A Heterometallic (Fe6Na8) Cage-like Silsesquioxane: Synthesis, Structure, Spin Glass Behavior and High Catalytic Activity
Bilyachenko, Alexey; Levitsky, Mikhail; Yalymov, Alexey; Korlyukov, Aleksander; Vologzhanina, Anna V.; Kozlov, Yuriy N.; Shul'pina, Lidia S.; Nesterov, Dmytro S.; Pombeiro, Armando J. L.; Lamaty, Frédéric; Bantreil, Xavier; Fetre, Amandine; Liu, Diyang; Martinez, Jean; Long, Jérôme; Larionova, Joulia; Guari, Yannick; Trigub, Alexander; Zubavichus, Yan V.; Golub, Igor; Filippov, Oleg A.; shubina, elena; Shul'pin, Georgiy; RSC Adv.  (2016) –; doi:10.1039/C6RA07081G

data_7225144
_publ_section_title
;
 A Heterometallic (Fe6Na8) Cage-like Silsesquioxane: Synthesis, Structure,
 Spin Glass Behavior and High Catalytic Activity
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C6RA07081G
_journal_year                    2016
_chemical_formula_moiety         'C158.8 H196.8 Fe6 Na8 O52.6 Si20, C7 H8'
_chemical_formula_sum            'C165.8 H204.8 Fe6 Na8 O52.6 Si20'
_chemical_formula_weight         4120.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-02-08 deposited with the CCDC.
2016-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.9200(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.0277(16)
_cell_length_b                   20.3021(11)
_cell_length_c                   32.2979(17)
_cell_measurement_reflns_used    5896
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.68
_cell_measurement_theta_min      2.33
_cell_volume                     19664.1(18)
_computing_cell_refinement       'SAINT v7.23A (Bruker, 2003)'
_computing_data_collection       'APEX2 (Bruker, 2005)'
_computing_data_reduction        'SAINT v7.23A (Bruker, 2003)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXTL ver. 5.1 (Sheldrick, 1998)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.861
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1094
_diffrn_reflns_av_unetI/netI     0.0805
_diffrn_reflns_Laue_measured_fraction_full 0.861
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            147601
_diffrn_reflns_point_group_measured_fraction_full 0.861
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         23.957
_diffrn_reflns_theta_min         1.403
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.647
_exptl_absorpt_correction_T_max  0.8295
_exptl_absorpt_correction_T_min  0.8295
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'APEX2 (Bruker, 2005)'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       cube
_exptl_crystal_F_000             8578
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.890
_refine_diff_density_min         -0.800
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2236
_refine_ls_number_reflns         30628
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1257
_refine_ls_R_factor_gt           0.0688
_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^)+(0.0977P)^2^+80.3745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1729
_refine_ls_wR_factor_ref         0.2094
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18901
_reflns_number_total             30628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra07081g2.cif
_cod_data_source_block           blch4
_cod_original_formula_sum        'C165.80 H204.80 Fe6 Na8 O52.60 Si20'
_cod_database_code               7225144
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.830
_shelx_estimated_absorpt_t_min   0.830
_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, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1F-C1F = O1G-C1G = O1H-C1H = O1K-C1K = O1L-C1L = O1J-C1J
 1.42 with sigma of 0.006
 O1A-C1A = O1B-C1B = O1C-C1C = O1D-C1D = O1E-C1E
 1.42 with sigma of 0.006
