Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides.
Bilyachenko, Alexey N.; Kulakova, Alena N.; Levitsky, Mikhail M.; Petrov, Artem A.; Korlyukov, Alexander A.; Shul'pina, Lidia S.; Khrustalev, Victor N.; Dorovatovskii, Pavel V.; Vologzhanina, Anna V.; Tsareva, Ulyana S.; Golub, Igor E.; Gulyaeva, Ekaterina S.; Shubina, Elena S.; Shul'pin, Georgiy B.; Inorganic chemistry 56 (2017) 4093–4103; doi:10.1021/acs.inorgchem.7b00061

data_4345631
_publ_section_title
;
 Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes:
 Synthesis, Structures, and Catalytic Activity in Oxidations with
 Peroxides.
;
_journal_issue                   7
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4093
_journal_page_last               4103
_journal_paper_doi               10.1021/acs.inorgchem.7b00061
_journal_volume                  56
_journal_year                    2017
_chemical_formula_moiety         'C28 H85 Cu9 O42 S5 Si18, 3(C2 H6 O S)'
_chemical_formula_sum            'C34 H103 Cu9 O45 S8 Si18'
_chemical_formula_weight         2566.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-12-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.750(6)
_cell_length_b                   20.975(4)
_cell_length_c                   15.835(3)
_cell_measurement_reflns_used    256
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.72
_cell_measurement_theta_min      2.12
_cell_volume                     10213(3)
_computing_cell_refinement       iMosflm
_computing_data_collection       Automar
_computing_data_reduction        iMosflm
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'Rayonix SX 165 area detector'
_diffrn_measured_fraction_theta_full 0.802
_diffrn_measured_fraction_theta_max 0.913
_diffrn_measurement_device
'MarExperts mardtb goniostat and Rayonix SX 165 detector'
_diffrn_measurement_device_type
'MarExperts mardtb goniostat and Rayonix SX 165 detector'
_diffrn_measurement_method       '/f scan'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.987
_diffrn_reflns_av_R_equivalents  0.1081
_diffrn_reflns_av_unetI/netI     0.0591
_diffrn_reflns_Laue_measured_fraction_full 0.802
_diffrn_reflns_Laue_measured_fraction_max 0.913
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            68725
_diffrn_reflns_point_group_measured_fraction_full 0.802
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        36.313
_diffrn_reflns_theta_max         34.513
_diffrn_reflns_theta_min         3.364
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    2.286
_exptl_absorpt_correction_T_max  0.61
_exptl_absorpt_correction_T_min  0.44
_exptl_absorpt_process_details   'Scala (Evans, 2005)'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.669
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5232
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.832
_refine_diff_density_min         -0.959
_refine_diff_density_rms         0.165
_refine_ls_extinction_coef       0.00122(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     628
_refine_ls_number_reflns         7624
_refine_ls_number_restraints     69
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1733
_refine_ls_R_factor_gt           0.1342
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1870P)^2^+97.3530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3459
_refine_ls_wR_factor_ref         0.3703
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4746
_reflns_number_total             7624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00061_si_005.cif
_cod_data_source_block           cu686
_cod_original_cell_volume        10213(4)
_cod_database_code               4345631
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.804
_shelx_estimated_absorpt_t_min   0.658
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 S7-O7 = S5-O6 = S4-O4 = S3-O3 = S2-O2
 1.54 with sigma of 0.003
 S7-C14 = S7-C13 = S5-C3 = S5-C4 = S4-C6 = S4-C5 = S3-C7 = S3-C8
 1.77 with sigma of 0.003
 S2-C12 = S2-C11
 1.77 with sigma of 0.003
 S6-O5 = S1-O1
 1.5 with sigma of 0.003
 S6-C1 = S6-C2 = S1-C9 = S1-C10
 1.76 with sigma of 0.003
3. Uiso/Uaniso restraints and constraints
Uanis(C7) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C6) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C3) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(C11) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C8) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C13) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: S2(0.5) S3(0.5) S4(0.5) S5(0.5) S7(0.5) H8(0.5) H3A(0.5) H3B(0.5)
 H3C(0.5) H4A(0.5) H4B(0.5) H4C(0.5) H5A(0.5) H5B(0.5) H5C(0.5) H6A(0.5)
 H6B(0.5) H6C(0.5) H7A(0.5) H7B(0.5) H7C(0.5) H8A(0.5) H8B(0.5) H8C(0.5)
 H11A(0.5) H11B(0.5) H11C(0.5) H12A(0.5) H12B(0.5) H12C(0.5) H13A(0.5)
 H13B(0.5) H13C(0.5) H14A(0.5) H14B(0.5) H14C(0.5) S1(0.5) O1(0.5) C9(0.5)
 H9A(0.5) H9B(0.5) H9C(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5) S6(0.5)
 O5(0.5) C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C2(0.5) H2A(0.5) H2B(0.5) H2C(0.5)
5.a Riding coordinates:
 O8(H8), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
5.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C1(H1A,
 H1B,H1C), C2(H2A,H2B,H2C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              31176
_shelx_hkl_checksum              70296
_olex2_submission_special_instructions 'No special instructions were received'