Unexpected dispersion-stabilized tris(terphenylthiolate) complexes, Ln(SAriPr6)3, arising from two-electron reduction by Ln(SAriPr6)2 [AriPr6 = C6H3-2,6-(C6H2-2,6,4-iPr3)2]
Luevano, Makayla R.; Stennett, Cary R.; Ma, Eric; Ziller, Joseph W.; Furche, Filipp; Evans, William J.; Chemical Science  (2026) –; doi:10.1039/D6SC00248J

data_1576790
_publ_section_title
;
 Unexpected dispersion-stabilized tris(terphenylthiolate) complexes,
 Ln(SAr <sup><i>i</i>Pr6</sup>)<sub>3</sub>, arising from two-electron
 reduction by Ln(SAr <sup><i>i</i>Pr6</sup>)<sub>2</sub> [Ar
 <sup><i>i</i>Pr6</sup> =
 C<sub>6</sub>H<sub>3</sub>-2,6-(C<sub>6</sub>H<sub>2</sub>-2,6,4-
 <sup><i>i</i></sup> Pr<sub>3</sub>)<sub>2</sub>].
;
_journal_issue                   16
_journal_name_full               'Chemical science'
_journal_page_first              8160
_journal_page_last               8167
_journal_paper_doi               10.1039/d6sc00248j
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C108 H147 Nd S3'
_chemical_formula_sum            'C108 H147 Nd S3'
_chemical_formula_weight         1685.67
_chemical_melting_point          ?
_chemical_properties_physical
Air-sensitive,Moisture-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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-12-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)

D. Kratzert, I. Krossing, (2018), J. Appl. Cryst. 51, 928-934.

Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Kratzert, D., Holstein, J.J. & Krossing, I. (2015). J. Appl. Cryst. 48, 933-938.

Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_audit_update_record
;
2025-12-19 deposited with the CCDC.	2026-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                77.9490(10)
_cell_angle_beta                 81.4490(10)
_cell_angle_gamma                83.2760(10)
_cell_formula_units_Z            2
_cell_length_a                   14.1230(2)
_cell_length_b                   18.5883(3)
_cell_length_c                   21.7952(3)
_cell_measurement_reflns_used    8393
_cell_measurement_temperature    93.15
_cell_measurement_theta_max      72.09
_cell_measurement_theta_min      2.44
_cell_volume                     5511.49(14)
_computing_cell_refinement       'Bruker SAINT 8.34a, 2013'
_computing_data_collection       'Bruker APEX2 2014.11-0, 2014'
_computing_data_reduction        'Bruker SAINT 8.34a, 2013'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'Bruker SHELXTL 2014/4 (XT)'
_diffrn_ambient_temperature      93.15
_diffrn_measured_fraction_theta_full 0.965
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0993
_diffrn_reflns_av_unetI/netI     0.0787
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            102450
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.235
_diffrn_reflns_theta_min         2.440
_diffrn_source                   'Bruker IuS'
_diffrn_source_current           0.65
_diffrn_source_power             0.0290745
_diffrn_source_voltage           44.73
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.410
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5711
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1020 before and 0.0801 after correction.
The Ratio of minimum to maximum transmission is 0.7578.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.016
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1806
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether'
_exptl_crystal_size_max          0.237
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.936
_refine_diff_density_min         -1.448
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1133
_refine_ls_number_reflns         20853
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0734
_refine_ls_R_factor_gt           0.0552
_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^)+(0.0732P)^2^+3.1447P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1362
_refine_ls_wR_factor_ref         0.1458
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16651
_reflns_number_total             20853
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00248j2.cif
_cod_data_source_block           mrl50
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1576785--1576790.cif.
;
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               1576790
_shelx_estimated_absorpt_t_max   0.766
_shelx_estimated_absorpt_t_min   0.421
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C85 \\sim C86 \\sim C86A \\sim C87 \\sim C87A: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
C32 \\sim C112: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C103 \\sim C104 \\sim C105 \\sim C109 \\sim C110 \\sim C111: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Fixed Sof: C28(0.7) H28(0.7) C28A(0.3) H28A(0.3) C29(0.7) H29A(0.7) H29B(0.7)
 H29C(0.7) C29A(0.3) H29D(0.3) H29E(0.3) H29F(0.3) C30(0.7) H30A(0.7) H30B(0.7)
 H30C(0.7) C30A(0.3) H30D(0.3) H30E(0.3) H30F(0.3) H31(0.5) H31A(0.5) C32(0.5)
 H32A(0.5) H32B(0.5) H32C(0.5) H85(0.6) H85A(0.4) C86(0.6) H86A(0.6) H86B(0.6)
 H86C(0.6) C86A(0.4) H86D(0.4) H86E(0.4) H86F(0.4) C87(0.6) H87A(0.6) H87B(0.6)
 H87C(0.6) C87A(0.4) H87D(0.4) H87E(0.4) H87F(0.4) C103(0.6) H103(0.6)
 C104(0.6) H10G(0.6) H10H(0.6) H10I(0.6) C105(0.4) H10J(0.4) H10K(0.4)
 H10L(0.4) C109(0.4) H109(0.4) C110(0.4) H11A(0.4) H11B(0.4) H11C(0.4)
 C111(0.6) H11D(0.6) H11E(0.6) H11F(0.6) C112(0.5) H11G(0.5) H11H(0.5) H11I(0.5)
4.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C28(H28), C28A(H28A), C31(H31), C31(H31A),
 C34(H34), C49(H49), C52(H52), C55(H55), C64(H64), C67(H67), C70(H70), C85(H85),
  C85(H85A), C88(H88), C91(H91), C100(H100), C103(H103), C106(H106), C109(H109)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C24(H24), C26(H26), C39(H39),
 C40(H40), C41(H41), C45(H45), C47(H47), C60(H60), C62(H62), C75(H75), C76(H76),
  C77(H77), C81(H81), C83(H83), C96(H96), C98(H98)
4.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C),
 C29A(H29D,H29E,H29F), C30(H30A,H30B,H30C), C30A(H30D,H30E,H30F), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C65(H65A,H65B,H65C), C66(H66A,H66B,
 H66C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C72(H72A,
 H72B,H72C), C86(H86A,H86B,H86C), C86A(H86D,H86E,H86F), C87(H87A,H87B,H87C),
 C87A(H87D,H87E,H87F), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C92(H92A,H92B,
 H92C), C93(H93A,H93B,H93C), C101(H10A,H10B,H10C), C102(H10D,H10E,H10F),
 C104(H10G,H10H,H10I), C105(H10J,H10K,H10L), C107(H10M,H10N,H10O), C108(H10P,
 H10Q,H10R), C110(H11A,H11B,H11C), C111(H11D,H11E,H11F), C112(H11G,H11H,H11I)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              21609
_shelx_fab_checksum              93043
_olex2_submission_special_instructions 'No special instructions were received'