Syntheses and crystal structures of 1,5-dioxaspiro[5.5]undecane-2,4-dione derivatives

Article abstract of DOI:10.1007/s10870-013-0408-z

The 3-(2,3,4-trimethoxybenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 1 and 3-(3,4,5-trimethoxybenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 2 have been synthesized and characterized by X-ray single-crystal diffraction, IR and UV-Vis. Compound 1 belongs to the orthorhombic system, space group Pna21 with a = 10.182(2) A, b = 11.828(2) A, c = 14.356(3) A, α = 90, β = 90, γ = 90, V = 1,729.0(6) A³, Z = 4. Compound 2 is of Triclinic system, space group P-1 with a = 8.7807(18) A, b = 9.4383(19) A, c = 11.450(2) A, α = 98.64(3), β = 103.28(3), γ = 99.44(3), V = 893.4(3) A³, Z = 2. It is very interesting that there are only C-H...O and C-H...π intermolecular interaction in the 1, while there are still π...π stacking interactions except for C-H...O and C-H...π intermolecular interaction in the structure of 2. Graphical Abstract: Two new spiro compounds, 3-(2,3,4-trimethoxybenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 1 and 3-(3,4,5-trimethoxybenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 2 have been synthesized and characterized by X-ray single-crystal diffraction, IR and UV-Vis.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-013-0408-z

J Chem Crystallogr (2013) 43:223–227
DOI 10.1007/s10870-013-0408-z
ORIGINAL PAPER
Syntheses and Crystal Structures of 1,5-Dioxaspiro[5.5]undecane-
2,4-dione Derivatives
•
Wulan Zeng Yufeng Li Huanmei Guo
•
Received: 10 July 2012 / Accepted: 28 February 2013 / Published online: 9 March 2013
Ó Springer Science+Business Media New York 2013
Abstract The 3-(2,3,4-trimethoxybenzylidene)-1,5-di-
oxaspiro[5.5]undecane-2,4-dione 1 and 3-(3,4,5-trimeth-
oxybenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 2
have been synthesized and characterized by X-ray single-
crystal diffraction, IR and UV–Vis. Compound 1 belongs to
the orthorhombic system, space group Pna21 with a =
considerable attention due to their biological activities such
as antifungal [7, 8], insecticidal [9], antitumor [10], her-
bicides with low toxicity to microorganisms [11], etc.
Therefore, many compounds containing oxaspirocyclic
skeleton have been reported over the past decades [12–14].
For these reasons, our group began to design and synthe-
size various oxaspirocyclic compounds derived from 1,5-
dioxaspiro[5.5]undecane-2,4-dione [15, 16]. In this paper,
we report the crystal structures and the characterization of
3-(2,3,4-trimethoxybenzylidene)-1,5-dioxaspiro[5.5] unde-
cane-2,4-dione 1 and 3-(3,4,5-trimethoxybenzylidene)-1,5-
dioxaspiro[5.5] undecane-2,4-dione 2.
˚
˚
˚
10.182(2) A, b = 11.828(2) A, c = 14.356(3) A, a = 90°,
3
˚
b = 90°, c = 90°, V = 1,729.0(6) A , Z = 4. Compound 2
is of Triclinic system, space group P-1 with a = 8.7807(18)
˚
˚
˚
A, b = 9.4383(19) A, c = 11.450(2) A, a = 98.64(3)°,
3
˚
b = 103.28(3)°, c = 99.44(3)°, V = 893.4(3) A , Z = 2. It
is very interesting that there are only C–HÁÁÁO and C–HÁÁÁp
intermolecular interaction in the 1, while there are still pÁÁÁp
stacking interactions except for C–HÁÁÁO and C–HÁÁÁp
intermolecular interaction in the structure of 2.
Experimental
Keywords Synthesis Á Crystal structure Á
Materials and Methods
1,5-Dioxaspiro[5.5]undecane-2,4-dione Á Spiro compound
All the reagents and solvents from commercial sources
were used without further purification. IR spectra (400–
4,000 cm-1) were recorded on a Nicolet FT-IR 510P Spec-
trometer. UV–Vis absorption spectra were recorded on a
Shimadzu UV3100 spectrometer in EtOH solution. Melting
points were measured by using a melting point apparatus
made in Shanghai Instrument Limited Company. X-ray
diffraction was performed on a SMART CCD area detector
diffractometer.
Introduction
Spiro compounds with special structures and functions
have wide application in various fields such as medicine
[1–3], catalysis [4] and optical material [5, 6]. Also it has
been found that selectivities and activities of spiro com-
pounds will be stronger by inducting oxygen atom.
Numerous oxaspirocyclic compounds have been attracting
Syntheses of 1 and 2
A mixture of 2,3,4-trimethoxybenzaldehyde (1.96 g, 0.01
mol) and 1,5-dioxaspiro[5.5]undecane-2,4-dione (1.84 g,
0.01 mol) was stirred in ethanol (20 mL) for 2.5 h at reflux
temperature. After cooling to room temperature, the pre-
cipitate was filtered off and dried. Yield 46 %, m.p.:
W. Zeng (&) Á Y. Li Á H. Guo
Department of Chemistry, Chemical Engineering and
Environmental Engineering, MicroScale Science Institute,
Weifang University, Weifang 261061, China
e-mail: wulanzeng@163.com
123

