Bi- and Tri-metallic Cage Silsesquioxanes: Features of Supramolecular Assembling and Magnetic Properties
Bilyachenko, Alexey; Korlyukov, Aleksander; Vologzhanina, Anna V. V.; Khrustalev, Victor N.; Kulakova, Alena Nikolaevna; Long, Jerome; Larionova, Joulia; Guari, Yannick; Dronova, Marina; Tsareva, Ulyana; Dorovatovskii, Pavel; Shubina, Elena; Levitsky, Mikhail; Dalton Trans.  (2017) –; doi:10.1039/C7DT02017A

data_7044097
_publ_section_title
;
 Bi- and Tri-metallic Cage Silsesquioxanes: Features of Supramolecular
 Assembling and Magnetic Properties
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT02017A
_journal_year                    2017
_chemical_formula_moiety
'C86 H96 Cs3 Cu4 N4 Na O30 S Si12, 1.5(C3 H7 N O)'
_chemical_formula_sum            'C90.5 H106.5 Cs3 Cu4 N5.5 Na O31.5 S Si12'
_chemical_formula_weight         2820.33
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-07-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-07-10 deposited with the CCDC.
2017-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                78.7430(10)
_cell_angle_beta                 82.0670(10)
_cell_angle_gamma                87.7670(10)
_cell_formula_units_Z            2
_cell_length_a                   14.0768(3)
_cell_length_b                   15.1880(3)
_cell_length_c                   28.3921(6)
_cell_measurement_reflns_used    9533
_cell_measurement_temperature    120
_cell_measurement_theta_max      67.49
_cell_measurement_theta_min      3.09
_cell_volume                     5896.0(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.939
_diffrn_measured_fraction_theta_max 0.931
_diffrn_measurement_device_type  'Bruker APEX II'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.939
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            74983
_diffrn_reflns_point_group_measured_fraction_full 0.939
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         67.913
_diffrn_reflns_theta_min         2.967
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    9.917
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.5488
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1131 before and 0.0417 after correction.
The Ratio of minimum to maximum transmission is 0.7288.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.589
_exptl_crystal_description       prism
_exptl_crystal_F_000             2832
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         2.912
_refine_diff_density_min         -1.675
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1243
_refine_ls_number_reflns         19955
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0677
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^+80.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1524
_refine_ls_wR_factor_ref         0.1540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18912
_reflns_number_total             19955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02017a2.cif
_cod_data_source_block           a_CCDC1
_cod_original_formula_sum
'C90.50 H106.50 Cs3 Cu4 N5.50 Na O31.50 S Si12'
_cod_database_code               7044097
_shelxl_version_number           2014-3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C03W-C03P
 2.5 with sigma of 0.02
 N02C-C16 = N02C-C03Y
 1.5 with sigma of 0.02
 C16-C045
 2.5 with sigma of 0.02
 N1-C0AA = N1-C1AA
 1.45 with sigma of 0.02
 O6-C0AA = O4-C1AA
 1.2 with sigma of 0.02
3. Restrained planarity
 C16, N02C, C03Y, C045, O02O
 with sigma of 0.1
 C03P, O026, C03W, N025, C04F
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(Na1B) \\sim Ueq, Uanis(Na1A) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.002
