Structural Evolution of Iron(III) Trifluoroacetate upon Thermal Decomposition: Chains, Layers, and Rings
Wörle, Michael; Guntlin, Christoph P.; Gyr, Luzia; Sougrati, Moulay T.; Lambert, Charles-Henri; Kravchyk, Kostiantyn V.; Zenobi, Renato; Kovalenko, Maksym V.; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.9b05004

data_4003478
_publ_section_title
;
 Structural Evolution of Iron(III) Trifluoroacetate upon Thermal
 Decomposition: Chains, Layers, and Rings
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.9b05004
_journal_year                    2020
_chemical_formula_moiety         'C32 F56 Fe8 O32'
_chemical_formula_sum            'C32 F56 Fe8 O32'
_chemical_formula_weight         2407.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                90.0
_cell_formula_units_Z            8
_cell_length_a                   16.9559(16)
_cell_length_b                   28.654(2)
_cell_length_c                   31.215(2)
_cell_measurement_reflns_used    6618
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      33.3810
_cell_measurement_theta_min      3.3430
_cell_volume                     15166(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -48.00  23.00   0.50    7.00    --   -0.94 -77.00-120.00  142
  2  \w    -13.00  75.00   0.50    7.00    --   -0.94  38.00-150.00  176
  3  \w     78.00 123.00   0.50    7.00    --   56.14  77.00  60.00   90
  4  \w     59.00 127.00   0.50    7.00    --   56.14 178.00  60.00  136
  5  \w     59.00 127.00   0.50    7.00    --   56.14 178.00 -30.00  136
  6  \w    -71.00  18.00   0.50    7.00    --  -58.01  19.00-180.00  178
  7  \w    -63.00   4.00   0.50    7.00    --  -58.01   0.00 -90.00  134
  8  \w    -74.00  11.00   0.50    7.00    --  -58.01  57.00 -90.00  170
  9  \w    -82.00   1.00   0.50    7.00    --  -58.01  77.00 -90.00  166
 10  \w   -119.00 -73.00   0.50    7.00    --  -58.01   0.00 -90.00   92
 11  \w   -123.00 -97.00   0.50    7.00    --  -58.01 -99.00 -90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0895695000
_diffrn_orient_matrix_UB_12      0.0059542000
_diffrn_orient_matrix_UB_13      -0.0062240000
_diffrn_orient_matrix_UB_21      0.0133379000
_diffrn_orient_matrix_UB_22      -0.0498792000
_diffrn_orient_matrix_UB_23      0.0168788000
_diffrn_orient_matrix_UB_31      -0.0071851000
_diffrn_orient_matrix_UB_32      -0.0191490000
_diffrn_orient_matrix_UB_33      -0.0459724000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1840
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30844
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        33.408
_diffrn_reflns_theta_max         33.408
_diffrn_reflns_theta_min         2.831
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    13.952
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38925
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.23a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.109
