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_7713469
_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 Co3 I6 K3 N18 O18, 2(C6 H4 Cl2)'
_chemical_formula_sum            'C96 H122 Cl4 Co3 I6 K3 N18 O18'
_chemical_formula_weight         3013.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-07-03
_audit_creation_method
;FinalCif V123 by Daniel Kratzert, Freiburg 2023, 
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2023-07-03 deposited with the CCDC.	2023-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.747(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4244(4)
_cell_length_b                   38.0773(10)
_cell_length_c                   22.1900(10)
_cell_measurement_reflns_used    21542
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      25.1240
_cell_measurement_theta_min      1.6820
_cell_volume                     12186.6(7)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.873
_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    -57.00  54.00   1.00  100.00    --   16.58 -37.00  30.00  111
  2  \w    -11.00  18.00   1.00  100.00    --  -16.73  77.00 -30.00   29
  3  \w     -9.00  82.00   1.00  100.00    --   16.58  57.00-150.00   91
  4  \w    -17.00  96.00   1.00  100.00    --   16.58  57.00 -30.00  113
;
_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_unetI/netI     0.1362
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.873
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -49
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            31373
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.873
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.131
_diffrn_reflns_theta_min         1.674
_exptl_absorpt_coefficient_mu    2.179
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84958
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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             5968
_exptl_crystal_size_max          0.374
_exptl_crystal_size_mid          0.177
_exptl_crystal_size_min          0.114
_refine_diff_density_max         1.643
_refine_diff_density_min         -1.647
_refine_diff_density_rms         0.188
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1294
_refine_ls_number_reflns         31373
_refine_ls_number_restraints     2177
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1520
_refine_ls_R_factor_gt           0.0955
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1075P)^2^+58.6359P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2269
_refine_ls_wR_factor_ref         0.2447
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17681
_reflns_number_total             31373
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9977\% 
around [-0.00 0.00 1.00] (reciprocal) or [0.02 -0.00 1.00] (direct)
;
_cod_data_source_file            d3dt01571h2.cif
_cod_data_source_block           exp_2492_int2_twin1_hklf4
_cod_database_code               7713469
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5147(12)
 0.4853(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
3. Restrained distances
 C130-C124 \\sim C129-C123 \\sim C128-C122 \\sim C127-C121 \\sim C126-C120
\\sim C125-C119
 with sigma of 0.02
 N107-C125 \\sim N108-C126 \\sim N109-C127 \\sim N110-C128 \\sim N111-C129
\\sim N112-C130
 with sigma of 0.02
 C128-C127 \\sim C125-C126 \\sim C129-C130
 with sigma of 0.02
 N107-N108 \\sim N109-N110 \\sim N111-N112
 with sigma of 0.02
 C115-N109 \\sim N109-C122
 with sigma of 0.02
 C121-C128 \\sim C128-C116
 with sigma of 0.02
 C115-C127 \\sim C127-C122
 with sigma of 0.02
 C121-N110 \\sim N110-C116
 with sigma of 0.02
 O203-C208 \\sim O2-C208
 with sigma of 0.02
