Magnetic behavior and ground spin states for coordination {L.[M(II)(Hal)2]3}(3-) assemblies (Hal = Cl or I) of radical trianion hexacyanohexaazatriphenylenes (L) with three coordinated high-spin Fe(II) (S = 2) or Co(II) (S = 3/2) centers
Mikhailenko, Maxim V.; Ivanov, Vladislav V.; Shestakov, Alexander F.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Konarev, Dmitri V.; Dalton Transactions  (2023) –; doi:10.1039/D3DT01571H

data_7713467
_publ_section_title
;
 Magnetic behavior and ground spin states for coordination
 {L.[M(II)(Hal)2]3}(3-) assemblies (Hal = Cl or I) of radical trianion
 hexacyanohexaazatriphenylenes (L) with three coordinated high-spin Fe(II)
 (S = 2) or Co(II) (S = 3/2) centers
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01571H
_journal_year                    2023
_chemical_formula_moiety         'C84 H114 Fe3 I6 K3 N18 O18, 2(C6 H4 Cl2)'
_chemical_formula_sum            'C96 H122 Cl4 Fe3 I6 K3 N18 O18'
_chemical_formula_weight         3004.16
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2022-11-18
_audit_creation_method
;FinalCif V113 by Daniel Kratzert, Freiburg 2022,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2022-11-18 deposited with the CCDC.	2023-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.1635(7)
_cell_length_b                   22.8533(4)
_cell_length_c                   14.3046(2)
_cell_measurement_reflns_used    25942
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      29.4400
_cell_measurement_theta_min      1.7770
_cell_volume                     12149.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.4566
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.886
_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    -31.00  31.00   0.50  150.00    --   12.05 -77.00 -90.00  124
  2  \w     -9.00  88.00   0.50  150.00    --   12.05  37.00  90.00  194
  3  \w     -8.00   5.00   0.50  150.00    --  -12.05 -77.00 120.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.886
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            56574
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.809
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.579
_diffrn_reflns_theta_min         1.679
_exptl_absorpt_coefficient_mu    2.134
_exptl_absorpt_correction_T_max  0.751
_exptl_absorpt_correction_T_min  0.576
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.642
_exptl_crystal_description       block
_exptl_crystal_F_000             5956
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.14
_refine_diff_density_max         2.159
_refine_diff_density_min         -1.148
_refine_diff_density_rms         0.133
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.680(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1334
_refine_ls_number_reflns         27590
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0556
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0687P)^2^+4.0302P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1295
_refine_ls_wR_factor_ref         0.1350
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.936
_reflns_Friedel_fraction_max     0.727
_reflns_number_gt                24598
_reflns_number_total             27590
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01571h2.cif
_cod_data_source_block           exp_2569_int3
_cod_database_code               7713467
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.320(19)
 0.680(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,
 H20J), C206(H20K,H20L), C207(H20M,H20N), C208(H20O,H20P), C209(H20Q,H20R),
 C210(H21A,H21B), C211(H21C,H21D), C212(H21E,H21F), C213(H21G,H21H), C214(H21I,
 H21J), C215(H21K,H21L), C216(H21M,H21N), C217(H21O,H21P), C218(H21Q,H21R),
 C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C305(H30I,
 H30J), C306(H30K,H30L), C307(H30M,H30N), C308(H30O,H30P), C309(H30Q,H30R),
 C310(H31A,H31B), C311(H31C,H31D), C312(H31E,H31F), C313(H31G,H31H), C314(H31I,
 H31J), C315(H31K,H31L), C316(H31M,H31N), C317(H31O,H31P), C318(H31Q,H31R),
 C401(H40A,H40B), C402(H40C,H40D), C403(H40E,H40F), C404(H40G,H40H), C405(H40I,
 H40J), C406(H40K,H40L), C407(H40M,H40N), C408(H40O,H40P), C409(H40Q,H40R),
 C410(H41A,H41B), C411(H41C,H41D), C412(H41E,H41F), C413(H41G,H41H), C414(H41I,
 H41J), C415(H41K,H41L), C416(H41M,H41N), C417(H41O,H41P), C418(H41Q,H41R)
3.b Aromatic/amide H refined with riding coordinates:
 C117(H117), C118(H118), C113(H113), C114(H114), C115(H115), C116(H116),
 C53(H53), C54(H54), C55(H55), C56(H56), C63(H63), C64(H64), C65(H65), C66(H66)
;
_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
;
_shelx_estimated_absorpt_t_min   0.440
_shelx_estimated_absorpt_t_max   0.754
_shelx_res_checksum              60725