Synthesis and crystal structure of 5-(4-methoxybenzylidene)-2,2-dimethyl-1, 3-dioxane-4,6-dione

Article abstract of DOI:10.14233/ajchem.2013.12965

A new Meldrum's acid compound 5-(4-methoxybenzylidene)-2,2-dimethyl-1,3- dioxane-4,6-dione was prepared by 2,2-dimethyl-1,3-dioxane- 4,6-dione with 4-methoxybenzaldehyde in ethanol and its crystal structure was determined by X-ray crystallographic techniq

Full text of DOI:10.14233/ajchem.2013.12965

Asian Journal of Chemistry; Vol. 25, No. 2 (2013), 864-866
http://dx.doi.org/10.14233/ajchem.2013.12965
Synthesis and Crystal Structure of 5-(4-Methoxybenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione
WULAN ZENG
MicroScale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, P.R. China
Corresponding author: Fax: +86 536 8785802; Tel: +86 536 8785802; E-mail: wulanzeng@163.com
(
Received: 31 October 2011;
Accepted: 22August 2012)
AJC-11997
A new Meldrum's acid compound 5-(4-methoxybenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione was prepared by 2,2-dimethyl-1,3-diox-
ane-4,6-dione with 4-methoxybenzaldehyde in ethanol and its crystal structure was determined by X-ray crystallographic techniques. It
crystallizes in triclinic, space group P-1 with a = 9.1249(6) Å, b = 9.9060(8) Å, c = 14.4640(16) Å, α = 85.1440(10)º, β = 84.7750(10)º, γ
3
3
-1
=
89.388(2)º, C14
H O
14 5
, Mr = 262.25, V = 1297.3(2) Å , Z = 4, D = 1.343 g/cm , F(000) = 552, µ = 0.102 mm . The 1,3-dioxane ring is in
c
a distorted envelope conformation. The crystal structure is stabilized by weak intermolecular C-H···O hydrogen bonds.
Key Words: Synthesis, Crystal structure, 2,2-Dimethyl-1,3-dioxane-4,6-dione, Meldrum's acid.
was stirred in ethanol (20 mL) for 2 h at reflux temperature.
INTRODUCTION
After cooling to room temperature, the precipitate was filtered
off and dried. Yield 48 %. m.p. 121.0-122.5 ºC. Anal. calcd.
Considerable interest has been focused on the Meldrum's
acid owing to its susceptibility to nucleophilic attack and to
electophilic attack, extensive experimental efforts have been
made to seek the compounds containing Meldrum's acid
(
%) for C14H
14
5
O : C, 67.53; H, 4.80, found: C, 68.74; H, 5.17.
The single crystal suitable for X-ray diffraction analysis was
obtained by evaporation for petroleum ether and ethyl acetate
1
-6
fragment . On the other hand, Meldrum's acid and its deriva-
tives have been widely used in fine chemical and pharmaceutical
industry. Therefore, it is important to design and synthesize a
new Meldrum's acid compound. The compound 5-(4-methoxy-
benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (I) was
synthesized by the uncatalyzed reaction of 2,2-dimethyl-1,3-
dioxane-4,6-dione and 4-methoxybenzaldehyde in ethanol.
In order to confirm its structure, single crystals of 5-(4-methoxy-
benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione were
obtained by evaporation of petroleum ether-ethylacetate (4:1)
solution of (I) at room temperature over a period of several
days and the molecular structure was determined by X-ray
diffraction.
(
4:1 = v/v) after a few days.
Data collection and structure determination:A selected
crystal of the title compound was mounted on a SMART CCD
diffractometer. The reflection data were measured at 293 K,
using a graphite monochromator MoK (λ = 0.071073 nm)
radiation with an ω scan mode. A total of 6740 reflections
were collected and 4495 were independent (Rint = 0.0281) in
the range of 2.40 < θ < 25.02º, of which 2561 reflections were
observed with I > 2σ(I).
α
The structure of the title compound was solved by direct
2
methods and refined by full-matrix least-squares on F using
the SHELXTL software package . All non-hydrogen atoms
7
were refined by full-matrix least-squares method, while all
hydrogen atoms were placed in the geometrically calculated
positions. The contributions of these hydrogen atoms were
included in the structure-factor calculations. The atomic
scattering factors and anomalous dispersion corrections were
EXPERIMENTAL
All the reagents and solvents from commercial sources
were used without further purification. Elemental analyses
were obtained using anAmerican Perkin Elmer 2400 analyzer.
8
taken from International Table for X-ray crystallography . The
crystal and experimental data are shown in Table-1.
-1
IR spectra (4000-400 cm ), were recorded on a Nicolet FT-IR
10P spectrometer. Melting points were measured by using a
5
RESULTS AND DISCUSSION
melting point apparatus made in Shanghai Instrument Limited
Company.
A mixture of 4-methoxybenzaldehyde (1.36 g, 0.01 mol)
and 2,2-dimethyl-1,3-dioxane-4,6-dione (1.44 g, 0.01 mol)
The atomic coordinates and equivalent isotropic thermal
parameters for the non-H atoms in 5-(4-methoxybenzylidene)-
2,2-dimethyl-1,3-dioxane-4,6-dione are given in Table-2 and

