Implementation of 2,2'-azobispyridine radical mono- and dianions in dinuclear rare earth metal complexes.
Delano, 4th, Francis; Demir, Selvan; Chemical communications (Cambridge, England) 60 (2024) 11702–11705; doi:10.1039/d4cc03222e

data_7133618
_publ_section_title
;
 Implementation of 2,2'-azobispyridine radical mono- and dianions in
 dinuclear rare earth metal complexes.
;
_journal_issue                   82
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11702
_journal_page_last               11705
_journal_paper_doi               10.1039/d4cc03222e
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety
'C46 H60 N4 Y2, C24 H20 B, C H2 Cl2, 1.5(C7 H8)'
_chemical_formula_sum            'C81.5 H94 B Cl2 N4 Y2'
_chemical_formula_weight         1389.13
_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
_audit_creation_date             2024-06-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-29 deposited with the CCDC.	2024-08-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.9119(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.24606(13)
_cell_length_b                   25.0683(2)
_cell_length_c                   21.28315(17)
_cell_measurement_reflns_used    23908
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      76.1090
_cell_measurement_theta_min      2.7130
_cell_volume                     7063.27(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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    -64.00  24.00   0.50    0.72    --  -47.33  61.00 150.00  176
  2  \w   -118.00 -31.00   0.50    0.72    --  -47.33 -61.00  11.00  174
  3  \w      2.00  39.00   0.50    0.72    --   47.33 -61.00  11.00   74
  4  \w     51.00  76.00   0.50    0.72    --   47.33  61.00 150.00   50
  5  \w   -143.00-118.00   0.50    2.87    --  -91.75 -61.00  11.00   50
  6  \w    -70.00 -45.00   0.50    2.87    --  -91.75  61.00 150.00   50
  7  \w    111.00 174.00   0.50    2.87    --  113.25  61.00 150.00  126
  8  \w     43.00  68.00   0.50    2.87    --  113.25 -61.00  11.00   50
  9  \w     61.00  93.00   0.50    0.72    --   47.33-125.00-150.00   64
 10  \w    -50.00 -24.00   0.50    2.87    --  -91.75  45.00   0.00   52
 11  \w    -53.00 -28.00   0.50    2.87    --  -91.75  45.00 -30.00   50
 12  \w    -42.00 -17.00   0.50    2.87    --  -91.75  15.00 -30.00   50
 13  \w    -42.00 -17.00   0.50    2.87    --  -91.75  15.00 -60.00   50
 14  \w     42.00  67.00   0.50    2.87    --  113.25 -61.00  90.00   50
 15  \w    101.00 177.00   0.50    2.87    --  113.25  15.00  90.00  152
 16  \w     44.00  69.00   0.50    2.87    --  113.25 -61.00 150.00   50
 17  \w     59.00  87.00   0.50    2.87    --  113.25 -77.00 -30.00   56
 18  \w     44.00 107.00   0.50    2.87    --  113.25-125.00 -30.00  126
 19  \w    100.00 138.00   0.50    2.87    --  113.25  15.00 120.00   76
 20  \w    143.00 168.00   0.50    2.87    --  113.25  15.00 120.00   50
 21  \w     42.00  94.00   0.50    2.87    --  113.25 -77.00 -60.00  104
 22  \w     50.00  77.00   0.50    2.87    --  113.25 -77.00-180.00   54
 23  \w    119.00 177.00   0.50    2.87    --  113.25  77.00  30.00  116
 24  \w     43.00  68.00   0.50    2.87    --  113.25 -61.00 -30.00   50
 25  \w     49.00  99.00   0.50    2.87    --  113.25 -94.00  90.00  100
 26  \w     42.00  67.00   0.50    2.87    --  113.25 -61.00 120.00   50
 27  \w     42.00  67.00   0.50    2.87    --  113.25 -61.00   0.00   50
 28  \w    109.00 135.00   0.50    2.87    --  113.25  61.00 120.00   52
 29  \w    150.00 175.00   0.50    2.87    --  113.25  61.00 120.00   50
 30  \w     47.00  91.00   0.50    2.87    --  113.25 -77.00-120.00   88
 31  \w    110.00 164.00   0.50    2.87    --  113.25  61.00 -90.00  108
 32  \w    104.00 151.00   0.50    2.87    --  113.25  45.00-150.00   94
 33  \w     63.00  89.00   0.50    2.87    --  113.25 -77.00  30.00   52
 34  \w     42.00  67.00   0.50    2.87    --  113.25 -61.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            60595
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.103
_diffrn_reflns_theta_min         2.724
_exptl_absorpt_coefficient_mu    3.239
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.561
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             2912
_exptl_crystal_size_max          0.221
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.642
_refine_diff_density_min         -1.399
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1068
_refine_ls_number_reflns         15090
_refine_ls_number_restraints     746
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0804P)^2^+10.4993P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1473
_refine_ls_wR_factor_ref         0.1539
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13058
_reflns_number_total             15090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc03222e2.cif
_cod_data_source_block           Cptet4Y2abpyRad
_cod_depositor_comments
'Adding full bibliography for 7133617--7133618.cif.'
