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_4345548
_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
'C34 H48 Cu6 N4 O22 Si10, C35.32 H49.32 Cu6 N4 O22.66 Si10, 4(C2 H6 O S), 4(H2 O)'
_chemical_formula_sum            'C77.32 H129.32 Cu12 N8 O52.66 S4 Si20'
_chemical_formula_weight         3466.12
_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             2016-08-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                94.7850(10)
_cell_angle_beta                 105.7280(10)
_cell_angle_gamma                102.666(2)
_cell_formula_units_Z            1
_cell_length_a                   14.3152(4)
_cell_length_b                   14.7500(4)
_cell_length_c                   16.6756(4)
_cell_measurement_reflns_used    9964
_cell_measurement_temperature    120
_cell_measurement_theta_max      71.50
_cell_measurement_theta_min      2.79
_cell_volume                     3268.25(15)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            44107
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.925
_diffrn_reflns_theta_min         2.785
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.182
_exptl_absorpt_correction_T_max  0.7535
_exptl_absorpt_correction_T_min  0.5393
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0862 before and 0.0474 after correction.
The Ratio of minimum to maximum transmission is 0.7157.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.761
_exptl_crystal_description       block
_exptl_crystal_F_000             1763
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.938
_refine_diff_density_min         -1.241
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     808
_refine_ls_number_reflns         12361
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0681P)^2^+7.9510P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1182
_refine_ls_wR_factor_ref         0.1306
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10354
_reflns_number_total             12361
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00061_si_002.cif
_cod_data_source_block           paa116
_cod_depositor_comments
'Adding full bibliography for 4345548--4345550.cif.'
_cod_database_code               4345548
_shelxl_version_number           2014/6
_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) groups
2. Restrained distances
 O2W-H2WB
 0.85 with sigma of 0.001
3. Others
 Fixed Sof: H1AC(0.67) O2AC(0.33) C1AC(0.33) C2AC(0.33) H2AD(0.33) H2AE(0.33)
 H2AF(0.33)
4.a Riding coordinates:
 O3(H3), O1AC(H1AC), O2W(H2WA,H2WB)
4.b Rotating group:
 O1W(H1WA,H1WB)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C6A(H6A), C7A(H7A), C8A(H8A), C12A(H12A), C13A(H13A), C14A(H14A), C15A(H15A),
 C16A(H16A)
4.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C1A(H1AA,H1AB,H1AD), C2A(H2AA,H2AB,H2AC), C2AC(H2AD,H2AE,H2AF),
 C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C1S(H1SA,H1SB,
 H1SC), C2S(H2SA,H2SB,H2SC), C3S(H3SA,H3SB,H3SC), C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              21484
_shelx_hkl_checksum              99734
_olex2_submission_special_instructions 'No special instructions were received'