224
J Chem Crystallogr (2013) 43:223–227
Table 1 Crystal and experimental data for 1 and 2
Compounds
1
2
Empirical formula
Color/shape
C19H22O7
Yellow/block
362.37
C19H22O7
Yellow/block
362.37
Formula weight
Crystal system
Space group
Orthorhombic
Pna21
Triclinic
P-1
˚
˚
Unit cell dimensions
a = 10.182(2) A a = 90°
a = 8.7807(18)A a = 98.64(2)°
˚
˚
b = 11.828(2) A b = 90°
b = 9.4383(19)A b = 103.28(3)°
˚
˚
c = 14.356(3) A c = 90°
1,729.0(6) A
c = 11.450(2)A c = 99.44(3)°
893.4(3) A
3
˚
3
˚
Volume
Z
4
2
Density(calculated)
Absorption coefficient
F(000)
1.392 g cm-3
0.106 mm-1
1.347 g cm-3
0.103 mm-1
768
0.15 9 0.11 9 0.09 mm3
608
0.34 9 0.30 9 0.28 mm3
Crystal size
Theta range for data collection
Limiting indices
3.00°–27.48°
-11 B h B 13, -15 B k B 15, -18 B l B 18
16,023
3.18–25.02°
-10 B h B 11, -11 B k B 11, -13 B l B 13
6,981
Reflections collected
Independent reflections
Reflections observed(I [ 2\r(I))
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
R indices (all data)
Weighting scheme
Largest diff. peak and hole
3,939 [R(int) = 0.0420]
2,973
Full-matrix least-squares on F2
3,148 [R(int) = 0.0273]
2,104
Full-matrix least-squares on F2
3,939/1/235
3,148/1/247
1.141
1.113
R1 = 0.0356, wR2 = 0.0817
R1 = 0.0588, wR2 = 0.1101
w = 1/[r2(F2o) ? (0.0603P)2
R1 = 0.0463, wR2 = 0.1344
R1 = 0.0726, wR2 = 0.1666
w = 1/[r2(F2o) ? (0.0962P)2 ? 0.0395P
-3
-3
˚
0.181 and -0.239e A
˚
0.260 and -0.279e A
˚
Table 2 Selected bond lengths (A) and bond angles (°) for 1 and 2
Selected bond lengths for 1
Selected bond lengths for 2
C(9)–C(8)
C(9)–C(4)
1.399(3)
1.419(3)
1.445(3)
1.353(3)
O(7)–C(13)
O(7)–C(14)
O(6)–C(11)
O(6)–C(14)
1.351(2)
1.437(2)
1.355(2)
1.438(2)
C(9)–C(4)
C(10)–C(4)
C(4)–C(5)
1.408(3)
1.454(3)
1.395(3)
1.363(3)
O(7)–C(14)
O(7)–C(11)
O(6)–C(12)
O(6)–C(11)
1.362(3)
1.435(3)
1.356(3)
1.430(3)
C(9)–C(10)
C(12)–C(10)
C(10)–C(13)
Selected bond angles for 1
Selected bond angles for 2
C(12)–C(10)–C(9)
C(8)–C(9)–C(10)
C(4)–C(9)–C(10)
136.78(18)
C(10)–C(12)–C(11)
C(10)–C(12)–C(13)
C(11)–C(12)–C(13)
115.34(17)
128.11(17)
116.53(17)
C(13)–C(10)–C(4)
C(5)–C(4)–C(9)
C(5)–C(4)–C(10)
136.5(2)
C(10)–C(13)–C(12)
C(10)–C(13)–C(14)
C(12)–C(13)–C(14)
128.1(2)
125.98(17)
116.91(17)
119.0(2)
125.9(2)
114.95(19)
116.90(19)
141.8*142.5 °C. The yellow single crystal of 1 were
obtained by evaporation for petroleum ether and ethyl
acetate (4:1 = v/v) after a few days.
Results and Discussion
A summary of the crystallographic data was given in
Table 1. The selected bond distances and bond angles of 1
and 2 are listed in Table 2. The structures of 1 and 2,
packing arrangement in a unit cell of 1 and 2 are shown in
Figs. 1 and 2, respectively. The structures of two compounds
The yellow single crystals of 2 were obtained by the
same method used for the synthesis of 1 by replacing 2,3,4-
trimethoxybenzaldehyde with 3,4,5-trimethoxybenzalde-
hyde at a yield of 48 %, m.p.: 152.0–153.5 °C.
123

