Adsorption structure of dimethyl ether on silicalite-1 zeolite determined using single-crystal X-ray diffraction

Fujiyama, S.; Seino, S.; Kamiya, N.; Nishi, K.; Yokomori, Y.

doi:10.1107/S2052520614015911

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STRUCTURAL SCIENCE
CRYSTAL ENGINEERING
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ISSN: 2052-5206

Volume 70| Part 5| October 2014| Pages 856-863

doi:10.1107/S2052520614015911

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Adsorption structure of dimethyl ether on silicalite-1 zeolite determined using single-crystal X-ray diffraction

Shinjiro Fujiyama,^a ^* Shintaro Seino,^a Natsumi Kamiya,^a Koji Nishi ^a and Yoshinobu Yokomori ^a

^aDepartment of Applied Chemistry, National Defense Academy, Hashirimizu, Yokosuka, Kanagawa 239-8686, Japan
^*Correspondence e-mail: shinjiro@2006.jukuin.keio.ac.jp

(Received 19 March 2014; accepted 8 July 2014; online 1 October 2014)

The adsorption structures of dimethyl ether (DME) on silicalite-1 zeolite (MFI-type) are determined using single-crystal X-ray diffraction. The structure of low-loaded DME-silicalite-1 indicates that all DME molecules are located in the sinusoidal channel, which is the most stable sorption site based on the van der Waals interaction between DME and the framework. The configuration of guest molecules (linear or bent) plays an important role in determining where the stable sorption site is in the pore system of MFI-type zeolites. Bent molecules favor the sinusoidal channel, while linear molecules favor the straight channel. The contribution of DME–DME interactions is considerable in the high-loaded DME-silicalite-1 structure.

Keywords: adsorption structure; MFI-type zeolite; silicalite-1; dimethyl ether; single-crystal structure analysis.

CCDC reference: 1012728

1. Introduction

Microporous materials such as zeolites, metal–organic frameworks and carbon nanomaterials are among the most important gas adsorbents. Gas molecules are physisorbed stably in micropores even around room temperature as a result of van der Waals interactions with the surrounding pore walls. The optimization of applications such as gas separation, storage and condensation requires knowledge of the effects of the pore structure on the adsorption behavior. Among the many potential microporous materials, zeolites are one of the most promising because of their high thermal, mechanical and chemical stability. The adsorption properties of various zeolites have been widely investigated. Above all, MFI-type zeolites, e.g. ZSM-5 and silicalite-1, have attracted much interest due to their two kinds of unique channels, a straight channel and a sinusoidal channel. Thermodynamic measurements were carried out on the adsorption of hydrocarbons (Richards & Rees, 1987 ; Shen & Rees, 1991 ; Choudhary & Mayadevi, 1996 ; Millot et al., 1998 , 1999 ; Sun et al., 1996 , 1998 ) and various other gases (Yamazaki et al., 1993 ; Wirawan & Creaser, 2006 ; Pope, 1993 ; Golden & Sircar, 1994 ; Ahunbay et al., 2008 ; Zhang et al., 2012 ). The mobility of guest molecules in the pore system was studied using NMR spectroscopy (Shen et al., 1990 ; Kolokolov et al., 2010 ; Nishchenko et al., 2012 ), and computational studies were also conducted to reveal the diffusion behavior (Makrodimitris et al., 2001 ; Krishna et al., 2006 ). A wide range of data has been reported, but very few actual adsorption structures have been reported except for aromatic molecules (van Koningsveld et al., 1989 ; van Koningsveld, Jansen & Man, 1996 , van Koningsveld, Jansen & van Bekkum, 1996 ; van Koningsveld & Jansen, 1996 ; van Koningsveld & Koegler, 1997 ; Nishi et al., 2005 ; Kamiya et al., 2011 , 2013 ) and CO₂ (Fujiyama et al., 2013 , 2014a ,b ). Determining the adsorption structures is important to understand the adsorption properties. Adsorption structures contain valuable information, such as stable sorption sites, the location and orientation of guest molecules, and guest–framework distances.

As mentioned above, many adsorption structures for aromatic molecules on MFI-type zeolites have been determined. These indicate that the intersection is the most stable sorption site based on van der Waals interactions between the guest molecules and the framework. This means that bulky aromatic molecules favor large intersections as the sorption site, rather than the narrow channels. Recently we revealed the adsorption process of CO₂ on silicalite-1 using single-crystal X-ray structural analysis (Fujiyama et al., 2014b). CO₂ molecules initially adsorb not at the intersection but in the straight channel through a CO₂ framework interaction. It is reasonable that small molecules such as CO₂ would favor the narrow channels rather than the large intersections. This can also be explained using an integrated Lennard–Jones potential model by treating the channels as simple cylinders (Tjatjopoulos et al., 1988 ). However, this model cannot explain why CO₂ molecules favor the straight channel rather than the sinusoidal channel. The difference in the pore sizes of the channels is too small to use the simple cylindrical potential model. The pore sizes of the channels are roughly the same, but the precise structures of the channels are quite different. This difference plays an important role and thus it should be considered in any discussion of the adsorption behavior in the channels. The channels are composed of two ten-membered rings (ten Si atoms and ten O atoms) with six O atoms connecting them. As discussed elsewhere (Fujiyama et al., 2013), the ten-membered rings of the straight channel are parallel while those of the sinusoidal channel are angled. Considering the structural difference between the channels, the configuration of guest molecules (linear or bent) should be a key factor in determining which channel is the stable sorption site. The adsorption of guest molecules on silicalite-1 is based on the van der Waals interaction. The distances between the atoms of the guest molecule and the framework are important factors in determining the stability of a sorption site. A guest molecule on a stable sorption site favors those distances that minimize the van der Waals interaction potentials. The linear configuration of the CO₂ molecule (O—C—O = 180°) may be compatible with the straight channel incorporating parallel ten-membered rings.

In this study we conducted a structural analysis of silicalite-1 loaded with dimethyl ether as a basic and simple example of guest molecules with a bent configuration (C—O—C = 111.7°). The direct comparison of the results with those of CO₂, which is also a basic and simple example of chain molecules with linear configuration, is permitted because they have similar chain lengths and bulkiness. Adsorption structures were determined for low and high loading to discuss the guest–framework and guest–guest interactions separately.

2. Experimental

2.1. Preparation of low- and high-loaded DME-silicalite-1

Silicalite-1 crystals were prepared as reported elsewhere (Kamiya et al., 2008 , 2011). EDX analysis confirmed that the composition of the crystals was SiO₂ with no Al or other cation species. Crystals selected for X-ray structural analysis were pressed by applying a mass of 2.0 g along the crystallographic c axis, while raising the temperature from ambient to 473 K and cooling back to ambient. This heating and cooling cycle was repeated three times for each specimen (Kamiya et al., 2011). The crystal was exposed to DME gas at 90 kPa, 298 K for 12 h (low-loaded) or 7 d (high-loaded) in a closed vacuum instrument (Bell jar-type vacuum oven BV-001, Sibata Scientific Technology Ltd).

2.2. Structure analysis of DME-silicalite-1

Single-crystal X-ray diffraction data was collected at room temperature using an APEX II X-ray diffractometer (Bruker AXS) with a CCD detector, Mo Kα radiation, and a graphite monochromator. The collected reflections were corrected for Lorentz polarization factors and the absorption effect. Structural analysis was conducted in the monoclinic twin in P2₁/n.1.1 as described in the report (Fujiyama et al., 2014a). The structure was solved using a direct method, and difference-Fourier synthesis was used for the remaining atoms (SHELXTL; Sheldrick, 2008 ). Refinement was performed on F² and Σw(F_o² − F_c²)² was minimized; w = 1/[σ²(F_o²) + (aP)² + bP], where P = (F_o² + 2F_c²)/3, and a and b are the weight parameters. Anisotropic displacement parameters were used and no restraints were introduced on the framework atoms. Isotropic displacement parameters were used on the DME atoms and the structures were constrained as rigid groups (C—O = 1.41 Å, C—O—C = 111.7°). The unstable displacement parameters of DME atoms were restrained. In the refinement of the high-loaded DME-silicalite-1, the sums of the occupancy factors of two pairs of disordered DMEs (STR2–INT and SIN1–INT in Fig. 2) were restrained to be 1.0. The full experimental details are given in Table 1 and the structures of DME-silicalite-1 are shown in Figs. 1 and 2. The structures were drawn using the software VESTA (Momma & Izumi, 2008 ).

Table 1
Crystal data and refinement details

	Low-loaded	High-loaded
Crystal data
Chemical formula	Si₂₄O₄₈·0.96C₂O	Si₂₄O₄₈·1.82C₂O
M_r	1480	1515
Crystal system, space group	Monoclinic, P2₁/n.1.1	Monoclinic, P2₁/n.1.1
Temperature (K)	296	296
a, b, c (Å)	20.186 (15), 19.990 (14), 13.435 (10)	20.169 (14), 19.951 (14), 13.427 (10)
α (°)	90.012 (13)	90.012 (13)
V (Å³)	5421 (7)	5421 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.67	0.67
Crystal size (mm)	0.16 × 0.11 × 0.08	0.14 × 0.12 × 0.08

Data collection
Diffractometer	Bruker P4	Bruker P4
Absorption correction	Analytical	Analytical
T_min, T_max	0.899, 0.950	0.912, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	63 627, 13 249, 6100	63 444, 13 209, 5947
R_int	0.091	0.115
(sin θ/λ)_max (Å⁻¹)	0.676	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.124, 0.85	0.054, 0.124, 0.83
No. of reflections	13 249	13 209
No. of parameters	664	669
No. of restraints	4	10
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.60	0.63, −0.50
Computer programs: XSCANS (Siemens, 1996 ), SHELXTL, SHELXS97, SHELXL97 (Sheldrick, 2008).

Figure 1
Packing of DME molecules in the low-loaded DME-silicalite-1 (a) along the c axis and (b) along the b axis, with the occupancy factors indicated in parentheses.

Figure 2
Packing of DME molecules in the high-loaded DME-silicalite-1 (a) along the c axis and (b) along the b axis, with the occupancy factors indicated in parentheses.

2.3. Thermogravimetric analysis

The amount of DME loading on silicalite-1 was measured thermogravimetrically to validate the occupancy factors of the DME-silicalite-1 structures. Silicalite-1 crystals weighing 10 mg each were exposed to DME gas at 90 kPa, 298 K, in a closed vacuum instrument (Bell jar type vacuum oven BV-001, Shibata Science Co.). The adsorption times used were 3, 6, 24, 48 h and 7 d. The resultant crystals were placed in a Bruker TG–DTA (thermogravimetry–differential thermal analysis) 2000SA sample holder and heated at 2 K min⁻¹ in flowing air. The weight loss of the crystals was measured up to 1000 K. The plot for each sample is shown in Fig. 3. The TG–DTA curves of the adsorption time (7 d) is inserted as a typical example.

Figure 3
DME loading on silicalite-1 measured by thermogravimetric analysis (diamonds), along with the DME amounts calculated using the occupancy factors of XRD analysis (double circles). Insert: TG–DTA curves of DME-silicalite-1 (adsorption time 7 d).

