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_4129160
_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
'C120 H84 Fe8 N72 O12, H12 Fe O6, 7(B F4), 6(C2 H3 N)'
_chemical_formula_sum            'C132 H114 B7 F28 Fe9 N78 O18'
_chemical_formula_weight         4191.33
_chemical_name_systematic
;
Dodecakis-[4,6-di(pyrazol-1-yl)-2-hydroxypyrimidinate]octa-iron(II) 
hexa-aqua-iron(III) hepta-tetrafluoroborate hexa-acetonitrile solvate
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-06-05
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 93.17(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   28.138(12)
_cell_length_b                   20.942(11)
_cell_length_c                   29.140(17)
_cell_measurement_reflns_used    13269
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.20
_cell_measurement_theta_min      1.61
_cell_volume                     17145(15)
_computing_cell_refinement       'XIA2 0.4.0.438-g4431aaa (Winter, 2010)'
_computing_data_reduction        'XIA2 0.4.0.438-g4431aaa (Winter, 2010)'
_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      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Fluid Film Devices'
_diffrn_measurement_method       'shutterless scans'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_radiation_source         'Diamond Light Source station I19'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.68890
_diffrn_reflns_av_R_equivalents  0.0617
_diffrn_reflns_av_unetI/netI     0.0404
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            125210
_diffrn_reflns_theta_full        24.82
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         1.18
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.789
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.971
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CCP4 7.0.027: AIMLESS, version 0.5.31 

Scaling & analysis of unmerged intensities,
absorption correction using spherical harmonics
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.624
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       'square prism'
_exptl_crystal_F_000             8468
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.489
_refine_diff_density_min         -0.839
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1254
_refine_ls_number_reflns         21605
_refine_ls_number_restraints     117
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0805
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1903P)^2^+7.7348P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2590
_refine_ls_wR_factor_ref         0.2741
_reflns_number_gt                15952
_reflns_number_total             21605
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b08862_si_004.cif
_cod_data_source_block           ic78100
_cod_depositor_comments
'Adding full bibliography for 4129157--4129168.cif.'
_cod_database_code               4129160
_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, All O(H,H) groups
2. Restrained distances
 B11A-F112 = B11A-F13A = B11A-F14A = B11A-F15A
 1.39011 with sigma of 0.02
 B11B-F112 = B11B-F13B = B11B-F14B = B11B-F15B
 1.39011 with sigma of 0.02
 F112-F13A = F112-F14A = F112-F15A = F13A-F14A = F13A-F15A = F14A-F15A
 2.27005 with sigma of 0.02
 F112-F13B = F112-F14B = F112-F15B = F13B-F14B = F13B-F15B = F14B-F15B
 2.27005 with sigma of 0.02
 B16A-F17A = B16A-F18A = B16A-F19A = B16A-F20A
 1.39011 with sigma of 0.02
 B16B-F17B = B16B-F18B = B16B-F19B = B16B-F20B
 1.39011 with sigma of 0.02
 B16C-F17C = B16C-F18C = B16C-F19C = B16C-F20C
 1.39011 with sigma of 0.02
 F17A-F18A = F17A-F19A = F17A-F20A = F18A-F19A = F18A-F20A = F19A-F20A
 2.27005 with sigma of 0.02
 F17B-F18B = F17B-F19B = F17B-F20B = F18B-F19B = F18B-F20B = F19B-F20B
 2.27005 with sigma of 0.02
 F17C-F18C = F17C-F19C = F17C-F20C = F18C-F19C = F18C-F20C = F19C-F20C
 2.27005 with sigma of 0.02
 B21A-F22A = B21A-F23A = B21A-F24A = B21A-F25A