_exptl_crystal_description       irregular
_exptl_crystal_F_000             9280
_exptl_crystal_recrystallization_method
'crystallized by sublimation from decomposition of iron(III)trifluoroactetate'
_exptl_crystal_size_max          0.203
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.092
_refine_diff_density_max         1.098
_refine_diff_density_min         -0.961
_refine_diff_density_rms         0.178
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.098
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         2893
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      2.098
_refine_ls_R_factor_all          0.1869
_refine_ls_R_factor_gt           0.1669
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4568
_refine_ls_wR_factor_ref         0.4732
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2355
_reflns_number_total             2893
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b05004_si_004.cif
_cod_data_source_block           exp_530_final
_cod_database_code               4003478
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'Fe8 C32 F56 O32'
_cell_oxdiff_angle_alpha         90.029(5)
_cell_oxdiff_angle_beta          89.974(6)
_cell_oxdiff_angle_gamma         90.066(7)
_cell_oxdiff_length_a            16.9588(18)
_cell_oxdiff_length_b            28.6566(19)
_cell_oxdiff_length_c            31.2064(18)
_cell_oxdiff_measurement_reflns_used 6618
_cell_oxdiff_volume              15166(2)
_shelx_estimated_absorpt_t_max   0.360
_shelx_estimated_absorpt_t_min   0.164
_reflns_odcompleteness_completeness 37.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     50.38
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uiso(F35) = Uiso(F34) = Uiso(F33) = Uiso(F40) = Uiso(F39) = Uiso(F38) =
Uiso(F37) = Uiso(F36)
Uiso(F30) = Uiso(F29) = Uiso(F28) = Uiso(F48) = Uiso(F47) = Uiso(F46) =
Uiso(F25) = Uiso(F27) = Uiso(F26) = Uiso(F4AA) = Uiso(F6AA) = Uiso(F5AA) =
Uiso(F39A) = Uiso(F38A) = Uiso(F37A) = Uiso(F1) = Uiso(F3) = Uiso(F2) =
Uiso(F7) = Uiso(F9) = Uiso(F8) = Uiso(F21) = Uiso(F20) = Uiso(F19) = Uiso(F10)
= Uiso(F12) = Uiso(F11) = Uiso(F2AA) = Uiso(F32) = Uiso(F31) = Uiso(F22) =
Uiso(F24) = Uiso(F23) = Uiso(F5A) = Uiso(F4A) = Uiso(F6A) = Uiso(F16) =
Uiso(F18) = Uiso(F17) = Uiso(F42) = Uiso(F41) = Uiso(F8AA) = Uiso(F15) =
Uiso(F14) = Uiso(F13) = Uiso(F43) = Uiso(F44) = Uiso(F45) = Uiso(F9A) =
Uiso(F8A) = Uiso(F7A) = Uiso(F27A) = Uiso(F26A) = Uiso(F25A) = Uiso(F19A) =
Uiso(F21A) = Uiso(F20A) = Uiso(F46A) = Uiso(F48A) = Uiso(F47A) = Uiso(F7AA) =
Uiso(F3AA) = Uiso(F0AA) = Uiso(F17A) = Uiso(F16A) = Uiso(F18A) = Uiso(F2A) =
Uiso(F1A) = Uiso(F3A) = Uiso(F5) = Uiso(F4) = Uiso(F6) = Uiso(F11A) =
Uiso(F10A) = Uiso(F12A) = Uiso(F13A) = Uiso(F15A) = Uiso(F14A) = Uiso(F31A) =
Uiso(F33A) = Uiso(F32A) = Uiso(F45A) = Uiso(F44A) = Uiso(F43A) = Uiso(F23A) =
