A rare earth metallocene containing a 2,2′-azopyridyl radical anion
Delano IV, Francis; Castellanos, Ernesto; McCracken, John; Demir, Selvan; Chemical Science  (2021) –; doi:10.1039/D1SC04285H

data_1565073
_publ_section_title
;
 A rare earth metallocene containing a 2,2&#x2032;-azopyridyl radical
 anion
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04285H
_journal_year                    2021
_chemical_formula_moiety
'0.5(C28 H34 N4 Y), 0.5(C22.604 H26.206 N4 Y), 0.3(C9 H13)'
_chemical_formula_sum            'C28 H34 N4 Y'
_chemical_formula_weight         515.50
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Heat-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-18
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-08-03 deposited with the CCDC.	2021-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                88.3450(12)
_cell_angle_beta                 82.9269(13)
_cell_angle_gamma                86.1875(12)
_cell_formula_units_Z            4
_cell_length_a                   9.27977(15)
_cell_length_b                   15.8832(2)
_cell_length_c                   17.3902(3)
_cell_measurement_reflns_used    20399
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.8850
_cell_measurement_theta_min      3.7400
_cell_volume                     2537.49(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
'SHELXL (Sheldrick, Acta Cryst. A64 2008, 112-122)'
_computing_structure_solution
'SHELXT (Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.959
_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    -40.00  26.00   0.50    0.12    --  -47.57  37.00  60.00  132
  2  \w    -42.00  26.00   0.50    0.12    --  -47.57  37.00   0.00  136
  3  \w    -41.00 -15.00   0.50    0.12    --  -47.57  77.00   0.00   52
  4  \w    -43.00 -18.00   0.50    0.49    --  -86.25  37.00   0.00   50
  5  \w    -41.00 -14.00   0.50    0.49    --  -86.25  37.00 -30.00   54
  6  \w    -43.00 -15.00   0.50    0.49    --  -86.25  37.00 -90.00   56
  7  \w    -43.00 -17.00   0.50    0.49    --  -86.25  37.00-120.00   52
  8  \w    -39.00 -13.00   0.50    0.49    --  -86.25  37.00 -60.00   52
  9  \w    -69.00 -36.00   0.50    0.12    --  -47.57  77.00  90.00   66
 10  \w    -40.00  26.00   0.50    0.12    --  -47.57  37.00 120.00  132
 11  \w    -45.00 -20.00   0.50    0.49    --  -86.25  97.00 129.00   50
 12  \w    -77.00  23.00   0.50    0.12    --  -47.57  97.00 129.00  200
 13  \w     -9.00  24.00   0.50    0.12    --   47.57 -19.00  90.00   66
 14  \w     42.00  70.00   0.50    0.12    --   47.57 -97.00  21.00   56
 15  \w     59.00  85.00   0.50    0.49    --  107.11 -97.00  21.00   52
 16  \w     65.00  91.00   0.50    0.49    --  107.11 -99.00 -30.00   52
 17  \w     54.00 104.00   0.50    0.49    --  107.11 -99.00 -60.00  100
 18  \w     66.00 105.00   0.50    0.49    --  107.11-125.00-120.00   78
 19  \w     77.00 104.00   0.50    0.49    --  107.11 -99.00-150.00   54
 20  \w     37.00  64.00   0.50    0.49    --  107.11 -57.00 -60.00   54
 21  \w     39.00  65.00   0.50    0.49    --  107.11 -57.00-120.00   52
 22  \w     38.00  67.00   0.50    0.49    --  107.11 -99.00-150.00   58
 23  \w     45.00  92.00   0.50    0.49    --  107.11 -99.00 -90.00   94
 24  \w     40.00 103.00   0.50    0.49    --  107.11 -99.00   0.00  126
 25  \w     74.00 101.00   0.50    0.49    --  107.11-125.00  90.00   54
 26  \w     66.00 103.00   0.50    0.49    --  107.11 -99.00 120.00   74
 27  \w     45.00 101.00   0.50    0.49    --  107.11 -99.00  90.00  112
 28  \w     36.00  65.00   0.50    0.49    --  107.11 -57.00  30.00   58
 29  \w     35.00  65.00   0.50    0.49    --  107.11 -57.00   0.00   60
 30  \w     37.00  65.00   0.50    0.49    --  107.11 -57.00  60.00   56
 31  \w     36.00  64.00   0.50    0.49    --  107.11 -57.00 150.00   56
 32  \w     35.00 103.00   0.50    0.49    --  107.11 -99.00 150.00  136
 33  \w     42.00  67.00   0.50    0.49    --  107.11-125.00  90.00   50
 34  \w     -4.00  30.00   0.50    0.12    --   47.57 -97.00  21.00   68
 35  \w     35.00  65.00   0.50    0.49    --  107.11 -57.00 -90.00   60
