Crystal structure of 2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undec-1-ylmethyl-2-methylacrylate

Article abstract of DOI:10.1134/S002247661703026X

The XRD method is used to determine the molecular and crystal structure of 2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undec-1-ylmethyl-2-methylacrylate (H₂C=C(Me)C(O)OCH₂Si(OCH₂CH₂)₃N). The crystallographic data are as follows: space group Р2₁2₁2₁, а = 9.7659(1) ?, b = 10.017(1) ?, с = 17.915(2) ?, V = 1753.3(3) ?³, Z = 4. The coordination polyhedron of the silicon atom is a distorted trigonal bipyramid. The length of the N→Si coordination bond is 2.099 ?.

Full text of DOI:10.1134/S002247661703026X

Journal of Structural Chemistry. Vol. 58, No. 3, pp. 611-614, 2017.
Original Russian Text © 2017 Yu. I. Bolgova, T. N. Borodina, O. M. Trofimova, V. I. Smirnov.
CRYSTAL STRUCTURE
OF 2,8,9-TRIOXA-5-AZA-1-SILABICYCLO[3.3.3]UNDEC-
1-YLMETHYL-2-METHYLACRYLATE
Yu. I. Bolgova, T. N. Borodina, O. M. Trofimova*,
and V. I. Smirnov
UDC 541.272:548.737
The XRD method is used to determine the molecular and crystal structure of 2,8,9-trioxa-5-aza-
1-silabicyclo[3.3.3]undec-1-ylmethyl-2-methylacrylate (H C=C(Me)C(O)OCH Si(OCH CH ) N). The
2
2
2
2 3
crystallographic data are as follows: space group Р2 2 2 , а = 9.7659(1) Å, b = 10.017(1) Å,
1 1 1
3
с = 17.915(2) Å, V = 1753.3(3) Å , Z = 4. The coordination polyhedron of the silicon atom is a distorted
trigonal bipyramid. The length of the N→Si coordination bond is 2.099 Å.
DOI: 10.1134/S002247661703026X
Keywords: (1-silatranylmethyl)methacrylate, crystal structure, X-ray diffraction analysis.
2,8,9-Trioxa-5-aza-1-silabicyclo[3.3.3]undec-1-ylmethyl-2-methylacrylate ((1-silatranylmethyl)methacrylate) (1)
has long been used for manufacturing glassfibers as dipping baths, laminating agents or lubricants, increasing the adhesion of
polyester and epoxy resins to glassfiber and thus increasing the elastic properties of ready fibers both while dry and wet [1].
Nevertheless, there are no data on the crystal and molecular structure of this compound in literature. We have obtained single
crystals of (1-silatranylmethyl)methacrylate with a sufficient diffraction quality. The aim of this work was to determine its
molecular and crystal structure.
Experimental. (1-Silatranylmethyl)methacrylate is synthesized by trans-etherification of (trimethoxysilyl)methyl-
2-methylacrylate with tris(2-hydroxyethyl)amine.
Scheme 1.
Contrary to the previously described methods [1, 2], the reaction was carried out at room temperature and released
alcohol was removed by keeping the reaction mixture under a pressure of 2 mmHg. Resulted desired product 1 is a colorless
crystalline substance with Т 154-155°C (a Boëtius micro heating stage), the yield is 95%.
melt
The elemental analysis was carried out on a FLASH 2000 CHNS analyzer, the gravimetric determination of silicon
was carried out according to the procedure described in [3]. For C H N О Si calculated (wt.%): C 48.33, Н 7.01, N 5.12,
11 19
1
5
1
Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Russia;
*omtrof@irioch.urk.ru. Translated from Zhurnal Strukturnoi Khimii, Vol. 58, No. 3, pp. 638-640, March-April, 2017.
Original article submitted April 28, 2016; revised August 3, 2016.
0022-4766/17/5803-0611 © 2017 by Pleiades Publishing, Ltd.
611