 C1F-C2F = C2F-C3F = C3F-C4F
 1.52 with sigma of 0.006
 C1G-C2G = C2G-C3G = C3G-C4G
 1.52 with sigma of 0.006
 C1H-C2H = C2H-C3H = C3H-C4H
 1.52 with sigma of 0.006
 C1J-C2J = C2J-C3J = C3J-C4J
 1.52 with sigma of 0.006
 C1K-C2K = C2K-C3K = C3K-C4K
 1.52 with sigma of 0.006
 C1L-C2L = C2L-C3L = C3L-C4L
 1.52 with sigma of 0.006
 C1A-C2A = C2A-C3A = C3A-C4A
 1.52 with sigma of 0.006
 C1B-C2B = C2B-C3B = C3B-C4B
 1.52 with sigma of 0.006
 C1C-C2C = C2C-C3C = C3C-C4C
 1.52 with sigma of 0.006
 C1E-C2E = C2E-C3E = C3E-C4E
 1.52 with sigma of 0.006
 C4DB-C2D
 2.42 with sigma of 0.01
 C4DA-C2D
 2.42 with sigma of 0.01
 C1D-C2D = C2D-C3DB = C3DB-C4DB
 1.52 with sigma of 0.006
 C3DA-C2D = C3DB-C2D
 1.51 with sigma of 0.005
 C4DB-C3DB = C4DA-C3DA
 1.51 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uiso(C3DA) = Uiso(C3DB)
4. Others
 Sof(H2DA)=Sof(H2DB)=Sof(C3DA)=Sof(H3DC)=Sof(H3DD)=1-FVAR(1)
 Sof(H2DC)=Sof(H2DD)=Sof(C3DB)=Sof(H3DA)=Sof(H3DB)=FVAR(1)
 Fixed Sof: Na8(0.6) Na9(0.4) C4DB(0.5) H4DA(0.5) H4DB(0.5) H4DC(0.5) O1K(0.6)
 H1K(0.6) C1K(0.6) H1KA(0.6) H1KB(0.6) C2K(0.6) H2KA(0.6) H2KB(0.6) C3K(0.6)
 H3KA(0.6) H3KB(0.6) C4K(0.6) H4KA(0.6) H4KB(0.6) H4KC(0.6) O1J(0.6) H1J(0.6)
 C2J(0.6) H2JA(0.6) H2JB(0.6) C3J(0.6) H3JA(0.6) H3JB(0.6) C4J(0.6) H4JA(0.6)
 H4JB(0.6) H4JC(0.6) O1L(0.4) H1L(0.4) C1L(0.4) H1LA(0.4) H1LB(0.4) C2L(0.4)
 H2LA(0.4) H2LB(0.4) C4L(0.4) H4LA(0.4) H4LB(0.4) H4LC(0.4) C3L(0.4) H3LA(0.4)
 H3LB(0.4) C4DA(0.5) H4DD(0.5) H4DE(0.5) H4DF(0.5)
 Fixed Uiso: C1J(0.151)
5.a Riding coordinates:
 O1A(H1A), O1B(H1B), O1C(H1C), O1D(H1D), O1E(H1E), O1F(H1F), O1G(H1G),
 O1H(H1H), O1K(H1K), O1J(H1J), O1L(H1L)
5.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C2A(H2AA,H2AB), C3A(H3AA,H3AB), C1B(H1BA,H1BB), C2B(H2BA,
 H2BB), C3B(H3BA,H3BB), C1C(H1CA,H1CB), C2C(H2CA,H2CB), C3C(H3CA,H3CB),
 C1D(H1DA,H1DB), C2D(H2DC,H2DD), C2D(H2DA,H2DB), C3DB(H3DA,H3DB), C1E(H1EA,
 H1EB), C2E(H2EA,H2EB), C3E(H3EA,H3EB), C1F(H1FA,H1FB), C2F(H2FA,H2FB),
 C3F(H3FA,H3FB), C1G(H1GA,H1GB), C2G(H2GA,H2GB), C3G(H3GA,H3GB), C1H(H1HA,H1HB),
  C2H(H2HA,H2HB), C3H(H3HA,H3HB), C1K(H1KA,H1KB), C2K(H2KA,H2KB), C3K(H3KA,
 H3KB), C1J(H1JA,H1JB), C2J(H2JA,H2JB), C3J(H3JA,H3JB), C1L(H1LA,H1LB),
 C2L(H2LA,H2LB), C3L(H3LA,H3LB), C3DA(H3DC,H3DD)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C52(H52), C53(H53),
 C54(H54), C55(H55), C56(H56), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C82(H82), C83(H83),
 C84(H84), C85(H85), C86(H86), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96),
  C102(H102), C103(H103), C104(H104), C105(H105), C106(H106), C112(H112),
 C113(H113), C114(H114), C115(H115), C116(H116), C122(H122), C123(H123),
 C124(H124), C125(H125), C126(H126), C132(H132), C133(H133), C134(H134),
 C135(H135), C136(H136), C142(H142), C143(H143), C144(H144), C145(H145),
 C146(H146), C152(H152), C153(H153), C154(H154), C155(H155), C156(H156),
 C162(H162), C163(H163), C164(H164), C165(H165), C166(H166), C172(H172),
 C173(H173), C174(H174), C175(H175), C176(H176), C182(H182), C183(H183),
 C184(H184), C185(H185), C186(H186), C192(H192), C193(H193), C194(H194),
 C195(H195), C196(H196), C202(H202), C203(H203), C204(H204), C205(H205),
 C206(H206), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S)
5.d Idealised Me refined as rotating group:
 C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,H4BC), C4C(H4CA,H4CB,H4CC), C4DB(H4DA,H4DB,
 H4DC), C4E(H4EA,H4EB,H4EC), C4F(H4FA,H4FB,H4FC), C4G(H4GA,H4GB,H4GC), C4H(H4HA,
 H4HB,H4HC), C4K(H4KA,H4KB,H4KC), C4J(H4JA,H4JB,H4JC), C4L(H4LA,H4LB,H4LC),
 C1S(H1SA,H1SB,H1SC), C4DA(H4DD,H4DE,H4DF)
;
_olex2_submission_special_instructions 'No special instructions were received'