33      -0.0350529000
_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  0.4110
_diffrn_reflns_av_unetI/netI     0.4746
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            33221
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.929
_diffrn_reflns_theta_min         2.651
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.743
_exptl_absorpt_correction_T_max  0.894
_exptl_absorpt_correction_T_min  0.699
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       plate
_exptl_crystal_F_000             2416
_exptl_crystal_preparation
'Reaction of YbCp*2 and 4,4'-bipyridine,Magnetic properties'
_exptl_crystal_recrystallization_method
'Crystals obtained from melt reaction of YbCp*2 and 4,4'-bipyridine'
_exptl_crystal_size_max          0.076
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.499
_refine_diff_density_min         -1.710
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.962
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         10841
_refine_ls_number_restraints     967
_refine_ls_restrained_S_all      0.928
_refine_ls_R_factor_all          0.3299
_refine_ls_R_factor_gt           0.1556
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     'w=1/[\s^2^(Fo^2^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3191
_refine_ls_wR_factor_ref         0.4491
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2387
_reflns_number_total             10841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04048e2.cif
_cod_data_source_block           YbCp2_bipy
_cod_depositor_comments
'Adding full bibliography for 1575484--1575485.cif.'
_cod_original_cell_volume        5228.2(18)
_cod_database_code               1575484
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C60 H73 N4 Yb2'
_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
2. Restrained distances
 N2-C7
 2.4 with sigma of 0.04
 C5-C2
 2.37 with sigma of 0.04
 C27-C21 \\sim C27-C23 \\sim C26-C22 \\sim C26-C25 \\sim C30-C21 \\sim C30-C24
\\sim C29-C25 \\sim C29-C23
 \\sim C28-C24 \\sim C28-C22
 with sigma of 0.04
 C23-C28 \\sim C24-C29 \\sim C25-C30 \\sim C21-C26 \\sim C22-C27
 with sigma of 0.02
 C32-C37 \\sim C33-C38 \\sim C34-C39 \\sim C35-C40 \\sim C31-C36
 with sigma of 0.02
 N2-C9 \\sim N2-C10
 with sigma of 0.02
 C9-C7 \\sim C7-C6 \\sim C6-C8 \\sim C8-C10
 with sigma of 0.02
 N1-C1 \\sim N1-C2
 with sigma of 0.02
 C1-C3 \\sim C3-C5 \\sim C5-C4 \\sim C4-C2
 with sigma of 0.02
 C23-C24 \\sim C22-C21 \\sim C23-C22 \\sim C21-C25 \\sim C23-C24 \\sim C21-C25
 with sigma of 0.02
 C34-C33 \\sim C33-C32 \\sim C32-C31 \\sim C35-C31 \\sim C35-C34
 with sigma of 0.02
 C29-C28 \\sim C26-C27
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim
C59 \\sim C60: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C30: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.02 within 2A
N3 \\sim N4 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim
C17 \\sim C18 \\sim C19 \\sim C20: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C38 \\sim C39 \\sim
C40: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.02 within 2A
N2 \\sim C10 \\sim C8 \\sim C6 \\sim C7 \\sim C9 \\sim C5 \\sim C4 \\sim C2
\\sim N1 \\sim C1 \\sim C3: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C38) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C51, C52, C53, C54, C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C42, C43, C44, C45, C46, C47, C48, C49, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N3, N4, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C23, C24, C25, C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C32, C33, C34, C35, C36, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2, C6, C7, C8, C9, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,
 H50C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C19(H19), C20(H20)
;
_shelx_res_checksum              99045
_shelx_hkl_checksum              22631
_olex2_exptl_crystal_mounting_method 'Mounted in polybutenes on a nylon loop'
_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 3.522
_oxdiff_exptl_absorpt_empirical_full_min 0.541