 36  \w     35.00  62.00   0.50    0.49    --  107.11 -57.00-150.00   54
 37  \w    135.00 174.00   0.50    0.49    --  107.11  57.00 -60.00   78
 38  \w    132.00 178.00   0.50    0.49    --  107.11  77.00 -30.00   92
 39  \w    137.00 178.00   0.50    0.49    --  107.11  57.00 -90.00   82
 40  \w    127.00 160.00   0.50    0.49    --  107.11  77.00-120.00   66
 41  \w    137.00 164.00   0.50    0.49    --  107.11  57.00-180.00   54
 42  \w    127.00 178.00   0.50    0.49    --  107.11  57.00  30.00  102
 43  \w    117.00 165.00   0.50    0.49    --  107.11  97.00 129.00   96
 44  \w   -114.00 -88.00   0.50    0.49    --  -86.25 -97.00  21.00   52
 45  \w   -151.00-115.00   0.50    0.49    --  -86.25 -37.00  60.00   72
 46  \w   -157.00-117.00   0.50    0.49    --  -86.25 -37.00 120.00   80
 47  \w   -158.00-133.00   0.50    0.49    --  -86.25 -57.00 120.00   50
 48  \w   -156.00-131.00   0.50    0.49    --  -86.25 -77.00   0.00   50
 49  \w   -155.00-129.00   0.50    0.49    --  -86.25 -77.00 -60.00   52
 50  \w   -151.00-126.00   0.50    0.49    --  -86.25 -77.00-120.00   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      0.1567944000
_diffrn_orient_matrix_UB_12      0.0267378000
_diffrn_orient_matrix_UB_13      -0.0209951000
_diffrn_orient_matrix_UB_21      -0.0354464000
_diffrn_orient_matrix_UB_22      0.0279929000
_diffrn_orient_matrix_UB_23      -0.0814943000
_diffrn_orient_matrix_UB_31      -0.0474499000
_diffrn_orient_matrix_UB_32      0.0891807000
_diffrn_orient_matrix_UB_33      0.0298217000
_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  0.0386
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            33611
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.278
_diffrn_reflns_theta_min         2.561
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    3.394
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.628
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.90a (Rigaku Oxford Diffraction, 2020)
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            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       plate
_exptl_crystal_F_000             1076
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexane'
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.089
_refine_diff_density_max         1.291
_refine_diff_density_min         -1.347
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     989
_refine_ls_number_reflns         10316
_refine_ls_number_restraints     1264
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0493P)^2^+4.1769P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1137
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9356
_reflns_number_total             10316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04285h2.cif
_cod_data_source_block           fed256a
_cod_original_cell_volume        2537.50(7)
_cod_database_code               1565073
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Y N4 C28 H34'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
C23B \\sim C20A \\sim C24A \\sim C24B \\sim C23A \\sim C20B \\sim C22A \\sim
C21B \\sim C22B \\sim C21A: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
C27C \\sim C26D \\sim C26C \\sim C27D \\sim C25C \\sim C28D \\sim C28C \\sim
C25D \\sim C24D \\sim C21C \\sim C23D \\sim C22C \\sim C22D \\sim C24C \\sim
C20C \\sim C20D \\sim C23C \\sim C21D: within 2A with sigma of 0.002 and sigma
for terminal atoms of 0.004 within 2A
C1A \\sim C6B \\sim C2A \\sim C7B \\sim C3A \\sim C8B \\sim C4A \\sim C9B \\sim
C5A \\sim C10B \\sim C6A \\sim C1B \\sim C2B \\sim C7A \\sim C3B \\sim C8A
\\sim C4B \\sim C9A \\sim C10A \\sim C5B \\sim C1C \\sim C6D \\sim C2C \\sim
C7D \\sim C8D \\sim C3C \\sim C9D \\sim C4C \\sim C5C \\sim C10D \\sim C1D
\\sim C6C \\sim C2D \\sim C7C \\sim C3D \\sim C8C \\sim C9C \\sim C4D \\sim C5D
\\sim C10C: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004
within 2A
Uanis(N1B) = Uanis(N2A) = Uanis(N2B) = Uanis(N1A)
Uanis(N1D) = Uanis(N1C) = Uanis(N2D) = Uanis(N2C)
Uanis(C28B) = Uanis(C28A)
Uanis(C25B) = Uanis(C26A)