3. Results

3.1. Packing of DME in silicalite-1

The packing of DME in low-loaded DME-silicalite-1 is shown in Fig. 1 with the occupancy factors in parenthesis. Two independent DME sorption sites are observed in the sinusoidal channel. SIN1–SIN1′ and SIN2–SIN2′ are related to the screw axis 2₁ along the a axis. SIN1 is located between the two ten-membered rings and SIN2 is located in the middle of one ring. The sum of the occupancy factors is 1.0, which means the sinusoidal channel is fully occupied. The amount of DME calculated using the occupancy factors is 4.0 molecules/u.c. Fig. 2 shows the packing of DME in the high-loaded DME-silicalite-1. Four independent sorption sites are observed. SIN1 is also observed in the high-loaded structure. STR1–STR1′ and STR2–STR2′ are related to the symmetric center in the middle of the straight channel, while SIN1–SIN1′ are related to the screw axis 2₁ along the a axis. C101 of the STR1 is at the symmetric inversion center. The amount of DME calculated using the occupancy factors is 7.3 molecules/u.c. The DME loading measured by thermogravimetric analysis is shown in Fig. 3 along with the amount of DME calculated using the occupancy factors of the XRD results. The results agree and thus validate the low- and high-loaded structures. The first weight loss from room temperature to about 400 K in the TG curve is mainly due to DME molecules adsorbed out of the pores. The DME-to-framework internuclear distances in low- and high-loaded DME-silicalite-1 are listed in Tables 2 and 3. The numbering of the framework atoms is identical to the single-crystal structure in P2₁/n.1.1 (van Koningsveld et al., 1990 ).

Table 2
DME-to-framework internuclear distances (Å) in the low-loaded DME-silicalite-1

SIN1 to framework		SIN2 to framework
C301—O25	3.90	C501—O4	3.91
C302—O4	3.42	C502—O21	3.68
O303—O17	3.92	O503—O26	3.90

Table 3
DME-to-framework internuclear distances (Å) in the high-loaded DME-silicalite-1

STR1 to framework
C101—O47	4.01	C201—O28	3.54
C102—O2	3.76	C202—O11	3.76
O103—O31	3.63	O203—O34	3.71

SIN1 to framework		INT to framework
C301—O18	3.84	C401—O15	4.02
C302—O31	3.87	C402—O34	4.13
O303—O17	3.59	O403—Si9	4.81

3.2. Framework geometry of DME-silicalite-1

The bond lengths and angles in the framework geometry and the diagonal O—O internuclear distances in the ten-membered rings of the channels are listed in Tables 4 and 5. The l/s value in Table 5 is the longest distance divided by the shortest distance, which indicates the local strain of the channel. The scatter diagram of 〈d(SiO)〉 (the average of the two Si—O distances of each Si—O—Si bridge) as a function of the Si—O—Si angle is shown in Fig. 4. The absolute value of the slope of the regression line indicates the strain in the whole framework geometry, and the larger values can be attributed to a more stressed structure.

Table 4
Bond lengths (Å) and angles (°) in the framework geometry

	Low-loaded	High-loaded
O—Si—O range (°)	106–112	107–113
Average O—Si—O (°)	109	109

Si—O range (Å)	1.56–1.62	1.56–1.62
Range of averages of Si—O/SiO₄ (Å)	1.59–1.60	1.59–1.60

Si—O—Si range (°)	143–179	143–175
Range of averages of Si—O—Si/Si(OSi)₄ (°)	149–163	148–161

Table 5
Diagonal O—O internuclear distances (Å) in ten-membered rings

	Low loaded	High loaded		Low loaded	High loaded
Straight channel
O5—O11	8.08	8.14	O31—O37	8.31	8.39
O1—O20	8.43	8.47	O44—O46	8.40	8.46
O34— O28	8.05	7.95	O8—O2	8.27	8.24
O33—O27	8.32	8.26	O7—O1	8.24	8.14
O22—O21	8.11	8.12	O48—O47	8.07	8.05
l/s†	1.05	1.06	l/s†	1.04	1.05

Sinusoidal channel
O15—O20	8.21	8.18	O18—O17	7.90	7.88
O1—O28	8.14	8.08	O5—O30	8.34	8.46
O2—O27	8.12	8.14	O4—O31	7.86	7.76
O46—O41	8.50	8.56	O43—O44	8.11	8.13
O24—O26	8.16	8.15	O23—O25	8.45	8.42
l/s†	1.05	1.06	l/s†	1.08	1.09

†Longest distance divided by the shortest distance.

Figure 4
Scatter diagram of 〈d(SiO)〉 as a function of the Si—O—Si angle, with the equations of the regression lines.

4. Discussion

4.1. Sorption sites based on DME–framework interaction

The structure of the low-loaded DME-silicalite-1 clearly indicates that the sinusoidal channel is the most stable sorption site of DME based on the DME–framework interaction. The DME–DME interaction in the low-loaded structure is negligibly small because the DME molecules are located separately. The shortest distance between neighboring DMEs is over 6.0 Å (SIN1 to SIN2), which is too long for the DME–DME interaction to work. As expected, DME does not adsorb at the intersection initially. As mentioned in §1, it is not surprising that small molecules such as DME favor the narrow channels rather than the large intersection. The precise structures of the framework atoms of the channels should be considered in order to explain why DME molecules favor the sinusoidal channel rather than the straight channel. The Lennard–Jones potential model can be used to estimate the guest–framework interaction by taking into account the precise structures of the channels. The guest–framework interaction potential exhibits additive properties for atoms of the guest molecule. For example, the experimental enthalpy variations of hydrocarbons increase linearly as a function of the carbon number. The increase is approximately 10 kJ mol⁻¹ per additional CH₂ group from butane to hexane (Richards & Rees, 1987). Thus the interaction potential between the guest molecule and the framework, U_{molecule–framework}, can be considered as the sum of the interaction potentials of all atoms of the guest molecule as follows

$[{U_{{\rm molecule}{\rm -}{\rm framework}} = \sum _i U_{{\rm atom}{\rm -}{\rm framework}}({x_i},{y_i},{z_i})}, \eqno(1)]$

where U_{atom–framework} (x_i, y_i, z_i) is the interaction potential of atom i at the position (x_i, y_i, z_i) in the coordinate space; i = 1, 2, 3 in the case of a triatomic molecule. The profile of U_{atom–framework} (x, y, z) in the channels helps to evaluate the stability of the sorption sites from the perspective of the configuration of the guest molecules. The atoms of a molecule on a stable sorption site would be located at positions where the U_{atom–framework} (x, y, z) is low. The U_{atom–framework} (x, y, z) can be expressed approximately as the sum of the Lennard–Jones potential between the atom at (x, y, z) and the overall framework atoms. For simplicity, U_{atom–framework} (x, y, z) is calculated under the following assumptions. The Si atoms of the framework are excluded from the calculation and 426 framework O atoms around the channels are counted. The van der Waals radius of the guest atom, which represents the radii of common atoms such as carbon, nitrogen and oxygen, is taken to be approximately 1.70 Å. Then, U_{atom–framework} (x, y, z) is given by

$[{U_{\rm atom - framework}}(x,y,z) = 4\varepsilon \sum _j {\{ {{(\sigma /{r_j})}^{12}} - {{(\sigma /{r_j})}^6}\} } \eqno(2)]$

$[{r_j} = \{ (x - x_j)^2 + (y - y_j)^2 + (z - z_j)^2\} ^{1/2}, \eqno(3)]$

where (x_j, y_j, z_j) is the position of the framework atom j, σ is the separation at which the potential becomes zero, and $[\varepsilon]$ is the depth of the potential well. The factor 4 $[\varepsilon]$ ; can be canceled by normalizing U_{atom–framework} (x, y, z). The value of σ is given by the relationship

$[\sigma = (r_{\rm atom}^0 + r_j^0) \times 2^{1/6}, \eqno(4)]$

where r⁰_atom and r⁰_j are the van der Waals radii of the atoms of the guest molecule and the framework. r⁰_atom is 1.70 Å, and r⁰_j is 1.52 Å for any j, which is the van der Waals radius of O. The isosurfaces of normalized U_{atom–framework} (x, y, z) at 0.0, −0.8 and −0.9 are shown in Fig. 5(a). The isosurface at 0.0 runs through the entire channel system. There are deep potential wells in the channels and a shallow local minimum is found in the area of the intersection. Figs. 5(b) and (c) show the details of the potential wells in the channels. Their depths in the sinusoidal channel and the straight channel are approximately the same, the difference being less than 2%. This stands to reason considering that their pore sizes are roughly the same. However, the configuration of the potential wells is clearly different. As can be seen in the minimum potential paths indicated by the dashed lines, the path of the sinusoidal channel is winding and that of the straight channel is linear. Thus, the sinusoidal and straight channels are more favorable for, respectively, bent and linear molecules to locate their atoms at stable positions. Fig. 6 shows the locations of the most stable sorption sites in low-loaded DME-silicalite-1 (this work) and low-loaded CO₂-silicalite-1 (Fujiyama et al., 2014b) with the potential well maps. They are located around the potential wells as expected. The bent molecular chains of DME fit exactly along the bent potential wells. The location of CO₂ does not coincide as perfectly with the potential well as that of DME, but CO₂ is along the linear minimum potential path, with the O atom on the potential minimum side. The matching between the configurations of the guest molecule and the potential wells of the channels determines which channel is the stable sorption site for the guest molecule. Bent molecules favor the sinusoidal channel, while linear molecules favor the straight channel.

Figure 5
Profile of normalized U_{atom–framework}. (a) Overview of the profile and the framework structure of the channels. Isosurfaces are at −0.9, −0.8 and 0.0. Contour maps of the (b) sinusoidal and (c) straight channels. The contour lines are −0.95 to 0.00 in increments of 0.05. Minimum potential paths of each channel are indicated by dashed lines.

Figure 6
Structures of guest molecules with U_{atom–framework} maps. (a) SIN1 and SIN2 of low-loaded DME. (b) STR2 of low-loaded CO₂ (Fujiyama et al., 2014b

4.2. Adsorption process of DME on silicalite-1

The DME molecules in the low-loaded structure undergo rearrangement in the high-loaded structure due to the DME–DME interaction. Fig. 7 illustrates the adsorption process of DME on silicalite-1. The initial adsorption behavior is governed by the DME–framework interaction. Up to a DME loading of 4 molecules/u.c., all DME molecules are located in the sinusoidal channel as a result of the DME–framework interaction. The additional DME molecules adsorb in the straight channel and/or at the intersection where the loading is over 4 molecules/u.c. Then the DME–DME interaction arises and some of the DME molecules in the sinusoidal channel move to the straight channel or the intersection. In the high-loaded DME-silicalite-1 structure, a considerable amount of DME is located at the intersection. The occupancy factor at the intersection (0.6) is larger than in the channels (0.4). The large intersection is less stable than the narrow channels for small molecules such as DME according to the DME–framework interaction. As listed in Table 3, the DME–framework distances of INT are larger than 4.0 Å, which is too long to minimize the DME–framework interaction potentials (see Table 2). Thus, DME molecules at INT are stabilized by the DME–DME interaction, which comprises a dipole–dipole interaction as well as a van der Waals interaction. The orientation of DME molecules at the large intersection has a high degree of freedom, and thus the dipole–dipole interactions in the high-loaded structure are optimized. The adsorption behavior of CO₂ on silicalite-1 shows the same tendency. A large number of CO₂ molecules are located at the large intersection stabilized by the CO₂–CO₂ interaction in the high-loaded structure.

Figure 7
Adsorption process of DME on silicalite-1. (a) Every DME molecule is initially located in the sinusoidal channel. (b) The sinusoidal channel is fully occupied (low-loaded structure). (c) Under equilibrium conditions at 90 kPa, 298 K (high-loaded structure).

4.3. Strain in silicalite-1 framework loaded with DME

The results relevant to the entire framework geometry in Table 4 and Fig. 4 and the local strain in the channels in Table 5 are identical to those for monoclinic single crystals with no guest molecules in their pores (van Koningsveld et al., 1990; Kamiya et al., 2010 ). Unlike bulky aromatic compounds, DME molecules and CO₂ are too small to exert any influence on the framework geometry. The framework geometry loaded with aromatic compounds is orthorhombic, and the absolute values of the slopes of the regression lines are around 0.5. The channels are also distorted with the bulky aromatic molecules in them and their l/s values are over 1.2.