Uiso(F22A) = Uiso(F24A) = Uiso(F35A) = Uiso(F34A) = Uiso(F36A) = Uiso(F40A) =
Uiso(F42A) = Uiso(F41A) = Uiso(F30A) = Uiso(F29A) = Uiso(F28A)
Uiso(O20) = Uiso(O19) = Uiso(O32) = Uiso(O31) = Uiso(O17) = Uiso(O18) =
Uiso(O23) = Uiso(O24) = Uiso(O26A) = Uiso(O25A) = Uiso(O1) = Uiso(O2) =
Uiso(O5) = Uiso(O6) = Uiso(O14) = Uiso(O13) = Uiso(O7) = Uiso(O8) = Uiso(O22) =
Uiso(O21) = Uiso(O15) = Uiso(O16) = Uiso(O4A) = Uiso(O3A) = Uiso(O11) =
Uiso(O12) = Uiso(O28) = Uiso(O27) = Uiso(O10) = Uiso(O9) = Uiso(O29) =
Uiso(O30) = Uiso(O6A) = Uiso(O5A) = Uiso(O18A) = Uiso(O17A) = Uiso(O13A) =
Uiso(O14A) = Uiso(O31A) = Uiso(O32A) = Uiso(O26) = Uiso(O25) = Uiso(O12A) =
Uiso(O11A) = Uiso(O1A) = Uiso(O2A) = Uiso(O4) = Uiso(O3) = Uiso(O8A) =
Uiso(O7A) = Uiso(O9A) = Uiso(O10A) = Uiso(O21A) = Uiso(O22A) = Uiso(O30A) =
Uiso(O29A) = Uiso(O16A) = Uiso(O15A) = Uiso(O24A) = Uiso(O23A) = Uiso(O27A) =
Uiso(O28A) = Uiso(O19A) = Uiso(O20A)
Uiso(C20) = Uiso(C19) = Uiso(C32) = Uiso(C31) = Uiso(C18) = Uiso(C17) =
Uiso(C24) = Uiso(C23) = Uiso(C26A) = Uiso(C25A) = Uiso(C2) = Uiso(C1) =
Uiso(C6) = Uiso(C5) = Uiso(C14) = Uiso(C13) = Uiso(C8) = Uiso(C7) = Uiso(C22) =
Uiso(C21) = Uiso(C16) = Uiso(C15) = Uiso(C4A) = Uiso(C3A) = Uiso(C12) =
Uiso(C11) = Uiso(C28) = Uiso(C27) = Uiso(C10) = Uiso(C9) = Uiso(C30) =
Uiso(C29) = Uiso(C5A) = Uiso(C6A) = Uiso(C18A) = Uiso(C17A) = Uiso(C14A) =
Uiso(C13A) = Uiso(C32A) = Uiso(C31A) = Uiso(C26) = Uiso(C25) = Uiso(C12A) =
Uiso(C11A) = Uiso(C2A) = Uiso(C1A) = Uiso(C4) = Uiso(C3) = Uiso(C8A) =
Uiso(C7A) = Uiso(C9A) = Uiso(C10A) = Uiso(C22A) = Uiso(C21A) = Uiso(C30A) =
Uiso(C29A) = Uiso(C16A) = Uiso(C15A) = Uiso(C24A) = Uiso(C23A) = Uiso(C28A) =
Uiso(C27A) = Uiso(C20A) = Uiso(C19A)
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(C6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(O5)=Sof(O6)=Sof(C5)=1-FVAR(1)
 Sof(C5A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(O5A)=Sof(O6A)=Sof(C6A)=FVAR(1)
 Sof(C18A)=Sof(F25A)=Sof(F26A)=Sof(F27A)=Sof(O17A)=Sof(O18A)=Sof(C17A)=1-FVAR(2)
 Sof(C18)=Sof(F25)=Sof(F26)=Sof(F27)=Sof(O17)=Sof(O18)=Sof(C17)=FVAR(2)
 Sof(C14A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(O13A)=Sof(O14A)=Sof(C13A)=1-FVAR(3)
 Sof(C14)=Sof(F19)=Sof(F20)=Sof(F21)=Sof(O13)=Sof(O14)=Sof(C13)=FVAR(3)
 Sof(C32A)=Sof(F46A)=Sof(F47A)=Sof(F48A)=Sof(O31A)=Sof(O32A)=Sof(C31A)=1-FVAR(4)
 Sof(C32)=Sof(F46)=Sof(F47)=Sof(F48)=Sof(O31)=Sof(O32)=Sof(C31)=FVAR(4)
 Sof(C26)=Sof(F0AA)=Sof(F3AA)=Sof(F7AA)=Sof(O25)=Sof(O26)=Sof(C25)=1-FVAR(5)
 Sof(C26A)=Sof(F37A)=Sof(F38A)=Sof(F39A)=Sof(O25A)=Sof(O26A)=Sof(C25A)=FVAR(5)
 Sof(C12A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=Sof(O11A)=Sof(O12A)=Sof(C11A)=1-FVAR(6)
 Sof(C12)=Sof(F16)=Sof(F17)=Sof(F18)=Sof(O11)=Sof(O12)=Sof(C11)=FVAR(6)
 Sof(C2A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O1A)=Sof(O2A)=Sof(C1A)=1-FVAR(7)
 Sof(C2)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O1)=Sof(O2)=Sof(C1)=FVAR(7)
