Trinuclear coordination assemblies of low-spin dicyano manganese(ii) (S = 1/2) and iron(ii) (S = 0) phthalocyanines with manganese(ii) acetylacetonate, tris(cyclopentadienyl)gadolinium(iii) and neodymium(iii)
Romanenko, Nikita R.; Kuzmin, Alexey V.; Mikhailenko, Maxim V.; Faraonov, Maxim A.; Khasanov, Salavat S.; Yudanova, Evgeniya I.; Shestakov, Alexander F.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Konarev, Dmitri V.; Dalton Transactions  (2022) –; doi:10.1039/D2DT01052F

data_7710495
_publ_section_title
;
 Trinuclear coordination assemblies of low-spin dicyano manganese(ii) (S =
 1/2) and iron(ii) (S = 0) phthalocyanines with manganese(ii)
 acetylacetonate, tris(cyclopentadienyl)gadolinium(iii) and neodymium(iii)
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01052F
_journal_year                    2022
_chemical_formula_moiety
'C64 H30 Cl16 Fe N10 Nd2, 2(C18 H36 K N2 O6), 1(C6 H4 Cl2)'
_chemical_formula_sum            'C106 H106 Cl18 Fe K2 N14 Nd2 O12'
_chemical_formula_weight         2828.67
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-22
_audit_creation_method
;
FinalCif V89 by Daniel Kratzert, Freiburg 2021,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2021-10-22 deposited with the CCDC.	2022-06-15 downloaded from the CCDC.
;
_cell_angle_alpha                108.677(3)
_cell_angle_beta                 95.219(2)
_cell_angle_gamma                110.988(2)
_cell_formula_units_Z            2
_cell_length_a                   16.2343(3)
_cell_length_b                   19.4760(5)
_cell_length_c                   20.9495(6)
_cell_measurement_reflns_used    19314
_cell_measurement_temperature    101(3)
_cell_measurement_theta_max      27.9580
_cell_measurement_theta_min      1.8370
_cell_volume                     5698.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      101(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -58.00 -30.00   1.00  120.00    --   11.89 -57.00   0.00   28
  2  \w    -84.00  11.00   1.00  120.00    --  -12.20 -57.00-180.00   95
  3  \w    -71.00  17.00   1.00  120.00    --  -12.20 -57.00 -60.00   88
  4  \w    -84.00   9.00   1.00  120.00    --  -12.20 -57.00  90.00   93
  5  \w    -65.00 -33.00   1.00  120.00    --  -12.20 -57.00  30.00   32
  6  \w    -30.00   9.00   1.00  120.00    --  -12.20 -57.00  30.00   39
  7  \w     15.00  40.00   1.00  120.00    --  -12.20  57.00   0.00   25
  8  \w     -1.00  59.00   1.00  120.00    --  -12.20  57.00-120.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0124515000
_diffrn_orient_matrix_UB_12      0.0339743000
_diffrn_orient_matrix_UB_13      0.0308617000
_diffrn_orient_matrix_UB_21      0.0109340000
_diffrn_orient_matrix_UB_22      0.0247750000
_diffrn_orient_matrix_UB_23      -0.0192435000
_diffrn_orient_matrix_UB_31      -0.0451716000
_diffrn_orient_matrix_UB_32      -0.0030746000
_diffrn_orient_matrix_UB_33      -0.0052524000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0920
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            60835
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.680
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87684
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.119a (Rigaku Oxford Diffraction, 2021)
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    1.649
_exptl_crystal_description       block
_exptl_crystal_F_000             2852
_exptl_crystal_size_max          0.315
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.112
_refine_diff_density_max         2.229
_refine_diff_density_min         -1.288
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1467
_refine_ls_number_reflns         22320
_refine_ls_number_restraints     832
_refine_ls_restrained_S_all      1.152
_refine_ls_R_factor_all          0.1131
_refine_ls_R_factor_gt           0.0775
_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^)+(0.0113P)^2^+29.0544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1165
_refine_ls_wR_factor_ref         0.1275