 O203-C210 \\sim O2-C210
 with sigma of 0.04
 O203-C209 \\sim O2-C2
 with sigma of 0.02
 K21-O203 \\sim K21-O2
 with sigma of 0.02
 C209-C210 \\sim C2-C210
 with sigma of 0.02
 K21-C209 \\sim K21-C2
 with sigma of 0.04
 C208-C209 \\sim C208-C2
 with sigma of 0.04
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C113) \\sim Ueq,
Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C116) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(C107) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C109) \\sim Ueq,
Uanis(C110) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C112) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(C121) \\sim Ueq,
Uanis(C122) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C124) \\sim Ueq,
Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C127) \\sim Ueq,
Uanis(C128) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C130) \\sim Ueq,
Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq, Uanis(C203) \\sim Ueq,
Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq, Uanis(C206) \\sim Ueq,
Uanis(C207) \\sim Ueq, Uanis(C208) \\sim Ueq, Uanis(C209) \\sim Ueq,
Uanis(C210) \\sim Ueq, Uanis(C211) \\sim Ueq, Uanis(C212) \\sim Ueq,
Uanis(C213) \\sim Ueq, Uanis(C214) \\sim Ueq, Uanis(C215) \\sim Ueq,
Uanis(C216) \\sim Ueq, Uanis(C217) \\sim Ueq, Uanis(C218) \\sim Ueq,
Uanis(C301) \\sim Ueq, Uanis(C302) \\sim Ueq, Uanis(C303) \\sim Ueq,
Uanis(C304) \\sim Ueq, Uanis(C305) \\sim Ueq, Uanis(C306) \\sim Ueq,
Uanis(C307) \\sim Ueq, Uanis(C308) \\sim Ueq, Uanis(C309) \\sim Ueq,
Uanis(C310) \\sim Ueq, Uanis(C311) \\sim Ueq, Uanis(C312) \\sim Ueq,
Uanis(C313) \\sim Ueq, Uanis(C314) \\sim Ueq, Uanis(C315) \\sim Ueq,
Uanis(C316) \\sim Ueq, Uanis(C317) \\sim Ueq, Uanis(C318) \\sim Ueq,
Uanis(C401) \\sim Ueq, Uanis(C402) \\sim Ueq, Uanis(C403) \\sim Ueq,
Uanis(C404) \\sim Ueq, Uanis(C405) \\sim Ueq, Uanis(C406) \\sim Ueq,
Uanis(C407) \\sim Ueq, Uanis(C408) \\sim Ueq, Uanis(C409) \\sim Ueq,
Uanis(C410) \\sim Ueq, Uanis(C411) \\sim Ueq, Uanis(C412) \\sim Ueq,
Uanis(C413) \\sim Ueq, Uanis(C414) \\sim Ueq, Uanis(C415) \\sim Ueq,
Uanis(C416) \\sim Ueq, Uanis(C417) \\sim Ueq, Uanis(C418) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq,
Uanis(C76) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq,
Uanis(C2) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(N101) \\sim Ueq, Uanis(N102) \\sim Ueq, Uanis(N103) \\sim Ueq,
Uanis(N104) \\sim Ueq, Uanis(N105) \\sim Ueq, Uanis(N106) \\sim Ueq,
Uanis(N111) \\sim Ueq, Uanis(N112) \\sim Ueq, Uanis(N107) \\sim Ueq,
Uanis(N108) \\sim Ueq, Uanis(N109) \\sim Ueq, Uanis(N110) \\sim Ueq,
Uanis(N201) \\sim Ueq, Uanis(N202) \\sim Ueq, Uanis(N301) \\sim Ueq,
Uanis(N302) \\sim Ueq, Uanis(N401) \\sim Ueq, Uanis(N402) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(O201) \\sim Ueq, Uanis(O202) \\sim Ueq, Uanis(O203) \\sim Ueq,
Uanis(O204) \\sim Ueq, Uanis(O205) \\sim Ueq, Uanis(O206) \\sim Ueq,
Uanis(O301) \\sim Ueq, Uanis(O302) \\sim Ueq, Uanis(O303) \\sim Ueq,
Uanis(O304) \\sim Ueq, Uanis(O305) \\sim Ueq, Uanis(O306) \\sim Ueq,
Uanis(O401) \\sim Ueq, Uanis(O402) \\sim Ueq, Uanis(O403) \\sim Ueq,
Uanis(O404) \\sim Ueq, Uanis(O405) \\sim Ueq, Uanis(O406) \\sim Ueq, Uanis(O2)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(N105) \\sim Ueq, Uanis(N102) \\sim Ueq, Uanis(N108) \\sim Ueq,
Uanis(N106) \\sim Ueq, Uanis(N101) \\sim Ueq, Uanis(C116) \\sim Ueq,
Uanis(C118) \\sim Ueq, Uanis(N110) \\sim Ueq, Uanis(C113) \\sim Ueq,
Uanis(N112) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(N103) \\sim Ueq,
Uanis(C114) \\sim Ueq, Uanis(N107) \\sim Ueq, Uanis(N111) \\sim Ueq,
