Double Spin Crossovers: A New Double Salt Strategy to Improve Magnetic and Memory Properties
Murray, Keith S.; Phonsri, Wasinee; Jameson, Guy N. L.; Lewis, Barnaby; Chemical Communications  (2019) –; doi:10.1039/C9CC07416C

data_7124390
_publ_section_title
;
 Double Spin Crossovers: A New Double Salt Strategy to Improve Magnetic
 and Memory Properties
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC07416C
_journal_year                    2019
_chemical_formula_moiety
'C26 H32 Fe N12, C24 H16 Fe N4 O4, Cl O4, C2 N'
_chemical_formula_sum            'C52 H48 Cl Fe2 N17 O8'
_chemical_formula_weight         1186.22
_chemical_name_systematic        '[Fe(3,5 Me2TPM)(TPM)][Fe(azp)2]ClO4 MeCN'
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-12 deposited with the CCDC.    2019-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.594(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.2993(8)
_cell_length_b                   10.5858(4)
_cell_length_c                   32.3862(14)
_cell_measurement_reflns_used    12566
_cell_measurement_temperature    370.0(2)
_cell_measurement_theta_max      75.0490
_cell_measurement_theta_min      4.1710
_cell_volume                     5809.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.49a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.49a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.49a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      370.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.961
_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     53.00  78.00   0.50    4.00    --   47.57  53.00 -78.00   50
  2  \w     96.00 178.00   0.50   14.57    --  106.49  53.00 -78.00  164
  3  \w    118.00 171.00   0.50   14.57    --  106.49  45.00-150.00  106
  4  \w     85.00 123.00   0.50   14.57    --  106.49 -61.00-150.00   76
  5  \w     43.00  76.00   0.50   14.57    --  106.49 -45.00   0.00   66
  6  \w     46.00  72.00   0.50   14.57    --  106.49 -45.00 -30.00   52
  7  \w     42.00  76.00   0.50   14.57    --  106.49 -45.00 -90.00   68
  8  \w     45.00  72.00   0.50   14.57    --  106.49 -45.00 -60.00   54
  9  \w     32.00  66.00   0.50   14.57    --  106.49 -30.00   0.00   68
 10  \w     34.00  65.00   0.50   14.57    --  106.49 -30.00 -60.00   62
 11  \w     41.00  66.00   0.50   14.57    --  106.49 -30.00 -90.00   50
 12  \w     36.00  64.00   0.50   14.57    --  106.49 -45.00-150.00   56
 13  \w     40.00  65.00   0.50   14.57    --  106.49 -61.00-150.00   50
 14  \w     34.00  66.00   0.50   14.57    --  106.49 -30.00 -30.00   64
 15  \w     34.00  59.00   0.50   14.57    --  106.49 -30.00  90.00   50
 16  \w     43.00  87.00   0.50   14.57    --  106.49 -53.00 137.00   88
 17  \w     79.00 104.00   0.50   14.57    --  106.49 -94.00  90.00   50
 18  \w     32.00  66.00   0.50   14.57    --  106.49 -30.00 150.00   68
 19  \w     32.00  64.00   0.50   14.57    --  106.49 -30.00 120.00   64
 20  \w     -9.00  20.00   0.50    4.00    --   47.57 -53.00 137.00   58
 21  \w    -61.00  19.00   0.50    4.00    --  -47.57  53.00 -78.00  160
 22  \w     -1.00  24.00   0.50    4.00    --  -47.57  37.00 -60.00   50
 23  \w    -74.00 -42.00   0.50   14.57    --  -86.25  53.00 -78.00   64
 24  \w   -117.00 -35.00   0.50    4.00    --  -47.57 -53.00 137.00  164
 25  \w   -113.00 -73.00   0.50    4.00    --  -47.57-125.00  60.00   80
 26  \w   -140.00-115.00   0.50   14.57    --  -86.25 -53.00 137.00   50
 27  \w   -118.00 -81.00   0.50    4.00    --  -47.57-125.00 -60.00   74
 28  \w   -128.00 -78.00   0.50   14.57    --  -86.25-125.00 -90.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0543933000
_diffrn_orient_matrix_UB_12      -0.0812909000
_diffrn_orient_matrix_UB_13      -0.0214529000
_diffrn_orient_matrix_UB_21      0.0442064000
_diffrn_orient_matrix_UB_22      -0.0456811000
_diffrn_orient_matrix_UB_23      0.0435231000
_diffrn_orient_matrix_UB_31      -0.0577986000
_diffrn_orient_matrix_UB_32      -0.1117968000
_diffrn_orient_matrix_UB_33      -0.0022486000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0675
_diffrn_reflns_av_unetI/netI     0.0549
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            40838
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.403
_diffrn_reflns_theta_min         4.183
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.979
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29224
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.49a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Black
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       Plate
_exptl_crystal_F_000             2448
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.633
_refine_diff_density_min         -0.860
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     802
_refine_ls_number_reflns         11855
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1064
_refine_ls_R_factor_gt           0.0815
_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^)+(0.1804P)^2^+0.3454P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2436
_refine_ls_wR_factor_ref         0.2681
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7877
_reflns_number_total             11855
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07416c2.cif
_cod_data_source_block           370k
_cod_database_code               7124390
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C54H54ClFe2N18O8
_shelx_estimated_absorpt_t_max   0.564
_shelx_estimated_absorpt_t_min   0.253
_diffrn_oxdiff_digest_frames
;
01c55cd1fc4c0730bc9d2373f62aff9b6f0002761ef
;
_diffrn_oxdiff_digest_hkl
;
01cddfb4654ed55470c31d4d0b243f245776d4
;
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C51-N17 = C53-N18
 1.1 with sigma of 0.01
 C51-C52 = C53-C54
 1.5 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(O4) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(N2')=Sof(N1')=1-FVAR(1)
 Sof(N2)=Sof(N1)=FVAR(1)
 Sof(N4')=Sof(N3')=1-FVAR(2)
 Sof(N3)=Sof(N4)=FVAR(2)
 Sof(O4)=1-FVAR(3)
 Sof(O4')=FVAR(3)
 Fixed Sof: N17(0.5) C51(0.5) C52(0.5) C53(0.5) C54(0.5) N18(0.5)
5.a Ternary CH refined with riding coordinates:
 C40(H40), C50(H50)
5.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C49(H49), C42(H42), C43(H43), C41(H41), C47(H47), C32(H32), C2(H2),
 C14(H14), C48(H48), C44(H44), C37(H37), C45(H45), C46(H46), C11(H11), C15(H15),
  C10(H10), C5(H5), C23(H23), C16(H16), C22(H22), C17(H17), C8(H8), C3(H3),
 C9(H9), C4(H4), C21(H21), C20(H20)
5.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C25(H25A,H25B,H25C), C39(H39A,H39B,H39C), C30(H30A,H30B,
 H30C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              9019
_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 4.837
_oxdiff_exptl_absorpt_empirical_full_min 0.321