3. Same fragment restrains
{N1A, N2A, N3A, N4A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A} sigma
for 1-2: 0.02, 1-3: 0.04
as in
{N1B, N2B, N3B, N4B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B}
{C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A} sigma for 1-2: 0.02,
1-3: 0.04
as in
{C20B, C21B, C22B, C23B, C24B, C25B, C26B, C27B, C28B}
{N1A, N2A, N3A, N4A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A} sigma
for 1-2: 0.02, 1-3: 0.04
as in
{N1C, N2C, N3C, N4C, C1C, C2C, C3C, C4C, C5C, C6C, C7C, C8C, C9C, C10C}
{N1A, N2A, N3A, N4A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A} sigma
for 1-2: 0.02, 1-3: 0.04
as in
{N1D, N2D, N3D, N4D, C1D, C2D, C3D, C4D, C5D, C6D, C7D, C8D, C9D, C10D}
{C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A} sigma for 1-2: 0.01,
1-3: 0.02
as in
{C20C, C21C, C22C, C23C, C24C, C25C, C26C, C27C, C28C}
{C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A} sigma for 1-2: 0.02,
1-3: 0.04
as in
{C20D, C21D, C22D, C23D, C24D, C25D, C26D, C27D, C28D}
4. Others
 Sof(N1B)=Sof(N2B)=Sof(N3B)=Sof(N4B)=Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=
 Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(H7B)=
 Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=1-FVAR(1)
 Sof(N1A)=Sof(N2A)=Sof(N3A)=Sof(N4A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=
 Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(H7A)=
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=FVAR(1)
 Sof(N1D)=Sof(N2D)=Sof(N3D)=Sof(N4D)=Sof(C1D)=Sof(C2D)=Sof(H2D)=Sof(C3D)=
 Sof(H3D)=Sof(C4D)=Sof(H4D)=Sof(C5D)=Sof(H5D)=Sof(C6D)=Sof(C7D)=Sof(H7D)=
 Sof(C8D)=Sof(H8D)=Sof(C9D)=Sof(H9D)=Sof(C10D)=Sof(H10D)=1-FVAR(2)
 Sof(N1C)=Sof(N2C)=Sof(N3C)=Sof(N4C)=Sof(C1C)=Sof(C2C)=Sof(H2C)=Sof(C3C)=
 Sof(H3C)=Sof(C4C)=Sof(H4C)=Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(C7C)=Sof(H7C)=
 Sof(C8C)=Sof(H8C)=Sof(C9C)=Sof(H9C)=Sof(C10C)=Sof(H10C)=FVAR(2)
 Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(C22B)=Sof(C23B)=Sof(C24B)=Sof(C25B)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27B)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28B)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=1-FVAR(3)
 Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(C25A)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28A)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=FVAR(3)
 Sof(C20D)=Sof(H20D)=Sof(C21D)=Sof(C22D)=Sof(C23D)=Sof(C24D)=Sof(C25D)=
 Sof(H25J)=Sof(H25K)=Sof(H25L)=Sof(C26D)=Sof(H26J)=Sof(H26K)=Sof(H26L)=
 Sof(C27D)=Sof(H27J)=Sof(H27K)=Sof(H27L)=Sof(C28D)=Sof(H28J)=Sof(H28K)=
 Sof(H28L)=1-FVAR(4)
 Sof(C20C)=Sof(H20C)=Sof(C21C)=Sof(C22C)=Sof(C23C)=Sof(C24C)=Sof(C25C)=
 Sof(H25G)=Sof(H25H)=Sof(H25I)=Sof(C26C)=Sof(H26G)=Sof(H26H)=Sof(H26I)=
 Sof(C27C)=Sof(H27G)=Sof(H27H)=Sof(H27I)=Sof(C28C)=Sof(H28G)=Sof(H28H)=
 Sof(H28I)=FVAR(4)
5.a Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C7A(H7A), C8A(H8A), C9A(H9A),
 C10A(H10A), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B), C7B(H7B), C8B(H8B),
 C9B(H9B), C10B(H10B), C11A(H11A), C20A(H20A), C20B(H20B), C2C(H2C), C3C(H3C),
 C4C(H4C), C5C(H5C), C7C(H7C), C8C(H8C), C9C(H9C), C10C(H10C), C2D(H2D),
 C3D(H3D), C4D(H4D), C5D(H5D), C7D(H7D), C8D(H8D), C9D(H9D), C10D(H10D),
 C11C(H11C), C20C(H20C), C20D(H20D)
5.b Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C19A(H19A,
 H19B,H19C), C25A(H25A,H25B,H25C), C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C),
 C28A(H28A,H28B,H28C), C25B(H25D,H25E,H25F), C26B(H26D,H26E,H26F), C27B(H27D,
 H27E,H27F), C28B(H28D,H28E,H28F), C16C(H16D,H16E,H16F), C17C(H17D,H17E,H17F),
 C18C(H18D,H18E,H18F), C19C(H19D,H19E,H19F), C25C(H25G,H25H,H25I), C26C(H26G,
 H26H,H26I), C27C(H27G,H27H,H27I), C28C(H28G,H28H,H28I), C25D(H25J,H25K,H25L),
 C26D(H26J,H26K,H26L), C27D(H27J,H27K,H27L), C28D(H28J,H28K,H28L)
;
_shelx_res_checksum              14799
_shelx_hkl_checksum              4340
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_original_sample_id FED256
_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 1.302
_oxdiff_exptl_absorpt_empirical_full_min 0.830