Tuning the spin-crossover properties of FeII4L<sub>6</sub> cages <i>via</i> the interplay of coordination motif and linker modifications.
Paschelke, Tobias; Trumpf, Eicke; Grantz, David; Pankau, Malte; Grocholski, Niclas; Näther, Christian; Sönnichsen, Frank D; McConnell, Anna J.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt01569f

data_7713779
_publ_section_title
;
 Tuning the spin-crossover properties of FeII4L<sub>6</sub> cages
 <i>via</i> the interplay of coordination motif and linker modifications.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt01569f
_journal_year                    2023
_chemical_formula_moiety         'C192 H144 Fe4 N36'
_chemical_formula_sum            'C200 H144 F24 Fe4 N36 O24 S8'
_chemical_formula_weight         4371.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2d2tv5
_audit_creation_date             2022-09-06
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-09-14 deposited with the CCDC.	2023-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   38.3429(5)
_cell_length_b                   18.0379(4)
_cell_length_c                   37.1508(6)
_cell_measurement_reflns_used    24307
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      75.6010
_cell_measurement_theta_min      2.3770
_cell_volume                     25694.4(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_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    -70.00 -31.00   0.50  120.00    --  -43.18 130.00-137.00   78
  2  \w   -118.00 -30.00   0.50  120.00    --  -43.18 -49.00-154.00  176
  3  \w    -67.00 -42.00   0.50  430.00    --  -96.00  72.00 160.00   50
  4  \w     46.00  85.00   0.50  430.00    --  117.50-140.00 -22.00   78
  5  \w    108.00 138.00   0.50  430.00    --  117.50  49.00  -6.00   60
  6  \w    153.00 178.00   0.50  430.00    --  117.50  49.00  -6.00   50
  7  \w    115.00 166.00   0.50  430.00    --  117.50 130.00-137.00  102
  8  \w    141.00 174.00   0.50  430.00    --  117.50  72.00 160.00   66
  9  \w    -54.00 -15.00   0.50  120.00    --  -43.18 125.00  60.00   78
 10  \w     -3.00  23.00   0.50  120.00    --   43.18 -72.00  30.00   52
 11  \w     21.00  76.00   0.50  120.00    --   43.18 -99.00-120.00  110
 12  \w    -53.00 -23.00   0.50  430.00    --  -96.00  77.00-120.00   60
 13  \w    -51.00 -26.00   0.50  430.00    --  -96.00  61.00-120.00   50
 14  \w     45.00  72.00   0.50  430.00    --  117.50 -77.00 120.00   54
 15  \w     48.00  74.00   0.50  430.00    --  117.50 -77.00 -60.00   52
 16  \w    109.00 136.00   0.50  430.00    --  117.50  15.00  90.00   54
 17  \w    103.00 136.00   0.50  430.00    --  117.50  15.00 120.00   66
 18  \w    103.00 131.00   0.50  430.00    --  117.50  15.00 -60.00   56
 19  \w     44.00  73.00   0.50  430.00    --  117.50 -77.00 -30.00   58
 20  \w     47.00  75.00   0.50  430.00    --  117.50 -77.00  60.00   56
 21  \w    107.00 133.00   0.50  430.00    --  117.50  15.00 -30.00   52
 22  \w    104.00 161.00   0.50  430.00    --  117.50  30.00 150.00  114
;
_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      -0.0029364000
_diffrn_orient_matrix_UB_12      0.0848127000
_diffrn_orient_matrix_UB_13      0.0039318000
_diffrn_orient_matrix_UB_21      0.0321337000
_diffrn_orient_matrix_UB_22      0.0098030000
_diffrn_orient_matrix_UB_23      -0.0244354000
_diffrn_orient_matrix_UB_31      -0.0239534000
_diffrn_orient_matrix_UB_32      0.0028331000
_diffrn_orient_matrix_UB_33      -0.0332579000
_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  0.0596
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            88529
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         2.379
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.040
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57651
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.130
_exptl_crystal_description       block
_exptl_crystal_F_000             8944
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.613
_refine_diff_density_min         -0.448
