Magnetic anisotropies of Ho(III) and Dy(III) single-molecule magnets experimentally determined via polarized neutron diffraction
Klahn, Emil Andreasen; Thiel, Andreas Munch; Degn, Rasmus B.; Kibalin, Iurii; Gukasov, Arsen; wilson, claire; Canaj, Angelos B.; Murrie, Mark; Overgaard, Jacob; Dalton Transactions  (2021) –; doi:10.1039/D1DT01959G

data_7708171
_publ_section_title
;
 Magnetic anisotropies of Ho(III) and Dy(III) single-molecule magnets
 experimentally determined via polarized neutron diffraction
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT01959G
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C12 H46 Ho N6 O7 P2, 3(I), 2(C6 H18 N3 O P)'
_chemical_formula_sum            'C24 H82 Ho I3 N12 O9 P4'
_chemical_formula_weight         1352.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-08-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-08-30 deposited with the CCDC.	2021-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.281(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2486(10)
_cell_length_b                   19.1836(14)
_cell_length_c                   21.6652(18)
_cell_measurement_reflns_used    9716
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      24.98
_cell_measurement_theta_min      2.97
_cell_volume                     5684.5(7)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      150.0
_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 0.990
_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  0.0385
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            49581
_diffrn_reflns_point_group_measured_fraction_full 0.950
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        25.088
_diffrn_reflns_theta_max         25.088
_diffrn_reflns_theta_min         2.263
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'INCOATEC I\ms 3.0'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.180
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.651
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1519 before and 0.0732 after correction. The Ratio of minimum to maximum transmission is 0.6514. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.580
_exptl_crystal_description       block
_exptl_crystal_F_000             2672
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.037
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.043(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     633
_refine_ls_number_reflns         9602
_refine_ls_number_restraints     742
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0349
_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^)+(0.0483P)^2^+6.5404P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0875
_refine_ls_wR_factor_ref         0.0903
_reflns_Friedel_coverage         0.918
_reflns_Friedel_fraction_full    0.910
_reflns_Friedel_fraction_max     0.910
_reflns_number_gt                8975
_reflns_number_total             9602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01959g2.cif
_cod_data_source_block           2
_cod_database_code               7708171
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.569
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.957(13)
 0.043(13)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
3. Restrained distances
 N7-C14A = N7-C13
 1.47 with sigma of 0.02
 N9-C17 = N9-C18
 1.47 with sigma of 0.02
 N8-C15
 1.47 with sigma of 0.02
 N8-C16 = N8A-C15A
 1.47 with sigma of 0.02
 N8A-C16A
 1.47 with sigma of 0.02
 N11-C22 = N11-C21 = N12-C24 = N12-C23 = N10-C20 = N10A-C19A = N10-C19
 1.47 with sigma of 0.01
 N12-C23 = N11-C21 = N10-C20 = N10-C19 = N10A-C19 = N10A-C19A
 1.47 with sigma of 0.01
