A new "bicycle helmet"-like copper(ii),sodiumphenylsilsesquioxane. Synthesis, structure and catalytic activity.
Kulakova, Alena N.; Bilyachenko, Alexey N.; Korlyukov, Alexander A.; Shul'pina, Lidia S.; Bantreil, Xavier; Lamaty, Frédéric; Shubina, Elena S.; Levitsky, Mikhail M.; Ikonnikov, Nikolay S.; Shul'pin, Georgiy B.; Dalton transactions (Cambridge, England : 2003) 47 (2018) 15666–15669; doi:10.1039/c8dt03209b

data_7047831
_publ_section_title
;
 A new &quot;bicycle helmet&quot;-like
 copper(ii),sodiumphenylsilsesquioxane. Synthesis, structure and catalytic
 activity.
;
_journal_issue                   44
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15666
_journal_page_last               15669
_journal_paper_doi               10.1039/c8dt03209b
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety
'C106 H93 Cu5 N6 Na O25 Si12, H2 O, 2(C4 H8 O), 0.33(O)'
_chemical_formula_sum            'C114 H111 Cu5 N6 Na O28.33 Si12'
_chemical_formula_weight         2696.17
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-01 deposited with the CCDC.
2018-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.820(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.8235(9)
_cell_length_b                   24.5281(8)
_cell_length_c                   20.8021(7)
_cell_measurement_reflns_used    9353
_cell_measurement_temperature    120
_cell_measurement_theta_max      71.80
_cell_measurement_theta_min      2.406
_cell_volume                     14149.7(8)
_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 0.991
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0702
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            242229
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.120
_diffrn_reflns_theta_min         2.405
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.377
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5638
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1119 before and 0.0666 after correction. The Ratio of minimum to maximum transmission is 0.7481. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5551
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.734
_refine_diff_density_min         -0.800
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1315
_refine_ls_number_reflns         27370
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1013
_refine_ls_R_factor_gt           0.0910
_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^)+(0.0807P)^2^+127.4361P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2299
_refine_ls_wR_factor_ref         0.2395
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23778
_reflns_number_total             27370
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03209b2.cif
_cod_data_source_block           760
_cod_depositor_comments          'Adding full bibliography for 7047831.cif.'
_cod_database_code               7047831
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.717
_shelx_estimated_absorpt_t_min   0.383
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Restrained distances
 C17-O10
 1.43 with sigma of 0.005
 C18-C17
 1.53 with sigma of 0.005
 C114-Si11
 1.89 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C113 \\sim C119: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C112 \\sim C118: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C111 \\sim C140: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C110 \\sim C116: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C109 \\sim C141: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C108 \\sim C114: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uiso(C114) = Uiso(C108)
Uiso(C113) = Uiso(C119)
Uiso(C112) = Uiso(C118)
Uiso(C117) = Uiso(C111)
Uiso(C116) = Uiso(C110)
Uiso(C115) = Uiso(C109)
4. Others
 Sof(C126)=Sof(C127)=Sof(H127)=Sof(C128)=Sof(H128)=Sof(C129)=Sof(H129)=
 Sof(C130)=Sof(H130)=Sof(C131)=Sof(H131)=1-FVAR(1)
 Sof(C120)=Sof(C121)=Sof(H121)=Sof(C125)=Sof(H125)=Sof(C122)=Sof(H122)=
 Sof(C123)=Sof(H123)=Sof(C124)=Sof(H124)=FVAR(1)
 Sof(C154)=Sof(H154)=Sof(C155)=Sof(H155)=Sof(C150)=Sof(C151)=Sof(H151)=
 Sof(C152)=Sof(H152)=Sof(C153)=Sof(H153)=1-FVAR(2)
 Sof(C144)=Sof(C145)=Sof(H145)=Sof(C149)=Sof(H149)=Sof(C148)=Sof(H148)=
