Crystallographic and dielectric studies of tetrahedral {NH4@Fe4} crystallized with halomethane molecules
Matsumoto, Daiki; Tanaka, Chiaki; Fujibayashi, Masaru; Nishihara, Sadafumi; Takahashi, Kiyonori; Nakamura, Takayoshi; Akutagawa, Tomoyuki; Masuya-Suzuki, Atsuko; Tsunashima, Ryo; CrystEngComm 25 (2023) 4793–4797; doi:10.1039/D3CE00429E

data_7247118
_publ_section_title
;
 Crystallographic and dielectric studies of tetrahedral {NH4@Fe4}
 crystallized with halomethane molecules
;
_journal_issue                   34
_journal_name_full               CrystEngComm
_journal_page_first              4793
_journal_page_last               4797
_journal_paper_doi               10.1039/D3CE00429E
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety
'C72 H72 Fe4 O60, 0.5(H8 N2), 2(C H2 Br2), [+ solvents]1.8[CH2Br2]'
_chemical_formula_sum            'C74 H80 Br4 Fe4 N O60'
_chemical_formula_weight         2486.43
_chemical_name_systematic        '[NH4<C72H72O60Fe4](CH2Br2)2'
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-07-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-07-24 deposited with the CCDC.	2023-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 133.441(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   27.2902(13)
_cell_length_b                   17.9198(3)
_cell_length_c                   15.0346(7)
_cell_measurement_reflns_used    17632
_cell_measurement_temperature    223.00(10)
_cell_measurement_theta_max      30.7100
_cell_measurement_theta_min      2.0630
_cell_volume                     5338.5(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      223.00(10)
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.806
_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    -47.00  29.00   0.50  317.14    --   -9.35  96.00  68.00  152
  2  \w    -28.00  29.00   0.50  317.14    --   10.05  96.00  68.00  114
  3  \w    -16.00  48.00   0.50  317.14    --   10.05 -96.00 -40.00  128
  4  \w    -17.00  47.00   0.50  317.14    --   10.05 -99.00 -90.00  128
  5  \w    -13.00  48.00   0.50  317.14    --   10.05 -99.00-150.00  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-DW'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.806
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            25043
_diffrn_reflns_point_group_measured_fraction_full 0.899
_diffrn_reflns_point_group_measured_fraction_max 0.694
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.491
_diffrn_reflns_theta_min         1.786
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              PhotonJet-DW
_exptl_absorpt_coefficient_mu    2.129
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82175
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       block
_exptl_crystal_F_000             2510
_exptl_crystal_preparation       'local laboratory'
_exptl_crystal_recrystallization_method
'vapor difusion from dibromomethane and hexane'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.526
_refine_diff_density_min         -2.297
_refine_diff_density_rms         0.155
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.39(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     652
_refine_ls_number_reflns         11309
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0709
_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^)+(0.1676P)^2^+6.0761P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2038
_refine_ls_wR_factor_ref         0.2077
_reflns_Friedel_coverage         0.671
_reflns_Friedel_fraction_full    0.800
_reflns_Friedel_fraction_max     0.574
_reflns_number_gt                10442
_reflns_number_total             11309
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ce00429e2.cif
_cod_data_source_block           1-ch2br2
_cod_depositor_comments
'Adding full bibliography for 7247116--7247119.cif.'
_cod_original_cell_volume        5338.5(7)
_cod_database_code               7247118
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.61(2)
 0.39(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N1-H1A
 1.065 with sigma of 0.02
 N1-H1D
 1.065 with sigma of 0.02
 N1-H1B
 1.065 with sigma of 0.02
 N1-H1C
 1.065 with sigma of 0.02
 C99-Br1
 1.96 with sigma of 0.02
 C99-Br2
 1.96 with sigma of 0.02
 H1A-H1D
 1.75 with sigma of 0.04
 H1A-H1B
 1.75 with sigma of 0.04
 H1A-H1C
 1.75 with sigma of 0.04
 H1D-H1B
 1.75 with sigma of 0.04
 H1D-H1C
 1.75 with sigma of 0.04
 H1B-H1C
 1.75 with sigma of 0.04
 Br1-Br2
 3.52 with sigma of 0.04
 O13-C15 \\sim O13-C15A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C99) = Uanis(Br1) = Uanis(Br2)
Uiso(H1A) = Uiso(H1B) = Uiso(H1D) = Uiso(H1C)
Uanis(C9) = Uanis(O8)
Uanis(O13) = Uanis(C15) = Uanis(C15A)
5. Others
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5) H1D(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C99(H99A,H99B)
6.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C14(H14A,H14B,H14C), C3(H3A,H3B,H3C), C33(H33A,H33B,
 H33C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C8(H8A,
 H8B,H8C), C32(H32A,H32B,H32C), C2(H2A,H2B,H2C), C9(H9A,H9B,H9C), C15(H15A,H15B,
 H15C), C15A(H15D,H15E,H15F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 282 electrons were 
found in a volume of 544\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
[+ solvents]1.8[CH2Br2] per Formula Unit 
which account for 281 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.0
_shelx_res_checksum              5327
_shelx_fab_checksum              91334
_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
;