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_7710496
_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
'C54 H44 Mn3 N10 O8, 2(C18 H36 K N2 O6), 5(C6 H4 Cl2)'
_chemical_formula_sum            'C120 H136 Cl10 K2 Mn3 N14 O20'
_chemical_formula_weight         2691.94
_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     dual
_audit_creation_date             2021-10-21
_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                90
_cell_angle_beta                 107.465(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.7101(5)
_cell_length_b                   18.1789(4)
_cell_length_c                   22.3440(7)
_cell_measurement_reflns_used    19679
_cell_measurement_temperature    109(3)
_cell_measurement_theta_max      29.1740
_cell_measurement_theta_min      1.7500
_cell_volume                     6474.6(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      109(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     37.00  71.00   1.00  120.00    --   11.89 178.00-150.00   34
  2  \w     13.00  39.00   1.00  120.00    --  -12.20-127.00  78.00   26
  3  \w   -102.00 -77.00   1.00  120.00    --  -12.20-178.00-180.00   25
  4  \w     27.00  62.00   1.00  120.00    --  -12.20  57.00  90.00   35
  5  \w    -86.00  10.00   1.00  120.00    --  -12.20 -57.00-180.00   96
  6  \w    -69.00 -10.00   1.00  120.00    --  -12.20 -37.00 120.00   59
  7  \w    -42.00  11.00   1.00  120.00    --  -12.20  57.00  90.00   53
  8  \w   -102.00 -77.00   1.00  120.00    --  -12.20-178.00  90.00   25
  9  \w    -27.00  -1.00   1.00  120.00    --  -12.20  57.00-150.00   26
 10  \w    -78.00  20.00   1.00  120.00    --  -12.20 -77.00 -60.00   98
;
_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      -0.0292526000
_diffrn_orient_matrix_UB_12      0.0131081000
_diffrn_orient_matrix_UB_13      0.0148393000
_diffrn_orient_matrix_UB_21      -0.0303897000
_diffrn_orient_matrix_UB_22      0.0043612000
_diffrn_orient_matrix_UB_23      -0.0297391000
_diffrn_orient_matrix_UB_31      -0.0141620000
_diffrn_orient_matrix_UB_32      -0.0364901000
_diffrn_orient_matrix_UB_33      0.0017695000
_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  0.0566
_diffrn_reflns_av_unetI/netI     0.0601
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            74099
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.699
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.628
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97324
_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    1.381
_exptl_crystal_description       block
_exptl_crystal_F_000             2794
_exptl_crystal_size_max          0.648
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.059
_refine_diff_density_max         1.920
_refine_diff_density_min         -2.212
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     762
_refine_ls_number_reflns         12731
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0840
_refine_ls_R_factor_gt           0.0594
_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^)+(0.0518P)^2^+13.0194P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1319
_refine_ls_wR_factor_ref         0.1461
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9592
_reflns_number_total             12731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01052f2.cif
_cod_data_source_block           exp_1365_int1
_cod_database_code               7710496
_chemical_oxdiff_formula         'C320  H0  N28  O30  K0  Mn0  Cl0  '
_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 1.058
_oxdiff_exptl_absorpt_empirical_full_min 0.911
_shelx_estimated_absorpt_t_min   0.686
_shelx_estimated_absorpt_t_max   0.964
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C61) = Uanis(C43) = Uanis(C41) = Uanis(C62) = Uanis(C44) = Uanis(C66) =
Uanis(C46) = Uanis(C63) = Uanis(C45) = Uanis(C65) = Uanis(C64) = Uanis(C42)
Uanis(Cl61) = Uanis(Cl42) = Uanis(Cl62) = Uanis(Cl41)
3. Same fragment restrains
{Cl41, Cl42, C41, C42, C43, C44, C45, C46} sigma for 1-2: 0.001, 1-3: 0.001
as in
{Cl61, Cl62, C61, C62, C63, C64, C65, C66}
4. Others
 Sof(Cl61)=Sof(Cl62)=Sof(C61)=Sof(C62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=
 Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=1-FVAR(1)
 Sof(Cl41)=Sof(Cl42)=Sof(C41)=Sof(C42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=
 Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=FVAR(1)
 Fixed Sof: Cl1(0.5) Cl2(0.5) C1(0.5) C2(0.5) C3(0.5) H3(0.5) C4(0.5) H4(0.5)
 C5(0.5) H5(0.5) C6(0.5) H6(0.5)
5.a Free rotating group:
 Cl1(Cl2,C1,C2,C3,C4,C5,C6)
5.b Secondary CH2 refined with riding coordinates:
 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)
5.c Aromatic/amide H refined with riding coordinates:
 C104(H104), C105(H105), C106(H106), C107(H107), C112(H112), C113(H113),
 C114(H114), C115(H115), C203(H203), C208(H208), C53(H53), C54(H54), C55(H55),
 C56(H56), C43(H43), C44(H44), C45(H45), C46(H46), C63(H63), C64(H64), C65(H65),
  C66(H66), C3(H3), C4(H4), C5(H5), C6(H6)
5.d Fitted hexagon refined as free rotating group:
 C41(C42,C43,C44,C45,C46)
5.e Idealised Me refined as rotating group:
 C201(H20A,H20B,H20C), C205(H20D,H20E,H20F), C206(H20G,H20H,H20I), C210(H21A,
 H21B,H21C)
;