5. Conclusion

The structures of low- and high-loaded DME-silicalite-1 were determined. The sinusoidal channel is found to be the most stable sorption site for DME molecules. Up to a DME loading of 4 molecules/u.c., all DME molecules are located in the sinusoidal channel as a result of the DME–framework interaction. The configuration of the guest molecules (linear or bent) plays an important role in determining which channel is the most stable sorption site based on the guest–framework interaction. Linear molecules favor the straight channel, while bent molecules favor the sinusoidal channel. In the high-loaded structure, a large amount of DME is located at the intersection owing to the DME–DME interaction.

Recently, we have reported the adsorption structures of C₄–C₆ hydrocarbons (Fujiyama, Seino et al., 2014 ). Linear 2-butyne prefers the straight channel, and bent n-butane prefers the sinusoidal channel as expected. Further investigations about other chain molecules are needed to reveal the adsorption behavior in the MFI-type zeolites.

Supporting information

CCDC reference: 1012728

Crystal structure: contains datablocks I, II. DOI: 10.1107/S2052520614015911/bp5065sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2052520614015911/bp5065Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2052520614015911/bp5065IIsup3.hkl

Comments on the checkcif (alerts level A and B). DOI: 10.1107/S2052520614015911/bp5065sup4.pdf

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

For both compounds, data collection: Bruker XSCANS; cell refinement: Bruker XSCANS; data reduction: Bruker SHELXTL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures top

(I) top

Crystal data top

C_1.9H₀O₄₉Si₂₄	Z = 4
M_r = 1480	F(000) = 2984
Monoclinic, P2₁/n.1.1	D_x = 1.823 Mg m⁻³
a = 20.186 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 19.990 (14) Å	µ = 0.67 mm⁻¹
c = 13.435 (10) Å	T = 296 K
β = 90°	0.16 × 0.11 × 0.08 mm
V = 5421 (7) Å³

Data collection top

Bruker P4 diffractometer	13249 independent reflections
Radiation source: fine-focus sealed tube	6100 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
ω scans	θ_max = 28.7°, θ_min = 1.4°
Absorption correction: analytical ?	h = −18→18
T_min = 0.899, T_max = 0.950	k = −27→25
63627 measured reflections	l = −26→25

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.049	Secondary atom site location: difference Fourier map
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0439P)²] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max < 0.001
13249 reflections	Δρ_max = 0.74 e Å⁻³
664 parameters	Δρ_min = −0.60 e Å⁻³

Crystal data top

C_1.9H₀O₄₉Si₂₄	V = 5421 (7) Å³
M_r = 1480	Z = 4
Monoclinic, P2₁/n.1.1	Mo Kα radiation
a = 20.186 (15) Å	µ = 0.67 mm⁻¹
b = 19.990 (14) Å	T = 296 K
c = 13.435 (10) Å	0.16 × 0.11 × 0.08 mm
β = 90°

Data collection top

Bruker P4 diffractometer	13249 independent reflections
Absorption correction: analytical ?	6100 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.950	R_int = 0.091
63627 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	664 parameters
wR(F²) = 0.124	4 restraints
S = 0.85	Δρ_max = 0.74 e Å⁻³
13249 reflections	Δρ_min = −0.60 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C301	0.6565 (18)	0.2387 (14)	0.252 (2)	0.252 (16)*	0.588 (16)
C302	0.656 (2)	0.3512 (14)	0.2786 (10)	0.85 (7)*	0.588 (16)
O303	0.6056 (12)	0.2994 (17)	0.2454 (16)	0.43 (2)*	0.588 (16)
C501	0.6510 (14)	0.3580 (14)	0.2495 (11)	0.192 (18)*	0.376 (16)
C502	0.749 (3)	0.4502 (12)	0.273 (3)	0.31 (3)*	0.376 (16)
O503	0.656 (2)	0.4277 (14)	0.249 (2)	0.42 (3)*	0.376 (16)
Si1	0.32629 (15)	0.42105 (9)	−0.05646 (12)	0.0150 (4)
Si2	0.17410 (16)	0.31099 (11)	−0.02991 (9)	0.0182 (5)
Si3	−0.04450 (15)	0.27935 (10)	−0.06211 (11)	0.0183 (5)
Si4	−0.03324 (14)	0.12346 (10)	−0.06285 (11)	0.0168 (5)
Si5	0.17951 (16)	0.07484 (10)	−0.02815 (9)	0.0150 (5)
Si6	0.32031 (15)	0.19164 (9)	−0.05674 (11)	0.0176 (4)
Si7	0.32194 (17)	0.42440 (10)	0.17170 (10)	0.0158 (5)
Si8	0.17912 (15)	0.31012 (10)	0.12764 (10)	0.0168 (4)
Si9	−0.03306 (15)	0.27396 (10)	0.17525 (10)	0.0164 (5)
Si10	−0.03039 (16)	0.11977 (10)	0.17528 (10)	0.0165 (5)
Si11	0.18000 (16)	0.07124 (9)	0.12969 (11)	0.0160 (4)
Si12	0.31753 (16)	0.18889 (10)	0.16818 (10)	0.0160 (4)
Si13	0.33621 (14)	0.42665 (9)	0.55812 (12)	0.0162 (4)
Si14	0.19045 (15)	0.31066 (11)	0.52809 (9)	0.0165 (4)
Si15	−0.02870 (14)	0.27843 (9)	0.56155 (11)	0.0158 (4)
Si16	−0.03074 (14)	0.12182 (10)	0.56371 (11)	0.0155 (4)
Si17	0.18216 (16)	0.07080 (9)	0.52796 (10)	0.0147 (5)
Si18	0.32245 (15)	0.18668 (9)	0.56182 (11)	0.0161 (4)
Si19	0.31886 (17)	0.42362 (10)	0.32790 (10)	0.0167 (5)
Si20	0.17629 (15)	0.31102 (10)	0.36955 (10)	0.0170 (4)
Si21	−0.03864 (15)	0.27354 (10)	0.33052 (10)	0.0165 (5)
Si22	−0.03429 (16)	0.11899 (10)	0.32915 (10)	0.0179 (5)
Si23	0.17949 (17)	0.07128 (9)	0.36993 (11)	0.0164 (4)
Si24	0.30662 (15)	0.19109 (10)	0.32234 (9)	0.0169 (4)
O1	0.2295 (4)	0.3755 (2)	−0.0565 (3)	0.0382 (14)
O2	0.0655 (3)	0.3081 (2)	−0.0639 (3)	0.0301 (12)
O3	−0.0419 (4)	0.2008 (2)	−0.0527 (3)	0.0469 (14)
O4	0.0813 (4)	0.1029 (2)	−0.0647 (3)	0.0322 (13)
O5	0.2737 (3)	0.1189 (2)	−0.0494 (3)	0.0299 (13)
O6	0.2339 (4)	0.2456 (2)	−0.0488 (3)	0.0411 (15)
O7	0.2331 (4)	0.3752 (3)	0.1556 (3)	0.0406 (17)
O8	0.0719 (4)	0.3050 (3)	0.1631 (2)	0.0338 (13)
O9	−0.0291 (4)	0.1962 (3)	0.1555 (2)	0.0322 (14)
O10	0.0788 (4)	0.0907 (3)	0.1669 (3)	0.0378 (15)
O11	0.2676 (4)	0.1194 (3)	0.1519 (2)	0.0297 (14)
O12	0.2448 (4)	0.2462 (3)	0.1434 (3)	0.0439 (17)
O13	0.1637 (4)	0.3154 (3)	0.0494 (3)	0.0508 (16)
O14	0.1623 (4)	0.0776 (2)	0.0511 (3)	0.0317 (12)
O15	0.3826 (4)	0.4150 (3)	−0.1265 (3)	0.0368 (15)
O16	0.3968 (5)	0.3993 (3)	0.0038 (3)	0.0470 (17)
O17	0.4213 (4)	0.4004 (3)	0.1329 (3)	0.0289 (13)
O18	0.3676 (3)	0.1973 (3)	−0.1295 (3)	0.0288 (12)
O19	0.4054 (4)	0.2028 (3)	−0.0017 (2)	0.0383 (15)
O20	0.4202 (4)	0.1958 (3)	0.1290 (3)	0.0316 (13)
O21	0.2036 (4)	0.0011 (2)	−0.0525 (3)	0.0271 (12)
O22	0.2103 (4)	−0.0033 (2)	0.1483 (3)	0.0265 (13)
O23	0.3459 (3)	0.42283 (18)	0.2503 (3)	0.0337 (10)
O24	0.3423 (3)	0.19562 (18)	0.2462 (3)	0.0306 (9)
O25	−0.0610 (3)	0.28320 (16)	0.2520 (3)	0.0270 (9)
O26	−0.0642 (2)	0.11064 (16)	0.2513 (3)	0.0240 (9)
O27	0.2448 (4)	0.3763 (2)	0.5544 (3)	0.0393 (15)
O28	0.0781 (3)	0.3113 (2)	0.5543 (3)	0.0293 (12)
O29	−0.0162 (4)	0.1995 (2)	0.5645 (3)	0.0453 (15)
O30	0.0731 (3)	0.0862 (2)	0.5571 (3)	0.0348 (13)
O31	0.2615 (4)	0.1190 (2)	0.5617 (3)	0.0298 (13)
O32	0.2468 (4)	0.2479 (2)	0.5576 (3)	0.0363 (14)
O33	0.2256 (4)	0.3766 (3)	0.3413 (3)	0.0306 (15)
O34	0.0597 (4)	0.3118 (2)	0.3527 (2)	0.0315 (13)
O35	−0.0248 (4)	0.1960 (2)	0.3475 (2)	0.0327 (14)
O36	0.0688 (4)	0.0842 (3)	0.3437 (3)	0.0467 (17)
O37	0.2588 (4)	0.1202 (3)	0.3347 (3)	0.0399 (16)
O38	0.2260 (4)	0.2471 (3)	0.3350 (3)	0.0387 (14)
O39	0.1921 (4)	0.3063 (3)	0.4489 (3)	0.0512 (15)
O40	0.1837 (4)	0.0823 (2)	0.4492 (3)	0.0384 (13)
O41	0.3911 (4)	0.4193 (3)	0.6285 (3)	0.0349 (15)
O42	0.4141 (4)	0.4118 (3)	0.4987 (3)	0.0344 (14)
O43	0.4148 (4)	0.3975 (3)	0.3682 (3)	0.0338 (14)
O44	0.3863 (4)	0.1894 (2)	0.6302 (2)	0.0269 (12)
O45	0.3958 (4)	0.1875 (3)	0.4985 (3)	0.0351 (14)
O46	−0.0972 (4)	0.2977 (3)	−0.1307 (3)	0.0423 (16)
O47	0.2090 (4)	−0.0041 (2)	0.5455 (3)	0.0245 (13)
O48	0.2099 (4)	−0.0032 (3)	0.3520 (3)	0.0325 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0191 (10)	0.0114 (9)	0.0145 (9)	0.0021 (8)	0.0005 (10)	−0.0012 (9)
Si2	0.0211 (11)	0.0154 (11)	0.0181 (10)	−0.0026 (10)	0.0015 (8)	−0.0002 (9)
Si3	0.0212 (11)	0.0163 (10)	0.0173 (11)	−0.0010 (8)	−0.0002 (9)	−0.0018 (9)
Si4	0.0184 (11)	0.0166 (11)	0.0153 (11)	−0.0008 (8)	−0.0020 (11)	−0.0005 (9)
Si5	0.0178 (11)	0.0135 (11)	0.0138 (10)	−0.0006 (9)	−0.0016 (9)	−0.0007 (8)
Si6	0.0217 (10)	0.0143 (9)	0.0167 (9)	−0.0046 (9)	0.0031 (10)	0.0006 (10)
Si7	0.0211 (12)	0.0148 (11)	0.0114 (11)	−0.0027 (9)	0.0026 (10)	−0.0008 (8)
Si8	0.0169 (10)	0.0168 (10)	0.0168 (10)	−0.0017 (10)	−0.0003 (9)	−0.0005 (10)
Si9	0.0209 (12)	0.0170 (11)	0.0113 (11)	0.0014 (9)	0.0012 (9)	0.0029 (8)
Si10	0.0227 (12)	0.0168 (11)	0.0102 (10)	−0.0007 (9)	0.0003 (10)	−0.0005 (8)
Si11	0.0209 (11)	0.0130 (11)	0.0141 (10)	−0.0001 (9)	0.0025 (11)	−0.0014 (9)
Si12	0.0191 (10)	0.0165 (10)	0.0124 (9)	−0.0007 (9)	0.0023 (8)	0.0010 (8)
Si13	0.0205 (11)	0.0139 (10)	0.0141 (10)	0.0003 (8)	−0.0002 (10)	0.0016 (9)
Si14	0.0180 (10)	0.0164 (11)	0.0152 (9)	−0.0002 (9)	0.0020 (8)	0.0017 (9)
Si15	0.0207 (11)	0.0133 (10)	0.0135 (10)	0.0018 (8)	0.0022 (9)	−0.0005 (9)
Si16	0.0158 (11)	0.0148 (10)	0.0159 (11)	−0.0001 (8)	0.0008 (10)	0.0001 (9)
Si17	0.0182 (11)	0.0101 (11)	0.0159 (11)	−0.0027 (9)	−0.0002 (9)	0.0010 (8)
Si18	0.0194 (10)	0.0145 (10)	0.0143 (10)	−0.0024 (9)	−0.0007 (9)	0.0009 (9)
Si19	0.0213 (12)	0.0142 (11)	0.0144 (11)	0.0003 (9)	−0.0001 (10)	0.0008 (8)
Si20	0.0182 (10)	0.0165 (10)	0.0163 (9)	−0.0008 (10)	0.0020 (9)	−0.0007 (10)
Si21	0.0191 (12)	0.0173 (11)	0.0130 (11)	−0.0004 (9)	−0.0010 (9)	−0.0014 (8)
Si22	0.0210 (12)	0.0169 (11)	0.0158 (11)	−0.0003 (9)	−0.0008 (10)	0.0019 (9)
Si23	0.0212 (11)	0.0120 (11)	0.0161 (11)	0.0004 (9)	−0.0012 (11)	−0.0009 (9)
Si24	0.0206 (10)	0.0167 (10)	0.0134 (9)	−0.0028 (10)	0.0044 (8)	−0.0011 (8)
O1	0.034 (3)	0.022 (3)	0.059 (4)	−0.007 (2)	−0.004 (3)	0.014 (3)
O2	0.019 (3)	0.040 (3)	0.031 (3)	−0.007 (3)	0.001 (2)	0.004 (3)
O3	0.064 (4)	0.013 (3)	0.064 (4)	−0.003 (3)	0.005 (4)	−0.007 (3)
O4	0.019 (3)	0.050 (3)	0.028 (3)	0.007 (2)	0.003 (2)	0.009 (3)
O5	0.020 (3)	0.014 (3)	0.055 (4)	−0.003 (2)	0.006 (3)	0.002 (3)
O6	0.031 (3)	0.019 (3)	0.073 (4)	0.010 (2)	0.012 (3)	−0.004 (3)
O7	0.041 (4)	0.024 (3)	0.057 (4)	−0.017 (3)	−0.005 (3)	−0.005 (3)
O8	0.019 (3)	0.040 (3)	0.042 (3)	−0.007 (3)	0.014 (2)	−0.006 (3)
O9	0.046 (4)	0.023 (3)	0.028 (3)	0.003 (3)	0.000 (3)	0.000 (3)
O10	0.031 (3)	0.053 (4)	0.030 (3)	0.018 (3)	0.014 (3)	0.014 (3)
O11	0.030 (3)	0.021 (3)	0.039 (3)	−0.005 (2)	−0.012 (2)	−0.010 (2)
O12	0.041 (4)	0.026 (3)	0.065 (4)	0.018 (3)	−0.006 (3)	0.003 (3)
O13	0.065 (4)	0.073 (4)	0.014 (3)	0.005 (3)	−0.005 (3)	−0.001 (3)
O14	0.037 (3)	0.039 (3)	0.019 (3)	0.006 (2)	0.005 (3)	−0.002 (3)
O15	0.045 (4)	0.054 (4)	0.012 (3)	0.025 (3)	0.013 (3)	−0.001 (3)
O16	0.047 (4)	0.070 (4)	0.024 (3)	0.020 (3)	−0.019 (3)	0.002 (3)
O17	0.026 (3)	0.043 (3)	0.017 (3)	0.004 (3)	0.006 (3)	−0.009 (3)
O18	0.024 (3)	0.049 (3)	0.013 (2)	0.000 (3)	0.010 (2)	0.003 (3)
O19	0.035 (3)	0.059 (4)	0.021 (3)	−0.011 (3)	−0.012 (3)	−0.008 (3)
O20	0.024 (3)	0.045 (3)	0.026 (3)	0.003 (3)	0.008 (2)	0.011 (3)
O21	0.029 (3)	0.016 (3)	0.036 (3)	−0.010 (2)	0.005 (3)	−0.006 (3)
O22	0.025 (3)	0.016 (3)	0.039 (3)	0.003 (3)	−0.001 (3)	0.006 (2)
O23	0.039 (3)	0.050 (3)	0.0115 (18)	0.007 (2)	0.000 (3)	−0.002 (3)
O24	0.037 (2)	0.039 (2)	0.015 (2)	−0.016 (2)	0.004 (3)	−0.004 (3)
O25	0.034 (2)	0.031 (2)	0.0160 (19)	0.0066 (17)	0.001 (3)	0.003 (3)
O26	0.024 (2)	0.034 (2)	0.0143 (18)	−0.0030 (17)	0.007 (3)	−0.001 (3)
O27	0.033 (3)	0.024 (3)	0.061 (4)	−0.018 (2)	0.005 (3)	−0.006 (3)
O28	0.014 (2)	0.025 (3)	0.049 (3)	−0.003 (2)	0.013 (3)	−0.006 (3)
O29	0.061 (4)	0.014 (3)	0.061 (4)	−0.004 (2)	0.007 (3)	0.000 (3)
O30	0.018 (3)	0.038 (3)	0.048 (3)	0.012 (2)	0.013 (3)	0.005 (3)
O31	0.034 (3)	0.023 (3)	0.032 (3)	−0.013 (2)	−0.011 (3)	0.006 (3)
O32	0.039 (3)	0.024 (3)	0.047 (3)	0.013 (2)	0.008 (3)	0.013 (3)
O33	0.019 (3)	0.017 (3)	0.056 (4)	−0.008 (2)	0.008 (3)	0.009 (3)
O34	0.021 (3)	0.021 (3)	0.053 (3)	−0.001 (2)	−0.012 (2)	−0.004 (2)
O35	0.059 (4)	0.011 (3)	0.029 (3)	−0.007 (3)	−0.008 (3)	0.000 (2)
O36	0.036 (4)	0.047 (4)	0.057 (4)	0.025 (3)	−0.021 (3)	−0.004 (3)
O37	0.056 (4)	0.025 (3)	0.039 (3)	−0.015 (3)	0.020 (3)	0.000 (3)
O38	0.038 (3)	0.024 (3)	0.055 (3)	0.011 (3)	0.004 (3)	−0.010 (3)
O39	0.049 (3)	0.091 (4)	0.014 (2)	−0.003 (3)	−0.002 (3)	0.004 (3)
O40	0.064 (4)	0.037 (3)	0.015 (3)	−0.009 (3)	0.002 (3)	−0.001 (3)
O41	0.048 (4)	0.035 (3)	0.022 (3)	0.010 (3)	−0.010 (3)	0.001 (3)
O42	0.031 (3)	0.048 (3)	0.024 (3)	0.009 (3)	0.007 (3)	−0.008 (3)
O43	0.024 (3)	0.056 (4)	0.021 (3)	0.011 (3)	−0.010 (3)	0.006 (3)
O44	0.034 (3)	0.024 (3)	0.023 (3)	−0.005 (2)	−0.013 (2)	−0.001 (2)
O45	0.044 (3)	0.034 (3)	0.028 (3)	0.000 (3)	0.016 (3)	0.006 (2)
O46	0.037 (3)	0.069 (4)	0.021 (3)	0.004 (3)	−0.014 (3)	0.011 (3)
O47	0.028 (3)	0.014 (3)	0.032 (3)	0.002 (2)	0.003 (3)	0.007 (2)
O48	0.033 (3)	0.019 (3)	0.046 (4)	0.000 (3)	−0.001 (3)	−0.007 (2)

