Reduction chemistry yields stable and soluble divalent lanthanide tris(pyrazolyl)borate complexes.
Chowdhury, Tajrian; Evans, Matthew J.; Coles, Martyn P.; Bailey, Anna G.; Peveler, William J.; Wilson, Claire; Farnaby, Joy H.; Chemical communications (Cambridge, England) 59 (2023) 2134–2137; doi:10.1039/d2cc03189b

data_7131261
_publ_section_title
;
 Reduction chemistry yields stable and soluble divalent lanthanide
 tris(pyrazolyl)borate complexes.
;
_journal_issue                   15
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2134
_journal_page_last               2137
_journal_paper_doi               10.1039/d2cc03189b
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety
'C22 H30 B2 N12 O2 Yb, 0.25(C18 H40 F6 K2 O14 S2)'
_chemical_formula_sum            'C26.5 H40 B2 F1.5 K0.5 N12 O5.5 S0.5 Yb'
_chemical_formula_weight         873.44
_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             2022-03-16
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2022-03-22 deposited with the CCDC.	2022-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90.550(2)
_cell_angle_beta                 95.543(2)
_cell_angle_gamma                99.885(2)
_cell_formula_units_Z            4
_cell_length_a                   11.4074(6)
_cell_length_b                   11.9061(6)
_cell_length_c                   27.7046(15)
_cell_measurement_reflns_used    9892
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.28
_cell_measurement_theta_min      2.36
_cell_volume                     3688.3(3)
_computing_cell_refinement       'SAINT V8.37A (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'charge integrating pixel array detector'
_diffrn_detector_area_resol_mean 7.4074
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'multilayer mirror optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            74067
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.276
_diffrn_reflns_theta_min         1.869
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'INCOATEC I\ms 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.681
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6258
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0703 before and 0.0497 after correction.
The Ratio of minimum to maximum transmission is 0.8392.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.573
_exptl_crystal_description       tablet
_exptl_crystal_F_000             1752
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.409
_refine_diff_density_min         -1.858
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1002
_refine_ls_number_reflns         18091
_refine_ls_number_restraints     234
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0144P)^2^+14.5264P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0790
_refine_ls_wR_factor_ref         0.0803
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16743
_reflns_number_total             18091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03189b2.cif
_cod_data_source_block           1_Yb_DME
_cod_depositor_comments
'Adding full bibliography for 7131257--7131266.cif.'
_cod_original_formula_sum        'C26.50 H40 B2 F1.50 K0.50 N12 O5.50 S0.50 Yb'
_cod_database_code               7131261
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.856
_shelx_estimated_absorpt_t_min   0.630
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F2-C45 \\sim F3A-C45 \\sim F2A-C45 \\sim F3-C45 \\sim F1A-C45 \\sim F1-C45
 with sigma of 0.02
 O10-C46A \\sim O10A-C46 \\sim O11A-C49A \\sim O11-C49
 with sigma of 0.02
 O11A-C49A \\sim O11-C49
 with sigma of 0.02
 S1-O6A \\sim S1-O6 \\sim S1-O7A \\sim S1-O7 \\sim S1-O5A \\sim S1-O5
 with sigma of 0.02
 O10-C47 \\sim O10A-C47 \\sim O11A-C48 \\sim O11-C48
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O10 \\sim O11 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim O10A \\sim O11A
\\sim C46A \\sim C49A: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 1.7A
F1 \\sim F2 \\sim F3 \\sim F1A \\sim F2A \\sim F3A: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 1.7A
O5 \\sim O6 \\sim O7 \\sim O5A \\sim O6A \\sim O7A: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 1.7A
C42 \\sim C43 \\sim C42A \\sim C43A: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 1.7A
: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=1-FVAR(1)
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=FVAR(1)
 Sof(O10)=Sof(O11)=Sof(H47A)=Sof(H47B)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=
 Sof(H49B)=Sof(H49C)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=
 Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(C46)=Sof(H46A)=Sof(H46B)=
 Sof(H46C)=Sof(H47C)=Sof(H47D)=Sof(H48C)=Sof(H48D)=Sof(O10A)=Sof(O11A)=
 Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 B1(H1), B2(H2), B3(H3), B4(H4)
5.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C42(H42A,H42B), C43(H43A,H43B), C47(H47A,
 H47B), C47(H47C,H47D), C48(H48A,H48B), C48(H48C,H48D), C51(H51A,H51B),
 C52(H52A,H52B), C42A(H42C,H42D), C43A(H43C,H43D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2A), C3(H3A), C4(H4A), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
  C18(H18), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
  C37(H37), C38(H38), C39(H39), C40(H40)
5.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C41(H41A,H41B,H41C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C53(H53A,
 H53B,H53C), C46A(H46D,H46E,H46F), C49A(H49D,H49E,H49F)
;
_shelx_res_checksum              54394
_shelx_hkl_checksum              28050
_olex2_submission_special_instructions 'No special instructions were received'