TABLE 1. Main Interatomic Distances (d, Å) and Bond Angles (ω, deg)
in the H C=C(Me)C(O)OCH Si(OCH CH ) N Molecule
2 2 2 2 3
Bond
d
Bond
d
Bond
d
Si(1)–N(1)
Si(1)–C(7)
Si(1)–O(1)
Si(1)–O(2)
Si(1)–O(3)
N(1)–C(1)
N(1)–C(3)
2.099(3)
1.892(4)
1.662(3)
1.671(3)
1.673(3)
1.480(6)
1.482(6)
N(1)–C(5)
C(1)–C(2)
C(3)–C(4)
C(5)–C(6)
O(1)–C(2)
O(2)–C(4)
O(3)–C(6)
1.488(6)
1.498(7)
1.501(7)
1.505(7)
1.428(6)
1.407(6)
1.426(5)
O(4)–C(7)
O(4)–C(8)
O(5)–C(8)
C(8)–C(9)
C(9)–C(10)
C(9)–C(11)
1.467(5)
1.331(5)
1.211(5)
1.494(6)
1.318(7)
1.485(7)
Angle
Angle
Angle
ω
ω
ω
N(1)–Si(1)–C(7)
О(1)–Si(1)–C(7)
О(2)–Si(1)–C(7)
О(3)–Si(1)–C(7)
176.5(2)
96.5(2)
92.2(2)
96.8(2)
О(1)–Si(1)–N(1)
О(2)–Si(1)–N(1)
О(3)–Si(1)–N(1)
О(2)–Si(1)–О(1)
85.1(1)
84.3(1)
85.1(1)
119.5(2)
О(1)–Si(1)–О(3)
О(2)–Si(1)–О(3)
Si(1)–C(7)–O(4)
O(4)–C(8)–O(5)
118.2(2)
120.0(2)
111.8(3)
123.0(4)
–1
Si 10.27; found: C 48.54, Н 7.04, N 5.38, Si 10.09. The IR spectrum (cm ) (recorded on a Bruker Vertex 70 spectrometer in
–1
the spectral range 4000-500 cm , KBr pellets): 1119, 1096, 1044, 1017, 945, 916, 785, 575 (silatrane fragment), 1699
+
(С=O), 1634 (С=С). The mass spectrum (GC-MS Agilent 5975C), m/z (%): 273 (9) [M ], 215 (68), 188 (41), 130 (55).
A colorless crystal of the size 0.156×0.164×0.355 mm was isolated from the saturated solution of compound 1 in the
chloroform:hexane (1:1) mixture. The X-ray diffraction study was carried out on a Bruker D8 Venture single crystal
diffractometer equipped with a Photon 100 CMOS detector (MoK radiation, λ = 0.71073 Å, ϕ and ω scanning) at 100 K.
α
The structure was solved by the direct method using the Bruker SAINT software package and refined by the full-matrix least
squares technique in the anisotropic approximation for non-hydrogen atoms using the SHELXL-13 software package [4]. The
absorption correction was applied using the SADABS program [5]. Hydrogen atoms were placed in geometrically idealized
positions and refined isotropically as a rigid body. The main crystallographic data and XRD parameters of the experiment are
as follows: C H N О Si ⋅CHCl , М = 392.73, orthorhombic crystal system, space group Р2 2 2 , а = 9.769(1) Å,
11 19
1
5
1
3
1 1 1
3
b = 10.017(1) Å, с = 17.915(2) Å, V = 1753.3(3) Å , Z = 4, d = 1.492 g/cm , μ = 0.611 mm , 44158 reflections were
3
–1
calc
measured (θ = 26.990°), including 3827 independent reflections, for 2995 reflections with I > 2σ(I) R = 0.0557,
max 1
3
wR = 0.1557, S = 1.114, Δρ(max/min) = 0.429/–0.664 e/Å . The main geometric parameters of the molecule of 1 are listed in
2
Table 1; the atomic numbering is given in Fig. 1. The CIF-file containing the complete information on the structure studied
has
been
deposited
with
the
Cambridge
Crystallographic
Data
Centre,
CCDC
1473736
(www.ccdc.cam.ac.uk/data_request/cif).
Results and discussion. The obtained single crystal is a crystalline solvate with chloroform, whose asymmetric unit
contains one molecule of the desired compound and one CHCl molecule. The coordination polyhedron of the silicon atom in
3
the molecule of 1 is a distorted trigonal bipyramid, as in other silatrane molecules [6]. The silicon atom is out of the
equatorial plane of the bipyramid formed by the О(1), О(2) and О(3) atoms by 0.15 Å toward the axially located С(7) atom.
The ΔN nitrogen atom is by 0.383 Å out of plane formed by three framing С(1), С(3) and С(5) carbon atoms. The axial
N(1)Si(1)C(7) bond angle is nearly linear. The length of the N→Si coordination bond in the molecule of 1 is within the range
of values typical of weak electron-withdrawing substituents at the silicon atom. The same short interatomic N→Si distance is
observed in 1-(N-heterylmethyl)silatranes (2.088-2.097 Å) that we have previously synthesized [7-12]. The lengths of all
endocyclic bonds in the silatrane fragment of molecule 1 (Si–O, O–C, C–C and C–N) (Table 1) are typical of silatranes [13].
Five-membered cycles of the silatrane fragment adopt an envelope conformation. The methacrylic moiety of the molecule of
1 adopts a coplanar conformation in the O(4)O(5)C(7)C(8) plane, the C(9), C(10), C(11) atoms are out of the plane by
maximum 0.022 Å, 0.038 Å, and 0.084 Å respectively. Interestingly, that the C(9)–C(10) double bond is relatively short,
612