Vol. 25, No. 2 (2013)
Synthesis and Crystal Structure of 5-(4-Methoxybenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione 865
TABLE-1
CRYSTAL DATA AND STRUCTURE REFINEMENT
FOR THE TITLE COMPOUND
Empirical formula
C H O
14 14 5
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
262.25
293(2)
0.71073
Triclinic
P-1
Unit cell dimensions
a = 9.1249(6) Å α = 85.1440(10)º
b = 9.9060(8) Å β = 84.7750(10)º
c = 14.4640(16) Å γ = 89.388(2)º
1297.3(2),4
1.343
0.102
3
Volume (Å ), Z
3
Calculated density (g/cm )
Absorption coefficient (mm )
F(000)
-1
552
Crystal size (mm)
Theta range for
0.50 mm × 0.40 mm × 0.39 mm
2.40-25.02
Data collection (º)
Limiting indices
-10 ⇐ h ⇐ 10, -6 ⇐ k ⇐ 11, -17
⇐
l ⇐ 17
Reflections collected/unique
Completeness to theta = 25.02
Refinement method
6740/4495 [R(int) = 0.0281]
98.4 %
Full-matrix least-squares on F
4495/0/350
2
Fig. 1. Molecular structure with atomic numbering scheme
Data/restraints/parameters
2
Goodness-of-fit on F
1.012
Final R indices [I > 2σ(I)]
R indices (all data)
R1 = 0.0444, wR2 = 0.0977
R1 = 0.0916, wR2 = 0.1223
0.145 and -0.163
Largest diff. peak and hole
-
3
(
Einstein Å )
the selected bond distances and bond angles in Table-3. A
displacement ellipsoid plot with atomic numbering scheme
is shown in Fig. 1 and a perspective view of the crystal packing
in the unit cell in Fig. 2.
The crystal lattices of 5-(4-methoxybenzylidene)-2,2-
dimethyl-1,3-dioxane-4,6-dione comprise two symmetry-
independent molecule in the unit cell. Each symmetry-
independent molecule consists of 1,3-dioxane ring and 4-
methoxypheneyl ring. The corresponding bond lengths and
angles for the independent molecules agree well with each
other. The bond lengths of C(2)-C(7) and C(16)-C(21)
Fig. 2. View of crystal packing
TABLE-2
4
2
3
ATOMIC COORDINATES (× 10 ) AND THERMAL PARAMETERS (Å × 10 )
Atom
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
x
y
Z
U(eq)
67(1)
64(1)
65(1)
89(1)
75(1)
60(1)
64(1)
67(1)
80(1)
64(1)
53(1)
49(1)
61(1)
64(1)
86(1)
104(1)
52(1)
47(1)
61(1)
Atom
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
x
y
Z
U(eq)
62(1)
54(1)
64(1)
59(1)
86(1)
50(1)
45(1)
56(1)
59(1)
93(1)
83(1)
49(1)
43(1)
50(1)
49(1)
47(1)
53(1)
52(1)
76(1)
3497(2)
1621(2)
4224(2)
409(3)
-324(2)
813(2)
317(2)
2504(2)
934(2)
8405(1)
9238(1)
6952(1)
8584(1)
3011(1)
11908(1)
10999(1)
13251(1)
11523(1)
17237(1)
7583(2)
7567(2)
8479(2)
9114(2)
8859(2)
10004(2)
6804(2)
5824(2)
5426(2)
2290(3)
1495(3)
670(3)
230(3)
4502(2)
3929(2)
4300(2)
5223(2)
2606(2)
12652(2)
12633(2)
11706(2)
11218(2)
10360(2)
11560(2)
13365(2)
14367(2)
14849(2)
15802(2)
16297(2)
15838(2)
14893(2)
17738(2)
1069(3)
2110(3)
2285(3)
-147(4)
5441(3)
6046(2)
6349(3)
4531(3)
4301(4)
3358(3)
6479(2)
6356(2)
5446(2)
5389(3)
6258(2)
7167(3)
7194(2)
5307(3)
648(3)
1413(2)
1813(2)
3865(2)
1099(2)
5348(2)
3060(2)
3275(3)
1928(3)
1246(3)
2288(3)
1177(4)
2948(4)
1290(3)
1451(3)
2272(3)
2213(3)
2095(3)
3552(3)
4352(3)
2984(3)
2252(4)
3903(3)
4173(3)
3808(3)
2817(3)
2541(3)
3264(3)
4280(3)
4555(3)
2094(3)
4793(2)
5716(2)
5541(2)
7137(2)
6286(2)
364(3)
1189(2)
1576(3)
-478(3)
-1458(3)
-896(4)
1684(2)
1457(2)
427(3)