 Sof(C146)=Sof(H146)=Sof(C147)=Sof(H147)=FVAR(2)
 Sof(C132)=Sof(C137)=Sof(H137)=Sof(C136)=Sof(H136)=Sof(C135)=Sof(H135)=
 Sof(C134)=Sof(H134)=Sof(C133)=Sof(H133)=1-FVAR(3)
 Sof(C138)=Sof(C139)=Sof(H139)=Sof(C141)=Sof(H141)=Sof(C140)=Sof(H140)=
 Sof(C143)=Sof(H143)=Sof(C142)=Sof(H142)=FVAR(3)
 Sof(C163)=Sof(C162)=Sof(H162)=Sof(C169)=Sof(H169)=Sof(C167)=Sof(H167)=
 Sof(C165)=Sof(H165)=Sof(C164)=Sof(H164)=1-FVAR(4)
 Sof(C156)=Sof(C157)=Sof(H157)=Sof(C158)=Sof(H158)=Sof(C161)=Sof(H161)=
 Sof(C159)=Sof(H159)=Sof(C168)=Sof(H168)=FVAR(4)
 Sof(C118)=Sof(H118)=Sof(C119)=Sof(H119)=Sof(C114)=Sof(C115)=Sof(H115)=
 Sof(C116)=Sof(H116)=Sof(C117)=Sof(H117)=1-FVAR(5)
 Sof(C108)=Sof(C109)=Sof(H109)=Sof(C110)=Sof(H110)=Sof(C111)=Sof(H111)=
 Sof(C112)=Sof(H112)=Sof(C113)=Sof(H113)=FVAR(5)
 Sof(C176)=Sof(C177)=Sof(H177)=Sof(C178)=Sof(H178)=Sof(C179)=Sof(H179)=
 Sof(C180)=Sof(H180)=Sof(C60)=Sof(H60)=1-FVAR(6)
 Sof(C173)=Sof(H173)=Sof(C172)=Sof(H172)=Sof(C171)=Sof(H171)=Sof(C170)=
 Sof(C175)=Sof(H175)=Sof(C174)=Sof(H174)=FVAR(6)
 Fixed Sof: O4(0.5) C28(0.5) H28A(0.5) H28B(0.5) C27(0.5) H27A(0.5) H27B(0.5)
 C26(0.5) H26A(0.5) H26B(0.5) C25(0.5) H25A(0.5) H25B(0.5) O9(0.5) C29(0.5)
 H29A(0.5) H29B(0.5) C30(0.5) H30A(0.5) H30B(0.5) C31(0.5) H31A(0.5) H31B(0.5)
 C32(0.5) H32A(0.5) H32B(0.5) O8(0.25) C37(0.25) H37A(0.25) H37B(0.25)
 C38(0.25) H38A(0.25) H38B(0.25) C39(0.25) H39A(0.25) H39B(0.25) C40(0.25)
 H40A(0.25) H40B(0.25) O3(0.5) C21(0.5) H21A(0.5) H21B(0.5) C22(0.5) H22A(0.5)
 H22B(0.5) C23(0.5) H23A(0.5) H23B(0.5) C24(0.5) H24A(0.5) H24B(0.5)
 O11(0.33333) C36(0.25) H36A(0.25) H36B(0.25) C35(0.25) H35A(0.25) H35B(0.25)
 C34(0.25) H34A(0.25) H34B(0.25) C33(0.25) H33A(0.25) H33B(0.25) O7(0.25)
 Fixed Uiso: C27(0.15) C26(0.15) C30(0.15) C38(0.15) C39(0.15) C22(0.15)
5.a Free rotating group:
 O24(H24C,H24D), O4(C28,C27,C26,C25), O9(C29,C30,C31,C32), O8(C37,C38,C39,C40),
  O3(C21,C22,C23,C24,C126,C127,C128,C129,C130,C131,C132,C137,C136,C135,C134,
 C133,O11), C36(C35,C34,C33,O7)
5.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C19(H19A,H19B), C18(H18A,H18B), C17(H17A,H17B), C28(H28A,
 H28B), C27(H27A,H27B), C26(H26A,H26B), C25(H25A,H25B), C29(H29A,H29B),
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C37(H37A,H37B), C38(H38A,H38B),
  C39(H39A,H39B), C40(H40A,H40B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,
 H23B), C24(H24A,H24B), C36(H36A,H36B), C35(H35A,H35B), C34(H34A,H34B),
 C33(H33A,H33B)
5.c Aromatic/amide H refined with riding coordinates:
 C71(H71), C98(H98), C78(H78), C58(H58), C67(H67), C65(H65), C46(H46),
 C54(H54), C42(H42), C100(H100), C87(H87), C88(H88), C109(H109), C110(H110),
 C111(H111), C112(H112), C113(H113), C101(H101), C145(H145), C107(H107),
 C44(H44), C99(H99), C149(H149), C70(H70), C43(H43), C45(H45), C86(H86),
 C61(H61), C84(H84), C81(H81), C68(H68), C104(H104), C91(H91), C57(H57),
 C64(H64), C106(H106), C52(H52), C90(H90), C48(H48), C49(H49), C97(H97),
 C85(H85), C121(H121), C69(H69), C62(H62), C50(H50), C79(H79), C80(H80),
 C56(H56), C73(H73), C77(H77), C63(H63), C89(H89), C55(H55), C94(H94), C96(H96),
  C105(H105), C95(H95), C125(H125), C76(H76), C51(H51), C139(H139), C74(H74),
 C122(H122), C141(H141), C148(H148), C173(H173), C172(H172), C171(H171),
 C175(H175), C174(H174), C75(H75), C140(H140), C123(H123), C146(H146),
 C124(H124), C147(H147), C143(H143), C157(H157), C142(H142), C158(H158),
 C161(H161), C159(H159), C168(H168), C127(H127), C128(H128), C129(H129),
 C130(H130), C131(H131), C137(H137), C136(H136), C135(H135), C134(H134),
 C133(H133), C154(H154), C155(H155), C151(H151), C152(H152), C153(H153),
 C162(H162), C169(H169), C167(H167), C165(H165), C164(H164), C118(H118),
 C119(H119), C115(H115), C116(H116), C117(H117), C177(H177), C178(H178),
 C179(H179), C180(H180), C60(H60)
5.d Fitted hexagon refined as free rotating group:
 C108(C109,C110,C111,C112,C113), C173(C172,C171,C170,C175,C174), C154(C155,
 C150,C151,C152,C153), C163(C162,C169,C167,C165,C164), C118(C119,C114,C115,C116,
 C117), C176(C177,C178,C179,C180,C60)
5.e Idealised tetrahedral OH refined as rotating group:
 O36(H36)
;
_shelx_res_checksum              9037
_shelx_fab_checksum              19691
_olex2_submission_special_instructions 'No special instructions were received'