Supramolecular Iron Metallocubanes Exhibiting Site-Selective Thermal and Light-Induced Spin-Crossover.
Berdiell, Izar Capel; Hochdörffer, Tim; Desplanches, Cédric; Kulmaczewski, Rafal; Shahid, Namrah; Wolny, Juliusz A.; Warriner, Stuart L.; Cespedes, Oscar; Schünemann, Volker; Chastanet, Guillaume; Halcrow, Malcolm A.; Journal of the American Chemical Society 141 (2019) 18759–18770; doi:10.1021/jacs.9b08862

data_4129161
_publ_section_title
;
 Supramolecular Iron Metallocubanes Exhibiting Site-Selective Thermal and
 Light-Induced Spin-Crossover.
;
_journal_issue                   47
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              18759
_journal_page_last               18770
_journal_paper_doi               10.1021/jacs.9b08862
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C144 H132 Fe8 N72 O12, H12 Fe O6, 7(B F4), 2.5(C2 H3 N), 2.5(C4 H10 O)'
_chemical_formula_sum            'C159 H176.5 B7 F28 Fe9 N74.5 O20.5'
_chemical_formula_weight         4569.57
_chemical_name_systematic
;
Dodecakis-[4,6-di(4-methylpyrazol-1-yl)-2-hydroxypyrimidinate]octa-iron(II) 
hexa-aqua-iron(III) hepta-tetrafluoroborate acetonitrile diethyl ether 
solvate
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-03-14
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 99.479(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   17.2790(4)
_cell_length_b                   24.2218(5)
_cell_length_c                   25.7224(4)
_cell_measurement_reflns_used    17088
_cell_measurement_temperature    125(2)
_cell_measurement_theta_max      73.31
_cell_measurement_theta_min      3.80
_cell_volume                     10618.6(4)
_computing_cell_refinement       'CrysAlisPro, Agilent Technologies'
_computing_data_collection       'CrysAlisPro, Agilent Technologies'
_computing_data_reduction        'CrysAlisPro, Agilent Technologies'
_computing_molecular_graphics    'XSEED (Barbour, 2001)'
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      125(2)
_diffrn_detector_area_resol_mean 5.3095
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            47892
_diffrn_reflns_theta_full        72.00
_diffrn_reflns_theta_max         73.83
_diffrn_reflns_theta_min         3.82
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.646
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.161
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             4674
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.566
_refine_diff_density_min         -1.002
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1417
_refine_ls_number_reflns         20478
_refine_ls_number_restraints     69
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0759
_refine_ls_R_factor_gt           0.0665
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1282P)^2^+14.9845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1862
_refine_ls_wR_factor_ref         0.1957
_reflns_number_gt                17608
_reflns_number_total             20478
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b08862_si_008.cif
_cod_data_source_block           icb161fe
_cod_depositor_comments
'Adding full bibliography for 4129157--4129168.cif.'
