Synthesis and Crystal Structures of Two Novel O, N-Containing Spiro Compounds
MicroScale Science Institute, Department of Chemistry, Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, China
*
Author to whom correspondence should be addressed.
Crystals 2016, 6(6), 69; https://doi.org/10.3390/cryst6060069
Submission received: 25 May 2016
/
Revised: 13 June 2016
/
Accepted: 13 June 2016
/
Published: 15 June 2016
Abstract
:Two novel O, N-containing spiro compounds, C16H16ClNO4 (1) and C16H16N2O6 (2), were prepared by reactions of monosubstituted benzenamine (substituent = –NO2, –Cl) and 1,5-dioxaspiro[5.5]undecane-2,4-dione in ethanol solution of trimethoxymethane. Their structures were characterized by elemental analysis, IR, UV-Vis and single-crystal X-ray diffraction. Compound 1 is triclinic with space group P-1 and cell constants: a = 5.9448(12), b = 9.782(2), c = 13.480(3) Å, α = 100.28(3)°, β = 100.66(3)°, γ = 97.83(3)°, Mr = 321.75, V = 746.3(3) Å3, Z = 2, Dc = 1.432 g/cm3, F(000) = 336, μ(MoKa) = 0.274 mm−1, the final R = 0.0544 and wR = 0.1538. Compound 2 is monoclinic with space group P21/c and cell constants: a = 12.472(3), b = 11.856(2), c = 10.643(2) Å, β = 99.83(3)°, Mr = 332.31, V = 1550.7(5) Å3, Z = 4, Dc = 1.423 g/cm3, F(000) = 696, μ(MoKa) = 0.110 mm−1, the final R = 0.0444 and wR = 0.1187. In 1, there exist some intra- and inter-molecular hydrogen bonds and C–H···π supramolecular interactions, while there are still π···π stacking interactions except for some intra- and intermolecular hydrogen bonds in 2. Two compounds both form a three-dimensional network structure via above intermolecular interactions.
1. Introduction
Spiro compounds with special structures and functions have been reported to possess diverse biological and pharmaceutical properties, such as antiplasmodias [1], antibacterial [2,3], antiviral [4], anxiolytic [5], estrogen potentiating [6], anticancer [7,8] antihistamic [9] and antiproliferative [10] agents. Application of spiro compounds in industry [11,12], catalysis [13] and hole-transporting materials [14] has been triggered great interest in recent years. For these reasons, our group has developed a new simple strategy to synthesize various spiro compounds [15,16,17]. However, to the best of our knowledge, among so many reported spiro-compounds, O, N-Containing spiro compounds derived from 1,5-dioxaspiro[5.5]undecane-2,4-dione are very rare. In this paper, we synthesize two novel compounds: 3-((4-chlorophenylamino)methylene)-1,5-dioxaspiro [5.5]undecane-2,4-dione 1 and 3-((2-nitrophenylamino)methylene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 2. Their structures are also characterized by elemental analysis, IR, UV-Vis and single-crystal X-ray diffraction.
2. Results and Discussion
2.1. Crystal Structures
The selected bond distances and bond angles of 1 and 2 are listed in Table 1. The molecular structures of 1 and 2 are shown in Figure 1. Packing arrangement in the unit cell of 1 and 2 are illustrated in Figure 2, respectively.
As can be seen from the crystal structures (Figure 1), the central C(10) (C(7) for 2) atom is linked by 1,5-dioxaspiro[5.5]undecane-2,4-dione group and phenylamino ring, forming the N(1)–C(10)–C(8) bond angle of 127.0(5)° (1), (N(2)–C(7)–C(9), 125.05(14)° (2). The double bond length C10–C8 (1.371(7) Å) in (1), (C7–C9) (1.366(2) Å) (2), is likewise in agreement with those described earlier reported (1.3454(2) Å, 1.336(2) Å) [15]. The double bond C10–N1 in (1) (1.308(7) Å), C7–N2 (2) (1.3248(18) Å) is typical C–N single bond. The 1,3-dioxane rings of the two compounds are both in a distorted screw-boat conformation. While the cyclohexane rings of the two compounds both exhibit a chair-like configuration, with puckering parameters [18] for compound 1: Q = 0.552(6) Å, q2 = 0.018(6) Å, q3 = 0.552(6) Å, ϑ = 0.4(6)°, ϕ = 157(19)°; compound 2: Q = 0.551(2) Å, q2 = 0.014(2) Å, q3 = −0.550(2) Å, ϑ = 178.2(2)°, ϕ = 295(9)°, respectively.