_cod_original_cell_volume        7063.26(11)
_cod_original_formula_sum        'C81.50 H94 B Cl2 N4 Y2'
_cod_database_code               7133618
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Restrained distances
 N1B-C5B = N1B-C1B
 1.33 with sigma of 0.02
 C5B-C4B = C2B-C1B
 1.38 with sigma of 0.02
 C4B-C3B = C3B-C2B
 1.37 with sigma of 0.02
 N4B-C10B = N4B-C6B
 1.33 with sigma of 0.02
 C10B-C9B = C7B-C6B
 1.38 with sigma of 0.02
 C9B-C8B = C8B-C7B
 1.37 with sigma of 0.02
 C78A-C77A = C76A-C75A = C75A-C74A
 1.38 with sigma of 0.02
 C72A-C73A
 1.51 with sigma of 0.02
 C73A-C78A = C73A-C74A = C77A-C76A
 1.39 with sigma of 0.02
 C78B-C77B = C76B-C75B = C75B-C74B
 1.38 with sigma of 0.02
 C72B-C73B
 1.51 with sigma of 0.02
 C73B-C78B = C73B-C74B = C77B-C76B
 1.39 with sigma of 0.02
 C81A-C82A = C83A-C84A = C84A-C85A
 1.38 with sigma of 0.02
 C80A-C81A = C80A-C85A = C82A-C83A
 1.39 with sigma of 0.02
 C79A-C80A
 1.51 with sigma of 0.02
 C79B-C80B
 1.51 with sigma of 0.02
 C80B-C81B = C80B-C85B = C82B-C83B
 1.39 with sigma of 0.02
 C81B-C82B = C83B-C84B = C84B-C85B
 1.38 with sigma of 0.02
 C4B-C2B
 2.35 with sigma of 0.04
 C10B-C8B
 2.36 with sigma of 0.04
 N4B-C9B
 2.4 with sigma of 0.04
 C8B-C6B
 2.37 with sigma of 0.04
 C5B-C3B
 2.36 with sigma of 0.04
 C3B-C1B
 2.37 with sigma of 0.04
 N4B-C7B
 2.39 with sigma of 0.04
 C9B-C7B
 2.35 with sigma of 0.04
 N1B-C4B
 2.4 with sigma of 0.04
 N1B-C2B
 2.39 with sigma of 0.04
 C72A-C78A = C72A-C74A
 2.52 with sigma of 0.04
 C73A-C77A
 2.42 with sigma of 0.04
 C73A-C75A
 2.41 with sigma of 0.04
 C78A-C76A
 2.39 with sigma of 0.04
 C77A-C75A = C76A-C74A
 2.4 with sigma of 0.04
 C72B-C78B = C72B-C74B
 2.52 with sigma of 0.04
 C73B-C77B
 2.42 with sigma of 0.04
 C73B-C75B
 2.41 with sigma of 0.04
 C78B-C76B
 2.39 with sigma of 0.04
 C77B-C75B = C76B-C74B
 2.4 with sigma of 0.04
 C80A-C84A
 2.41 with sigma of 0.04
 C79A-C81A = C79A-C85A
 2.52 with sigma of 0.04
 C80A-C82A
 2.42 with sigma of 0.04
 C82A-C84A = C83A-C85A
 2.4 with sigma of 0.04
 C81A-C83A
 2.39 with sigma of 0.04
 C81B-C83B
 2.39 with sigma of 0.04
 C80B-C84B
 2.41 with sigma of 0.04
 C82B-C84B = C83B-C85B
 2.4 with sigma of 0.04
 C79B-C81B = C79B-C85B
 2.52 with sigma of 0.04
 C80B-C82B
 2.42 with sigma of 0.04
 N1B-C5B \\sim N1B-C1B
 with sigma of 0.02
 C5B-C4B \\sim C4B-C3B \\sim C3B-C2B \\sim C2B-C1B
 with sigma of 0.02
 N1B-C2B \\sim N1B-C4B
 with sigma of 0.04
 C3B-C1B \\sim C3B-C5B \\sim C2B-C4B \\sim C1B-C5B
 with sigma of 0.04
 N4B-C10B \\sim N4B-C6B
 with sigma of 0.02
 C10B-C9B \\sim C9B-C8B \\sim C8B-C7B \\sim C7B-C6B
 with sigma of 0.02
 N4B-C7B \\sim N4B-C9B
 with sigma of 0.04
 C8B-C6B \\sim C8B-C10B \\sim C7B-C9B \\sim C6B-C10B
 with sigma of 0.04
 N3B-C6B \\sim N3A-C6A
 with sigma of 0.02
 N3B-N2B \\sim N3A-N2A
 with sigma of 0.02