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.455(8)
_refine_ls_extinction_coef       0.00019(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.185
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2091
_refine_ls_number_reflns         36631
_refine_ls_number_restraints     3877
_refine_ls_restrained_S_all      1.182
_refine_ls_R_factor_all          0.1630
_refine_ls_R_factor_gt           0.1165
_refine_ls_shift/su_max          0.067
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3123
_refine_ls_wR_factor_ref         0.3504
_reflns_Friedel_coverage         0.968
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                21859
_reflns_number_total             36631
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01569f2.cif
_cod_data_source_block           mcconnell34a
_cod_original_cell_volume        25694.5(7)
_cod_database_code               7713779
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C200H144N36Fe4F24S8O24
_chemical_oxdiff_usercomment     'Tobias Paschelke tp119'
_reflns_odcompleteness_completeness 80.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.545(8)
 0.455(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Fe1-N1
 2 with sigma of 0.02
 Fe1-N3
 2 with sigma of 0.02
 Fe1-N1A
 2 with sigma of 0.02
 Fe1-N3A
 2 with sigma of 0.02
 Fe1-N1B
 2 with sigma of 0.02
 Fe1-N3B
 2 with sigma of 0.02
 Fe2-N4
 2 with sigma of 0.02
 Fe2-N5
 2 with sigma of 0.02
 Fe2-N1C
 2 with sigma of 0.02
 Fe2-N3C
 2 with sigma of 0.02
 Fe2-N4E
 2 with sigma of 0.02
 Fe2-N5E
 2 with sigma of 0.02
 Fe3-N4A
 2 with sigma of 0.02
 Fe3-N5A
 2 with sigma of 0.02
 Fe3-N1D
 2 with sigma of 0.02
 Fe3-N3D
 2 with sigma of 0.02
 Fe3-N1E
 2 with sigma of 0.02
 Fe3-N3E
 2 with sigma of 0.02
 Fe4-N4B
 2 with sigma of 0.02
 Fe4-N5B
 2 with sigma of 0.02
 Fe4-N4C
 2 with sigma of 0.02
 Fe4-N5C
 2 with sigma of 0.02
 Fe4-N4D
 2 with sigma of 0.02
 Fe4-N5D
 2 with sigma of 0.02
4. Restrained planarity
 C1A, C2A, C3A, C4A, C5A, C6A
 with sigma of 0.0001
 C14E, C15E, C16E, C17E, C18E, C19E
 with sigma of 0.0001
5. Rigid body (RIGU) restrains
 N1, C1, C2, C3, C4, C5, C6, N2, C7, C8, C9, N3, C10, C11, C12, C13, C14, C15,
 C16, C17, C18, C19, C20, C21, N4, C22, C23, C24, C25, N5, C26, C27, C28, C29,
 C30, C31, N6, C32
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 N1A, C1A, C2A, C3A, C4A, C5A, C6A, N2A, C7A, C8A, C9A, N3A, C10A, C11A, C12A,
 C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, N4A, C22A, C23A, C24A,
 C25A, N5A, C26A, C27A, C28A, C29A, C30A, C31A, N6A, C32A
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 N1B, C1B, C2B, C3B, C4B, C5B, C6B, N2B, C7B, C8B, C9B, N3B, C10B, C11B, C12B,
 C13B, C14B, C15B, C16B, C17B, C18B, C19B, C20B, C21B, N4B, C22B, C23B, C24B,
 C25B, N5B, C26B, C27B, C28B, C29B, C30B, C31B, N6B, C32B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 N1C, C1C, C2C, C3C, C4C, C5C, C6C, N2C, C7C, C8C, C9C, N3C, C10C, C11C, C12C,
 C13C, C14C, C15C, C16C, C17C, C18C, C19C, C20C, C21C, N4C, C22C, C23C, C24C,
 C25C, N5C, C26C, C27C, C28C, C29C, C30C, C31C, N6C, C32C
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 N1D, C1D, C2D, C3D, C4D, C5D, C6D, N2D, C7D, C8D, C9D, N3D, C10D, C11D, C12D,
 C13D, C14D, C15D, C16D, C17D, C18D, C19D, C20D, C21D, N4D, C22D, C23D, C24D,
 C25D, N5D, C26D, C27D, C28D, C29D, C30D, C31D, N26D, C32D
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 N1E, C1E, C2E, C3E, C4E, C5E, C6E, N2E, C7E, C8E, C9E, N3E, C10E, C11E, C12E,
 C13E, C14E, C15E, C16E, C17E, C18E, C19E, C20E, C21E, N4E, C22E, C23E, C24E,
 C25E, N5E, C26E, C27E, C28E, C29E, C30E, C31E, N6E, C32E
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 Fe1, N1, N3, N1A, N3A, N1B, N3B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 Fe2, N4, N5, N1C, N3C, N4E, N5E
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 Fe3, N4A, N5A, N1D, N3D, N1E, N3E
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 Fe4, N4B, N5B, N4C, N5C, N4D, N5D
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