Geometric parameters (Å, º) top

C301—O303	1.4097	Si14—O28	1.598 (5)
C302—O303	1.4097	Si14—O27	1.601 (5)
C501—O503	1.4084	Si15—O28	1.587 (5)
C502—O503	1.4084	Si15—O19ⁱⁱⁱ	1.589 (5)
Si1—O1	1.593 (5)	Si15—O20ⁱⁱⁱ	1.600 (5)
Si1—O16	1.593 (6)	Si15—O29	1.603 (5)
Si1—O15	1.596 (5)	Si16—O30	1.575 (5)
Si1—O47ⁱ	1.599 (5)	Si16—O29	1.580 (5)
Si2—O1	1.591 (5)	Si16—O17ⁱⁱⁱ	1.591 (5)
Si2—O6	1.591 (5)	Si16—O16ⁱⁱⁱ	1.602 (6)
Si2—O13	1.594 (6)	Si17—O40	1.591 (6)
Si2—O2	1.610 (5)	Si17—O31	1.593 (5)
Si3—O46	1.586 (5)	Si17—O47	1.593 (5)
Si3—O2	1.588 (5)	Si17—O30	1.607 (5)
Si3—O3	1.598 (5)	Si18—O31	1.594 (5)
Si3—O45ⁱⁱ	1.600 (5)	Si18—O32	1.602 (5)
Si4—O3	1.578 (5)	Si18—O45	1.605 (5)
Si4—O42ⁱⁱ	1.588 (5)	Si18—O44	1.615 (5)
Si4—O4	1.595 (5)	Si19—O23	1.594 (6)
Si4—O43ⁱⁱ	1.602 (5)	Si19—O33	1.594 (5)
Si5—O21	1.599 (5)	Si19—O22ⁱ	1.598 (5)
Si5—O14	1.601 (6)	Si19—O43	1.609 (5)
Si5—O5	1.604 (5)	Si20—O33	1.585 (5)
Si5—O4	1.611 (5)	Si20—O34	1.603 (5)
Si6—O18	1.591 (5)	Si20—O39	1.604 (5)
Si6—O6	1.599 (5)	Si20—O38	1.608 (5)
Si6—O19	1.602 (5)	Si21—O34	1.592 (5)
Si6—O5	1.604 (5)	Si21—O18ⁱⁱⁱ	1.604 (5)
Si7—O7	1.586 (6)	Si21—O25	1.610 (6)
Si7—O48ⁱ	1.595 (5)	Si21—O35	1.612 (5)
Si7—O23	1.603 (6)	Si22—O36	1.580 (6)
Si7—O17	1.618 (5)	Si22—O15ⁱⁱⁱ	1.582 (5)
Si8—O13	1.581 (5)	Si22—O35	1.602 (5)
Si8—O12	1.595 (5)	Si22—O26	1.616 (6)
Si8—O7	1.601 (6)	Si23—O48	1.598 (6)
Si8—O8	1.608 (5)	Si23—O36	1.598 (6)
Si9—O8	1.562 (5)	Si23—O40	1.601 (6)
Si9—O44ⁱⁱ	1.590 (5)	Si23—O37	1.614 (6)
Si9—O25	1.591 (6)	Si24—O38	1.587 (5)
Si9—O9	1.620 (5)	Si24—O37	1.588 (6)
Si10—O10	1.589 (6)	Si24—O24	1.598 (6)
Si10—O9	1.592 (5)	Si24—O46^iv	1.614 (5)
Si10—O26	1.596 (6)	O15—Si22^v	1.582 (5)
Si10—O41ⁱⁱ	1.615 (6)	O16—Si16^v	1.601 (6)
Si11—O11	1.589 (5)	O17—Si16^v	1.591 (5)
Si11—O14	1.595 (6)	O18—Si21^v	1.604 (5)
Si11—O10	1.599 (6)	O19—Si15^v	1.589 (5)
Si11—O22	1.602 (5)	O20—Si15^v	1.600 (5)
Si12—O11	1.589 (5)	O21—Si13^vi	1.598 (4)
Si12—O20	1.592 (5)	O22—Si19^vi	1.598 (5)
Si12—O12	1.593 (5)	O41—Si10^iv	1.615 (6)
Si12—O24	1.601 (6)	O42—Si4^iv	1.588 (5)
Si13—O41	1.595 (6)	O43—Si4^iv	1.602 (5)
Si13—O27	1.596 (5)	O44—Si9^iv	1.590 (5)
Si13—O21ⁱ	1.599 (4)	O45—Si3^iv	1.600 (5)
Si13—O42	1.611 (6)	O46—Si24ⁱⁱ	1.614 (5)
Si14—O39	1.585 (5)	O47—Si1^vi	1.599 (5)
Si14—O32	1.590 (5)	O48—Si7^vi	1.595 (5)

