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_7126790
_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 H66 Fe2 N12 O6 S6, 4(B F4), 0.5(C2 N), 3.5(C2 H3 N), 0.5(C O)'
_chemical_formula_sum            'C104.5 H76.5 B4 F16 Fe2 N16 O6.5 S6'
_chemical_formula_weight         2311.61
_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             2020-03-23
_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                   19.637(4)
_cell_length_b                   27.707(6)
_cell_length_c                   19.921(4)
_cell_measurement_reflns_used    7353
_cell_measurement_temperature    100
_cell_measurement_theta_max      20.00
_cell_measurement_theta_min      2.27
_cell_volume                     10839(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      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.895
_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  0.0455
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            193699
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.246
_diffrn_reflns_theta_min         1.259
_diffrn_source
'silicon double crystal monochromated radiation'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.472
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.417
_exptl_crystal_description       prism
_exptl_crystal_F_000             4718
_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         1.286
_refine_diff_density_min         -1.015
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.51(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1598
_refine_ls_number_reflns         34115
_refine_ls_number_restraints     316
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0688
_refine_ls_R_factor_gt           0.0582
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1209P)^2^+4.3370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1770
_refine_ls_wR_factor_ref         0.1904
_reflns_Friedel_coverage         0.951
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.895
_reflns_number_gt                28205
_reflns_number_total             34115
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03708g2.cif
_cod_data_source_block           fl665_a
_cod_depositor_comments
'Adding full bibliography for 7126790--7126793.cif.'
_cod_original_formula_sum        'C104.50 H76.50 B4 F16 Fe2 N16 O6.50 S6'
_cod_database_code               7126790
_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: 0.49(2)
 0.51(2)
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
 O2C1-C18C
 1.415 with sigma of 0.01
 B03R-F00J = B03R-F02C = B03R-F02D = B03R-F02H = B03R-F0AA = B03R-F02E
 1.32 with sigma of 0.02
 F02E-F0AA
 2.28987 with sigma of 0.02
 F02{-F01I
 2.28987 with sigma of 0.02
 F02{-F03X
 2.28987 with sigma of 0.02
 F03X-F01I
 2.28987 with sigma of 0.02
 F03W-F01H
 2.28987 with sigma of 0.02
 F03W-F02Z
 2.28987 with sigma of 0.02
 F02Z-F01H
 2.28987 with sigma of 0.02
 F02H-F02D
 2.28987 with sigma of 0.02
 F02H-F02C
 2.28987 with sigma of 0.02
 F1AA-B03R
 1.40225 with sigma of 0.01
 F1AA-F0AA
 2.28987 with sigma of 0.01
 F1AA-F02E
 2.28987 with sigma of 0.01
 F1AA-F00J
 2.28987 with sigma of 0.01
 F0AA-F02E
 2.28987 with sigma of 0.01
 F0AA-F00J
 2.28987 with sigma of 0.01
 F02E-F00J
 2.28987 with sigma of 0.01
 F02C-F02D
 2.28987 with sigma of 0.01
 F02C-F02H
 2.28987 with sigma of 0.01
 F02C-F00J
 2.28987 with sigma of 0.01
 F02D-F02H
 2.28987 with sigma of 0.01
 F02D-F00J
 2.28987 with sigma of 0.01
 N0AA-C15
 1.12 with sigma of 0.02
 O1-C7AB
 1.45 with sigma of 0.02
 F01H-B03P \\sim F01I-B03P
 with sigma of 0.02
 F02Z-B03P \\sim F02{-B03P
 with sigma of 0.02
 B03P-F03W \\sim B03P-F03X
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 N039, C02Y, C049
