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_4129164
_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             2018-08-09
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.571(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   28.4475(3)
_cell_length_b                   21.1969(2)
_cell_length_c                   29.3353(4)
_cell_measurement_reflns_used    11493
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      23.33
_cell_measurement_theta_min      1.57
_cell_volume                     17671.3(3)
_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      250(2)
_diffrn_measured_fraction_theta_full 0.772
_diffrn_measured_fraction_theta_max 0.752
_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  0.0337
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            36842
_diffrn_reflns_theta_full        24.82
_diffrn_reflns_theta_max         25.07
_diffrn_reflns_theta_min         1.33
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.766
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.970
_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    1.575
_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         0.768
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1271
_refine_ls_number_reflns         12946
_refine_ls_number_restraints     194
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0947
_refine_ls_R_factor_gt           0.0799
_refine_ls_shift/su_max          0.056
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2479
_refine_ls_wR_factor_ref         0.2638
_reflns_number_gt                9414
_reflns_number_total             12946
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b08862_si_007.cif
_cod_data_source_block           ic78250
_cod_depositor_comments
'Adding full bibliography for 4129157--4129168.cif.'
_cod_database_code               4129164
_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
 B111-F12A = B111-F13A = B111-F14A = B111-F15A
 1.38598 with sigma of 0.02
 B111-F12B = B111-F13B = B111-F14B = B111-F15B
 1.38598 with sigma of 0.02
 B111-F12C = B111-F13C = B111-F14C = B111-F15C
 1.38598 with sigma of 0.02
 B111-F12D = B111-F13D = B111-F14D = B111-F15D
 1.38598 with sigma of 0.02
 F12A-F13A = F12A-F14A = F12A-F15A = F13A-F14A = F13A-F15A = F14A-F15A
 2.263305 with sigma of 0.02
 F12B-F13B = F12B-F14B = F12B-F15B = F13B-F14B = F13B-F15B = F14B-F15B
 2.263305 with sigma of 0.02
 F12C-F13C = F12C-F14C = F12C-F15C = F13C-F14C = F13C-F15C = F14C-F15C
 2.263305 with sigma of 0.02
 F12D-F13D = F12D-F14D = F12D-F15D = F13D-F14D = F13D-F15D = F14D-F15D
 2.263305 with sigma of 0.02
 B16A-F17A = B16A-F18A = B16A-F19A = B16A-F20A
 1.38598 with sigma of 0.02
 B16B-F17B = B16B-F18B = B16B-F19B = B16B-F20B
 1.38598 with sigma of 0.02
 B16C-F17C = B16C-F18C = B16C-F19C = B16C-F20C
 1.38598 with sigma of 0.02
 F17A-F18A = F17A-F19A = F17A-F20A = F18A-F19A = F18A-F20A = F19A-F20A
 2.263305 with sigma of 0.02
 F17B-F18B = F17B-F19B = F17B-F20B = F18B-F19B = F18B-F20B = F19B-F20B
 2.263305 with sigma of 0.02
 F17C-F18C = F17C-F19C = F17C-F20C = F18C-F19C = F18C-F20C = F19C-F20C
 2.263305 with sigma of 0.02
 B21A-F22A = B21A-F23A = B21A-F24A = B21A-F25A
 1.38598 with sigma of 0.02
 B21A-F22B = B21A-F23B = B21A-F24B = B21A-F25B
 1.38598 with sigma of 0.02
 B21C-F22C = B21C-F23C = B21C-F24C = B21C-F25C
 1.38598 with sigma of 0.02
 F22A-F23A = F22A-F24A = F22A-F25A = F23A-F24A = F23A-F25A = F24A-F25A
 2.263305 with sigma of 0.02
 F22B-F23B = F22B-F24B = F22B-F25B = F23B-F24B = F23B-F25B = F24B-F25B
 2.263305 with sigma of 0.02
 F22C-F23C = F22C-F24C = F22C-F25C = F23C-F24C = F23C-F25C = F24C-F25C
 2.263305 with sigma of 0.02
 B26A-F27A = B26A-F28A = B26A-F29A = B26A-F30A
 1.38598 with sigma of 0.02
 B26B-F27B = B26B-F28B = B26B-F29B = B26B-F30B
 1.38598 with sigma of 0.02
 F27A-F28A = F27A-F29A = F27A-F30A = F28A-F29A = F28A-F30A = F29A-F30A
 2.263305 with sigma of 0.02
 F27B-F28B = F27B-F29B = F27B-F30B = F28B-F29B = F28B-F30B = F29B-F30B
 2.263305 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-N39C
 1.15 with sigma of 0.02
 C37A-N39C = C37B-N39C
 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
3. Uiso/Uaniso restraints and constraints
F12A \\sim F13A \\sim F14A \\sim F15A \\sim F12B \\sim F13B \\sim F14B \\sim F15B \\sim F12C \\sim F13C \\sim F14C \\sim F15C \\sim F12D \\sim F13D \\sim F14D \\sim F15D: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
B26A \\sim F27A \\sim F28A \\sim F29A \\sim F30A \\sim B26B \\sim F27B \\sim F28B \\sim F29B \\sim F30B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Others
 1(DFIX)=1(DFIX)=1(DFIX)=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(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) F12A(0.25) F13A(0.25) F14A(0.25)
 F15A(0.25) F12B(0.25) F13B(0.25) F14B(0.25) F15B(0.25) F12C(0.25) F13C(0.25)
 F14C(0.25) F15C(0.25) F12D(0.25) F13D(0.25) F14D(0.25) F15D(0.25) 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(0.8) F22A(0.4) F23A(0.4) F24A(0.4) F25A(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)
 B26A(0.35) F27A(0.35) F28A(0.35) F29A(0.35) F30A(0.35) B26B(0.15) F27B(0.15)
 F28B(0.15) F29B(0.15) F30B(0.15) C31A(0.25) H31C(0.25) H31D(0.25) H31E(0.25)
 C32A(0.25) N33A(0.25) C31B(0.5) H28B(0.5) H31A(0.5) H31B(0.5) C32B(0.5)
 N33B(0.5) 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) C37B(0.5) H37D(0.5)
 H37E(0.5) H37F(0.5) C38B(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)
5.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)
5.b Idealised Me refined as rotating group:
 C31A(H31C,H31D,H31E), C31B(H28B,H31A,H31B), C134(H13A,H13B,H13C), C37A(H37A,
 H37B,H37C), C37B(H37D,H37E,H37F), C40C(H40C,H40D,H40E), C40D(H40F,H40G,H40H)
;