Transition Metal Redox Switches for Reversible “On/Off” and “Slow/Fast” Single-Molecule Magnet Behaviour in Dysprosium and Erbium bis-Diamidoferrocene Complexes
Dickie, Courtney M.; Laughlin, Alexander L.; Wofford, Joshua D.; Bhuvanesh, Nattamai; Nippe, Michael; Chem. Sci.  (2017) –; doi:10.1039/C7SC03380J

data_1547516
_publ_section_title
;
 Transition Metal Redox Switches for Reversible &#x201C;On/Off&#x201D; and
 &#x201C;Slow/Fast&#x201D; Single-Molecule Magnet Behaviour in Dysprosium
 and Erbium bis-Diamidoferrocene Complexes
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03380J
_journal_year                    2017
_chemical_formula_moiety         'C44 H76 Dy Fe2 N4 Si4'
_chemical_formula_sum            'C44 H76 Dy Fe2 N4 Si4'
_chemical_formula_weight         1047.64
_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'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-18
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-08-01 deposited with the CCDC.
2017-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.025(4)
_cell_length_b                   19.663(4)
_cell_length_c                   24.499(5)
_cell_measurement_reflns_used    9614
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      27.284
_cell_measurement_theta_min      2.207
_cell_volume                     9647(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0859
_diffrn_reflns_av_unetI/netI     0.0429
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            89008
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.662
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.260
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.1221 before and 0.0743 after correction.
The Ratio of minimum to maximum transmission is 0.6541.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             4336
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.114
_refine_diff_density_max         1.093
_refine_diff_density_min         -0.902
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.125
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         8495
_refine_ls_number_restraints     280
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0650
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0099P)^2^+47.8851P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0753
_refine_ls_wR_factor_ref         0.0947
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6263
_reflns_number_total             8495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03380j2.cif
_cod_data_source_block           mncmd023
_cod_original_cell_volume        9646(3)
_cod_database_code               1547516
_shelx_estimated_absorpt_t_max   0.783
_shelx_estimated_absorpt_t_min   0.514
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si4-N4 \\sim Si4A-N4
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si4 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim Si4A
\\sim C39A \\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim C44A: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 Si4, C39, C40, C41, C42, C43, C44, Si4A, C39A, C40A, C41A, C42A, C43A, C44A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{Si4, C39, C40, C41, C42, C43, C44} sigma for 1-2: 0.005, 1-3: 0.04
as
{Si4A, C39A, C40A, C41A, C42A, C43A, C44A}
6. Others
 Sof(Si4A)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C44A)=Sof(H44D)=Sof(H44E)=
 Sof(H44F)=1-FVAR(1)
 Sof(Si4)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=
 Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(1)
7.a Riding coordinates:
 C40(H40A,H40B,H40C)
7.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C16(H16),
 C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37), C38(H38)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C),
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C39(H39A,
 H39B,H39C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C),
 C39A(H39D,H39E,H39F), C40A(H40D,H40E,H40F), C42A(H42D,H42E,H42F), C43A(H43D,
 H43E,H43F), C44A(H44D,H44E,H44F)
;
_shelx_res_checksum              28175
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'