A large dinuclear Fe(ii) triple helicate demonstrating a two-step spin crossover.
Howard-Smith, Kyle J; Craze, Alexander R.; Zenno, Hikaru; Yagyu, Junya; Hayami, Shinya; Li, Feng; Chemical communications (Cambridge, England) 56 (2020) 8838–8841; doi:10.1039/d0cc03708g

data_7126791
_publ_section_title
;
 A large dinuclear Fe(ii) triple helicate demonstrating a two-step spin
 crossover.
;
_journal_issue                   62
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              8838
_journal_page_last               8841
_journal_paper_doi               10.1039/d0cc03708g
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety
'C96.27 H66.18 Fe2 N12 O6 S6, 4(B F4), 2.5(C2 H3 N), 0.5(C2 N), 0.25(O)'
_chemical_formula_sum            'C102.22 H75.65 B4 F16 Fe2 N15 O6.25 S6'
_chemical_formula_weight         2265.38
_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   geom
_audit_creation_date             2020-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-04-16 deposited with the CCDC.	2020-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.690(4)
_cell_length_b                   27.779(6)
_cell_length_c                   19.967(4)
_cell_measurement_reflns_used    7422
_cell_measurement_temperature    150
_cell_measurement_theta_max      20.00
_cell_measurement_theta_min      2.27
_cell_volume                     10921(4)
_computing_cell_refinement       XDS
_computing_data_collection       XDS
_computing_data_reduction        XDS
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'MX1 beamline Australian Synchrotron'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0646
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            170538
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.281
_diffrn_reflns_theta_min         1.256
_diffrn_source
'silicon double crystal monochromated radiation'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.467
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       prism
_exptl_crystal_F_000             4616
_exptl_crystal_preparation
'To a stirring suspension of 0.35 mmol of L, an excess of Fe(II)BF4.6H2O (0.23 mmol) in 10 mL of acetonitrile was added dropwise at room temperature. The reaction mixture was then stirred and heated to reflux for 3 hours.,Magnetic properties'
_exptl_crystal_recrystallization_method 'Diethyl ether vapour diffusion.'
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.886
_refine_diff_density_min         -0.719
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.53(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1576
_refine_ls_number_reflns         27015
_refine_ls_number_restraints     377
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0571
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1245P)^2^+2.3933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1733
_refine_ls_wR_factor_ref         0.1901
_reflns_Friedel_coverage         0.945
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                21543
_reflns_number_total             27015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03708g2.cif
_cod_data_source_block           fl665_150k_a
_cod_depositor_comments
'Adding full bibliography for 7126790--7126793.cif.'
_cod_database_code               7126791
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.991
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.47(3)
 0.53(3)
2. 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
3. Restrained distances
 F00X-F03S
 2.28987 with sigma of 0.02
 F00X-F00V
 2.28987 with sigma of 0.02
 F00X-F03N
 2.28987 with sigma of 0.02
 F03N-F03S
 2.28987 with sigma of 0.02
 F03N-F00V
 2.28987 with sigma of 0.02
 F03S-F00V
 2.28987 with sigma of 0.02
 F0-B03L
 1.40225 with sigma of 0.02
 F00X-B03T \\sim F00Y-B03T
 with sigma of 0.02
 F03N-B03T \\sim F03O-B03T
 with sigma of 0.02
 F03S-B03T \\sim F03T-B03T
 with sigma of 0.02
4. Restrained angles
 N03S-C4AA-C3AA
