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_7131266
_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         'C32 H44 B2 F6 K N12 O12 S2 Y, 1.5(C7 H8)'
_chemical_formula_sum            'C42.5 H56 B2 F6 K N12 O12 S2 Y'
_chemical_formula_weight         1254.74
_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             2022-01-31
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-03-22 deposited with the CCDC.	2022-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                89.056(7)
_cell_angle_beta                 69.647(6)
_cell_angle_gamma                76.348(6)
_cell_formula_units_Z            4
_cell_length_a                   17.124(3)
_cell_length_b                   18.094(3)
_cell_length_c                   19.856(3)
_cell_measurement_reflns_used    9948
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.50
_cell_measurement_theta_min      2.32
_cell_volume                     5590.6(16)
_computing_data_collection       'APEX3 Ver. 2016.9-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (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 0.976
_diffrn_measured_fraction_theta_max 0.970
_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  0.2363
_diffrn_reflns_av_unetI/netI     0.2483
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            100588
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.587
_diffrn_reflns_theta_min         1.161
_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    1.280
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6433
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1462 before and 0.0823 after correction.
The Ratio of minimum to maximum transmission is 0.8630.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_description       block
_exptl_crystal_F_000             2580
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.332
_refine_diff_density_min         -0.636
_refine_diff_density_rms         0.148
_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     1391
_refine_ls_number_reflns         22692
_refine_ls_number_restraints     1632
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.2332
_refine_ls_R_factor_gt           0.1035
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1278P)^2^+21.1086P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2556
_refine_ls_wR_factor_ref         0.3159
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9848
_reflns_number_total             22692
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03189b2.cif
_cod_data_source_block           2_Y
_cod_depositor_comments
'Adding full bibliography for 7131257--7131266.cif.'
_cod_original_cell_volume        5590.7(16)
_cod_original_formula_sum        'C42.50 H56 B2 F6 K N12 O12 S2 Y'
_cod_database_code               7131266
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C67-C66 = C68-C67 = C69-C68 = C70-C69 = C70-C65 = C66-C65
 1.39 with sigma of 0.02
 C81-C80 = C82-C81 = C84-C82 = C84-C83 = C85-C83 = C85-C80
 1.39 with sigma of 0.02
 C80-C79
 1.51 with sigma of 0.02
 C71-C66
 1.51 with sigma of 0.02
 C87-C86 = C88-C87 = C88-C82 = C89-C82
 1.39 with sigma of 0.02
 C90-C80
 1.51 with sigma of 0.02
 C95-C68 = C91-C68 = C95-C94 = C94-C93 = C93-C92 = C92-C91
 1.39 with sigma of 0.02
 C96-C95
 1.51 with sigma of 0.02
 C65-C68 \\sim C67-C70 \\sim C66-C69
 with sigma of 0.02
 C87-C89 \\sim C88-C80 \\sim C86-C82
 with sigma of 0.02
 C68-C93 \\sim C92-C95 \\sim C94-C91
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
B3: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
1.7A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H82A)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=Sof(C89)=
 Sof(H89)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=1-FVAR(1)
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C81)=Sof(H81)=Sof(H82)=Sof(C83)=
 Sof(H83)=Sof(C84)=Sof(H84)=Sof(C85)=Sof(H85)=FVAR(1)
 Sof(H68)=Sof(C91)=Sof(H91)=Sof(C92)=Sof(H92)=Sof(C93)=Sof(H93)=Sof(C94)=
 Sof(H94)=Sof(C95)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=1-FVAR(2)
 Sof(C65)=Sof(H65)=Sof(C66)=Sof(C67)=Sof(H67)=Sof(H68A)=Sof(C69)=Sof(H69)=
 Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 B1(H1), B2(H2), B3(H3A), B4(H4A)
6.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B),
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C53(H53A,H53B), C54(H54A,H54B),
  C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,
 H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B),
 C64(H64A,H64B)
6.c Me refined with riding coordinates:
 C71(H71A,H71B,H71C), C96(H96A,H96B,H96C), C79(H79A,H79B,H79C), C90(H90A,H90B,
 H90C)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2A), C3(H3), C4(H4), 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), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38),
 C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
  C47(H47), C48(H48), C49(H49), C50(H50), C65(H65), C67(H67), C68(H68A),
 C68(H68), C69(H69), C70(H70), C91(H91), C92(H92), C93(H93), C94(H94), C73(H73),
  C74(H74), C75(H75), C76(H76), C77(H77), C81(H81), C82(H82), C82(H82A),
 C83(H83), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89)
6.e Idealised Me refined as rotating group:
 C78(H78A,H78B,H78C)
;
_shelx_res_checksum              72160
_shelx_hkl_checksum              5056
_olex2_submission_special_instructions 'No special instructions were received'