# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/1828 data_General _audit_creation_date 'Wed Jul 28 11:44:01 1999' _audit_creation_method 'by teXsan' _audit_update_record ? #------------------------------------------------------------------------------ # PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_coeditor_code ? #------------------------------------------------------------------------------ # SUBMISSION DETAILS _publ_contact_author_name 'T. Don Tilley' _publ_contact_author_address ; Department of Chemistry and the Department of Chemical Engineering, University of California, Berkeley, Berkeley, California 94720-1460, USA ; _publ_contact_author_email ' tdtilley@socrates.berkeley.edu ' _publ_contact_author_fax ' (510) 642-8940 ' _publ_contact_author_phone ' (510) 642-8939 ' _publ_contact_letter ; ; _publ_requested_journal ' Chem Comm' _publ_requested_category ? _publ_requested_coeditor_name ? #------------------------------------------------------------------------------ # TITLE AND AUTHOR LIST _publ_section_title ; Synthesis and Structure of the (Tetrahydroxy)oligosiloxane [(tBuO)3SiOSi(OH)2]2O ; _publ_section_title_footnote ; ENTER FOOTNOTE TO TITLE OF PAPER ; loop_ _publ_author_name _publ_author_footnote _publ_author_address ' T. Don Tilley ' ; FIRST AUTHORS FOOTNOTES ; ; Department of Chemistry and the Department of Chemical Engineering, University of California, Berkeley, Berkeley, California 94720-1460, USA ; _publ_section_synopsis ; ENTER SYNOPSIS ; #------------------------------------------------------------------------------ # TEXT _publ_section_abstract ; The solid-state structure of the oligomeric (tetrahydroxy)polysiloxane [(tBuO)3SiOSi(OH)2]2O, synthesized by the hydrolysis of (tBuO)3SiOSiCl3, reveals two intramolecular hydrogen bonds and two types of intermolecular hydrogen bonds that arrange the molecules into infinite chains. ; _publ_section_comment ; Silanol compounds serve as interesting models for the surface hydroxyl groups of silica, and are useful in the synthesis of metal siloxy derivatives containing Si-O-M linkages.1-4 However, as the number of hydroxyl functionalities per silicon atom increases, these compounds become more unstable toward condensation reactions, hampering the application of silanediols (R2Si(OH)2) and silanetriols (RSi(OH)3) in molecular chemistry. Silanetriols are particularly susceptible to polycondensation in solution to afford closo- silsesquioxane species such as R8Si8O12.5 The judicious choice of R groups, and modifications of synthetic procedures, allow isolation of the incompletely condensed silsesquioxanes R7Si7O9(OH)3,6 which have been used as ligands in main-group and transition-metal complexes.2 In addition, sterically demanding groups on silicon have allowed isolation of a number of silanediols, silanetriols and disiloxanediols.1-4 Cyclic structures containing multiple Si-OH functionalities include compounds of the type [ArN(SiMe3)Si(OH)O]37 and cis-cis-cis- [(C6H5)4Si4O4(OH)4].8 We are interested in the design and synthesis of oxygen-rich metallasiloxane derivatives that undergo facile, low temperature pyrolyses to