6. Same fragment restrains
{N1, C1, C2, C3, C4, C5, C6, N2, C7, C8, C9, N3, C10, C11, C12, C13, C14, C15,
C16, C17, C18, C19, C20, C21, N4, C22, C23, C24, C25, N5, C26, C27, C28, C29,
C30, C31, N6, C32} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1A, C1A, C2A, C3A, C4A, C5A, C6A, N2A, C7A, C8A, C9A, N3A, C10A, C11A, C12A,
C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, N4A, C22A, C23A, C24A,
C25A, N5A, C26A, C27A, C28A, C29A, C30A, C31A, N6A, C32A}
{N1, C1, C2, C3, C4, C5, C6, N2, C7, C8, C9, N3, C10, C11, C12, C13, C14, C15,
C16, C17, C18, C19, C20, C21, N4, C22, C23, C24, C25, N5, C26, C27, C28, C29,
C30, C31, N6, C32} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1B, C1B, C2B, C3B, C4B, C5B, C6B, N2B, C7B, C8B, C9B, N3B, C10B, C11B, C12B,
C13B, C14B, C15B, C16B, C17B, C18B, C19B, C20B, C21B, N4B, C22B, C23B, C24B,
C25B, N5B, C26B, C27B, C28B, C29B, C30B, C31B, N6B, C32B}
{N1, C1, C2, C3, C4, C5, C6, N2, C7, C8, C9, N3, C10, C11, C12, C13, C14, C15,
C16, C17, C18, C19, C20, C21, N4, C22, C23, C24, C25, N5, C26, C27, C28, C29,
C30, C31, N6, C32} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1C, C1C, C2C, C3C, C4C, C5C, C6C, N2C, C7C, C8C, C9C, N3C, C10C, C11C, C12C,
C13C, C14C, C15C, C16C, C17C, C18C, C19C, C20C, C21C, N4C, C22C, C23C, C24C,
C25C, N5C, C26C, C27C, C28C, C29C, C30C, C31C, N6C, C32C}
{N1, C1, C2, C3, C4, C5, C6, N2, C7, C8, C9, N3, C10, C11, C12, C13, C14, C15,
C16, C17, C18, C19, C20, C21, N4, C22, C23, C24, C25, N5, C26, C27, C28, C29,
C30, C31, N6, C32} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1D, C1D, C2D, C3D, C4D, C5D, C6D, N2D, C7D, C8D, C9D, N3D, C10D, C11D, C12D,
C13D, C14D, C15D, C16D, C17D, C18D, C19D, C20D, C21D, N4D, C22D, C23D, C24D,
C25D, N5D, C26D, C27D, C28D, C29D, C30D, C31D, N26D, C32D}
{N1, C1, C2, C3, C4, C5, C6, N2, C7, C8, C9, N3, C10, C11, C12, C13, C14, C15,
C16, C17, C18, C19, C20, C21, N4, C22, C23, C24, C25, N5, C26, C27, C28, C29,
C30, C31, N6, C32} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1E, C1E, C2E, C3E, C4E, C5E, C6E, N2E, C7E, C8E, C9E, N3E, C10E, C11E, C12E,
C13E, C14E, C15E, C16E, C17E, C18E, C19E, C20E, C21E, N4E, C22E, C23E, C24E,
C25E, N5E, C26E, C27E, C28E, C29E, C30E, C31E, N6E, C32E}
7.a Riding coordinates:
 C7(H7A,H7B,H7C), C32(H32A,H32B,H32C), C7A(H7AA,H7AB,H7AC), C32A(H32D,H32E,
 H32F), C7B(H7BA,H7BB,H7BC), C32B(H32G,H32H,H32I), C7C(H7CA,H7CB,H7CC),
 C32C(H32J,H32K,H32L), C7D(H7DA,H7DB,H7DC), C32D(H32M,H32N,H32O), C7E(H7EA,H7EB,
 H7EC), C32E(H32P,H32Q,H32R)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C12(H12), C13(H13), C15(H15),
 C16(H16), C18(H18), C19(H19), C21(H21), C23(H23), C24(H24), C27(H27), C28(H28),
  C29(H29), C30(H30), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C10A(H10A),
 C12A(H12A), C13A(H13A), C15A(H15A), C16A(H16A), C18A(H18A), C19A(H19A),
 C21A(H21A), C23A(H23A), C24A(H24A), C27A(H27A), C28A(H28A), C29A(H29A),
 C30A(H30A), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B), C10B(H10B), C12B(H12B),
 C13B(H13B), C15B(H15B), C16B(H16B), C18B(H18B), C19B(H19B), C21B(H21B),
 C23B(H23B), C24B(H24B), C27B(H27B), C28B(H28B), C29B(H29B), C30B(H30B),
 C2C(H2C), C3C(H3C), C4C(H4C), C5C(H5C), C10C(H10C), C12C(H12C), C13C(H13C),
 C15C(H15C), C16C(H16C), C18C(H18C), C19C(H19C), C21C(H21C), C23C(H23C),
 C24C(H24C), C27C(H27C), C28C(H28C), C29C(H29C), C30C(H30C), C2D(H2D), C3D(H3D),
  C4D(H4D), C5D(H5D), C10D(H10D), C12D(H12D), C13D(H13D), C15D(H15D),
 C16D(H16D), C18D(H18D), C19D(H19D), C21D(H21D), C23D(H23D), C24D(H24D),
 C27D(H27D), C28D(H28D), C29D(H29D), C30D(H30D), C2E(H2E), C3E(H3E), C4E(H4E),
 C5E(H5E), C10E(H10E), C12E(H12E), C13E(H13E), C15E(H15E), C16E(H16E),
 C18E(H18E), C19E(H19E), C21E(H21E), C23E(H23E), C24E(H24E), C27E(H27E),
 C28E(H28E), C29E(H29E), C30E(H30E)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              57893
_shelx_fab_checksum              78013
_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 1.970
_oxdiff_exptl_absorpt_empirical_full_min 0.652