C302—O303—C301	111.6	O17ⁱⁱⁱ—Si16—O16ⁱⁱⁱ	109.2 (3)
C502—O503—C501	111.6	O40—Si17—O31	108.8 (3)
O1—Si1—O16	109.1 (3)	O40—Si17—O47	110.6 (3)
O1—Si1—O15	110.0 (3)	O31—Si17—O47	109.6 (3)
O16—Si1—O15	111.1 (3)	O40—Si17—O30	110.0 (3)
O1—Si1—O47ⁱ	107.7 (3)	O31—Si17—O30	109.8 (3)
O16—Si1—O47ⁱ	109.4 (3)	O47—Si17—O30	108.0 (3)
O15—Si1—O47ⁱ	109.5 (3)	O31—Si18—O32	109.6 (3)
O1—Si2—O6	111.3 (3)	O31—Si18—O45	108.9 (3)
O1—Si2—O13	109.1 (3)	O32—Si18—O45	109.9 (3)
O6—Si2—O13	109.1 (3)	O31—Si18—O44	107.7 (3)
O1—Si2—O2	108.2 (3)	O32—Si18—O44	110.8 (3)
O6—Si2—O2	109.1 (3)	O45—Si18—O44	110.0 (3)
O13—Si2—O2	110.0 (3)	O23—Si19—O33	109.6 (3)
O46—Si3—O2	108.1 (3)	O23—Si19—O22ⁱ	110.8 (3)
O46—Si3—O3	110.1 (3)	O33—Si19—O22ⁱ	107.9 (3)
O2—Si3—O3	110.2 (3)	O23—Si19—O43	107.5 (3)
O46—Si3—O45ⁱⁱ	109.4 (3)	O33—Si19—O43	110.6 (3)
O2—Si3—O45ⁱⁱ	109.3 (3)	O22ⁱ—Si19—O43	110.5 (3)
O3—Si3—O45ⁱⁱ	109.7 (3)	O33—Si20—O34	109.0 (3)
O3—Si4—O42ⁱⁱ	108.1 (3)	O33—Si20—O39	110.4 (3)
O3—Si4—O4	109.4 (3)	O34—Si20—O39	109.8 (3)
O42ⁱⁱ—Si4—O4	109.4 (3)	O33—Si20—O38	110.1 (3)
O3—Si4—O43ⁱⁱ	109.9 (3)	O34—Si20—O38	108.9 (3)
O42ⁱⁱ—Si4—O43ⁱⁱ	110.7 (3)	O39—Si20—O38	108.8 (3)
O4—Si4—O43ⁱⁱ	109.3 (3)	O34—Si21—O18ⁱⁱⁱ	109.6 (3)
O21—Si5—O14	111.3 (3)	O34—Si21—O25	111.5 (3)
O21—Si5—O5	106.0 (3)	O18ⁱⁱⁱ—Si21—O25	107.1 (3)
O14—Si5—O5	110.8 (3)	O34—Si21—O35	108.5 (3)
O21—Si5—O4	110.8 (3)	O18ⁱⁱⁱ—Si21—O35	110.0 (3)
O14—Si5—O4	108.5 (3)	O25—Si21—O35	110.1 (2)
O5—Si5—O4	109.4 (3)	O36—Si22—O15ⁱⁱⁱ	108.8 (3)
O18—Si6—O6	109.3 (3)	O36—Si22—O35	108.6 (3)
O18—Si6—O19	109.4 (3)	O15ⁱⁱⁱ—Si22—O35	110.4 (3)
O6—Si6—O19	110.8 (3)	O36—Si22—O26	110.4 (3)
O18—Si6—O5	107.8 (3)	O15ⁱⁱⁱ—Si22—O26	108.6 (3)
O6—Si6—O5	109.4 (3)	O35—Si22—O26	110.0 (2)
O19—Si6—O5	110.1 (3)	O48—Si23—O36	108.5 (3)
O7—Si7—O48ⁱ	108.2 (3)	O48—Si23—O40	110.1 (3)
O7—Si7—O23	109.7 (3)	O36—Si23—O40	109.5 (3)
O48ⁱ—Si7—O23	111.3 (3)	O48—Si23—O37	108.0 (3)
O7—Si7—O17	109.6 (3)	O36—Si23—O37	111.8 (3)
O48ⁱ—Si7—O17	110.7 (3)	O40—Si23—O37	108.9 (3)
O23—Si7—O17	107.3 (3)	O38—Si24—O37	109.9 (3)
O13—Si8—O12	108.8 (3)	O38—Si24—O24	108.4 (3)
O13—Si8—O7	110.4 (3)	O37—Si24—O24	108.8 (3)
O12—Si8—O7	110.1 (3)	O38—Si24—O46^iv	110.7 (3)
O13—Si8—O8	108.8 (3)	O37—Si24—O46^iv	111.1 (3)
O12—Si8—O8	110.9 (3)	O24—Si24—O46^iv	107.8 (3)
O7—Si8—O8	107.7 (3)	Si2—O1—Si1	148.7 (4)
O8—Si9—O44ⁱⁱ	109.9 (3)	Si3—O2—Si2	147.9 (4)
O8—Si9—O25	108.5 (3)	Si4—O3—Si3	165.5 (5)
O44ⁱⁱ—Si9—O25	109.3 (3)	Si4—O4—Si5	150.6 (4)
O8—Si9—O9	108.7 (3)	Si5—O5—Si6	147.1 (3)
O44ⁱⁱ—Si9—O9	109.6 (3)	Si2—O6—Si6	162.7 (4)
O25—Si9—O9	110.9 (2)	Si7—O7—Si8	157.7 (4)
O10—Si10—O9	108.7 (3)	Si9—O8—Si8	154.6 (4)
O10—Si10—O26	108.7 (3)	Si10—O9—Si9	151.4 (3)
O9—Si10—O26	110.6 (2)	Si10—O10—Si11	157.7 (4)
O10—Si10—O41ⁱⁱ	111.2 (3)	Si12—O11—Si11	155.5 (4)
O9—Si10—O41ⁱⁱ	109.6 (3)	Si12—O12—Si8	171.3 (4)
O26—Si10—O41ⁱⁱ	108.0 (3)	Si8—O13—Si2	165.6 (4)
O11—Si11—O14	109.6 (3)	Si11—O14—Si5	161.9 (3)
O11—Si11—O10	110.5 (3)	Si22^v—O15—Si1	149.3 (4)
O14—Si11—O10	108.2 (3)	Si1—O16—Si16^v	179.0 (5)
O11—Si11—O22	108.8 (3)	Si16^v—O17—Si7	146.7 (4)
O14—Si11—O22	110.1 (3)	Si6—O18—Si21^v	142.7 (4)
O10—Si11—O22	109.8 (3)	Si15^v—O19—Si6	167.6 (4)
O11—Si12—O20	110.0 (3)	Si12—O20—Si15^v	144.6 (4)
O11—Si12—O12	108.6 (3)	Si13^vi—O21—Si5	146.0 (4)
O20—Si12—O12	108.4 (3)	Si19^vi—O22—Si11	150.9 (4)
O11—Si12—O24	111.3 (3)	Si19—O23—Si7	155.2 (3)
O20—Si12—O24	107.0 (3)	Si24—O24—Si12	149.4 (3)
O12—Si12—O24	111.6 (3)	Si9—O25—Si21	151.9 (2)
O41—Si13—O27	109.7 (3)	Si10—O26—Si22	146.5 (2)
O41—Si13—O21ⁱ	107.7 (3)	Si13—O27—Si14	153.3 (4)
O27—Si13—O21ⁱ	109.8 (3)	Si15—O28—Si14	151.6 (3)
O41—Si13—O42	109.5 (3)	Si16—O29—Si15	166.7 (4)
O27—Si13—O42	110.3 (3)	Si16—O30—Si17	157.9 (4)
O21ⁱ—Si13—O42	109.9 (3)	Si17—O31—Si18	150.2 (4)
O39—Si14—O32	108.6 (3)	Si14—O32—Si18	159.4 (4)
O39—Si14—O28	110.0 (3)	Si20—O33—Si19	152.3 (4)
O32—Si14—O28	109.5 (3)	Si21—O34—Si20	149.8 (3)
O39—Si14—O27	111.6 (3)	Si22—O35—Si21	152.2 (3)
O32—Si14—O27	108.7 (3)	Si22—O36—Si23	161.5 (4)
O28—Si14—O27	108.4 (3)	Si24—O37—Si23	152.4 (4)
O28—Si15—O19ⁱⁱⁱ	109.3 (3)	Si24—O38—Si20	157.5 (4)
O28—Si15—O20ⁱⁱⁱ	109.2 (3)	Si14—O39—Si20	169.3 (4)
O19ⁱⁱⁱ—Si15—O20ⁱⁱⁱ	110.7 (3)	Si17—O40—Si23	163.4 (3)
O28—Si15—O29	108.9 (3)	Si13—O41—Si10^iv	149.1 (4)
O19ⁱⁱⁱ—Si15—O29	109.0 (3)	Si4^iv—O42—Si13	160.7 (4)
O20ⁱⁱⁱ—Si15—O29	109.7 (3)	Si4^iv—O43—Si19	150.0 (4)
O30—Si16—O29	110.2 (3)	Si9^iv—O44—Si18	149.0 (4)
O30—Si16—O17ⁱⁱⁱ	107.7 (3)	Si3^iv—O45—Si18	155.4 (4)
O29—Si16—O17ⁱⁱⁱ	108.7 (3)	Si3—O46—Si24ⁱⁱ	153.2 (4)
O30—Si16—O16ⁱⁱⁱ	110.7 (3)	Si17—O47—Si1^vi	149.3 (4)
O29—Si16—O16ⁱⁱⁱ	110.3 (3)	Si7^vi—O48—Si23	149.3 (4)

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x+1/2, −y+1/2, z−1/2; (vi) −x+1/2, y−1/2, −z+1/2.