homogeneous (atomically well-mixed) metal-silica materials, and have previously shown that tris(tert-butoxy)silanol, HOSi(OtBu)39 (1), and bis(tert-butoxy)silanediol, (HO)2Si(OtBu)210 (2), are excellent starting materials for the preparation of suitable metal siloxide precursors.11 Furthermore, the oxygen environment of the silicon atoms in these molecular species makes them interesting soluble models for heterogeneous, silica-supported catalysts.11j,k In this communication we describe efforts to synthesize a novel hydroxy-substituted siloxane for use in the synthesis of precursors to silica-based materials. Initial efforts began with attempts to synthesize the reported silanetriol (tBuO)3SiOSi(OH)3 (3),9 which instead resulted in isolation of the (tetrahydroxy)oligosiloxane [(tBuO)3SiOSi(OH)2]2O (4). This unusual siloxane is of interest as a model for reactive intermediates in the hydrolytic condensation of tetra(alkoxy)silanes Si(OR)4 to silica gel.12 Attempts to reproduce the literature synthesis of 3 afforded a white crystalline product which exhibits spectroscopic (ir and 1H, 13C nmr) and physical (appearance, melting point) characteristics which are very similar to those originally reported.9,+ To unambiguously determine the structure of the product a single crystal X-ray study was performed, and this revealed the true identity of the product as [(tBuO)3SiOSi(OH)2]2O (4).13 Presumably, 4 forms via condensation of the intermediate silanetriol 3 (equation 1). The infrared spectra of 1, 2 and 4 (KBr pellet) contain Si-OH vibrations in the range 3200-3500 cm-1, indicating the presence of hydrogen bonding within the molecules.1 These values are shifted from those for silanol functionalities of dehydrated silica, which exhibit bands at ca. 3750 +/- 10 cm-1 (uOH) and 770-840 cm-1 (dOH).14 The broad nature of the u(OH) band in 3 results from the presence of a number of hydrogen-bonding interactions, as revealed in the solid state structure (vide infra). The presence of a Si-O-Si group in 4 results in a Si-O vibration at 1138 cm-1. The 29Si NMR spectrum of 4 (CDCl3) contains a sharp peak at d -90.3 for the Si(OtBu)3 group, and a broad peak at d -103.2 for the Si(OH)2 silicon atoms. The molecular structure of 4 contains two intramolecular hydrogen bonds (H(55)...O(11) = 2.35(3) A; H(57)...O(1) = 2.02(3) A) which appear to distort the silicon-oxygen backbone of the molecule into a parabolic shape (Figure 1). As a consequence, the central Si(2)-O(7)-Si(3) angle of 137.7(1) is much smaller than the Si(1)-O(4)-Si(2) and Si(3)-O(10)-Si(4) angles of 165.7(2) and 163.6(2), respectively. A similar bending in [Os(CO)Cl(PPh3)2Si(OH)2]2O arises from an intramolecular interaction between one SiOH group and a chloride ligand.15 The compound [ArN(SiMe3)Si(OH)2]2O also adopts a bent structure, which apparently results from association of the molecules in the solid state to form a trimeric cage.7 The lack of intramolecular interactions in [tBuSi(OH)2]2O16 and [ArN(SiMe3)SiCl2]2O (Ar = 2,6-iPrC6H3)7 results in linear Si-O-Si linkages. Also present within the structure of 4 are two sets of intermolecular