 C73A-C78A \\sim C78A-C77A \\sim C77A-C76A \\sim C76A-C75A \\sim C75A-C74A
\\sim C74A-C73A
 with sigma of 0.02
 C73A-C75A \\sim C73A-C77A \\sim C74A-C76A \\sim C78A-C74A \\sim C77A-C75A
\\sim C78A-C76A
 with sigma of 0.04
 C72A-C74A \\sim C72A-C78A
 with sigma of 0.04
 C73B-C78B \\sim C78B-C77B \\sim C77B-C76B \\sim C76B-C75B \\sim C75B-C74B
\\sim C74B-C73B
 with sigma of 0.02
 C73B-C75B \\sim C73B-C77B \\sim C74B-C76B \\sim C78B-C74B \\sim C77B-C75B
\\sim C78B-C76B
 with sigma of 0.04
 C72B-C74B \\sim C72B-C78B
 with sigma of 0.04
 C80A-C84A \\sim C80A-C82A \\sim C85A-C83A \\sim C81A-C85A \\sim C82A-C84A
\\sim C81A-C83A
 with sigma of 0.04
 C79A-C85A \\sim C79A-C81A
 with sigma of 0.04
 C80A-C81A \\sim C81A-C82A \\sim C82A-C83A \\sim C83A-C84A \\sim C84A-C85A
\\sim C85A-C80A
 with sigma of 0.02
 C80B-C81B \\sim C81B-C82B \\sim C82B-C83B \\sim C83B-C84B \\sim C84B-C85B
\\sim C85B-C80B
 with sigma of 0.02
 C79B-C85B \\sim C79B-C81B
 with sigma of 0.04
 C80B-C84B \\sim C80B-C82B \\sim C85B-C83B \\sim C81B-C85B \\sim C82B-C84B
\\sim C81B-C83B
 with sigma of 0.04
2. Restrained planarity
 N1B, C5B, C4B, C3B, C2B, C1B
 with sigma of 0.1
 N4B, C10B, C9B, C8B, C7B, C6B
 with sigma of 0.1
 C72A, C73A, C78A, C77A, C76A, C75A, C74A
 with sigma of 0.1
 C72B, C73B, C78B, C77B, C76B, C75B, C74B
 with sigma of 0.1
 C79A, C80A, C81A, C82A, C83A, C84A, C85A
 with sigma of 0.1
 C79B, C80B, C81B, C82B, C83B, C84B, C85B
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
N4B \\sim C10B \\sim C9B \\sim C8B \\sim C7B \\sim C6B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N1B \\sim C5B \\sim C4B \\sim C3B \\sim C2B \\sim C1B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C72A \\sim C73A \\sim C78A \\sim C77A \\sim C76A \\sim C75A \\sim C74A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C72B \\sim C73B \\sim C78B \\sim C77B \\sim C76B \\sim C75B \\sim C74B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C79A \\sim C80A \\sim C81A \\sim C82A \\sim C83A \\sim C84A \\sim C85A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C79B \\sim C80B \\sim C81B \\sim C82B \\sim C83B \\sim C84B \\sim C85B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(N2A) = Uanis(N3B)
Uanis(N3B) = Uanis(N3A)
Uanis(N2B) = Uanis(N3A)
Uanis(N2A) = Uanis(N2B)
Uanis(C77B) = Uanis(C77A)
Uanis(C78B) = Uanis(C78A)
Uanis(C76B) = Uanis(C76A)
Uanis(C74B) = Uanis(C74A)
Uanis(C75B) = Uanis(C75A)
Uanis(C72A) = Uanis(C72B)
Uanis(C73B) = Uanis(C73A)
Uanis(C71B) = Uanis(C71A)
Uanis(Cl2B) = Uanis(Cl2A)
Uanis(C81A) = Uanis(C81B)
Uanis(C82A) = Uanis(C82B)
Uanis(C79A) = Uanis(C79B)
Uanis(C84A) = Uanis(C84B)
4. Rigid body (RIGU) restrains