(II) top

Crystal data top

C_3.6H₀O_49.8Si₂₄	Z = 4
M_r = 1515	F(000) = 2952
Monoclinic, P2₁/n.1.1	D_x = 1.810 Mg m⁻³
a = 20.169 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 19.951 (14) Å	µ = 0.67 mm⁻¹
c = 13.427 (10) Å	T = 296 K
β = 90°	0.14 × 0.12 × 0.08 mm
V = 5403 (7) Å³

Data collection top

Bruker P4 diffractometer	13209 independent reflections
Radiation source: fine-focus sealed tube	5947 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.115
ω scans	θ_max = 28.7°, θ_min = 1.4°
Absorption correction: analytical ?	h = −18→17
T_min = 0.912, T_max = 0.951	k = −27→27
63444 measured reflections	l = −26→26

Refinement top

Refinement on F²	10 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.054	Secondary atom site location: difference Fourier map
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0408P)²] where P = (F_o² + 2F_c²)/3
S = 0.83	(Δ/σ)_max = 0.001
13209 reflections	Δρ_max = 0.63 e Å⁻³
669 parameters	Δρ_min = −0.50 e Å⁻³

Crystal data top

C_3.6H₀O_49.8Si₂₄	V = 5403 (7) Å³
M_r = 1515	Z = 4
Monoclinic, P2₁/n.1.1	Mo Kα radiation
a = 20.169 (14) Å	µ = 0.67 mm⁻¹
b = 19.951 (14) Å	T = 296 K
c = 13.427 (10) Å	0.14 × 0.12 × 0.08 mm
β = 90°

Data collection top

Bruker P4 diffractometer	13209 independent reflections
Absorption correction: analytical ?	5947 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.951	R_int = 0.115
63444 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	669 parameters
wR(F²) = 0.124	10 restraints
S = 0.83	Δρ_max = 0.63 e Å⁻³
13209 reflections	Δρ_min = −0.50 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C101	0.0000	0.5000	1.0000	0.197 (17)*	0.78 (2)
C102	−0.0001 (3)	0.4842 (5)	0.88432 (7)	0.32 (4)*	0.392 (12)
O103	0.0071 (2)	0.5307 (3)	0.93677 (14)	0.39 (3)*	0.392 (12)
C201	0.9837 (11)	0.4750 (10)	0.5238 (10)	0.26 (3)*	0.421 (10)
C202	0.9966 (8)	0.4851 (7)	0.6398 (10)	0.177 (18)*	0.421 (10)
O203	0.9949 (10)	0.5190 (8)	0.5781 (11)	0.29 (2)*	0.421 (10)
C301	0.1419 (11)	0.2349 (9)	0.7546 (12)	0.32 (3)*	0.410 (12)
C302	0.1606 (14)	0.1203 (9)	0.7469 (17)	0.52 (5)*	0.410 (12)
O303	0.0928 (13)	0.1736 (10)	0.7477 (15)	0.71 (5)*	0.410 (12)
C401	1.1622 (5)	0.5056 (11)	0.7715 (12)	1.02 (9)*	0.595 (10)
C402	1.0185 (7)	0.4970 (7)	0.7066 (11)	0.29 (2)*	0.595 (10)
O403	1.0586 (5)	0.4944 (9)	0.7718 (11)	0.94 (6)*	0.595 (10)
Si1	0.82361 (16)	0.07928 (9)	0.44407 (12)	0.0151 (4)
Si2	0.66986 (17)	0.18795 (10)	0.46985 (10)	0.0171 (5)
Si3	0.45160 (16)	0.22053 (10)	0.43768 (11)	0.0172 (5)
Si4	0.46566 (15)	0.37647 (10)	0.43706 (11)	0.0151 (5)
Si5	0.67838 (17)	0.42413 (10)	0.47185 (10)	0.0146 (5)
Si6	0.81755 (16)	0.30664 (10)	0.44413 (11)	0.0164 (4)
Si7	0.82096 (17)	0.07521 (10)	0.67155 (11)	0.0150 (5)
Si8	0.67664 (16)	0.18929 (10)	0.62716 (10)	0.0160 (5)
Si9	0.46572 (16)	0.22648 (10)	0.67563 (10)	0.0158 (5)
Si10	0.46784 (17)	0.38056 (10)	0.67581 (10)	0.0160 (5)
Si11	0.67769 (17)	0.42867 (9)	0.62941 (11)	0.0153 (5)
Si12	0.81620 (16)	0.31023 (10)	0.66691 (10)	0.0157 (4)
Si13	0.83583 (15)	0.07264 (9)	1.05757 (12)	0.0147 (5)
Si14	0.68938 (16)	0.18849 (11)	1.02744 (10)	0.0162 (5)
Si15	0.47131 (15)	0.22239 (10)	1.06139 (11)	0.0144 (5)
Si16	0.46781 (15)	0.37808 (10)	1.06401 (11)	0.0162 (5)
Si17	0.68054 (17)	0.42925 (10)	1.02721 (10)	0.0142 (5)
Si18	0.82030 (16)	0.31312 (9)	1.06240 (11)	0.0150 (5)
Si19	0.81702 (18)	0.07629 (10)	0.82790 (10)	0.0163 (5)
Si20	0.67306 (16)	0.18841 (10)	0.86923 (11)	0.0167 (5)
Si21	0.45808 (16)	0.22647 (10)	0.83089 (10)	0.0160 (5)
Si22	0.46391 (17)	0.38119 (10)	0.82955 (11)	0.0163 (5)
Si23	0.67854 (17)	0.42820 (9)	0.86943 (11)	0.0155 (5)
Si24	0.80276 (16)	0.30773 (10)	0.82092 (10)	0.0165 (5)
O1	0.7256 (4)	0.1244 (2)	0.4414 (3)	0.0337 (14)
O2	0.5620 (4)	0.1905 (2)	0.4349 (2)	0.0254 (12)
O3	0.4560 (4)	0.2982 (2)	0.4500 (3)	0.0409 (14)
O4	0.5803 (4)	0.3967 (2)	0.4337 (2)	0.0257 (13)
O5	0.7731 (4)	0.3796 (2)	0.4541 (3)	0.0238 (13)
O6	0.7295 (4)	0.2530 (2)	0.4523 (3)	0.0382 (15)
O7	0.7306 (5)	0.1245 (3)	0.6538 (3)	0.0380 (17)
O8	0.5715 (4)	0.1960 (3)	0.6650 (2)	0.0324 (14)
O9	0.4705 (4)	0.3038 (2)	0.6557 (2)	0.0278 (14)
O10	0.5772 (4)	0.4102 (3)	0.6680 (3)	0.0356 (15)
O11	0.7662 (4)	0.3801 (3)	0.6515 (3)	0.0331 (16)
O12	0.7437 (4)	0.2528 (3)	0.6401 (3)	0.0390 (16)
O13	0.6583 (4)	0.1820 (3)	0.5482 (3)	0.0458 (16)
O14	0.6583 (4)	0.4221 (2)	0.5506 (3)	0.0279 (13)
O15	0.8799 (4)	0.0854 (3)	0.3746 (3)	0.0347 (16)
O16	0.8948 (5)	0.1042 (3)	0.5045 (3)	0.0435 (18)
O17	0.9188 (4)	0.0987 (3)	0.6336 (3)	0.0278 (14)
O18	0.8644 (3)	0.3006 (3)	0.3705 (3)	0.0259 (13)
O19	0.9037 (4)	0.2933 (3)	0.4976 (3)	0.0355 (15)
O20	0.9207 (4)	0.3048 (3)	0.6283 (3)	0.0271 (13)
O21	0.7037 (4)	0.4978 (2)	0.4480 (3)	0.0219 (12)
O22	0.7090 (4)	0.5031 (2)	0.6481 (3)	0.0286 (14)
O23	0.8450 (3)	0.07663 (19)	0.7504 (3)	0.0308 (11)
O24	0.8404 (3)	0.3033 (2)	0.7449 (3)	0.0299 (11)
O25	0.4349 (3)	0.21751 (17)	0.7528 (3)	0.0232 (10)
O26	0.4328 (3)	0.39003 (18)	0.7524 (3)	0.0225 (10)
O27	0.7435 (4)	0.1226 (2)	1.0519 (3)	0.0350 (15)
O28	0.5759 (4)	0.1866 (2)	1.0538 (3)	0.0288 (13)
O29	0.4875 (4)	0.3005 (2)	1.0660 (3)	0.0384 (15)
O30	0.5698 (4)	0.4162 (2)	1.0544 (3)	0.0345 (14)
O31	0.7581 (4)	0.3805 (2)	1.0645 (2)	0.0253 (13)
O32	0.7468 (4)	0.2512 (2)	1.0593 (3)	0.0337 (14)
O33	0.7230 (4)	0.1217 (3)	0.8407 (3)	0.0316 (15)
O34	0.5570 (4)	0.1865 (2)	0.8540 (2)	0.0247 (13)
O35	0.4738 (5)	0.3037 (2)	0.8480 (2)	0.0316 (15)
O36	0.5694 (4)	0.4160 (3)	0.8435 (3)	0.0375 (16)
O37	0.7553 (4)	0.3787 (3)	0.8332 (3)	0.0349 (16)
O38	0.7219 (4)	0.2517 (2)	0.8330 (3)	0.0359 (15)
O39	0.6926 (4)	0.1945 (3)	0.9483 (3)	0.0476 (15)
O40	0.6840 (4)	0.4160 (2)	0.9486 (3)	0.0368 (14)
O41	0.8906 (4)	0.0809 (3)	1.1284 (3)	0.0329 (15)
O42	0.9137 (4)	0.0861 (3)	0.9983 (3)	0.0307 (14)
O43	0.9133 (4)	0.1040 (3)	0.8685 (3)	0.0303 (14)
O44	0.8854 (4)	0.3111 (2)	1.1292 (3)	0.0250 (13)
O45	0.8925 (4)	0.3135 (3)	0.9979 (3)	0.0319 (14)
O46	0.3973 (4)	0.2046 (3)	0.3690 (3)	0.0394 (16)
O47	0.7088 (4)	0.5046 (2)	1.0442 (3)	0.0239 (14)
O48	0.7115 (4)	0.5018 (3)	0.8521 (3)	0.0296 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0227 (12)	0.0108 (9)	0.0120 (10)	−0.0020 (9)	0.0022 (11)	0.0009 (9)
Si2	0.0246 (12)	0.0108 (10)	0.0158 (10)	0.0005 (10)	0.0014 (9)	0.0005 (9)
Si3	0.0219 (12)	0.0137 (10)	0.0160 (11)	0.0001 (8)	−0.0002 (10)	0.0014 (9)
Si4	0.0174 (11)	0.0141 (11)	0.0138 (11)	0.0008 (9)	−0.0009 (11)	0.0011 (9)
Si5	0.0188 (12)	0.0112 (11)	0.0137 (11)	0.0010 (10)	−0.0006 (10)	0.0010 (8)
Si6	0.0224 (11)	0.0124 (9)	0.0142 (9)	0.0031 (10)	0.0046 (10)	−0.0014 (10)
Si7	0.0198 (12)	0.0130 (11)	0.0121 (11)	0.0029 (10)	0.0040 (11)	0.0013 (9)
Si8	0.0174 (11)	0.0153 (11)	0.0152 (10)	0.0010 (10)	−0.0008 (10)	0.0009 (10)
Si9	0.0203 (13)	0.0156 (11)	0.0115 (11)	−0.0014 (9)	0.0023 (10)	−0.0028 (9)
Si10	0.0232 (13)	0.0155 (11)	0.0092 (11)	0.0000 (9)	0.0013 (10)	0.0022 (9)
Si11	0.0215 (12)	0.0111 (11)	0.0135 (11)	−0.0002 (9)	0.0036 (11)	−0.0003 (9)
Si12	0.0190 (11)	0.0159 (10)	0.0121 (9)	0.0005 (10)	0.0027 (9)	−0.0010 (9)
Si13	0.0195 (12)	0.0108 (9)	0.0137 (10)	0.0003 (8)	0.0021 (10)	0.0003 (9)
Si14	0.0196 (11)	0.0145 (11)	0.0144 (10)	0.0009 (10)	0.0025 (8)	−0.0013 (9)
Si15	0.0194 (12)	0.0132 (10)	0.0108 (10)	−0.0007 (8)	0.0042 (10)	0.0015 (9)
Si16	0.0184 (12)	0.0138 (11)	0.0163 (12)	−0.0008 (9)	0.0004 (11)	0.0002 (10)
Si17	0.0192 (12)	0.0089 (11)	0.0145 (11)	0.0019 (9)	−0.0001 (10)	−0.0005 (8)
Si18	0.0215 (11)	0.0131 (10)	0.0103 (10)	0.0022 (9)	−0.0008 (9)	−0.0010 (9)
Si19	0.0246 (13)	0.0125 (11)	0.0119 (11)	0.0003 (10)	0.0032 (11)	0.0000 (8)
Si20	0.0198 (11)	0.0146 (11)	0.0159 (10)	0.0028 (10)	0.0014 (10)	0.0002 (10)
Si21	0.0216 (13)	0.0157 (11)	0.0106 (11)	0.0006 (9)	0.0017 (10)	0.0004 (9)
Si22	0.0207 (13)	0.0148 (11)	0.0135 (11)	−0.0002 (9)	−0.0004 (10)	0.0003 (9)
Si23	0.0234 (12)	0.0095 (11)	0.0138 (11)	0.0002 (9)	0.0009 (11)	−0.0005 (9)
Si24	0.0230 (11)	0.0124 (10)	0.0140 (10)	0.0024 (10)	0.0050 (9)	0.0011 (9)
O1	0.033 (3)	0.017 (3)	0.050 (4)	0.005 (2)	0.000 (3)	−0.008 (3)
O2	0.025 (3)	0.026 (3)	0.025 (3)	0.006 (3)	0.006 (2)	−0.007 (3)
O3	0.056 (4)	0.010 (3)	0.056 (3)	0.001 (3)	0.005 (3)	0.003 (3)
O4	0.020 (3)	0.038 (3)	0.019 (3)	−0.003 (2)	0.011 (2)	−0.009 (2)
O5	0.018 (3)	0.011 (2)	0.042 (4)	0.006 (2)	0.008 (3)	0.000 (3)
O6	0.035 (3)	0.016 (3)	0.064 (4)	−0.008 (2)	0.019 (3)	−0.002 (3)
O7	0.043 (4)	0.020 (3)	0.051 (4)	0.021 (3)	−0.002 (3)	0.014 (3)
O8	0.019 (3)	0.039 (3)	0.039 (3)	0.007 (3)	0.016 (3)	0.006 (3)
O9	0.045 (4)	0.011 (3)	0.027 (3)	−0.003 (3)	0.004 (3)	0.000 (3)
O10	0.026 (3)	0.052 (4)	0.029 (3)	−0.020 (3)	0.018 (3)	−0.010 (3)
O11	0.033 (4)	0.020 (3)	0.046 (4)	0.009 (3)	−0.009 (3)	0.010 (3)
O12	0.043 (4)	0.021 (3)	0.052 (4)	−0.019 (3)	−0.001 (3)	−0.003 (3)
O13	0.054 (4)	0.064 (4)	0.020 (3)	−0.014 (3)	−0.003 (3)	0.006 (3)
O14	0.036 (3)	0.031 (3)	0.016 (3)	−0.002 (2)	−0.004 (3)	0.004 (3)
O15	0.043 (4)	0.048 (4)	0.013 (3)	−0.017 (3)	0.016 (3)	0.003 (3)
O16	0.052 (4)	0.060 (4)	0.019 (3)	−0.020 (3)	−0.015 (3)	−0.004 (3)
O17	0.025 (3)	0.040 (3)	0.018 (3)	−0.007 (3)	0.009 (3)	0.004 (3)
O18	0.017 (3)	0.046 (3)	0.014 (2)	0.005 (3)	0.006 (2)	−0.005 (3)
O19	0.035 (3)	0.055 (4)	0.017 (3)	0.010 (3)	−0.008 (3)	0.003 (3)
O20	0.020 (3)	0.037 (3)	0.024 (3)	−0.004 (3)	0.008 (2)	−0.006 (3)
O21	0.021 (3)	0.011 (2)	0.034 (3)	0.004 (2)	0.009 (3)	0.004 (3)
O22	0.028 (3)	0.014 (3)	0.044 (4)	0.002 (3)	0.001 (3)	−0.006 (2)
O23	0.042 (3)	0.040 (3)	0.010 (2)	−0.006 (2)	0.003 (3)	−0.003 (3)
O24	0.044 (3)	0.037 (2)	0.009 (2)	0.011 (2)	0.003 (3)	0.000 (3)
O25	0.030 (3)	0.028 (2)	0.012 (2)	−0.0045 (19)	0.000 (3)	−0.004 (3)
O26	0.021 (3)	0.034 (2)	0.012 (2)	0.0070 (19)	0.003 (3)	0.001 (3)
O27	0.029 (3)	0.018 (3)	0.058 (4)	0.013 (2)	0.004 (3)	0.002 (3)
O28	0.019 (3)	0.023 (3)	0.045 (3)	−0.001 (2)	0.012 (3)	0.005 (3)
O29	0.061 (4)	0.012 (3)	0.042 (3)	0.000 (3)	0.003 (3)	−0.003 (3)
O30	0.021 (3)	0.028 (3)	0.055 (4)	−0.009 (2)	0.014 (3)	−0.004 (3)
O31	0.038 (3)	0.021 (3)	0.017 (3)	0.013 (2)	−0.005 (3)	−0.003 (2)
O32	0.037 (3)	0.023 (3)	0.041 (3)	−0.015 (2)	0.010 (3)	−0.008 (3)
O33	0.020 (3)	0.019 (3)	0.056 (4)	0.008 (3)	0.009 (3)	−0.006 (3)
O34	0.026 (3)	0.014 (3)	0.034 (3)	0.001 (2)	−0.003 (2)	0.007 (2)
O35	0.058 (4)	0.009 (3)	0.028 (3)	0.006 (3)	−0.002 (3)	−0.001 (3)
O36	0.033 (4)	0.034 (3)	0.045 (4)	−0.018 (3)	−0.014 (3)	0.006 (3)
O37	0.056 (4)	0.021 (3)	0.028 (3)	0.011 (3)	0.021 (3)	−0.003 (3)
O38	0.040 (4)	0.020 (3)	0.048 (4)	−0.006 (3)	0.008 (3)	0.010 (3)
O39	0.044 (3)	0.081 (4)	0.018 (3)	−0.001 (3)	0.002 (3)	0.001 (4)
O40	0.065 (4)	0.030 (3)	0.015 (3)	0.005 (3)	−0.002 (3)	−0.001 (3)
O41	0.046 (4)	0.031 (3)	0.022 (3)	−0.017 (3)	−0.011 (3)	0.003 (3)
O42	0.029 (3)	0.032 (3)	0.031 (3)	−0.012 (3)	0.011 (3)	0.008 (3)
O43	0.026 (3)	0.044 (4)	0.021 (3)	−0.009 (3)	−0.008 (3)	−0.005 (3)
O44	0.030 (3)	0.022 (3)	0.023 (3)	0.007 (3)	−0.013 (3)	−0.001 (3)
O45	0.041 (3)	0.026 (3)	0.029 (3)	−0.002 (3)	0.020 (3)	−0.007 (3)
O46	0.030 (3)	0.069 (4)	0.019 (3)	−0.006 (3)	−0.013 (3)	−0.010 (3)
O47	0.026 (3)	0.010 (3)	0.036 (3)	−0.002 (2)	0.012 (3)	−0.010 (2)
O48	0.033 (4)	0.014 (3)	0.042 (4)	−0.003 (3)	0.000 (3)	0.006 (2)