hydrogen bonds which link the molecules together to form 8- and 12-membered rings, each of which includes an inversion center (Figure 2). The O(9)-H(58)...O(8) hydrogen bond (2.12(3) A) supports the 8-membered ring, whereas the O(6)-H(56)...O(9) interaction (1.93(3) A) is part of the 12-membered ring. Together, these intermolecular hydrogen bonds link the molecules into a chain structure which repeats along the a-direction. Multiple intermolecular hydrogen bonds are also present in [tBuSi(OH)2]2O, resulting in assembly of the molecules into a sheet-like structure in the solid state.16 Compound 4 is relatively stable towards further condensation in the solid state and in solution, but exposure to air for extended periods results in an insoluble material. The thermogravimetric analysis of 4 (heating rate 2 C min-1 to 600 C, 10 C min-1 to 1100 C, oxygen flow) revealed a 50 % weight loss between 60 an d 140 C. Further heating resulted in an additional sharp weight loss to 26.9 wt % (between 240 and 290 C), corresponding to the theoretical yield for 3 SiO2 (27.0 wt %). These data indicate that 4 may serve as a useful precursor for silica at relatively low temperatures. In contrast, 1 sublimes under similar conditions, so that its use in pyrolytic transformations to silica-based materials is somewhat limited. Preliminary reactivity studies with 4 have shown that the siloxide backbone is cleaved by nBuLi, with formation of LiOSi(OtBu)3 as the only isolated product. In conclusion, the compound previously reported as (tBuO)3SiOSi(OH)39 has been reformulated as the condensation product [(tBuO)3SiOSi(OH)2]2O. Further studies will focus on the synthesis of transition metal derivatives of this species. ; _publ_section_acknowledgements ; This work was supported by the Director, Office of Energy Research, Office of Basic Energy Sciences, Chemical Sciences Division, of the U. S. Department of Energy under Contract No. DE-AC03-76SF00098. ; _publ_section_exptl_prep ; ENTER COMPOUND PREPARATION DETAILS ; _publ_section_exptl_refinement ; ENTER SPECIAL DETAILS OF THE REFINEMENT ; #------------------------------------------------------------------------------ data_Rulken's_starting_material #------------------------------------------------------------------------------ # CHEMICAL DATA _chemical_formula_sum 'C24 H60 O13 Si4 ' _chemical_formula_moiety 'C24 H60 O13 Si4 ' _chemical_formula_weight 669.07 _chemical_melting_point ? #------------------------------------------------------------------------------ # CRYSTAL DATA _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1 ' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z _cell_length_a 9.4952(6) _cell_length_b 14.1078(8) _cell_length_c 15.3210(9) _cell_angle_alpha 112.688(1) _cell_angle_beta 93.374(1) _cell_angle_gamma 90.217(1) _cell_volume 1889.5(2) _cell_formula_units_Z 2 _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _cell_measurement_temperature 273.2 #------------------------------------------------------------------------------ _exptl_crystal_description 'column' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max 0.400 _exptl_crystal_size_mid 