Synergistic construction of highly symmetrical lanthanide single-ion magnets using neutral phosphoryl and anionic thiocyanate ligands.
Liu, Bei; Dong, Xiao-Yan; Gong, Hui-Wen; Sun, Zheng; Sun, Rong; Zhu, Wen-Hua; Zhang, Lei; Sun, Hao-Ling; Zhao, Man-Yun; Huang, Ning-Ning; Bian, Qing-Yan; Gao, Song; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9039–9048; doi:10.1039/d5dt00339c

data_7718590
_publ_section_title
;
 Synergistic construction of highly symmetrical lanthanide single-ion
 magnets using neutral phosphoryl and anionic thiocyanate ligands.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9039
_journal_page_last               9048
_journal_paper_doi               10.1039/d5dt00339c
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C26 H72 Dy N14 O4 P4 S2, F6 P'
_chemical_formula_sum            'C26 H72 Dy F6 N14 O4 P5 S2'
_chemical_formula_weight         1140.44
_chemical_name_common            '[Dy(HMPA)4(SCN)2](PF6), DongXY-25Mar26a'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-04-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-04-25 deposited with the CCDC.	2025-05-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.6565(13)
_cell_length_b                   24.4382(11)
_cell_length_c                   16.7250(7)
_cell_measurement_reflns_used    13906
_cell_measurement_temperature    150.15
_cell_measurement_theta_max      0.907
_cell_measurement_theta_min      0.813
_cell_volume                     10895.3(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.15
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1208
_diffrn_reflns_av_unetI/netI     0.0868
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            53430
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.249
_diffrn_reflns_theta_min         2.064
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52308
_exptl_absorpt_correction_type   'multi-scan & gaussian'
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (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            yellow
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       block
_exptl_crystal_F_000             4680
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.310
_refine_diff_density_min         -1.590
_refine_diff_density_rms         0.130
_refine_ls_extinction_coef       0.00024(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     665
_refine_ls_number_reflns         9814
_refine_ls_number_restraints     447
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1272
_refine_ls_R_factor_gt           0.0929
_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^)+(0.0334P)^2^+139.2405P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2112
_refine_ls_wR_factor_ref         0.2295
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6501
_reflns_number_total             9814
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00339c2.cif
_cod_data_source_block           CCDC_2422428
_cod_depositor_comments
'Adding full bibliography for 7718589--7718592.cif.'
_cod_database_code               7718590
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.907
_shelx_estimated_absorpt_t_min   0.813
_exptl_absorpt_special_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-C5 = N4A-C5A = N4-C6 = N5-C7 = N5A-C7A = N5A-C8A = N5-C8 = N3-C4 = N3A-C4A
 = N3-C3 = N3A-C3A = N4A-C6A
 1.46 with sigma of 0.01
 N10-C17 = N10A-C17A = N10-C18 = N10A-C18A = N9A-C16A = N9-C16 = N9-C15 = N9A-
 C15A = N11A-C19A = N11-C19 = N11-C20 = N11A-C20A
 1.46 with sigma of 0.01
 P3A-N11A = P3-N11 = P3A-N9A = P3-N9 = P3A-N10A = P3-N10
 1.64 with sigma of 0.01
 P1-N4 = P1A-N4A = P1A-N3A = P1-N3 = P1-N5 = P1A-N5A
 1.64 with sigma of 0.01
 C6A-C5A = C4-C3 = C7-C8 = C4A-C3A = C6-C5 = C19-C20 = C7A-C8A = C19A-C20A =