Fig. 1. Molecular structure of (1-silatranylmethyl)methacrylate
1 (atomic thermal vibration ellipsoids are drawn at the 50%
probability level).
which makes it possible, according to the literature data [14], to draw the conclusion about the absence of a delocalized π
system. The position of the methacrylic moiety is fixed by the intramolecular С(10)–H(10А)…O(4) (0.951 Å, 2.352 Å,
2.702(6) Å, 101.1°) and С(7)–H(7А)…O(5) (0.991 Å, 2.512 Å, 2.650(5) Å, 86.9°) hydrogen bonds.
The crystal 2D structure is formed by the intermolecular С–Н…О hydrogen bonds, in which the О(5) carbonyl
oxygen atom is linked with two hydrogen atoms. The С(5)–H(5B)…O(5) (0.990 Å, 2.439 Å, 3.252(6) Å, 139.0°) bond is
formed via the methylene group proton of the silatranyl cycle of the neighboring molecule. It is this bond that is responsible
for the formation of stacks parallel to the b axis of the unit cell, in which the neighboring molecules of silatrane 1 are oriented
head-to-head. The second С(10)–H(10B)…O(5) hydrogen bond (0.950 Å, 2.360 Å, 3.274(6) Å, 161.3°), which links the
molecules into a layer is formed via the methacrylic substituent proton of another molecule. The CHCl molecule plays
3
an important role in the formation of the layers. The solvate chloroform molecule in the layer is surrounded by four silatrane
molecules, with one of which being linked by the intermolecular C(12)–H(12)⋯O(3) hydrogen bond (1.001 Å, 2.338 Å,
3.235(5) Å, 148.6°), and with another by a short C(12)–Cl(3)⋯O(3) contact (3.214(3) Å). Moreover, the C(2)…C(8)
(3.352 Å) and C(10)…H(6A) (2.830 Å) short contacts participate in the interstack connection.
The studies are carried out using the materials and technical facilities of the Baikal Analytical Center for Collective
Use of the Siberian Branch of the Russian Academy of Sciences.
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613

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