0.230 _exptl_crystal_size_min 0.150 _exptl_crystal_size_rad ? _exptl_crystal_density_diffrn 1.176 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_absorpt_coefficient_mu 0.209 _exptl_absorpt_correction_type none #------------------------------------------------------------------------------ # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_measurement_device_type ? _diffrn_reflns_number 0 _diffrn_reflns_av_R_equivalents 0.034 _diffrn_reflns_theta_max ? _diffrn_measured_fraction_theta_max ? _diffrn_reflns_theta_full ? _diffrn_measured_fraction_theta_full ? _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 0 #------------------------------------------------------------------------------ # REFINEMENT DATA _refine_special_details ; Refinement using reflections with F^2^ > 3.0 sigma(F^2^). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F^2^ > 2.0 sigma(F^2^) is used only for calculating R-factor (gt). ; _reflns_number_total 0 _reflns_number_gt 0 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.0000 _refine_ls_wR_factor_ref 0.0579 _refine_ls_hydrogen_treatment ? _refine_ls_number_reflns 4741 _refine_ls_number_parameters 383 _refine_ls_goodness_of_fit_ref 2.150 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(Fo) + 0.00024|Fo|^2^]' _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 0.37 _refine_diff_density_min -0.38 _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'Si' 'Si' 0.082 0.070 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; 'O' 'O' 0.011 0.006 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; 'C' 'C' 0.003 0.002 ;International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.1) ; 'H' 'H' 0.000 0.000 ;International Tables for Crystallography (1992, Vol. C, Table 6.1.1.2) ; #------------------------------------------------------------------------------ # ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Si1 Si 0.28692(9) 0.27073(6) 0.32826(6) 0.0232(2) Uani 1.00 d . . . Si2 Si 0.06551(9) 0.10684(7) 0.18374(6) 0.0228(2) Uani 1.00 d . . . Si3 Si 0.30142(8) -0.00712(6) 0.06766(6) 0.0202(2) Uani 1.00 d . . . Si4 Si 0.33737(9) -0.15758(7) 0.17640(6) 0.0260(2) Uani 1.00 d . . . O1 O 0.4340(2) 0.2121(2) 0.2948(1) 0.0257(6) Uani 1.00 d . . . O2 O 0.2664(2) 0.2760(2) 0.4333(1) 0.0274(6) Uani 1.00 d . . . O3 O 0.2892(2) 0.3857(2) 0.3294(1) 0.0332(6) Uani 1.00 d . . . O4 O 0.1684(2) 0.1999(2) 0.2523(1) 0.0327(6) Uani 1.00 d . . . O5 O 0.0212(3) 0.0321(2) 0.2340(2) 0.0430(9) Uani 1.00 d . . . O6 O -0.0702(2) 0.1597(2) 0.1586(2) 0.0307(7) Uani 1.00 d . . . O7 O 0.1512(2) 0.0449(1) 0.0906(1) 0.0252(6) Uani 1.00 d . . . O8 O 0.4316(2) 0.0759(2) 0.1115(2) 0.0303(6) Uani 1.00 d . . . O9 O 0.3079(2) -0.0560(2) -0.0461(1) 0.0260(6) Uani 1.00 d . . . O10 O 0.3135(2) -0.0959(2) 0.1082(1) 0.0328(7) Uani 1.00 d . . . O11 O 0.2367(2) -0.1015(2) 0.2632(1) 0.0326(6) Uani 1.00 d . . . O12 O 0.4971(2) -0.1492(2) 0.2203(1) 0.0305(6) Uani 1.00 d . . . O13 O 0.2955(2) -0.2776(2) 0.1182(1) 0.0316(6) Uani 1.00 d . . . C1 C 0.5806(3) 0.2413(2) 0.3343(2) 0.0280(9) Uani 1.00 d . . . C2 C 0.6480(3) 0.2930(3) 0.2765(2) 0.0355(10) Uani 1.00 d . . . C3 C 0.5850(3) 