J Chem Crystallogr (2013) 43:223–227
225
Fig. 1 The molecular structures
of 1 and 2 with atomic
numbering scheme
Fig. 2 The packing
arrangement in a unit cell of 1
and 2
Table 3 Intermolecula
˚
˚
˚
D–HÁÁÁA
Symmetry
D–H (A) HÁÁÁA (A) DÁÁÁA (A) \D–HÁÁÁA (°)
hydrogen bonds and C–HÁÁÁp
supramolecular interactions in 1
and 2
C(15)–H(15A)ÁÁÁO(4) (1) 1/2 ? x, 3/2 - y, z
0.97
0.93
0.97
2.550
2.384
2.565
3.326
3.392(3)
3.294(3)
3.399(3)
4.199
144.9
165.8
144.1
150.65
C(9)–H(9A)ÁÁÁO(8) (2)
1 - x, 2 - y, 2 - z
C(15)–H(15A)ÁÁÁO(3) (2) -x, 2 - y, 2 - z
C(15)–H(15B)ÁÁÁphenyl
1/-x,1/2 ? y,1/2 ? z 0.97
ring (1)
C(17)–H(17A)ÁÁÁphenyl
ring (2)
x, y, -1 ? z 0.97
3.266
3.978
131.72
were solved by direct methods and refined by full-matrix
least-squares techniques on F2 using SHELXS-97 and
SHELXL-97 programs [17]. The atomic scattering factors
and anomalous dispersion corrections were taken from
International Table for X-ray Crystallography [18].
As can be seen from the crystal structure (Fig. 1), the
central C(10) atom is linked by 1,5-dioxaspiro[5.5]unde-
cane-2,4-dione group and phenyl ring in 1 and 2, forming
the C(9)–C(10)–C(12) bond angle of 136.78(18)° (C(13)–
C(10)–C(4), 136.5(2)° for 2). The C10–C12 (C10–C13 for
123