 fixed at 180 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(C03D) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N03S) \\sim Ueq, Uanis(F03T) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
6. Rigid body (RIGU) restrains
 C7C, C8C, C9C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11C, C12C, C13C, C14C, C15C, C16C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, C7, C8, C9, C10, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C13, C14, C15, C16, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22C, C21C, C20C, C19C, C18C, C17C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28C, C27C, C4, C3, C2, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27C, C28C, C23C, C24C, C25C, C26C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5C, C6C, C7C1, C8C1, C9C1, C10C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5C, C6C, C7C, C8C, C9C, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F03O
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F03N, F00X, F03S, B03T, F00V
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F00V, F03T, F00Y, F03O
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F00M, F03H, F0, F0AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F00M, F032, F03G, F03M
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4AA, N03S, C3AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C04C, C03D, N048
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32B, S2B, C31B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, S1A, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(C15)=Sof(H15)=Sof(C16)=
 Sof(H16)=Sof(C17)=1-FVAR(1)
 Fixed Sof: F00X(0.5) O7C(0.5) C23C(0.6) C24C(0.6) H24C(0.6) C25C(0.6)
 H25C(0.6) C26C(0.6) F032(0.75) O03A(0.5) C03D(0.5) F03G(0.75) C10C(0.5)
 C9C1(0.5) H9C1(0.5) C8C1(0.5) H8C1(0.5) C7C1(0.5) C9C(0.5) H9C(0.5) C8C(0.5)
 H8C(0.5) C7C(0.5) H6C(0.5) H6CA(0.5) H5C(0.5) H5CA(0.5) C1(0.5) F03M(0.25)
 F03N(0.75) F03S(0.5) N048(0.5) C04C(0.5) H04A(0.5) H04B(0.5) H04C(0.5)
 C17C(0.5) C22C(0.5) H22C(0.5) C21C(0.5) H21C(0.5) C20C(0.5) C19C(0.5)
 H19C(0.5) C18C(0.5) H18C(0.5) C13C(0.6) H13C(0.6) C14C(0.6) C15C(0.6)
 H15C(0.6) C16C(0.6) H16C(0.6) C11C(0.6) C12C(0.6) H12C(0.6) C2(0.4) H2(0.4)
 C3(0.4) H3(0.4) C4(0.4) H27C(0.6) H27D(0.4) H28C(0.6) H28D(0.4) C5(0.4)
 C6(0.4) H6(0.4) C7(0.4) H7(0.4) C8(0.4) C9(0.4) H9(0.4) C10(0.4) H10(0.4)
 C11(0.4) O8C1(0.5) O7C1(0.5) F03O(0.5) F03T(0.25) F00Y(0.5) F03H(0.25)
 F0AA(0.5) F0(0.5) C3AA(0.5) N03S(0.5) C4AA(0.5) O1(0.25)
8.a Aromatic/amide H refined with riding coordinates:
 C29C(H29C), C15A(H15A), C13B(H13B), C31C(H31C), C4A(H4A), C25A(H25A),
 C32A(H32A), C29A(H29A), C16A(H16A), C12B(H12B), C22A(H22A), C19A(H19A),
 C22B(H22B), C13A(H13A), C24A(H24A), C7B(H7B), C31B(H31B), C6B(H6B), C25B(H25B),
  C9B(H9B), C31A(H31A), C27A(H27A), C19B(H19B), C21B(H21B), C21A(H21A),
 C6A(H6A), C1C(H1C), C7A(H7A), C18A(H18A), C15B(H15B), C27B(H27B), C32C(H32C),
 C28A(H28A), C24C(H24C), C25C(H25C), C12A(H12A), C16B(H16B), C28B(H28B),
 C32B(H32B), C10B(H10B), C1A(H1A), C29B(H29B), C9A(H9A), C4C(H4C), C4B(H4B),
 C18B(H18B), C24B(H24B), C1B(H1B), C2C(H2C), C10A(H10A), C2A(H2A), C9C1(H9C1),
 C8C1(H8C1), C9C(H9C), C8C(H8C), C6C(H6C), C6C(H6CA), C5C(H5C), C5C(H5CA),
 C2B(H2B), C22C(H22C), C21C(H21C), C19C(H19C), C18C(H18C), C13C(H13C),
 C15C(H15C), C16C(H16C), C12C(H12C), C2(H2), C3(H3), C27C(H27C), C27C(H27D),
 C28C(H28C), C28C(H28D), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C16(H16)
8.b Fitted hexagon refined as free rotating group:
 C9C(C8C,C7C,C6C,C5C,C1), C17C(C22C,C21C,C20C,C19C,C18C), C13C(C14C,C15C,C16C,
 C11C,C12C), C2(C3,C4,C27C,C28C,C5), C6(C7,C8,C9,C10,C11), C12(C13,C14,C15,C16,
 C17)
8.c Idealised Me refined as rotating group:
 C02U(H02A,H02B,H02C), C03Y(H03A,H03B,H03C), C04C(H04A,H04B,H04C)
;
_shelx_fab_file                  -28
_olex2_exptl_crystal_mounting_method
'Cold mounted in a CO2 atmosphere in cryotox crystallographic oil. '
_olex2_submission_special_instructions 'No special instructions were received'