0.3121(3) 0.4380(2) 0.043(1) Uani 1.00 d . . . C4 C 0.6510(4) 0.1408(3) 0.3211(3) 0.040(1) Uani 1.00 d . . . C5 C 0.1693(3) 0.3298(2) 0.5042(2) 0.0314(9) Uani 1.00 d . . . C6 C 0.1815(5) 0.2793(4) 0.5751(3) 0.073(2) Uani 1.00 d . . . C7 C 0.0223(4) 0.3188(4) 0.4590(3) 0.072(1) Uani 1.00 d . . . C8 C 0.2166(5) 0.4413(3) 0.5501(3) 0.065(1) Uani 1.00 d . . . C9 C 0.2577(4) 0.4261(3) 0.2567(2) 0.0349(10) Uani 1.00 d . . . C10 C 0.3006(4) 0.3529(3) 0.1610(2) 0.044(1) Uani 1.00 d . . . C11 C 0.1004(4) 0.4437(3) 0.2531(3) 0.057(1) Uani 1.00 d . . . C12 C 0.3423(5) 0.5262(3) 0.2889(3) 0.058(1) Uani 1.00 d . . . C13 C 0.2443(4) -0.0964(3) 0.3602(2) 0.037(1) Uani 1.00 d . . . C14 C 0.2913(7) -0.1947(4) 0.3637(4) 0.109(2) Uani 1.00 d . . . C15 C 0.1006(5) -0.0689(4) 0.3963(3) 0.077(2) Uani 1.00 d . . . C16 C 0.3463(6) -0.0086(5) 0.4170(3) 0.094(2) Uani 1.00 d . . . C17 C 0.6255(3) -0.1981(3) 0.1802(2) 0.0362(10) Uani 1.00 d . . . C18 C 0.6186(4) -0.3103(3) 0.1686(3) 0.061(1) Uani 1.00 d . . . C19 C 0.6445(4) -0.1866(3) 0.0880(3) 0.059(1) Uani 1.00 d . . . C20 C 0.7441(4) -0.1414(3) 0.2525(3) 0.046(1) Uani 1.00 d . . . C21 C 0.1991(3) -0.3329(3) 0.0381(2) 0.0359(10) Uani 1.00 d . . . C22 C 0.1913(4) -0.4414(3) 0.0346(3) 0.055(1) Uani 1.00 d . . . C23 C 0.2606(4) -0.3340(3) -0.0517(3) 0.055(1) Uani 1.00 d . . . C24 C 0.0572(4) -0.2836(3) 0.0507(3) 0.063(1) Uani 1.00 d . . . H1 H 0.7425 0.3134 0.3008 0.0426 Uiso 1.00 calc . . . H2 H 0.6476 0.2464 0.2122 0.0426 Uiso 1.00 calc . . . H3 H 0.5962 0.3518 0.2803 0.0426 Uiso 1.00 calc . . . H4 H 0.6803 0.3296 0.4616 0.0512 Uiso 1.00 calc . . . H5 H 0.5359 0.3728 0.4446 0.0512 Uiso 1.00 calc . . . H6 H 0.5415 0.2783 0.4728 0.0512 Uiso 1.00 calc . . . H7 H 0.6028 0.1070 0.3540 0.0478 Uiso 1.00 calc . . . H8 H 0.6477 0.0981 0.2555 0.0478 Uiso 1.00 calc . . . H9 H 0.7466 0.1543 0.3454 0.0478 Uiso 1.00 calc . . . H10 H 0.1187 0.3103 0.6236 0.0880 Uiso 1.00 calc . . . H11 H 0.1581 0.2082 0.5440 0.0880 Uiso 1.00 calc . . . H12 H 0.2756 0.2879 0.6023 0.0880 Uiso 1.00 calc . . . H13 H -0.0407 0.3547 0.5058 0.0864 Uiso 1.00 calc . . . H14 H 0.0201 0.3467 0.4115 0.0864 Uiso 1.00 calc . . . H15 H -0.0054 0.2482 0.4310 0.0864 Uiso 1.00 calc . . . H16 H 0.3097 0.4463 0.5781 0.0781 Uiso 1.00 calc . . . H17 H 0.2153 0.4703 0.5035 0.0781 Uiso 1.00 calc . . . H18 H 0.1546 0.4774 0.5976 0.0781 Uiso 1.00 calc . . . H19 H 0.2523 0.2886 0.1441 0.0527 Uiso 1.00 calc . . . H20 H 0.2771 0.3806 0.1147 0.0527 Uiso 1.00 calc . . . H21 H 0.3996 0.3434 0.1640 0.0527 Uiso 1.00 calc . . . H22 H 0.0756 0.4914 0.3131 0.0681 Uiso 1.00 calc . . . H23 H 0.0769 0.4703 0.2060 0.0681 Uiso 1.00 calc . . . H24 H 0.0502 0.3804 0.2381 0.0681 Uiso 1.00 calc . . . H25 H 0.4399 0.5130 0.2936 0.0699 Uiso 1.00 calc . . . H26 H 0.3257 0.5573 0.2443 0.0699 Uiso 1.00 calc . . . H27 H 0.3144 0.5712 0.3491 0.0699 Uiso 1.00 calc . . . H28 H 0.2253 -0.2481 0.3273 0.1305 Uiso 1.00 calc . . . H29 H 0.3813 -0.2100 0.3384 0.1305 Uiso 1.00 calc . . . H30 H 0.2975 -0.1893 0.4275 0.1305 Uiso 1.00 calc . . . H31 H 0.1012 -0.0640 0.4599 0.0928 Uiso 1.00 calc . . . H32 H 0.0758 -0.0047 0.3939 0.0928 Uiso 1.00 calc . . . H33 