Solvent-controlled synthesis of tetranuclear cage-like copper(II) silsesquioxanes. Remarkable features of the cage structures and their high catalytic activity in oxidation with peroxides.
Dronova, Marina S.; Bilyachenko, Alexey N.; Yalymov, Alexey I.; Kozlov, Yuriy N.; Shul'pina, Lidia S.; Korlyukov, Alexander A.; Arkhipov, Dmitry E.; Levitsky, Mikhail M.; Shubina, Elena S.; Shul'pin, Georgiy B.; Dalton transactions (Cambridge, England : 2003) 43 (2014) 872–882; doi:10.1039/c3dt52508b

data_7028318
_publ_section_title
;
 Solvent-controlled synthesis of tetranuclear cage-like copper(II)
 silsesquioxanes. Remarkable features of the cage structures and their
 high catalytic activity in oxidation with peroxides.
;
_journal_issue                   2
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              872
_journal_page_last               882
_journal_paper_doi               10.1039/c3dt52508b
_journal_volume                  43
_journal_year                    2014
_chemical_formula_moiety         'C104 H140 Cu4 Na4 O32 Si12'
_chemical_formula_sum            'C104 H140 Cu4 Na4 O32 Si12'
_chemical_formula_weight         2585.36
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a'
_symmetry_space_group_name_Hall  '-I 4ad'
_symmetry_space_group_name_H-M   'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-08-22
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   30.9472(19)
_cell_length_b                   30.9472(19)
_cell_length_c                   12.6009(8)
_cell_measurement_reflns_used    5944
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.26
_cell_measurement_theta_min      2.19
_cell_volume                     12068.2(13)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XLMP, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEX II 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  0.1104
_diffrn_reflns_av_unetI/netI     0.1207
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            75164
_diffrn_reflns_theta_full        30.54
_diffrn_reflns_theta_max         30.54
_diffrn_reflns_theta_min         1.32
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.902
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6296
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0713 before and 0.0595 after correction.
The Ratio of minimum to maximum transmission is 0.8439.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5392
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.304
_refine_diff_density_min         -0.792
_refine_diff_density_rms         0.203
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         9234
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.2194
_refine_ls_R_factor_gt           0.0859
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0400P)^2^+177.5766P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1704
_refine_ls_wR_factor_ref         0.2440
_reflns_number_gt                3757
_reflns_number_total             9234
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c3dt52508b.txt
_cod_data_source_block           yaai93
_cod_original_cell_volume        12068.3(13)
_cod_database_code               7028318
_olex2_refinement_description
;
1. Shared sites
{C21A, C21}
{H33A, H33}
2. Others
 Fixed Sof: C11(0.5) C12(0.5) H12(0.5) C13(0.5) H13(0.5) C14(0.5) H14(0.5)
 C15(0.5) H15(0.5) C16(0.5) H16(0.5) C21(0.5) C22(0.5) H22(0.5) C23(0.5)
 H23(0.5) C24(0.5) H24(0.5) C25(0.5) H25(0.5) C26(0.5) H26(0.5) C31(0.5)
 C32(0.5) H32(0.5) C33(0.5) H33(0.5) C34(0.5) H34(0.5) C35(0.5) H35(0.5)
 C36(0.5) H36(0.5) C11A(0.5) C12A(0.5) H12A(0.5) C13A(0.5) H13A(0.5) C14A(0.5)
 H14A(0.5) C15A(0.5) H15A(0.5) C16A(0.5) H16A(0.5) C21A(0.5) C22A(0.5)
 H22A(0.5) C23A(0.5) H23A(0.5) C24A(0.5) H24A(0.5) C25A(0.5) H25A(0.5)
 C26A(0.5) H26A(0.5) C31A(0.5) C32A(0.5) H32A(0.5) C33A(0.5) H33A(0.5)
 C34A(0.5) H34A(0.5) C35A(0.5) H35A(0.5) C36A(0.5) H36A(0.5) O1S(0.5) H1AB(0.5)
 C1S(0.5) H1SA(0.5) H1SB(0.5) C2S(0.5) H2SA(0.5) H2SB(0.5) C3S(0.5) H3SA(0.5)