Uanis(C03K) \\sim Ueq, Uanis(C03V) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C03Y) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C03I) \\sim Ueq, Uanis(C03R) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O01T) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(N02C) \\sim Ueq, Uanis(O02O) \\sim Ueq, Uanis(C03C) \\sim Ueq,
Uanis(C03E) \\sim Ueq, Uanis(C04B) \\sim Ueq: with sigma of 0.006 and sigma for
terminal atoms of 0.006
Uanis(Na1B) = Uanis(Na1A)
Uanis(C022) = Uanis(C03F) = Uanis(C03V) = Uanis(C048) = Uanis(C03H) =
Uanis(C03K)
Uanis(C02H) = Uanis(C032) = Uanis(C03J) = Uanis(C03G) = Uanis(C038)
Uiso(C11) = Uiso(C04A)
Uiso(C2) = Uiso(C1)
Uiso(C3) = Uiso(C8)
Uiso(C9) = Uiso(C17)
Uiso(C036) = Uiso(C2AA)
Uanis(C01L) = Uanis(C041) = Uanis(C03S) = Uanis(C02F) = Uanis(C03N) =
Uanis(C039)
Uanis(C02Y) = Uanis(C03U) = Uanis(C02Z)
Uanis(C041) = Uanis(C03S) = Uanis(C02F) = Uanis(C03N) = Uanis(C039) =
Uanis(C01L)
Uanis(N01I) = Uanis(C040) = Uanis(C044) = Uanis(C037)
5. Rigid body (RIGU) restrains
 C04B, N01S, C03L, C035, O01D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O01T, C04D, N03B, C04C, C047
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O02O, C045, N02C, C03Y, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O026, C03W, C03P, N025, C04F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C040, N01I, C044, C037
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Na1A(0.5) C11(0.5) H11(0.5) C2(0.5) H2(0.5) C8(0.5) H8(0.5)
 C9(0.5) H9(0.5) C2AA(0.5) H2AA(0.5) C04A(0.5) H04A(0.5) C036(0.5) H036(0.5)
 O01T(0.5) N025(0.5) O026(0.5) N03B(0.5) C03P(0.5) H03O(0.5) H03P(0.5)
 H03Q(0.5) C03W(0.5) H03Y(0.5) C047(0.5) H04H(0.5) H04I(0.5) H04J(0.5)
 C04C(0.5) H04K(0.5) H04L(0.5) H04M(0.5) C04D(0.5) H04N(0.5) C04F(0.5)
 H04O(0.5) H04P(0.5) H04Q(0.5) Na1B(0.5) N1(0.5) C0AA(0.5) H0AB(0.5) H0AC(0.25)
 H0AD(0.25) O4(0.25) O6(0.25) C1AA(0.5) H1AA(0.25) H1AB(0.25) H1AC(0.25)
 H1AD(0.25) C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5) C1(0.5) H1(0.5) C3(0.5)
 H3(0.5) C17(0.5) H17(0.5)
7.a Rotating group:
 O01F(H01A,H01B)
7.b Me refined with riding coordinates:
 C0AA(H0AB,H0AC,H0AD), C1AA(H1AA,H1AB,H1AC)
7.c Aromatic/amide H refined with riding coordinates:
 C01K(H01K), C039(H039), C03N(H03N), C02F(H02F), C03S(H03S), C041(H041),
 C11(H11), C2(H2), C8(H8), C9(H9), C2AA(H2AA), C04A(H04A), C036(H036),
 C01V(H01V), C01W(H01W), C01X(H01X), C01Z(H01Z), C020(H020), C021(H021),
 C03F(H03F), C03V(H03V), C048(H048), C03H(H03H), C03K(H03K), C024(H024),
 C027(H027), C028(H028), C029(H029), C02A(H02A), C02B(H02B), C02D(H02D),
 C02E(H02E), C02G(H02G), C02H(H02H), C02I(H02I), C02K(H02L), C02L(H02M),
 C02M(H02N), C02N(H02O), C02P(H02P), C02Q(H02Q), C02R(H02R), C02S(H02S),
 C02T(H02T), C02V(H02X), C02W(H02Y), C02X(H02Z), C02Y(H02), C02Z(H0AA),
 C031(H031), C032(H032), C033(H033), C034(H034), C035(H035), C037(H037),
 C038(H038), C03A(H03A), C03C(H03C), C03D(H03D), C03E(H03E), C03G(H03G),
 C03I(H03I), C03J(H03J), C03R(H03W), C03U(H03X), C03W(H03Y), C045(H045),
 C04D(H04N), C1AA(H1AD), C1(H1), C3(H3), C17(H17)
7.d Fitted hexagon refined as free rotating group:
 C01L(C039,C03N,C02F,C03S,C041), C01M(C11,C2,C8,C9,C2AA), C022(C03F,C03V,C048,
 C03H,C03K)
7.e Idealised Me refined as rotating group:
 C02J(H02C,H02J,H02K), C02U(H02U,H02V,H02W), C03L(H03,H,HA), C03O(H03B,H03L,
 H03M), C03P(H03O,H03P,H03Q), C03Q(H03R,H03T,H03U), C03Y(H03Z,HB,HC), C040(H04B,
 H04C,H04D), C044(H04E,H04F,H04G), C047(H04H,H04I,H04J), C04B(H04R,H04S,H04T),
 C04C(H04K,H04L,H04M), C04F(H04O,H04P,H04Q), C16(H16A,H16B,H16C), C15(H15A,H15B,
 H15C)
;
_shelx_res_checksum              17159
_olex2_submission_special_instructions 'No special instructions were received'