H 0.0336 -0.1205 0.3579 0.0928 Uiso 1.00 calc . . . H34 H 0.3553 -0.0028 0.4810 0.1132 Uiso 1.00 calc . . . H35 H 0.4360 -0.0216 0.3909 0.1132 Uiso 1.00 calc . . . H36 H 0.3119 0.0536 0.4148 0.1132 Uiso 1.00 calc . . . H37 H 0.6102 -0.3138 0.2287 0.0737 Uiso 1.00 calc . . . H38 H 0.5391 -0.3440 0.1275 0.0737 Uiso 1.00 calc . . . H39 H 0.7023 -0.3429 0.1423 0.0737 Uiso 1.00 calc . . . H40 H 0.7290 -0.2183 0.0625 0.0707 Uiso 1.00 calc . . . H41 H 0.5665 -0.2186 0.0446 0.0707 Uiso 1.00 calc . . . H42 H 0.6499 -0.1157 0.0988 0.0707 Uiso 1.00 calc . . . H43 H 0.8316 -0.1706 0.2306 0.0552 Uiso 1.00 calc . . . H44 H 0.7456 -0.0709 0.2613 0.0552 Uiso 1.00 calc . . . H45 H 0.7292 -0.1471 0.3111 0.0552 Uiso 1.00 calc . . . H46 H 0.1591 -0.4404 0.0925 0.0660 Uiso 1.00 calc . . . H47 H 0.1277 -0.4820 -0.0165 0.0660 Uiso 1.00 calc . . . H48 H 0.2824 -0.4700 0.0257 0.0660 Uiso 1.00 calc . . . H49 H 0.3481 -0.3678 -0.0598 0.0655 Uiso 1.00 calc . . . H50 H 0.1970 -0.3694 -0.1047 0.0655 Uiso 1.00 calc . . . H51 H 0.2753 -0.2653 -0.0467 0.0655 Uiso 1.00 calc . . . H52 H 0.0674 -0.2147 0.0557 0.0755 Uiso 1.00 calc . . . H53 H -0.0055 -0.3209 -0.0023 0.0755 Uiso 1.00 calc . . . H54 H 0.0202 -0.2842 0.1068 0.0755 Uiso 1.00 calc . . . H55 H 0.058(4) 0.004(3) 0.242(3) 0.016(5) Uiso 1.00 calc . . . H56 H -0.125(3) 0.130(2) 0.132(2) 0.0156 Uiso 1.00 calc . . . H57 H 0.425(3) 0.109(2) 0.159(2) 0.0156 Uiso 1.00 calc . . . H58 H 0.383(3) -0.065(2) -0.063(2) 0.0156 Uiso 1.00 calc . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Si1 0.0207(5) 0.0248(5) 0.0201(4) 0.0004(4) -0.0007(3) 0.0047(4) Si2 0.0173(4) 0.0255(5) 0.0238(5) 0.0003(3) 0.0009(3) 0.0074(4) Si3 0.0175(4) 0.0236(5) 0.0176(4) 0.0001(3) 0.0004(3) 0.0058(4) Si4 0.0285(5) 0.0259(5) 0.0244(5) 0.0032(4) 0.0029(4) 0.0105(4) O1 0.019(1) 0.027(1) 0.022(1) -0.0025(9) -0.0029(9) 0.0011(9) O2 0.025(1) 0.032(1) 0.024(1) 0.0028(9) 0.0036(9) 0.0093(10) O3 0.050(1) 0.027(1) 0.022(1) 0.001(1) -0.006(1) 0.0105(10) O4 0.023(1) 0.036(1) 0.029(1) -0.0018(10) -0.0046(10) 0.003(1) O5 0.038(2) 0.047(2) 0.057(2) 0.011(1) 0.019(1) 0.031(1) O6 0.019(1) 0.028(1) 0.036(1) -0.0004(10) -0.005(1) 0.002(1) O7 0.020(1) 0.028(1) 0.023(1) 0.0024(9) 0.0012(9) 0.0057(9) O8 0.025(1) 0.035(1) 0.019(1) -0.006(1) 0.003(1) -0.003(1) O9 0.016(1) 0.037(1) 0.020(1) -0.0036(10) 0.0014(9) 0.0050(10) O10 0.039(1) 0.033(1) 0.033(1) 0.008(1) 0.007(1) 0.019(1) O11 0.037(1) 0.037(1) 0.026(1) 0.007(1) 0.0064(10) 0.015(1) O12 0.027(1) 0.032(1) 0.030(1) 0.0035(10) 0.0003(10) 0.009(1) O13 0.033(1) 0.028(1) 0.031(1) 0.0006(10) -0.0044(10) 0.010(1) C1 0.015(2) 0.032(2) 0.031(2) -0.003(1) -0.004(1) 0.006(1) C2 0.028(2) 0.033(2) 0.040(2) -0.002(1) 0.004(2) 0.008(2) C3 0.024(2) 0.059(2) 0.028(2) -0.008(2) -0.006(1) -0.002(2) C4 0.030(2) 0.044(2) 0.044(2) 0.001(2) -0.008(2) 0.016(2) C5 0.030(2) 0.034(2) 0.028(2) 0.004(1) 0.010(1) 0.008(2) C6 0.099(4) 0.088(4) 0.049(3) 0.024(3) 0.037(3) 0.040(3) C7 0.029(2) 0.111(4) 0.052(3) 0.006(2) 0.013(2) 0.004(3) C8 0.070(3) 0.049(3) 0.054(3) -0.004(2) 0.029(2) -0.008(2) C9 0.048(2) 0.030(2) 0.026(2) 0.009(2) 0.001(2) 0.012(2) C10 0.065(3) 0.047(2) 0.026(2) 0.012(2) 0.005(2) 