 H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5) O2S(0.5) H1AA(0.5) C5S(0.5)
 H5SA(0.5) H5SB(0.5) C6S(0.5) H6SA(0.5) H6SB(0.5) C7S(0.5) H7SA(0.5) H7SB(0.5)
 C8S(0.5) H8SA(0.5) H8SB(0.5) H8SC(0.5) O1SA(0.5) H1B(0.5) C4SA(0.5) H4SD(0.5)
 H4SE(0.5) H4SF(0.5) C1SA(0.5) H1SC(0.5) H1SD(0.5) C2SA(0.5) H2SC(0.5)
 H2SD(0.5) C3SA(0.5) H3SC(0.5) H3SD(0.5) O2SA(0.5) H2SE(0.5) C5SA(0.5)
 H5SC(0.5) H5SD(0.5) C6SA(0.5) H6SC(0.5) H6SD(0.5) C8SA(0.5) H8SD(0.5)
 H8SE(0.5) H8SF(0.5) C7SA(0.5) H7SC(0.5) H7SD(0.5)
 Fixed Uiso: H12(0.066) H13(0.076) H14(0.085) H15(0.087) H16(0.067) H22(0.059)
 H23(0.063) H24(0.055) H25(0.061) H26(0.052) H32(0.21) H33(0.109) H34(0.077)
 H35(0.074) H36(0.063) H12A(0.085) H13A(0.096) H14A(0.1) H15A(0.076)
 H16A(0.056) H22A(0.158) H23A(0.156) H24A(0.143) H25A(0.221) H26A(0.166)
 H32A(0.057) H33A(0.14) H34A(0.117) H35A(0.121) H36A(0.087) H1AB(0.105)
 H1SA(0.082) H1SB(0.082) H2SA(0.151) H2SB(0.151) H3SA(0.341) H3SB(0.341)
 H4SA(0.165) H4SB(0.165) H4SC(0.165) H1AA(0.061) H5SA(0.185) H5SB(0.185)
 H6SA(0.124) H6SB(0.124) H7SA(0.13) H7SB(0.13) H8SA(0.169) H8SB(0.169)
 H8SC(0.169) H1B(0.199) H4SD(0.253) H4SE(0.253) H4SF(0.253) H1SC(0.185)
 H1SD(0.185) H2SC(0.196) H2SD(0.196) H3SC(0.172) H3SD(0.172) H2SE(0.303)
 H5SC(0.075) H5SD(0.075) H6SC(0.299) H6SD(0.299) H8SD(0.371) H8SE(0.371)
 H8SF(0.371) H7SC(0.22) H7SD(0.22)
 Fixed X: H12(0.6529) H13(0.6613) H14(0.6031) H15(0.5364) H16(0.528)
 H22(0.7072) H23(0.7647) H24(0.7624) H25(0.7027) H26(0.6452) H32(0.4566)
 H33(0.4412) H34(0.4254) H35(0.4249) H36(0.4403) H12A(0.6523) H13A(0.6649)
 H14A(0.6072) H15A(0.5369) H16A(0.5244) H22A(0.7222) H23A(0.7726) H24A(0.7491)
 H25A(0.6752) H26A(0.6248) H32A(0.454) H33A(0.4465) H34A(0.449) H35A(0.4589)
 H36A(0.4663) H1SA(0.6837) H1SB(0.6604) H2SA(0.6392) H2SB(0.631) H3SA(0.7168)
 H3SB(0.6978) H4SA(0.6625) H4SB(0.6566) H4SC(0.7021) H5SA(0.5713) H5SB(0.5455)
 H6SA(0.6028) H6SB(0.6202) H7SA(0.6309) H7SB(0.6521) H8SA(0.6999) H8SB(0.6716)
 H8SC(0.6987) H4SD(0.6854) H4SE(0.6782) H4SF(0.7233) H1SC(0.6761) H1SD(0.6811)
 H2SC(0.6597) H2SD(0.7071) H3SC(0.6447) H3SD(0.6921) H5SC(0.5437) H5SD(0.5516)
 H6SC(0.6064) H6SD(0.6107) H8SD(0.7022) H8SE(0.6935) H8SF(0.7186) H7SC(0.651)
 H7SD(0.6561)
 Fixed Y: H12(0.7806) H13(0.7854) H14(0.8067) H15(0.8231) H16(0.8184)
 H22(0.7535) H23(0.7308) H24(0.6628) H25(0.6177) H26(0.6404) H32(0.6133)
 H33(0.5574) H34(0.4881) H35(0.4746) H36(0.5305) H12A(0.8051) H13A(0.8217)
 H14A(0.8238) H15A(0.8093) H16A(0.7928) H22A(0.7214) H23A(0.6932) H24A(0.6531)
 H25A(0.6412) H26A(0.6694) H32A(0.6104) H33A(0.5497) H34A(0.4803) H35A(0.4718)
 H36A(0.5325) H1SA(0.5917) H1SB(0.5452) H2SA(0.5953) H2SB(0.545) H3SA(0.5747)
 H3SB(0.5271) H4SA(0.5486) H4SB(0.5969) H4SC(0.5818) H5SA(0.5614) H5SB(0.5341)
 H6SA(0.491) H6SB(0.5176) H7SA(0.5484) H7SB(0.5704) H8SA(0.5215) H8SB(0.4829)
 H8SC(0.5137) H4SD(0.5248) H4SE(0.5642) H4SF(0.559) H1SC(0.6099) H1SD(0.5639)
 H2SC(0.5349) H2SD(0.5526) H3SC(0.5908) H3SD(0.6099) H5SC(0.5572) H5SD(0.5287)
 H6SC(0.5064) H6SD(0.5514) H8SD(0.5449) H8SE(0.4978) H8SF(0.5332) H7SC(0.5317)
 H7SD(0.5759)
 Fixed Z: H12(0.2905) H13(0.1063) H14(-0.0001) H15(0.0777) H16(0.2619)
 H22(0.4357) H23(0.3286) H24(0.2472) H25(0.2729) H26(0.38) H32(0.275)
 H33(0.1555) H34(0.2188) H35(0.4015) H36(0.521) H12A(0.3033) H13A(0.1247)
 H14A(0.0048) H15A(0.0635) H16A(0.242) H22A(0.4962) H23A(0.3763) H24A(0.2298)
 H25A(0.2032) H26A(0.3231) H32A(0.2658) H33A(0.1567) H34A(0.2306) H35A(0.4135)
 H36A(0.5225) H1SA(0.6869) H1SB(0.6678) H2SA(0.8509) H2SB(0.8356) H3SA(0.8713)
 H3SB(0.8938) H4SA(1.041) H4SB(0.9984) H4SC(1.0459) H5SA(0.28) H5SB(0.3661)
 H6SA(0.3363) H6SB(0.4381) H7SA(0.223) H7SB(0.3263) H8SA(0.2251) H8SB(0.2732)
 H8SC(0.3506) H4SD(0.9725) H4SE(1.0529) H4SF(0.9924) H1SC(0.6806) H1SD(0.6285)
 H2SC(0.7944) H2SD(0.778) H3SC(0.9113) H3SD(0.8932) H5SC(0.307) H5SD(0.4131)
 H6SC(0.3117) H6SD(0.2536) H8SD(0.2637) H8SE(0.3115) H8SF(0.3806) H7SC(0.4461)
 H7SD(0.3838)
;