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16309
_reflns_number_total             22320
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01052f2.cif
_cod_data_source_block           exp_1353_int1
_cod_database_code               7710495
_chemical_oxdiff_formula         'C276  H0  N24  O26  Nb0  K0  Fe0  Cl0  Nd0  '
_shelx_shelxl_version_number     2018/3
_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 1.189
_oxdiff_exptl_absorpt_empirical_full_min 0.890
_shelx_estimated_absorpt_t_min   0.635
_shelx_estimated_absorpt_t_max   0.842
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C43B-C404 \\sim C43A-C404
 with sigma of 0.02
 O41B-C43B \\sim O41A-C43A
 with sigma of 0.02
 O41B-C41B \\sim O41A-C41A
 with sigma of 0.02
 C41B-C401 \\sim C41A-C401
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C71 \\sim C72 \\sim
C73 \\sim C74 \\sim C75 \\sim C76: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 1.7A
C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim
C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim C113 \\sim C114 \\sim
C115 \\sim C116 \\sim C117 \\sim C118 \\sim C119 \\sim C120 \\sim C121 \\sim
C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim
C129 \\sim C130 \\sim C131 \\sim C132 \\sim C133 \\sim C134: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
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(C113) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq,
Uanis(C116) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C118) \\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(C131) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C133) \\sim Ueq,
Uanis(C134) \\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(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(N101) \\sim Ueq, Uanis(N102) \\sim Ueq,
Uanis(N103) \\sim Ueq, Uanis(N104) \\sim Ueq, Uanis(N105) \\sim Ueq,
Uanis(N106) \\sim Ueq, Uanis(N107) \\sim Ueq, Uanis(N108) \\sim Ueq,
Uanis(N109) \\sim Ueq, Uanis(N110) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C41B) \\sim Ueq, Uanis(C41A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O41B) = Uanis(O41A)
Uanis(C43B) = Uanis(C43A)
Uanis(C41B) = Uanis(C41A)
Uanis(N101) = Uanis(N105)
Uanis(N103) = Uanis(N107)
4. Same fragment restrains
{Cl61, Cl62, C61, C62, C63, C64, C65, C66} sigma for 1-2: 0.001, 1-3: 0.001
as in
{Cl71, Cl72, C71, C72, C73, C74, C75, C76}
5. Others
 Sof(Cl71)=Sof(Cl72)=Sof(C71)=Sof(C72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=
 Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=1-FVAR(1)
 Sof(Cl61)=Sof(Cl62)=Sof(C61)=Sof(C62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=
 Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=FVAR(1)
 Sof(H40C)=Sof(H40D)=Sof(H40G)=Sof(H40H)=Sof(O41B)=Sof(C41B)=Sof(H41U)=
 Sof(H41V)=Sof(C43B)=Sof(H43C)=Sof(H43D)=1-FVAR(2)
 Sof(H40A)=Sof(H40B)=Sof(H40E)=Sof(H40F)=Sof(O41A)=Sof(C41A)=Sof(H41S)=
 Sof(H41T)=Sof(C43A)=Sof(H43A)=Sof(H43B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C401(H40A,H40B), C401(H40C,H40D), C404(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),
 C41A(H41S,H41T), C43A(H43A,H43B), C41B(H41U,H41V), C43B(H43C,H43D), C501(H50A,
 H50B), C502(H50C,H50D), C503(H50E,H50F), C504(H50G,H50H), C505(H50I,H50J),
 C506(H50K,H50L), C507(H50M,H50N), C508(H50O,H50P), C509(H50Q,H50R), C510(H51A,
 H51B), C511(H51C,H51D), C512(H51E,H51F), C513(H51G,H51H), C514(H51I,H51J),
 C515(H51K,H51L), C516(H51M,H51N), C517(H51O,H51P), C518(H51Q,H51R)
6.b Aromatic/amide H refined with riding coordinates:
 C201(H201), C202(H202), C203(H203), C204(H204), C205(H205), C206(H206),
 C207(H207), C208(H208), C209(H209), C210(H210), C211(H211), C212(H212),
 C213(H213), C214(H214), C215(H215), C301(H301), C302(H302), C303(H303),
 C304(H304), C305(H305), C306(H306), C307(H307), C308(H308), C309(H309),
 C310(H310), C311(H311), C312(H312), C313(H313), C314(H314), C315(H315),
 C63(H63), C64(H64), C65(H65), C66(H66), C73(H73), C74(H74), C75(H75), C76(H76)
;