0.020(2) C11 0.057(3) 0.073(3) 0.052(3) 0.027(2) 0.009(2) 0.035(2) C12 0.095(3) 0.036(2) 0.046(2) -0.011(2) -0.012(2) 0.020(2) C13 0.038(2) 0.050(2) 0.026(2) 0.003(2) 0.006(2) 0.017(2) C14 0.193(7) 0.098(4) 0.074(4) 0.071(4) 0.060(4) 0.068(3) C15 0.060(3) 0.142(5) 0.046(3) 0.016(3) 0.020(2) 0.051(3) C16 0.099(4) 0.120(5) 0.041(3) -0.030(3) -0.010(3) 0.008(3) C17 0.028(2) 0.038(2) 0.038(2) 0.011(2) 0.000(2) 0.011(2) C18 0.047(2) 0.036(2) 0.092(3) 0.009(2) -0.008(2) 0.016(2) C19 0.042(2) 0.088(3) 0.049(3) 0.023(2) 0.017(2) 0.027(2) C20 0.031(2) 0.047(2) 0.061(3) 0.006(2) -0.003(2) 0.023(2) C21 0.035(2) 0.035(2) 0.035(2) -0.004(2) -0.004(2) 0.011(2) C22 0.062(3) 0.044(2) 0.053(3) -0.017(2) -0.007(2) 0.014(2) C23 0.069(3) 0.054(3) 0.037(2) -0.009(2) -0.004(2) 0.014(2) C24 0.038(2) 0.070(3) 0.066(3) 0.002(2) -0.010(2) 0.012(2) #------------------------------------------------------------------------------ _computing_data_collection 'MSC/AFC Diffractometer Control' _computing_cell_refinement 'MSC/AFC Diffractometer Control' _computing_data_reduction 'teXsan' _computing_structure_solution SIR92 _computing_structure_refinement 'teXsan' _computing_publication_material 'teXsan' _computing_molecular_graphics ? #------------------------------------------------------------------------------ _geom_special_details ; ? ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag SI1 O1 1.632(2) . . yes SI1 O2 1.607(2) . . yes SI1 O3 1.615(2) . . yes SI1 O4 1.599(2) . . yes SI2 O4 1.609(2) . . yes SI2 O5 1.594(3) . . yes SI2 O6 1.593(2) . . yes SI2 O7 1.625(2) . . yes SI3 O7 1.602(2) . . yes SI3 O8 1.624(2) . . yes SI3 O9 1.613(2) . . yes SI3 O10 1.600(2) . . yes SI4 O10 1.605(2) . . yes SI4 O11 1.629(2) . . yes SI4 O12 1.608(2) . . yes SI4 O13 1.615(2) . . yes O1 C1 1.476(3) . . yes O2 C5 1.446(3) . . yes O3 C9 1.452(4) . . yes O11 C13 1.458(4) . . yes O12 C17 1.452(4) . . yes O13 C21 1.442(4) . . yes C1 C2 1.512(4) . . yes C1 C3 1.514(4) . . yes C1 C4 1.516(5) . . yes C5 C6 1.510(5) . . yes C5 C7 1.501(5) . . yes C5 C8 1.508(5) . . yes C9 C10 1.513(5) . . yes C9 C11 1.516(5) . . yes C9 C12 1.513(5) . . yes C13 C14 1.477(6) . . yes C13 C15 1.499(5) . . yes C13 C16 1.513(6) . . yes C17 C18 1.523(5) . . yes C17 C19 1.503(5) . . yes C17 C20 1.516(5) . . yes C21 C22 1.513(5) . . yes C21 C23 1.521(5) . . yes C21 C24 1.507(5) . . yes #------------------------------------------------------------------------------ loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag # -- ENTER ANGLES HERE, ONE PER LINE -- # e.g. C1 C2 C3 109.4(3) . . . yes ? ? ? ? ? ? ? ? #------------------------------------------------------------------------------ loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag # -- ENTER TORSION ANGLES HERE, ONE PER LINE -- # e.g. C1 C2 C3 C4 109.4(3) . . . . yes ? ? ? ? ? ? ? ? ? ? #------------------------------------------------------------------------------ loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag O6 O9 2.788(3) . 2_555 ? O6 C2 3.457(4) . 1_455 ? O8 O9 2.698(3) . 2_655 ? O8 O8 3.584(4) . 2_655 ? #------------------------------------------------------------------------------