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8, C9, C10, C11, C21C, C22C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15C, C16C, C17C, C18C, C19C, C20C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9C2, C10C, C11C, C12C, C13C, C14C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1C, C2, C8C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1C1, C8C2, C9C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5C, C6C, C7C, C8C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5C2, C6C2, C7C2, C8C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28C, C29C, C12, C13, C14, C23C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28C, C29C, C24C, C25C, C26C, C27C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C02Y
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F02C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N048, C03T, C046
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N039
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N0AA, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, C7AB
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O1C)=1-FVAR(1)
 Sof(O1C1)=FVAR(1)
 Fixed Sof: O2C1(0.4) C6C2(0.4) H6C2(0.4) C5C2(0.4) H1AA(0.4) H1BB(0.6)
 H9C(0.4) H9CA(0.6) C8C2(0.4) C7C2(0.4) H7C2(0.4) C9C2(0.4) C10C(0.4) H10C(0.4)
 C11C(0.4) H11C(0.4) C12C(0.4) C13C(0.4) H13C(0.4) C14C(0.4) H14C(0.4) C12(0.4)
 H29D(0.6) H29C(0.4) H28C(0.4) H28D(0.6) C13(0.4) C23C(0.4) H23C(0.4) C14(0.4)
 H14(0.4) C16C(0.4) H16C(0.4) C17C(0.4) H17C(0.4) C18C(0.4) C19C(0.4) H19C(0.4)
 C20C(0.4) H20C(0.4) C15C(0.4) O2C(0.6) C2(0.6) C3(0.6) H3(0.6) C4(0.6) H4(0.6)
 C5(0.6) C6(0.6) H6(0.6) C7(0.6) H7(0.6) C5C(0.6) C6C(0.6) H6C(0.6) C7C(0.6)
 H7C(0.6) C8C(0.6) C22C(0.6) H22C(0.6) C8(0.6) C9(0.6) H9(0.6) C10(0.6)
 H10(0.6) C11(0.6) C21C(0.6) H21C(0.6) C24C(0.6) C25C(0.6) H25C(0.6) C26C(0.6)
 H26C(0.6) C27C(0.6) F01H(0.5) F02Z(0.5) F03W(0.5) F01I(0.5) F02{(0.5)
 F03X(0.5) F02D(0.5) F02C(0.75) F02H(0.5) F0AA(0.5) F1AA(0.25) F02E(0.5)
 N0AA(0.5) C15(0.5) C16(0.5) N039(0.75) C02Y(0.75) C049(0.75) H04A(0.75)
 H04B(0.75) H04C(0.75) O1(0.5) C7AB(0.5) N048(0.75) C03T(0.75) C046(0.75)
 H04D(0.75) H04E(0.75) H04F(0.75)
6.a Aromatic/amide H refined with riding coordinates:
 C1C(H1C), C1A(H1A), C1B(H1B), C2B(H2B), C2C(H2C), C2A(H2A), C4C(H4C),
 C4A(H4A), C4B(H4B), C6B(H6B), C6A(H6A), C7B(H7B), C7A(H7A), C9B(H9B), C9A(H9A),
  C10B(H10B), C10A(H10A), C12B(H12B), C12A(H12A), C13A(H13A), C13B(H13B),
 C15B(H15B), C15A(H15A), C16A(H16A), C16B(H16B), C18A(H18A), C18B(H18B),
 C19A(H19A), C19B(H19B), C21A(H21A), C21B(H21B), C22A(H22A), C22B(H22B),
 C24A(H24A), C24B(H24B), C25B(H25B), C25A(H25A), C27B(H27B), C27A(H27A),
 C28A(H28A), C28B(H28B), C29A(H29A), C29B(H29B), C30C(H30C), C31B(H31B),
 C31A(H31A), C32C(H32C), C32A(H32A), C32B(H32B), C33C(H33C), C6C2(H6C2),
 C1(H1AA), C1(H1BB), C9C(H9C), C9C(H9CA), C7C2(H7C2), C10C(H10C), C11C(H11C),
 C13C(H13C), C14C(H14C), C29C(H29D), C29C(H29C), C28C(H28C), C28C(H28D),
 C23C(H23C), C14(H14), C16C(H16C), C17C(H17C), C19C(H19C), C20C(H20C), C3(H3),
 C4(H4), C6(H6), C7(H7), C6C(H6C), C7C(H7C), C22C(H22C), C9(H9), C10(H10),
 C21C(H21C), C25C(H25C), C26C(H26C)
6.b Fitted hexagon refined as free rotating group:
 C6C2(C5C2,C1,C9C,C8C2,C7C2), C9C2(C10C,C11C,C12C,C13C,C14C), C12(C29C,C28C,
 C13,C23C,C14), C16C(C17C,C18C,C19C,C20C,C15C), C2(C3,C4,C5,C6,C7), C22C(C8,C9,
 C10,C11,C21C)
6.c Idealised Me refined as rotating group:
 C02X(H02A,H02B,H02C), C03L(H03A,H03B,H03C), C049(H04A,H04B,H04C), C046(H04D,
 H04E,H04F)
;
_olex2_exptl_crystal_mounting_method
'Cold mounted in a carbon dioxide atomosphere in cryotox oil.'
_olex2_submission_special_instructions 'No special instructions were received'