 C16-C15 = C16A-C15A = C18-C17 = C17A-C18A
 2.44 with sigma of 0.03
 N11A-N9A = N9A-N10A = N10A-N11A = N9-N10 = N10-N11 = N11-N9
 2.64 with sigma of 0.03
 N3-N5 = N5-N4 = N4-N3 = N3A-N5A = N5A-N4A = N4A-N3A
 2.64 with sigma of 0.03
 P5-F1 \\sim P5-F1A
 with sigma of 0.02
 P5-F2 \\sim P5-F2A
 with sigma of 0.02
 P5-F3 \\sim P5-F3A
 with sigma of 0.02
 N10-C17 \\sim N10-C18
 with sigma of 0.01
 P5-F4 \\sim P5-F4A
 with sigma of 0.02
 P5-F5 \\sim P5-F5A
 with sigma of 0.02
 P5-F6 \\sim P5-F6A
 with sigma of 0.02
 P3-O3 \\sim P3A-O3
 with sigma of 0.01
 P1-O1 \\sim P1A-O1
 with sigma of 0.01
 N13-C23 \\sim N13-C24 \\sim N12-C21 \\sim N12-C22 \\sim N14-C26 \\sim N14-C25
\\sim N7-C11 \\sim N7-C12 ~
 N8-C14 \\sim N6-C10 \\sim N6-C9 \\sim N8-C13
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N9 \\sim C16: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N11 \\sim C19: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
N14 \\sim C25: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
P5 \\sim F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim F4 \\sim F4A
\\sim F5 \\sim F5A \\sim F6 \\sim F6A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C5) = Uanis(C5A)
Uanis(C7) = Uanis(C7A)
Uanis(C3A) = Uanis(C3)
Uanis(C15) = Uanis(C15A)
Uanis(C6) = Uanis(C4A)
Uanis(C16A) = Uanis(C16)
Uanis(C17) = Uanis(C17A)
Uanis(C8) = Uanis(C8A)
Uanis(C20) = Uanis(C20A)
Uanis(C18) = Uanis(C18A)
Uanis(P3) = Uanis(P3A)
Uanis(N9) = Uanis(N9A)
Uanis(N11A) = Uanis(N11)
Uanis(N10) = Uanis(N10A)
Uanis(P1) = Uanis(P1A)
Uanis(N4) = Uanis(N4A)
Uanis(N5A) = Uanis(N5)
Uanis(N3A) = Uanis(N3)
4. Rigid body (RIGU) restrains
 N4, N3, C5, C3, C4, C6, N3A, C3A, C4A, N4A, C5A, N5, C8, C7, C7A, N5A, C6A, C8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N9, C15, C16, N9A, C16A, C15A, N11, C20, C19, N11A, C20A, C19A, N10, C17, C18,
  C18A, N10A, C17A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(F3A)=Sof(F6A)=Sof(F1A)=Sof(F5A)=Sof(F2A)=Sof(F4A)=1-FVAR(1)
 Sof(F6)=Sof(F5)=Sof(F3)=Sof(F2)=Sof(F4)=Sof(F1)=FVAR(1)
 Sof(P3A)=Sof(N11A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C19A)=
 Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(N10A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(N9A)=Sof(C16A)=Sof(H16D)=
 Sof(H16E)=Sof(H16F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(2)
 Sof(P3)=Sof(N9)=Sof(N11)=Sof(N10)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(2)
 Sof(P1A)=Sof(N3A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(H4AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(N5A)=Sof(N4A)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=1-FVAR(3)
 Sof(P1)=Sof(N5)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(N4)=Sof(N3)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=
 Sof(H4B)=Sof(H4C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H7C)=FVAR(3)
6.a Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C20(H20A,H20B,H20C), C15(H15A,H15B,H15C), C5(H5A,H5B,H5C),
 C3(H3A,H3B,H3C), C17(H17A,H17B,H17C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C16(H16A,H16B,H16C), C19(H19A,H19B,H19C), C18(H18A,H18B,H18C),
 C20A(H20D,H20E,H20F), C19A(H19D,H19E,H19F), C18A(H18D,H18E,H18F), C17A(H17D,
 H17E,H17F), C16A(H16D,H16E,H16F), C15A(H15D,H15E,H15F), C3A(H3AA,H3AB,H3AC),
 C4A(H4AA,H4AB,H4AC), C7A(H7AA,H7AB,H7AC), C5A(H5AA,H5AB,H5AC), C6A(H6AA,H6AB,
 H6AC), C8A(H8AA,H8AB,H8AC)
6.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C10(H10A,H10B,H10C), C23(H23A,H23B,
 H23C), C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C24(H24A,
 H24B,H24C), C22(H22A,H22B,H22C), C26(H26A,H26B,H26C), C25(H25A,H25B,H25C),
 C21(H21A,H21B,H21C)
;
_shelx_res_checksum              29473
_shelx_hkl_checksum              88100
_olex2_submission_special_instructions 'No special instructions were received'