Geometric parameters (Å, º) top

C101—O103	1.4086	Si13—O42	1.604 (6)
C101—O103ⁱ	1.4086	Si14—O39	1.584 (6)
C102—O103	1.4083	Si14—O27	1.591 (5)
C201—O203	1.4083	Si14—O32	1.610 (5)
C201—C201ⁱⁱ	1.45 (3)	Si14—O28	1.613 (5)
C202—O203	1.4085	Si15—O28	1.586 (5)
C301—O303	1.4082	Si15—O29	1.592 (5)
C302—O303	1.4084	Si15—O19^v	1.593 (5)
C401—O403	1.4083	Si15—O20^v	1.597 (5)
C402—O403	1.4074	Si16—O16^v	1.579 (6)
Si1—O47ⁱⁱⁱ	1.585 (5)	Si16—O30	1.583 (5)
Si1—O15	1.586 (6)	Si16—O29	1.588 (5)
Si1—O1	1.601 (5)	Si16—O17^v	1.608 (6)
Si1—O16	1.617 (6)	Si17—O40	1.592 (6)
Si2—O13	1.576 (6)	Si17—O47	1.603 (5)
Si2—O6	1.577 (5)	Si17—O30	1.606 (5)
Si2—O1	1.589 (5)	Si17—O31	1.612 (5)
Si2—O2	1.606 (5)	Si18—O44	1.592 (5)
Si3—O46	1.583 (5)	Si18—O32	1.594 (5)
Si3—O3	1.586 (5)	Si18—O31	1.596 (5)
Si3—O45^iv	1.596 (5)	Si18—O45	1.613 (5)
Si3—O2	1.603 (5)	Si19—O33	1.581 (6)
Si4—O43^iv	1.587 (6)	Si19—O22ⁱⁱⁱ	1.590 (5)
Si4—O4	1.594 (5)	Si19—O23	1.592 (6)
Si4—O42^iv	1.597 (5)	Si19—O43	1.623 (6)
Si4—O3	1.606 (5)	Si20—O34	1.588 (6)
Si5—O14	1.595 (6)	Si20—O39	1.603 (6)
Si5—O5	1.598 (5)	Si20—O33	1.608 (5)
Si5—O21	1.598 (5)	Si20—O38	1.608 (5)
Si5—O4	1.618 (5)	Si21—O18^v	1.585 (5)
Si6—O19	1.595 (5)	Si21—O25	1.599 (6)
Si6—O5	1.601 (5)	Si21—O35	1.608 (5)
Si6—O18	1.604 (5)	Si21—O34	1.619 (5)
Si6—O6	1.611 (5)	Si22—O15^v	1.593 (5)
Si7—O17	1.590 (6)	Si22—O26	1.604 (6)
Si7—O23	1.605 (6)	Si22—O36	1.604 (6)
Si7—O7	1.608 (6)	Si22—O35	1.612 (5)
Si7—O48ⁱⁱⁱ	1.614 (6)	Si23—O36	1.573 (6)
Si8—O7	1.585 (5)	Si23—O48	1.587 (6)
Si8—O12	1.587 (5)	Si23—O40	1.600 (6)
Si8—O13	1.600 (6)	Si23—O37	1.608 (6)
Si8—O8	1.609 (5)	Si24—O37	1.586 (6)
Si9—O8	1.562 (5)	Si24—O38	1.586 (5)
Si9—O25	1.604 (6)	Si24—O24	1.601 (5)
Si9—O44^iv	1.611 (5)	Si24—O46^vi	1.609 (5)
Si9—O9	1.611 (5)	O15—Si22^vii	1.593 (5)
Si10—O10	1.594 (6)	O16—Si16^vii	1.579 (6)
Si10—O9	1.599 (5)	O17—Si16^vii	1.608 (6)
Si10—O41^iv	1.603 (6)	O18—Si21^vii	1.585 (5)
Si10—O26	1.611 (6)	O19—Si15^vii	1.593 (5)
Si11—O14	1.599 (6)	O20—Si15^vii	1.596 (5)
Si11—O10	1.599 (6)	O21—Si13^viii	1.604 (4)
Si11—O11	1.601 (6)	O22—Si19^viii	1.590 (5)
Si11—O22	1.603 (5)	O41—Si10^vi	1.603 (6)
Si12—O11	1.591 (6)	O42—Si4^vi	1.597 (5)
Si12—O24	1.596 (6)	O43—Si4^vi	1.587 (6)
Si12—O12	1.604 (5)	O44—Si9^vi	1.611 (5)
Si12—O20	1.606 (5)	O45—Si3^vi	1.596 (5)
Si13—O41	1.600 (6)	O46—Si24^iv	1.609 (5)
Si13—O27	1.601 (5)	O47—Si1^viii	1.585 (5)
Si13—O21ⁱⁱⁱ	1.604 (5)	O48—Si7^viii	1.614 (6)

