Slow magnetic relaxation in distorted tetrahedral Dy(III) aryloxide complexes.
Parmar, Vijay S.; Gransbury, Gemma K.; Whitehead, George F. S.; Mills, David P.; Winpenny, Richard E. P.; Chemical communications (Cambridge, England) 57 (2021) 9208–9211; doi:10.1039/d1cc02707g

data_7128798
_publ_section_title
;
 Slow magnetic relaxation in distorted tetrahedral Dy(III) aryloxide
 complexes.
;
_journal_issue                   73
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              9208
_journal_page_last               9211
_journal_paper_doi               10.1039/d1cc02707g
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C54 H91 B Dy O3, C24 H48 Na O6, 2(C4 H8 O)'
_chemical_formula_sum            'C86 H155 B Dy Na O11'
_chemical_formula_weight         1561.39
_chemical_name_systematic        '[Dy(OMes*)3(BH4)][Na(THF)6]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-05-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-05-21 deposited with the CCDC.	2021-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.6173(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.72802(17)
_cell_length_b                   19.6357(2)
_cell_length_c                   28.9797(3)
_cell_measurement_reflns_used    14276
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.6300
_cell_measurement_theta_min      2.7060
_cell_volume                     8940.48(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.7b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.7b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.7b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -77.00  43.00   1.00    1.00    --  -45.00  57.00-150.00  120
  2  \w    -40.00 -13.00   1.00    1.00    --  -45.00 -57.00-150.00   27
  3  \w    -74.00 -48.00   1.00    1.00    --  -45.00 -57.00-150.00   26
  4  \w    -69.00  -6.00   1.00    1.00    --  -45.00  57.00   0.00   63
  5  \w     -9.00  17.00   1.00    1.00    --  -45.00  57.00 120.00   26
  6  \w    -72.00 -23.00   1.00    1.00    --  -45.00  57.00 120.00   49
  7  \w   -109.00 -65.00   1.00    3.00    -- -110.00  57.00-120.00   44
  8  \w    -75.00 -49.00   1.00    3.00    -- -110.00  38.00-150.00   26
  9  \w   -187.00 -78.00   1.00    3.00    -- -110.00 -57.00 150.00  109
 10  \w   -147.00 -94.00   1.00    3.00    -- -110.00  38.00-150.00   53
 11  \w    -64.00 -21.00   1.00    3.00    -- -110.00  57.00-120.00   43
 12  \w   -142.00 -24.00   1.00    3.00    -- -110.00  57.00  60.00  118
 13  \w   -148.00 -40.00   1.00    3.00    -- -110.00  76.00-120.00  108
 14  \w    -49.00 -24.00   1.00    3.00    -- -110.00  57.00 -90.00   25
 15  \w   -177.00 -69.00   1.00    3.00    -- -110.00 -38.00-180.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0207559000
_diffrn_orient_matrix_UB_12      0.0695162000
_diffrn_orient_matrix_UB_13      -0.0213814000
_diffrn_orient_matrix_UB_21      -0.0944979000
_diffrn_orient_matrix_UB_22      0.0202637000
_diffrn_orient_matrix_UB_23      0.0010319000
_diffrn_orient_matrix_UB_31      0.0160147000
_diffrn_orient_matrix_UB_32      0.0300124000
_diffrn_orient_matrix_UB_33      0.0487675000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0479
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            52900
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.164
_diffrn_reflns_theta_min         3.053
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    4.924
_exptl_absorpt_correction_T_max  0.735
_exptl_absorpt_correction_T_min  0.471
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.7b (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.160
_exptl_crystal_description       block
_exptl_crystal_F_000             3364
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'crystallised in THF'
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.898
_refine_diff_density_min         -1.559
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1308
_refine_ls_number_reflns         18351
_refine_ls_number_restraints     4045
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0578P)^2^+4.5263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1212
_refine_ls_wR_factor_ref         0.1286
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14731
_reflns_number_total             18351
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc02707g2.cif
_cod_data_source_block           rdpm150_Complex3
_cod_depositor_comments
'Adding full bibliography for 7128795--7128798.cif.'