 N10A-C20A = N8-C15A = N8-C15 = N9-C17 = N9-C18 = N7-C13 = N7-C14
 1.47 with sigma of 0.01
 N9-C17 = N9-C18 = N9A-C17A = N9A-C18A
 1.47 with sigma of 0.02
 N6-C11 = N6-C12 = N4-C7 = N4-C8
 1.47 with sigma of 0.01
 P2-C10
 2.7 with sigma of 0.02
 N4-C7 = N4-C8 = N6-C11 = N6-C12 = N5A-C9A = N5-C10 = N6A-C11A
 1.47 with sigma of 0.01
 N5-C9 = N6A-C12A
 1.47 with sigma of 0.01
 N5A-C11
 1.47 with sigma of 0.02
 P3-N7 \\sim P3-N8A \\sim P3-N8 \\sim P3-N9
 with sigma of 0.02
 C15-C16 \\sim C15A-C16A \\sim C18-C17 \\sim C13-C14
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 P3-N9 \\sim P3-N9A \\sim P3-N8A \\sim P3-N8 \\sim P3-N7
 with sigma of 0.02
 C10-C9 \\sim C12A-C11A \\sim C11-C12 \\sim C7-C8
 with sigma of 0.01
 N5A-C10A \\sim N6-C11
 with sigma of 0.02
 Ho1-H3WA \\sim Ho1-H3WB
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
N11 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim N12: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C20 \\sim C20A \\sim N10 \\sim N10A \\sim C19 \\sim C19A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C8 \\sim N4 \\sim C7: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 1.7A
N6 \\sim C11 \\sim N5A \\sim N5 \\sim N6A: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
N9A \\sim N9 \\sim N8A \\sim N8 \\sim N7 \\sim C13 \\sim C14A \\sim C14 \\sim
C11A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 1.7A
C11A \\sim C10 \\sim C12A \\sim C9 \\sim C9A \\sim C11 \\sim C10A \\sim C12:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C18A \\sim C18 \\sim C17A \\sim C17 \\sim C16A \\sim C16 \\sim C15A \\sim C15
\\sim C14A \\sim C14: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 1.7A
5. 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
6. Others
 Fixed Sof: C11(0.3) H11A(0.3) H11B(0.3) H11C(0.3) N8(0.5) N9(0.5) C14(0.5)
 H14A(0.5) H14B(0.5) H14C(0.5) C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5) C17(0.5)
 H17A(0.5) H17B(0.5) H17C(0.5) C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) N10A(0.5)
 C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C19A(0.5) H19D(0.5) H19E(0.5) H19F(0.5)
 N10(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) N6A(0.7) N5A(0.7) C9A(0.7)
 H9AA(0.7) H9AB(0.7) H9AC(0.7) C11A(0.7) H11D(0.7) H11E(0.7) H11F(0.7) N6(0.3)
 C12(0.3) H12A(0.3) H12B(0.3) H12C(0.3) N5(0.3) C10(0.3) H10A(0.3) H10B(0.3)
 H10C(0.3) C15A(0.5) H15D(0.5) H15E(0.5) H15F(0.5) C20A(0.5) H20D(0.5)
 H20E(0.5) H20F(0.5) C14A(0.5) H14D(0.5) H14E(0.5) H14F(0.5) C12A(0.7)
 H12D(0.7) H12E(0.7) H12F(0.7) C9(0.3) H9A(0.3) H9B(0.3) H9C(0.3) N8A(0.5)
 C16(0.5) H16A(0.5) H16B(0.5) H16C(0.5) C16A(0.5) H16D(0.5) H16E(0.5) H16F(0.5)
 N9A(0.5) C17A(0.5) H17D(0.5) H17E(0.5) H17F(0.5) C18A(0.5) H18D(0.5) H18E(0.5)
 H18F(0.5) C10A(0.7) H10D(0.7) H10E(0.7) H10F(0.7)
7.a Free rotating group:
 O3W(H3WA,H3WB)
7.b Rotating group:
 O1W(H1WA,H1WB), O2W(H2WA,H2WB), O4W(H4WA,H4WB), O5W(H5WA,H5WB)
7.c Me refined with riding coordinates:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C15(H15A,
 H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19A(H19D,H19E,H19F),
 C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C), C9A(H9AA,H9AB,
 H9AC), C8(H8A,H8B,H8C), C11A(H11D,H11E,H11F), C7(H7A,H7B,H7C), C12(H12A,H12B,
 H12C), C10(H10A,H10B,H10C), C15A(H15D,H15E,H15F), C22(H22A,H22B,H22C),
 C24(H24A,H24B,H24C), C14A(H14D,H14E,H14F), C12A(H12D,H12E,H12F), C9(H9A,H9B,
 H9C), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F),
 C18A(H18D,H18E,H18F), C10A(H10D,H10E,H10F)
7.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              24580
_olex2_submission_special_instructions 'No special instructions were received'