O103—C101—O103ⁱ	180.0 (4)	O16^v—Si16—O17^v	109.2 (3)
C102—O103—C101	111.6	O30—Si16—O17^v	108.6 (3)
O203—C201—C201ⁱⁱ	92 (2)	O29—Si16—O17^v	109.5 (3)
C201—O203—C202	111.6	O40—Si17—O47	111.1 (3)
C301—O303—C302	111.6	O40—Si17—O30	109.5 (3)
C402—O403—C401	111.5	O47—Si17—O30	107.6 (3)
O47ⁱⁱⁱ—Si1—O15	109.6 (3)	O40—Si17—O31	109.4 (3)
O47ⁱⁱⁱ—Si1—O1	108.6 (3)	O47—Si17—O31	109.2 (3)
O15—Si1—O1	108.6 (3)	O30—Si17—O31	110.0 (3)
O47ⁱⁱⁱ—Si1—O16	110.3 (3)	O44—Si18—O32	110.6 (3)
O15—Si1—O16	110.2 (3)	O44—Si18—O31	106.6 (3)
O1—Si1—O16	109.5 (3)	O32—Si18—O31	110.2 (3)
O13—Si2—O6	109.6 (3)	O44—Si18—O45	109.7 (3)
O13—Si2—O1	109.9 (3)	O32—Si18—O45	110.2 (3)
O6—Si2—O1	110.6 (3)	O31—Si18—O45	109.4 (3)
O13—Si2—O2	110.1 (3)	O33—Si19—O22ⁱⁱⁱ	108.3 (3)
O6—Si2—O2	109.5 (3)	O33—Si19—O23	110.1 (3)
O1—Si2—O2	107.2 (3)	O22ⁱⁱⁱ—Si19—O23	110.4 (3)
O46—Si3—O3	110.6 (3)	O33—Si19—O43	110.8 (3)
O46—Si3—O45^iv	109.6 (3)	O22ⁱⁱⁱ—Si19—O43	110.2 (3)
O3—Si3—O45^iv	109.0 (3)	O23—Si19—O43	107.0 (3)
O46—Si3—O2	108.5 (3)	O34—Si20—O39	110.4 (3)
O3—Si3—O2	110.2 (3)	O34—Si20—O33	108.8 (3)
O45^iv—Si3—O2	109.0 (3)	O39—Si20—O33	110.2 (3)
O43^iv—Si4—O4	109.0 (3)	O34—Si20—O38	109.6 (3)
O43^iv—Si4—O42^iv	110.4 (3)	O39—Si20—O38	108.4 (3)
O4—Si4—O42^iv	109.6 (3)	O33—Si20—O38	109.5 (3)
O43^iv—Si4—O3	110.3 (3)	O18^v—Si21—O25	107.1 (3)
O4—Si4—O3	109.7 (3)	O18^v—Si21—O35	109.4 (3)
O42^iv—Si4—O3	107.8 (3)	O25—Si21—O35	110.0 (2)
O14—Si5—O5	109.9 (3)	O18^v—Si21—O34	109.7 (3)
O14—Si5—O21	110.8 (3)	O25—Si21—O34	112.3 (3)
O5—Si5—O21	106.6 (3)	O35—Si21—O34	108.3 (3)
O14—Si5—O4	108.4 (3)	O15^v—Si22—O26	108.1 (3)
O5—Si5—O4	110.5 (3)	O15^v—Si22—O36	110.0 (3)
O21—Si5—O4	110.6 (3)	O26—Si22—O36	110.2 (3)
O19—Si6—O5	110.0 (3)	O15^v—Si22—O35	109.8 (3)
O19—Si6—O18	108.3 (3)	O26—Si22—O35	110.4 (2)
O5—Si6—O18	109.3 (3)	O36—Si22—O35	108.2 (3)
O19—Si6—O6	110.5 (3)	O36—Si23—O48	109.5 (3)
O5—Si6—O6	109.4 (3)	O36—Si23—O40	110.0 (3)
O18—Si6—O6	109.3 (3)	O48—Si23—O40	110.3 (3)
O17—Si7—O23	107.2 (3)	O36—Si23—O37	110.7 (3)
O17—Si7—O7	109.6 (3)	O48—Si23—O37	107.7 (3)
O23—Si7—O7	110.8 (3)	O40—Si23—O37	108.7 (3)
O17—Si7—O48ⁱⁱⁱ	110.9 (3)	O37—Si24—O38	110.1 (3)
O23—Si7—O48ⁱⁱⁱ	110.9 (3)	O37—Si24—O24	109.0 (3)
O7—Si7—O48ⁱⁱⁱ	107.5 (3)	O38—Si24—O24	108.8 (3)
O7—Si8—O12	110.6 (3)	O37—Si24—O46^vi	111.4 (3)
O7—Si8—O13	108.8 (3)	O38—Si24—O46^vi	109.8 (3)
O12—Si8—O13	108.7 (3)	O24—Si24—O46^vi	107.8 (3)
O7—Si8—O8	108.2 (3)	Si2—O1—Si1	146.5 (4)
O12—Si8—O8	110.7 (3)	Si3—O2—Si2	146.1 (3)
O13—Si8—O8	109.7 (3)	Si3—O3—Si4	161.6 (4)
O8—Si9—O25	108.8 (3)	Si4—O4—Si5	148.5 (3)
O8—Si9—O44^iv	110.1 (3)	Si5—O5—Si6	147.3 (3)
O25—Si9—O44^iv	109.0 (3)	Si2—O6—Si6	162.7 (4)
O8—Si9—O9	108.1 (3)	Si8—O7—Si7	158.1 (4)
O25—Si9—O9	110.9 (2)	Si9—O8—Si8	153.6 (4)
O44^iv—Si9—O9	110.0 (3)	Si10—O9—Si9	151.0 (3)
O10—Si10—O9	108.5 (3)	Si10—O10—Si11	155.9 (4)
O10—Si10—O41^iv	110.9 (3)	Si12—O11—Si11	155.2 (4)
O9—Si10—O41^iv	109.7 (3)	Si8—O12—Si12	168.8 (4)
O10—Si10—O26	108.6 (3)	Si2—O13—Si8	162.5 (4)
O9—Si10—O26	111.0 (2)	Si5—O14—Si11	159.9 (4)
O41^iv—Si10—O26	108.2 (3)	Si1—O15—Si22^vii	150.0 (4)
O14—Si11—O10	108.6 (3)	Si16^vii—O16—Si1	174.9 (4)
O14—Si11—O11	109.8 (3)	Si7—O17—Si16^vii	146.9 (4)
O10—Si11—O11	110.5 (3)	Si21^vii—O18—Si6	142.8 (4)
O14—Si11—O22	110.4 (3)	Si15^vii—O19—Si6	168.2 (4)
O10—Si11—O22	109.1 (3)	Si15^vii—O20—Si12	143.0 (4)
O11—Si11—O22	108.4 (3)	Si5—O21—Si13^viii	145.6 (3)
O11—Si12—O24	110.6 (3)	Si19^viii—O22—Si11	151.8 (4)
O11—Si12—O12	108.6 (3)	Si19—O23—Si7	154.7 (3)
O24—Si12—O12	112.6 (3)	Si12—O24—Si24	148.7 (3)
O11—Si12—O20	109.7 (3)	Si21—O25—Si9	150.7 (3)
O24—Si12—O20	106.6 (3)	Si22—O26—Si10	145.2 (3)
O12—Si12—O20	108.7 (3)	Si14—O27—Si13	154.2 (4)
O41—Si13—O27	110.6 (3)	Si15—O28—Si14	149.0 (3)
O41—Si13—O21ⁱⁱⁱ	108.1 (3)	Si16—O29—Si15	162.0 (4)
O27—Si13—O21ⁱⁱⁱ	109.3 (3)	Si16—O30—Si17	157.3 (4)
O41—Si13—O42	109.6 (3)	Si18—O31—Si17	147.7 (4)
O27—Si13—O42	110.3 (3)	Si18—O32—Si14	158.0 (4)
O21ⁱⁱⁱ—Si13—O42	109.0 (3)	Si19—O33—Si20	151.1 (4)
O39—Si14—O27	110.8 (3)	Si20—O34—Si21	147.8 (3)
O39—Si14—O32	108.6 (3)	Si21—O35—Si22	151.6 (4)
O27—Si14—O32	108.5 (3)	Si23—O36—Si22	161.3 (4)
O39—Si14—O28	110.7 (3)	Si24—O37—Si23	152.7 (4)
O27—Si14—O28	108.2 (3)	Si24—O38—Si20	156.1 (4)
O32—Si14—O28	110.0 (3)	Si14—O39—Si20	166.0 (4)
O28—Si15—O29	109.6 (3)	Si17—O40—Si23	161.0 (3)
O28—Si15—O19^v	109.7 (3)	Si13—O41—Si10^vi	150.1 (4)
O29—Si15—O19^v	108.7 (3)	Si4^vi—O42—Si13	158.5 (4)
O28—Si15—O20^v	107.6 (3)	Si4^vi—O43—Si19	150.0 (4)
O29—Si15—O20^v	110.4 (3)	Si18—O44—Si9^vi	149.2 (4)
O19^v—Si15—O20^v	110.9 (3)	Si3^vi—O45—Si18	154.0 (4)
O16^v—Si16—O30	109.5 (3)	Si3—O46—Si24^iv	155.3 (4)
O16^v—Si16—O29	110.2 (3)	Si1^viii—O47—Si17	150.1 (4)
O30—Si16—O29	109.8 (3)	Si23—O48—Si7^viii	147.9 (4)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x−1/2, −y+1/2, z−1/2; (v) x−1/2, −y+1/2, z+1/2; (vi) x+1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+1/2, z−1/2; (viii) −x+3/2, y+1/2, −z+3/2.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C_1.9H₀O₄₉Si₂₄	C_3.6H₀O_49.8Si₂₄
M_r	1480	1515
Crystal system, space group	Monoclinic, P2₁/n.1.1	Monoclinic, P2₁/n.1.1
Temperature (K)	296	296
a, b, c (Å)	20.186 (15), 19.990 (14), 13.435 (10)	20.169 (14), 19.951 (14), 13.427 (10)
β (°)	90.012 (13), 90, 90	90.130 (13), 90, 90
V (Å³)	5421 (7)	5403 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.67	0.67
Crystal size (mm)	0.16 × 0.11 × 0.08	0.14 × 0.12 × 0.08

Data collection
Diffractometer	Bruker P4 diffractometer	Bruker P4 diffractometer
Absorption correction	Analytical	Analytical
T_min, T_max	0.899, 0.950	0.912, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	63627, 13249, 6100	63444, 13209, 5947
R_int	0.091	0.115
(sin θ/λ)_max (Å⁻¹)	0.676	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.124, 0.85	0.054, 0.124, 0.83
No. of reflections	13249	13209
No. of parameters	664	669
No. of restraints	4	10
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.60	0.63, −0.50

Computer programs: Bruker XSCANS, Bruker SHELXTL, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

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Volume 70| Part 5| October 2014| Pages 856-863

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research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Adsorption structure of di­methyl ether on silicalite-1 zeolite determined using single-crystal X-ray diffraction

1. Introduction

2. Experimental

2.1. Preparation of low- and high-loaded DME-silicalite-1

2.2. Structure analysis of DME-silicalite-1

2.3. Thermogravimetric analysis

3. Results

3.1. Packing of DME in silicalite-1

3.2. Framework geometry of DME-silicalite-1

4. Discussion

4.1. Sorption sites based on DME–framework interaction

4.2. Adsorption process of DME on silicalite-1

4.3. Strain in silicalite-1 framework loaded with DME

5. Conclusion

Supporting information

References

research papers

Adsorption structure of dimethyl ether on silicalite-1 zeolite determined using single-crystal X-ray diffraction