 N1B, C5B, C4B, C3B, C2B, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4B, C10B, C9B, C8B, C7B, C6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C72A, C73A, C78A, C77A, C76A, C75A, C74A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C72B, C73B, C78B, C77B, C76B, C75B, C74B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79A, C80A, C81A, C82A, C83A, C84A, C85A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79B, C80B, C81B, C82B, C83B, C84B, C85B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Y2A(0.75) Y1A(0.75) C6A(0.75) C5A(0.75) N1A(0.75) N2A(0.75)
 N4A(0.75) C3A(0.75) H(0.75) N3A(0.75) C9A(0.75) HF(0.75) C8A(0.75) HI(0.75)
 C2A(0.75) HQ(0.75) C4A(0.75) HS(0.75) C7A(0.75) HZ(0.75) C1A(0.75) H22(0.75)
 C10A(0.75) H38(0.75) N2B(0.25) N3B(0.25) N1B(0.25) C5B(0.25) C4B(0.25)
 H54(0.25) C3B(0.25) H55(0.25) C2B(0.25) H56(0.25) C1B(0.25) H57(0.25)
 N4B(0.25) C10B(0.25) H58(0.25) C9B(0.25) H59(0.25) C8B(0.25) H60(0.25)
 C7B(0.25) H61(0.25) C6B(0.25) Y2B(0.25) Y1B(0.25) Cl2A(0.75) Cl1A(0.75)
 Cl1B(0.25) C71B(0.25) H62(0.25) H63(0.25) C72A(0.5) H64(0.5) H65(0.5) H66(0.5)
 C73A(0.5) C78A(0.5) H67(0.5) C77A(0.5) H68(0.5) C76A(0.5) H69(0.5) C75A(0.5)
 H70(0.5) C74A(0.5) H71(0.5) C72B(0.5) H72(0.5) H73(0.5) H74(0.5) C73B(0.5)
 C78B(0.5) H75(0.5) C77B(0.5) H76(0.5) C76B(0.5) H77(0.5) C75B(0.5) H78(0.5)
 C74B(0.5) H79(0.5) Cl2B(0.25) C71A(0.75) H80(0.75) H81(0.75) C79A(0.25)
 H79A(0.25) H79B(0.25) H79C(0.25) C80A(0.25) C81A(0.25) H81A(0.25) C82A(0.25)
 H82A(0.25) C83A(0.25) H83A(0.25) C84A(0.25) H84A(0.25) C85A(0.25) H85A(0.25)
 C79B(0.25) H82(0.25) H83(0.25) H84(0.25) C80B(0.25) C81B(0.25) H85(0.25)
 C82B(0.25) H86(0.25) C83B(0.25) H87(0.25) C84B(0.25) H88(0.25) C85B(0.25)
 H89(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C71B(H62,H63), C71A(H80,H81)
6.b Aromatic/amide H refined with riding coordinates:
 C3A(H), C48(HA), C11(HB), C70(HC), C60(HD), C52(HE), C9A(HF), C38(HG),
 C58(HH), C8A(HI), C61(HJ), C54(HK), C29(HL), C20(HM), C64(HN), C66(HO),
 C49(HP), C2A(HQ), C69(HR), C4A(HS), C50(HT), C51(HU), C55(HV), C7A(HZ),
 C62(H1), C67(H2), C56(H3), C63(H4), C57(H8), C68(H21), C1A(H22), C10A(H38),
 C4B(H54), C3B(H55), C2B(H56), C1B(H57), C10B(H58), C9B(H59), C8B(H60),
 C7B(H61), C78A(H67), C77A(H68), C76A(H69), C75A(H70), C74A(H71), C78B(H75),
 C77B(H76), C76B(H77), C75B(H78), C74B(H79), C81A(H81A), C82A(H82A), C83A(H83A),
  C84A(H84A), C85A(H85A), C81B(H85), C82B(H86), C83B(H87), C84B(H88), C85B(H89)
6.c Idealised Me refined as rotating group:
 C43(HW,HX,HY), C25(H5,H6,H7), C18(H9,H10,H11), C16(H12,H13,H14), C44(H15,H16,
 H17), C46(H18,H19,H20), C27(H23,H24,H25), C26(H26,H27,H28), C28(H29,H30,H31),
 C19(H32,H33,H34), C17(H35,H36,H37), C45(H39,H40,H41), C35(H42,H43,H44),
 C36(H45,H46,H47), C34(H48,H49,H50), C37(H51,H52,H53), C72A(H64,H65,H66),
 C72B(H72,H73,H74), C79A(H79A,H79B,H79C), C79B(H82,H83,H84)
;
_shelx_res_checksum              50789
_shelx_hkl_checksum              54173
_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
;