_cod_original_formula_sum        'C159 H176.50 B7 F28 Fe9 N74.50 O20.50'
_cod_database_code               4129161
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 B38A-F39A = B38A-F40A = B38A-F41A = B38A-F42A
 1.37 with sigma of 0.02
 B38B-F39B = B38B-F40B = B38B-F41B = B38B-F42B
 1.37 with sigma of 0.02
 B38C-F39C = B38C-F40C = B38C-F41C = B38C-F42C
 1.37 with sigma of 0.02
 F39A-F40A = F39A-F41A = F39A-F42A = F40A-F41A = F40A-F42A = F41A-F42A
 2.24 with sigma of 0.02
 F39B-F40B = F39B-F41B = F39B-F42B = F40B-F41B = F40B-F42B = F41B-F42B
 2.24 with sigma of 0.02
 F39C-F40C = F39C-F41C = F39C-F42C = F40C-F41C = F40C-F42C = F41C-F42C
 2.24 with sigma of 0.02
 C149-C150 = C152-C153 = C154-C155 = C157-C158
 1.52 with sigma of 0.02
 C150-O151 = O151-C152 = C155-O156 = O156-C157
 1.43 with sigma of 0.02
 C150-C152 = C155-C157
 2.34 with sigma of 0.02
 C149-O151 = O151-C153 = C154-O156 = O156-C158
 2.42 with sigma of 0.02
 C162-C163 = C165-C166
 1.52 with sigma of 0.02
 C163-O164 = O164-C165
 1.43 with sigma of 0.02
 C163-C165
 2.34 with sigma of 0.02
 C162-O164 = O164-C166
 2.42 with sigma of 0.02
 C159-C160
 1.48 with sigma of 0.02
 C160-N161
 1.15 with sigma of 0.02
 C159-N161
 2.63 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F39A \\sim F40A \\sim F41A \\sim F42A \\sim F39B \\sim F40B \\sim F41B \\sim F42B \\sim F39C \\sim F40C \\sim F41C \\sim F42C: within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: B38A(0.17) F39A(0.17) F40A(0.17) F41A(0.17) F42A(0.17) B38B(0.17)
 F39B(0.17) F40B(0.17) F41B(0.17) F42B(0.17) B38C(0.16) F39C(0.16) F40C(0.16)
 F41C(0.16) F42C(0.16) C143(0.5) H14D(0.5) H14E(0.5) H14F(0.5) C144(0.5)
 N145(0.5) C146(0.5) H14G(0.5) H14H(0.5) H14I(0.5) C147(0.5) N148(0.5)
 C149(0.5) H14A(0.5) H14B(0.5) H14C(0.5) O151(0.5) C152(0.5) H15A(0.5)
 H15B(0.5) C153(0.5) H15C(0.5) H15D(0.5) H15E(0.5) C154(0.5) H15H(0.5)
 H15I(0.5) H15J(0.5) C155(0.5) H15K(0.5) H15L(0.5) O156(0.5) C157(0.5)
 H15M(0.5) H15N(0.5) C158(0.5) H15O(0.5) H15P(0.5) H15Q(0.5) C150(0.5)
 H15F(0.5) H15G(0.5) C159(0.25) H15R(0.25) H15S(0.25) H15T(0.25) C160(0.25)
 N161(0.25) C162(0.25) H16A(0.25) H16B(0.25) H16C(0.25) C163(0.25) H16D(0.25)
 H16E(0.25) O164(0.25) C165(0.25) H16F(0.25) H16G(0.25) C166(0.25) H16H(0.25)
 H16I(0.25) H16J(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C152(H15A,H15B), C155(H15K,H15L), C157(H15M,H15N), C150(H15F,H15G), C163(H16D,
 H16E), C165(H16F,H16G)
5.b Me refined with riding coordinates:
 C149(H14A,H14B,H14C), C153(H15C,H15D,H15E), C154(H15H,H15I,H15J), C158(H15O,
 H15P,H15Q), C162(H16A,H16B,H16C), C166(H16H,H16I,H16J)
5.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C18(H18), C20(H20), C24(H24), C26(H26), C32(H32), C37(H37),
 C39(H39), C43(H43), C45(H45), C51(H51), C56(H56), C58(H58), C62(H62), C64(H64),
  C70(H70), C75(H75), C77(H77), C81(H81), C83(H83), C89(H89), C94(H94),
 C96(H96), C100(H100), C102(H102), C108(H108), C113(H113), C115(H115),
 C119(H119), C121(H121)
5.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C27(H27A,H27B,H27C), C40(H40A,H40B,H40C), C46(H46A,H46B,
 H46C), C59(H59A,H59B,H59C), C65(H65A,H65B,H65C), C78(H78A,H78B,H78C), C84(H84A,
 H84B,H84C), C97(H97A,H97B,H97C), C103(H10A,H10B,H10C), C116(H11A,H11B,H11C),
 C122(H12A,H12B,H12C), C143(H14D,H14E,H14F), C146(H14G,H14H,H14I), C159(H15R,
 H15S,H15T)
;