Uanis(N104) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(N109) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C110) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C124) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C129) \\sim Ueq,
Uanis(C112) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C123) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C128) \\sim Ueq,
Uanis(C109) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C120) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C130) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C61) = Uanis(C62) = Uanis(C63) = Uanis(C64) = Uanis(C65) = Uanis(C66)
Uanis(C72) = Uanis(C71) = Uanis(C76) = Uanis(C75) = Uanis(C74) = Uanis(C73)
Uanis(C2) = Uanis(C209)
Uanis(Cl71) = Uanis(Cl72)
Uanis(O2) = Uanis(O203)
6. Rigid body (RIGU) restrains
 C212, C211, O204, C210, C209, O203, C208, C207
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C312, C311, O304, C310, C309, O303, C308, C307
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C206, C205, O202, C204, C203, O201, C202, C201
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C218, C217, O206, C216, C215, O205, C214, C213
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C306, C305, O302, C304, C303, O301, C302, C301
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C318, C317, O306, C316, C315, O305, C314, C313
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C418, C417, O406, C416, C415, O405, C414, C413
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C412, C411, O404, C410, C409, O403, C408, C407
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C406, C405, O402, C404, C403, O401, C402, C401
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{K21, O201, O202, O203, O204, O205, O206, N201, N202, C201, C202, C203, C204,
C205, C206, C207, C208, C209, C210, C211, C212, C213, C214, C215, C216, C217,
C218} sigma for 1-2: 0.0001, 1-3: 0.0001
as in
{K41, O401, O402, O403, O404, O405, O406, N401, N402, C401, C402, C403, C404,
C405, C406, C407, C408, C409, C410, C411, C412, C413, C414, C415, C416, C417,
C418}
{K21, O201, O202, O203, O204, O205, O206, N201, N202, C201, C202, C203, C204,
C205, C206, C207, C208, C209, C210, C211, C212, C213, C214, C215, C216, C217,
C218} sigma for 1-2: 0.0001, 1-3: 0.0001
as in
{K31, O301, O302, O303, O304, O305, O306, N301, N302, C301, C302, C303, C304,
C305, C306, C307, C308, C309, C310, C311, C312, C313, C314, C315, C316, C317,
C318}
8. Others
 Sof(Cl62)=Sof(Cl61)=Sof(C61)=Sof(C62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=
 Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=1-FVAR(1)
 Sof(Cl71)=Sof(Cl72)=Sof(C71)=Sof(C72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=
 Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=FVAR(1)
 Sof(H20Q)=Sof(H20R)=Sof(H21C)=Sof(H21D)=Sof(O2)=Sof(C2)=Sof(H2A)=Sof(H2B)=1-
 FVAR(2)
 Sof(O203)=Sof(H20O)=Sof(H20P)=Sof(C209)=Sof(H20S)=Sof(H20T)=Sof(H21A)=
 Sof(H21B)=FVAR(2)
9.a Free rotating group:
 Cl52(Cl51,C51,C52,C53,C54,C55,C56), Cl71(Cl72,C71,C72,C73,C74,C75,C76),
 Cl62(Cl61,C61,C62,C63,C64,C65,C66)
9.b 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), C208(H20Q,H20R),
 C209(H20S,H20T), C210(H21A,H21B), C210(H21C,H21D), C211(H21E,H21F), C212(H21G,
 H21H), C213(H21I,H21J), C214(H21K,H21L), C215(H21M,H21N), C216(H21O,H21P),
 C217(H21Q,H21R), C218(H21S,H21T), 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), C2(H2A,H2B)
9.c 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), C73(H73), C74(H74), C75(H75), C76(H76),
  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_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.496
_shelx_estimated_absorpt_t_max   0.789
_shelx_res_checksum              22949