_cod_original_cell_volume        8940.47(17)
_cod_database_code               7128798
_manchester_internal_coll_name   RDPM150
_manchester_internal_coll_client VP/DPM
_manchester_internal_coll_type   custom
_manchester_internal_coll_frame_time '1 & 3'
_manchester_internal_coll_frame_width 1
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_user   Inigo
_manchester_internal_coll_date   28/08/2018
_manchester_internal_process_user VP/DPM
_manchester_internal_process_date 28/08/2018
_manchester_internal_solution_user VP
_manchester_internal_solution_date 29/08/2018
_manchester_internal_refinement_user VP
_manchester_internal_refinement_date 10/12/2018
_manchester_internal_validation_date 10/05/21
_manchester_internal_validation_user GW
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C78H125BDyNaO9
_chemical_oxdiff_usercomment     JB
_shelx_estimated_absorpt_t_max   0.668
_shelx_estimated_absorpt_t_min   0.415
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Restrained distances
 H1D-H1A \\sim H1D-H1C \\sim H1C-H1A \\sim H1A-H1B \\sim H1D-H1B \\sim H1C-H1B
 with sigma of 0.06
 O10-C87 \\sim O10-C84 \\sim O11-C82 \\sim O11-C79
 with sigma of 0.02
 C87-C86 \\sim C86-C85 \\sim C85-C84 \\sim C82-C81 \\sim C81-C80 \\sim C80-C79
 with sigma of 0.02
 O10-C86 \\sim O10-C85 \\sim O11-C81 \\sim O11-C80
 with sigma of 0.02
 C82-C80 \\sim C81-C79 \\sim C86-C84 \\sim C87-C85
 with sigma of 0.02
 Na1-O4A \\sim Na1-O4 \\sim Na1-O5A \\sim Na1-O5 \\sim Na1-O7A \\sim Na1-O7
\\sim Na1-O8 \\sim Na1-O8A ~
 Na1-O9 \\sim Na1-O9A \\sim Na1-O6 \\sim Na1-O6A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
O10 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim O11 \\sim C79 \\sim C80 \\sim
C81 \\sim C82 \\sim O4 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim O5 \\sim
C59 \\sim C60 \\sim C61 \\sim C62 \\sim O6 \\sim C63 \\sim C64 \\sim C65 \\sim
C66 \\sim O7 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim O8 \\sim C71 \\sim
C72 \\sim C73 \\sim C74 \\sim O9 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim
O4A \\sim C55A \\sim C56A \\sim C57A \\sim C58A \\sim O5A \\sim C59A \\sim C60A
\\sim C61A \\sim C62A \\sim O6A \\sim C63A \\sim C64A \\sim C65A \\sim C66A
\\sim O7A \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim O8A \\sim C71A
\\sim C72A \\sim C73A \\sim C74A \\sim O9A \\sim C75A \\sim C76A \\sim C77A
\\sim C78A \\sim O10A \\sim C84A \\sim C85A \\sim C86A \\sim C87A \\sim O11A
\\sim C79A \\sim C80A \\sim C81A \\sim C82A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 O10, C84, C85, C86, C87, O11, C79, C80, C81, C82, O4, C55, C56, C57, C58, O5,
 C59, C60, C61, C62, O6, C63, C64, C65, C66, O7, C67, C68, C69, C70, O8, C71,
 C72, C73, C74, O9, C75, C76, C77, C78, O4A, C55A, C56A, C57A, C58A, O5A, C59A,
 C60A, C61A, C62A, O6A, C63A, C64A, C65A, C66A, O7A, C67A, C68A, C69A, C70A,
 O8A, C71A, C72A, C73A, C74A, O9A, C75A, C76A, C77A, C78A, O10A, C84A, C85A,
 C86A, C87A, O11A, C79A, C80A, C81A, C82A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O11, C79, C80, C81, C82}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O4, C55, C56, C57, C58}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O5, C59, C60, C61, C62}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O6, C63, C64, C65, C66}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O7, C67, C68, C69, C70}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O8, C71, C72, C73, C74}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O9, C75, C76, C77, C78}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O4A, C55A, C56A, C57A, C58A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O5A, C59A, C60A, C61A, C62A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O6A, C63A, C64A, C65A, C66A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O7A, C67A, C68A, C69A, C70A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O8A, C71A, C72A, C73A, C74A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O9A, C75A, C76A, C77A, C78A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O10A, C84A, C85A, C86A, C87A}