866 Zeng
Asian J. Chem.
TABLE-4
INTERMOLECULAR INTERACTION DISTANCES (Å)
D-H-A
C(14)-H(14A)···O(3)
C(7)-H(7)···O(4)
C(9)-H(9)···O(3)
C(21)-H(21)···O(9)
C(23)-H(23)···O(8)
Symmetry
1-x, -y, 1-z
D-H
H···A
2.4398
2.3902
2.2649
2.3893
2.2856
D···A
D-H···A
163.09
107.33
130.45
106.96
123.52
0.9600
0.9295
0.9297
0.9298
0.9299
3.370(3)
2.811(3)
2.954(3)
2.805(3)
2.904(3)
–
–
–
–
TABLE-3
In the crystal structure lattice of the title compound, the
molecules form a three dimensional net work through hydrogen
bonds. Five hydrogen bonds of C-H···O are divided into two
types, one intermolecular hydrogen bond and four intramole-
cular hydrogen bonds. The hydrogen bond lengths and bond
angles are listed in Table-4. In solid state, all above hydrogen
bonds stabilize the crystal structure.
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º)
Bond
C(7)-C(8)
C(2)-C(7)
O(1)-C(1)
O(1)-C(4)
O(3)-C(1)
O(4)-C(3)
O(5)-C(11)
O(5)-C(14)
O(2)-C(3)
O(2)-C(4)
Angles
Å
Bond
C(21)-C(22)
C(16)-C(21)
O(5)-C(11)
O(5)-C(14)
O(6)-C(15)
O(6)-C(18)
O(7)-C(17)
O(7)-C(18)
Å
1.449(3)
1.348(3)
1.350(3)
1.436(3)
1.204(3)
1.200(3)
1.354(3)
1.427(3)
1.347(3)
1.428(3)
(º)
1.452(3)
1.347(3)
1.354(3)
1.427(3)
1.344(3)
1.432(3)
1.354(3)
1.427(3)
1.358(3)
1.424(3)
(º)
ACKNOWLEDGEMENTS
This project supported by the Natural Science Foundation
of Shandong Province (No. ZR2010CL011) and (No.
ZR2010BM033).
O(10)-C(25)
O(10)-C(28)
Angles
C(2)-C(7)-C(8)
C(9)-C(8)-C(7)
C(13)-C(8)-C(7)
135.6(2)
125.8(2)
117.8(2)
C(16)-C(21)-C(22)
C(23)-C(22)-C(21)
C(27)-C(22)-C(21)
134.6(2)
125.6(2)
117.4(2)
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[
1.348(3) and 1.347(3) Å] confirm the localization of the
double bond at this position and are consistent with those of
8
,9
the related structure reported earlier . The C(7)-C(8) and
C(21)-C(22) distances of 1.449(3), 1.452(3) Å in molecules,
respectively, are in good agree with the values reported in the
6
7
8
9
.
.
.
.
10
literature . The 1,3-dioxane rings of the two molecules have
the same almost identical distorted envelope conformations.
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