 1.39011 with sigma of 0.02
 B21B-F22B = B21B-F23B = B21B-F24B = B21B-F25B
 1.39011 with sigma of 0.02
 B21C-F22C = B21C-F23C = B21C-F24C = B21C-F25C
 1.39011 with sigma of 0.02
 F22A-F23A = F22A-F24A = F22A-F25A = F23A-F24A = F23A-F25A = F24A-F25A
 2.27005 with sigma of 0.02
 F22B-F23B = F22B-F24B = F22B-F25B = F23B-F24B = F23B-F25B = F24B-F25B
 2.27005 with sigma of 0.02
 F22C-F23C = F22C-F24C = F22C-F25C = F23C-F24C = F23C-F25C = F24C-F25C
 2.27005 with sigma of 0.02
 B126-F127 = B126-F128 = B126-F129 = B126-F130
 1.39011 with sigma of 0.02
 F127-F128 = F127-F129 = F127-F130 = F128-F129 = F128-F130 = F129-F130
 2.27005 with sigma of 0.02
 C31A-C32A = C31B-C32B
 1.48 with sigma of 0.02
 C32A-N33A = C32B-N33B
 1.15 with sigma of 0.02
 C31A-N33A = C31B-N33B
 2.63 with sigma of 0.02
 C37A-C38A = C37B-C38B
 1.48 with sigma of 0.02
 C38A-N39C = C38B-N39D
 1.15 with sigma of 0.02
 C37A-N39C = C37B-N39D
 2.63 with sigma of 0.02
 C40C-C41C = C40D-C41D
 1.48 with sigma of 0.02
 C41C-N42C = C41D-N42D
 1.15 with sigma of 0.02
 C40C-N42C = C40D-N42D
 2.63 with sigma of 0.02
 O6-H6A = O6-H6B = O7-H7A = O7-H7B = O8-H8A = O8-H8B
 0.9 with sigma of 0.01
 H6A-H6B = H7A-H7B = H8A-H8B
 1.56 with sigma of 0.01
3. Others
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1.633*
 FVAR(2)
 Fixed Sof: N16A(0.5) N17A(0.5) C18A(0.5) H18A(0.5) C19A(0.5) H19A(0.5)
 C20A(0.5) H20A(0.5) N16B(0.5) N17B(0.5) C18B(0.5) H18B(0.5) C19B(0.5)
 H19B(0.5) C20B(0.5) H20B(0.5) N38A(0.5) N39A(0.5) C40A(0.5) H40A(0.5)
 C41A(0.5) H41A(0.5) C42A(0.5) H42A(0.5) N38B(0.5) N39B(0.5) C40B(0.5)
 H40B(0.5) C41B(0.5) H41B(0.5) C42B(0.5) H42B(0.5) N50A(0.5) N51A(0.5)
 C52A(0.5) H52A(0.5) C53A(0.5) H53A(0.5) C54A(0.5) H54A(0.5) N50B(0.5)
 N51B(0.5) C52B(0.5) H52B(0.5) C53B(0.5) H53B(0.5) C54B(0.5) H54B(0.5)
 N84A(0.5) N85A(0.5) C86A(0.5) H86A(0.5) C87A(0.5) H87A(0.5) C88A(0.5)
 H88A(0.5) N84B(0.5) N85B(0.5) C86B(0.5) H86B(0.5) C87B(0.5) H87B(0.5)
 C88B(0.5) H88B(0.5) N01A(0.5) N02A(0.5) C03A(0.5) H03A(0.5) C04A(0.5)
 H04A(0.5) C05A(0.5) H05A(0.5) N01B(0.5) N02B(0.5) C03B(0.5) H03B(0.5)
 C04B(0.5) H04B(0.5) C05B(0.5) H05B(0.5) B11A(0.5) F13A(0.5) F14A(0.5)
 F15A(0.5) B11B(0.5) F13B(0.5) F14B(0.5) F15B(0.5) B16A(0.34) F17A(0.34)
 F18A(0.34) F19A(0.34) F20A(0.34) B16B(0.33) F17B(0.33) F18B(0.33) F19B(0.33)
 F20B(0.33) B16C(0.33) F17C(0.33) F18C(0.33) F19C(0.33) F20C(0.33) B21A(0.4)
 F22A(0.4) F23A(0.4) F24A(0.4) F25A(0.4) B21B(0.4) F22B(0.4) F23B(0.4)
 F24B(0.4) F25B(0.4) B21C(0.2) F22C(0.2) F23C(0.2) F24C(0.2) F25C(0.2)
 B126(0.5) F127(0.5) F128(0.5) F129(0.5) F130(0.5) C31A(0.5) H31A(0.5)
 H31B(0.5) H31C(0.5) C32A(0.5) N33A(0.5) C31B(0.25) H31D(0.25) H31E(0.25)
 H31F(0.25) C32B(0.25) N33B(0.25) C134(0.5) H13A(0.5) H13B(0.5) H13C(0.5)
 C135(0.5) N136(0.5) C37A(0.5) H37A(0.5) H37B(0.5) H37C(0.5) C38A(0.5)
 N39C(0.5) C37B(0.5) H37D(0.5) H37E(0.5) H37F(0.5) C38B(0.5) N39D(0.5)
 C40C(0.5) H40C(0.5) H40D(0.5) H40E(0.5) C41C(0.5) N42C(0.5) C40D(0.25)
 H40F(0.25) H40G(0.25) H40H(0.25) C41D(0.25) N42D(0.25)
4.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C18A(H18A), C19A(H19A), C20A(H20A), C18B(H18B), C19B(H19B),
 C20B(H20B), C23(H23), C24(H24), C25(H25), C30(H30), C35(H35), C36(H36),
 C37(H37), C40A(H40A), C41A(H41A), C42A(H42A), C40B(H40B), C41B(H41B),
 C42B(H42B), C47(H47), C52A(H52A), C53A(H53A), C54A(H54A), C52B(H52B),
 C53B(H53B), C54B(H54B), C57(H57), C58(H58), C59(H59), C64(H64), C69(H69),
 C70(H70), C71(H71), C74(H74), C75(H75), C76(H76), C81(H81), C86A(H86A),
 C87A(H87A), C88A(H88A), C86B(H86B), C87B(H87B), C88B(H88B), C91(H91), C92(H92),
  C93(H93), C98(H98), C03A(H03A), C04A(H04A), C05A(H05A), C03B(H03B),
 C04B(H04B), C05B(H05B), C108(H108), C109(H109), C110(H110)
4.b Idealised Me refined as rotating group:
 C31A(H31A,H31B,H31C), C31B(H31D,H31E,H31F), C134(H13A,H13B,H13C), C37A(H37A,
 H37B,H37C), C37B(H37D,H37E,H37F), C40C(H40C,H40D,H40E), C40D(H40F,H40G,H40H)
;