Mixed-valence {FeII2FeIII4} hexanuclear complexes with thermally induced Fe(III) spin crossover behavior
Jia, Shuwen; Fan, Lingyue; Zheng, Chun-Yang; Jin, Sai; Li, Dongfeng; Dalton Transactions  (2022) –; doi:10.1039/D2DT02041F

data_7710876
_publ_section_title
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 Mixed-valence {FeII2FeIII4} hexanuclear complexes with thermally induced
 Fe(III) spin crossover behavior
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_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02041F
_journal_year                    2022
_chemical_formula_moiety
'C106 H111.476 B2 Cl0.841 Fe6 N34 O5.366, 5.159(Cl O4), 6[C2H5OH]'
_chemical_formula_sum            'C106 H111.47 B2 Cl6 Fe6 N34 O26'
_chemical_formula_weight         2847.18
_chemical_name_systematic        2-100K
_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
_audit_creation_date             2021-11-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
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2021-12-07 deposited with the CCDC.	2022-07-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.057(2)
_cell_length_b                   22.1418(18)
_cell_length_c                   24.2605(19)
_cell_measurement_reflns_used    9862
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.37
_cell_measurement_theta_min      2.46
_cell_volume                     13392.0(19)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_unetI/netI     0.0442
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            62711
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.000
_diffrn_reflns_theta_min         1.444
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.831
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       block
_exptl_crystal_F_000             5846
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.331
_refine_diff_density_min         -1.339
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     861
_refine_ls_number_reflns         19464
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0546
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0819P)^2^+34.8071P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1492
_refine_ls_wR_factor_ref         0.1650
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14424
_reflns_number_total             19464
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02041f2.cif
_cod_data_source_block           mo_150616d_0m_sq
_cod_original_cell_volume        13392.1(19)
_cod_database_code               7710876
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.789
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O10A-O13A = O10A-O11A = O10A-O12A = O13A-O11A = O13A-O12A = O11A-O12A
 2.35 with sigma of 0.01
 O10-O11 = O10-O12 = O10-O13 = O11-O12 = O11-O13 = O12-O13
 2.35 with sigma of 0.01
 Cl3A-O10A = Cl3A-O13A = Cl3-O13 = Cl3A-O11A = Cl3-O11 = Cl3-O10 = Cl3-O12 =
 Cl3A-O12A
 1.44 with sigma of 0.01
 Cl3A-O10A
 1.4 with sigma of 0.01
3. Rigid bond restraints
 O10, O11, O12, O13, O10A, O13A, O11A, O12A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O10 \\sim O11 \\sim O12 \\sim O13 \\sim O10A \\sim O13A \\sim O11A \\sim O12A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(O11) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O11)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O10A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O12A) \\sim Ueq, Uanis(O11A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 Sof(Cl3A)=Sof(O10A)=Sof(O12A)=Sof(O11A)=Sof(O13A)=1-FVAR(1)
 Sof(Cl3)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(O13)=Sof(O12)=Sof(O11)=Sof(O10)=
 FVAR(1)
6.a Ternary CH refined with riding coordinates:
 B1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C22(H22A,H22B), C16(H16A,H16B), C40(H40A,H40B), C39(H39A,
 H39B), C46(H46A,H46B), C53(H53A,H53B)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C14(H14), C12(H12), C10(H10), C8(H8), C33(H33), C32(H32),
 C31(H31), C30(H30), C24(H24), C25(H25), C26(H26), C27(H27), C18(H18), C19(H19),
  C20(H20), C21(H21), C45(H45), C44(H44), C43(H43), C42(H42), C37(H37),
 C36(H36), C35(H35), C34(H34), C48(H48), C49(H49), C50(H50), C51(H51)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              59542
_shelx_fab_checksum              39145
_platon_squeeze_special_details
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A solvent mask was calculated and 568 electrons were 
found in a volume of 1676\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
6[C2H5OH] per Formula Unit 
which account for 624 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'