226
J Chem Crystallogr (2013) 43:223–227
˚
Table 4 Hydrogen bond lengths (A) and bond angles (°) of compound 2
Ring
Symmetry
Distance between ring
˚
centroids (A)
Perpendicular distance
˚
of Cg(I) on ring J(A)
Perpendicular distance
˚
of Cg(J) on ring I(A)
Phenyl ringÁÁÁphenyl ring
-x, 2 - y, 2 - z
3.906
3.418
3.418
noteworthy that the cyclohexane rings of two title com-
pounds both exhibit a chair-like configuration, with puck-
˚
ering parameters [19] for Q = 0.543(3) A (0.554(3) A),
˚
˚
˚
q2 = 0.005(2) A (0.028(3) A), q3 = 0.543(3) A (0.553(3)
˚
˚
1
2
A), 0 = 1.7(2)° (3.3(3)°), u = 259(32)° (187(6)°).
The salient feature in two crystal packings is that they
both form strong intermolecular hydrogen bonding net-
works. In the compound 1, there are one classical C–HÁÁÁO
intermolecular hydrogen bonds, one type of C–HÁÁÁp
supramolecular interactions. However, in the compound 2,
there are two classical C–HÁÁÁO intermolecular hydrogen
bonds, one type of C–HÁÁÁp supramolecular interactions and
one type of pÁÁÁp stacking interactions (Tables 3 and 4). In
these two crystal lattices, all above hydrogen bonds and
intermolecular interactions play a significant role in stabi-
lizing the crystal structures.
3500
3000
2500
2000
1500
1000
500
Wavenumbers(cm-1
)
The two compounds have a similar feature in the IR
spectra. As can be seen from Fig. 3, 1 and 2 show an
intense band at 1,710 and 1,715 cm-1, respectively, due to
the C=O stretching vibration of the 1,3-dioxane ring. The
broad absorptions at 1,287, 1,090 cm-1 for 1 and at 1,260,
1,127 cm-1 for 2 are assigned to the C–O stretching
vibration of the 1,3-dioxane ring. Meanwhile, a similar
band at 1,556 and 1,561 cm-1 was observed in the IR
spectra of 1 and 2, respectively, confirming that the 1,5-
dioxaspiro[5.5]undecane-2,4-dione group connects central
C(10) atom by C=C. These facts are consistent with the
X-ray diffraction results.
Fig. 3 IR spectra of 1 and 2
3.0
2.5
2.0
1.5
1.0
0.5
0.0
1
The UV–Vis spectra of 1 and 2 were measured in EtOH
solution at room temperature (Fig. 4). They both show
three broad bands around 211, 255, 377 nm for 1 and 209,
264, 370 nm for 2, respectively. The former two absorption
band are ascribed to n?p* electron transition of the C=O
group, while the latter absorption band is associated with
p?p* transition of the phenyl group.
2
200
300
400
500
600
700
800
Supporting Information
Wavelength(nm)
Fig. 4 UV–Vis spectra of 1 and 2
Crystallographic data for the structures reported in this
paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no.
CCDC-879130 and CCDC-858992. Copies of available
material can be obtained, free of charge, on application to
the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (Fax: 44-(0)-1223-336033 or e-mail: deposit@ccdc.
cam.ac.uk).
˚
2) bond length of 1.353(3) A (1.363(3) A) is indicative of
˚
the considerable double-bond character, while C10–C9
˚
˚
(C10–C4 for 2) bond length of 1.445(3) A (1.454(3) A) is
typical C–C single bond. The 1,3-dioxane ring is in a dis-
torted envelope conformation with atom C(14) (C(11) for 2)
common to the cyclohexane ring forming the flap. It is
123

J Chem Crystallogr (2013) 43:223–227
227
Acknowledgments This research was supported by the Natural
Science Foundation of Shandong Province (No.ZR2010CL011) and
(No.ZR2010BM033).
9. Schaper W, Preus R, Braun P, Kem M, Knauf W, Sachse B, Sanft
U, Waltersdorfer A, Bonin, W. DE 4436509 (1996) [Chem Abstr
1996, 125, 33670]
10. Wei RB, Liu B, Liu Y, Guo JJ, Zhang DW (2008) Chin J Org
Chem 28:1501
11. Zvonok AM, Okaev EB (1993) Chem Heterocycl Compd
29:1291
12. Liu F, Xie LH, Tang C, Liang J, Chen QQ, Peng B, Wei W, Cao
Y, Huang W (2009) Org Lett 11:3850
13. Shaune LM, Leah SC, Davin GP, Robert M, Jonathan GCV
(2008) Macromolecules 41:7780
14. Stanetty P, Sigl B, Schnu¨rch M, Mihovilovic MD (2009) Acta
Chim Slov 56:513
15. Zeng WL, Li YF, Liu Y, Jian FF (2010) Z Kristallogr NCS
225:498
16. Zeng WL (2011) Asian J Chem 23:4145
17. Sheldrick GM (2008) Acta Crystallogr A64:112
18. Siemens (1996) Area detector control and integration software
USA. Analytical X-ray Instruments Inc., Madison
19. Cremer D, Pople JA (1975) J Am Chem Soc 97:1354
References
1. Lian Y, Guo JJ, Liu XM, Wei RB (2008) Chem Res Chin Univ
24:441
2. Ding Y, Tian Z, Zhu N (2010) Chin J Org Chem 30:1156
3. Pradhan R, Patra M, Behera AK, Mishra B, Behera RK (2006)
Tetrahedron 62:779
4. Jiang Y, Xue S, Li Z, Deng J, Mi A, Chan ASC (1998) Tetra-
hedron 9:3185
5. Wei RB, Liu Y, Guo JJ, Liu B, Zhang DW (2008) Chin J Org
Chem 28:390
6. Kim JH, Jeon YM, Jang JG, Ryu S, Chang HJ, Lee CW, Kim JW,
Gong MS (2009) Bull Korean Chem Soc 30:647
7. Jiao P, Swenson DC, Gloer JB, Campbell J, Shearer CA (2006) J
Nat Prod 69(12):1667
8. Guiraud P, Steiman R, Seigle-Murandi F, Buarque de Gusmao N
(1999) J Nat Prod 62:1222
123