{O10, C84, C85, C86, C87} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O11A, C79A, C80A, C81A, C82A}
5. Others
 Sof(O9A)=Sof(C75A)=Sof(H75C)=Sof(H75D)=Sof(C76A)=Sof(H76C)=Sof(H76D)=
 Sof(C77A)=Sof(H77C)=Sof(H77D)=Sof(C78A)=Sof(H78C)=Sof(H78D)=1-FVAR(1)
 Sof(O9)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(C77)=
 Sof(H77A)=Sof(H77B)=Sof(C78)=Sof(H78A)=Sof(H78B)=FVAR(1)
 Sof(O4A)=Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56C)=Sof(H56D)=
 Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=Sof(H58C)=Sof(H58D)=1-FVAR(2)
 Sof(O4)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=
 Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=FVAR(2)
 Sof(O5A)=Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(H60C)=Sof(H60D)=
 Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=1-FVAR(3)
 Sof(O5)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=
 Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=FVAR(3)
 Sof(O7A)=Sof(C67A)=Sof(H67C)=Sof(H67D)=Sof(C68A)=Sof(H68C)=Sof(H68D)=
 Sof(C69A)=Sof(H69C)=Sof(H69D)=Sof(C70A)=Sof(H70C)=Sof(H70D)=1-FVAR(4)
 Sof(O7)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(C69)=
 Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=FVAR(4)
 Sof(O6A)=Sof(C63A)=Sof(H63C)=Sof(H63D)=Sof(C64A)=Sof(H64C)=Sof(H64D)=
 Sof(C65A)=Sof(H65C)=Sof(H65D)=Sof(C66A)=Sof(H66C)=Sof(H66D)=1-FVAR(5)
 Sof(O6)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C65)=
 Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=FVAR(5)
 Sof(O8A)=Sof(C71A)=Sof(H71C)=Sof(H71D)=Sof(C72A)=Sof(H72C)=Sof(H72D)=
 Sof(C73A)=Sof(H73C)=Sof(H73D)=Sof(C74A)=Sof(H74C)=Sof(H74D)=1-FVAR(6)
 Sof(O8)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=
 Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=FVAR(6)
 Sof(O10A)=Sof(C84A)=Sof(H84C)=Sof(H84D)=Sof(C85A)=Sof(H85C)=Sof(H85D)=
 Sof(C86A)=Sof(H86C)=Sof(H86D)=Sof(C87A)=Sof(H87C)=Sof(H87D)=1-FVAR(7)
 Sof(O10)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(C86)=
 Sof(H86A)=Sof(H86B)=Sof(C87)=Sof(H87A)=Sof(H87B)=FVAR(7)
 Sof(O11A)=Sof(C79A)=Sof(H79C)=Sof(H79D)=Sof(C80A)=Sof(H80C)=Sof(H80D)=
 Sof(C81A)=Sof(H81C)=Sof(H81D)=Sof(C82A)=Sof(H82C)=Sof(H82D)=1-FVAR(8)
 Sof(O11)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(C81)=
 Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=FVAR(8)
6.a Secondary CH2 refined with riding coordinates:
 C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C79(H79A,
 H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), 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), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
  C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C55A(H55C,
 H55D), C56A(H56C,H56D), C57A(H57C,H57D), C58A(H58C,H58D), C59A(H59C,H59D),
 C60A(H60C,H60D), C61A(H61C,H61D), C62A(H62C,H62D), C63A(H63C,H63D), C64A(H64C,
 H64D), C65A(H65C,H65D), C66A(H66C,H66D), C67A(H67C,H67D), C68A(H68C,H68D),
 C69A(H69C,H69D), C70A(H70C,H70D), C71A(H71C,H71D), C72A(H72C,H72D), C73A(H73C,
 H73D), C74A(H74C,H74D), C75A(H75C,H75D), C76A(H76C,H76D), C77A(H77C,H77D),
 C78A(H78C,H78D), C84A(H84C,H84D), C85A(H85C,H85D), C86A(H86C,H86D), C87A(H87C,
 H87D), C79A(H79C,H79D), C80A(H80C,H80D), C81A(H81C,H81D), C82A(H82C,H82D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C21(H21), C23(H23), C39(H39), C41(H41)
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C), C54(H54A,H54B,H54C), C30A(H30A,H30B,H30C), C31A(H31A,H31B,H31C),
 C32A(H32A,H32B,H32C)
;
_shelx_res_checksum              88618
_shelx_hkl_checksum              79046
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.208
_oxdiff_exptl_absorpt_empirical_full_min 0.765