 Sof(C4)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O3)=Sof(O4)=Sof(C3)=1-FVAR(8)
 Sof(C4A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O3A)=Sof(O4A)=Sof(C3A)=FVAR(8)
 Sof(C8A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O7A)=Sof(O8A)=Sof(C7A)=1-FVAR(9)
 Sof(C8)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(O7)=Sof(O8)=Sof(C7)=FVAR(9)
 Sof(C9A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(O9A)=Sof(O10A)=Sof(C10A)=1-FVAR(10)
 Sof(C10)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O9)=Sof(O10)=Sof(C9)=FVAR(10)
 Sof(C22A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(O21A)=Sof(O22A)=Sof(C21A)=1-
 FVAR(11)
 Sof(C22)=Sof(F2AA)=Sof(F31)=Sof(F32)=Sof(O21)=Sof(O22)=Sof(C21)=FVAR(11)
 Sof(C30A)=Sof(F43A)=Sof(F44A)=Sof(F45A)=Sof(O29A)=Sof(O30A)=Sof(C29A)=1-
 FVAR(12)
 Sof(C30)=Sof(F43)=Sof(F44)=Sof(F45)=Sof(O29)=Sof(O30)=Sof(C29)=FVAR(12)
 Sof(C16A)=Sof(F22A)=Sof(F23A)=Sof(F24A)=Sof(O15A)=Sof(O16A)=Sof(C15A)=1-
 FVAR(13)
 Sof(C16)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(O15)=Sof(O16)=Sof(C15)=FVAR(13)
 Sof(C24A)=Sof(F34A)=Sof(F35A)=Sof(F36A)=Sof(O23A)=Sof(O24A)=Sof(C23A)=1-
 FVAR(14)
 Sof(C24)=Sof(F4AA)=Sof(F5AA)=Sof(F6AA)=Sof(O23)=Sof(O24)=Sof(C23)=FVAR(14)
 Sof(C28A)=Sof(F40A)=Sof(F41A)=Sof(F42A)=Sof(O27A)=Sof(O28A)=Sof(C27A)=1-
 FVAR(15)
 Sof(C28)=Sof(F8AA)=Sof(F41)=Sof(F42)=Sof(O27)=Sof(O28)=Sof(C27)=FVAR(15)
 Sof(C20A)=Sof(F28A)=Sof(F29A)=Sof(F30A)=Sof(O19A)=Sof(O20A)=Sof(C19A)=1-
 FVAR(16)
 Sof(C20)=Sof(F28)=Sof(F29)=Sof(F30)=Sof(O19)=Sof(O20)=Sof(C19)=FVAR(16)
4.a Free rotating group:
 C2A(F1A,F2A,F3A,O1A,O2A,C1A), C4A(F4A,F5A,F6A,O3A,O4A,C3A), C5A(F7A,F8A,F9A,
 O5A,O6A,C6A), C8A(F10A,F11A,F12A,O7A,O8A,C7A), C9A(F13A,F14A,F15A,O9A,O10A,
 C10A), C12A(F16A,F17A,F18A,O11A,O12A,C11A), C14A(F19A,F20A,F21A,O13A,O14A,
 C13A), C16A(F22A,F23A,F24A,O15A,O16A,C15A), C18A(F25A,F26A,F27A,O17A,O18A,
 C17A), C20A(F28A,F29A,F30A,O19A,O20A,C19A), C22A(F31A,F32A,F33A,O21A,O22A,
 C21A), C24A(F34A,F35A,F36A,O23A,O24A,C23A), C26A(F37A,F38A,F39A,O25A,O26A,
 C25A), C28A(F40A,F41A,F42A,O27A,O28A,C27A), C30A(F43A,F44A,F45A,O29A,O30A,
 C29A), C32A(F46A,F47A,F48A,O31A,O32A,C31A), C2(F1,F2,F3,O1,O2,C1), C4(F4,F5,F6,
 O3,O4,C3), C6(F7,F8,F9,O5,O6,C5), C8(F10,F11,F12,O7,O8,C7), C10(F13,F14,F15,O9,
 O10,C9), C12(F16,F17,F18,O11,O12,C11), C14(F19,F20,F21,O13,O14,C13), C16(F22,
 F23,F24,O15,O16,C15), C18(F25,F26,F27,O17,O18,C17), C20(F28,F29,F30,O19,O20,
 C19), C22(F2AA,F31,F32,O21,O22,C21), C24(F4AA,F5AA,F6AA,O23,O24,C23), C26(F0AA,
 F3AA,F7AA,O25,O26,C25), C28(F8AA,F41,F42,O27,O28,C27), C30(F43,F44,F45,O29,O30,
 C29), C32(F46,F47,F48,O31,O32,C31)
;
_shelx_res_checksum              85768
_shelx_hkl_checksum              45653
_olex2_exptl_crystal_mounting_method tip-mounted
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.993
_oxdiff_exptl_absorpt_empirical_full_min 0.516