In the crystal, weak N–H···O and C–H···O intra- and intermolecular interactions are observed in the two compounds (Table 2). In addition, one type of C–H···π supramolecular interactions in 1 are also present. The π···π stacking interactions in 2 are observed between nearby phenyl rings (Cg2···Cg2). In these two crystal lattices, all of the above intermolecular interactions in both compounds form a three-dimensional network structure.
2.2. Spectroscopic Properties
The IR spectra of the two compounds show a little difference. The broad bands at 3231 cm−1 1 and at 3208 cm−1 2 are assigned to the N–H stretching vibration. The strong bands at 1732 cm−1 1 and 1736 cm−1 2 are due to the C=O stretching vibration of the 1,3-dioxane ring. For the compounds 1 and 2, the C–O stretching vibration of the 1,3-dioxane ring is observed at 1248 cm−1, 1095 cm−1 and at 1259 cm−1, 1158 cm−1. Meanwhile, a similar band at 1617 cm−1 and 1597 cm−1 was observed in the IR spectra of 1 and 2, respectively, indicting C=C stretching vibration by 1,5-dioxaspiro[5.5]undecane-2,4-dione group connected with central C(10) 1 (C(7) 2) atom. These facts are consistent with the X-ray diffraction results.
For the two compounds, UV-Vis spectra are measured in EtOH solution at room temperature (Figure 3). The strong absorption bands at about 226 nm, 328 nm and 218 nm, 312 nm are observed in 1 and 2, respectively. The former may be associated with K band of the phenyl group, and the latter may attribute to R band of the C=O group [19].
3. Experimental Section
3.1. Materials and Methods
All the reagents and solvents from commercial sources were used without further purification. Germany). IR spectra were recorded as KBr pellets with a Nicolet FT-IR 510P Spectrometer. The analyses of C, H, and N were made on an Elementar Vario EL III elemental analyzer (Elementar, Hanau, Germany). 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. The X-ray single-crystal data collection for the compounds 1 and 2 were performed on a Bruker Smart-1000 CCD diffractometer.
3.2. Preparation of Two Spiro Compounds
The synthetic route is shown in Scheme 1.
The intermediate compound (1,5-dioxaspiro[5.5]undecane-2,4-dione) was prepared according to our earlier report [16]. The synthesis of two title compounds are described below.
Trimethoxymethane (1.27 g, 0.012 mol) and 1,5-dioxaspiro[5.5]undecane-2,4-dione (1.84 g, 0.01 mol) were dissolved in 30 mL of 95% ethanol, the 3-chlorobenzenamine (1.27 g, 0.01 mol) was added. The mixture was stirred for 2 h and finally refluxed for another 6 h. Then, the solution was filtered. Yield 16.2%. m.p.: 167.9~168.5 °C. Anal. Calcd. for C16H16ClNO4: C, 59.73; H, 5.05; N, 4.35. Found: C, 59.82; H, 4.98; N, 4.55. The yellow crystals for X-ray analysis were grown by slow evaporation of a solution in petroleum ether and ethyl acetate (2:1 = v/v).
The synthesis procedure of 2 was similar to that of 1 except that 3-chlorobenzenamine (1.27 g, 0.01 mol) was replaced by 2-nitrobenzenamine (1.38 g, 0.01 mol). Yield 52.7%. m.p.: 175.3~175.8 °C. Anal. Calcd. for C16H16N2O6: C, 57.83; H, 4.85; N, 8.43. Found: C, 57.73; H, 4.78; N, 8.58. The yellow crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in petroleum ether and ethyl acetate (3:1 = v/v).
3.3. Crystallography
The structure of the two compounds were solved by direct methods and refined by full-matrix least-squares techniques on F2 using SHELXS-97 and SHELXL-97 programs [20]. The non-hydrogen atoms were refined anisotropically, the hydrogen atoms were placed in calculated positions and refined as a riding (C–H = 0.93–0.97 Å in 1 and 2, Uiso(H) = 1.2Ueq(C)). The contributions of hydrogen atoms were included in the structure-factor calculations. The atomic scattering factors and anomalous dispersion corrections were taken from International Table for X-ray Crystallography [21]. The final cycle of refinement gave R1 = 0.0544 and wR2 = 0.1538 (R1= 0.0444 and wR2 = 0.1187 for 2) with w = 1/(σ2(Fo2) + (0.1284P)2 + 0.000P) (w = 1/(σ2(Fo2) + (0.0665P)2 + 0.1456P) for 2) where P = (Fo2 + 2Fc2)/3. Crystallographic data are summarized in Table 3. Crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication No. CCDC-888961 and CCDC-888962. 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: [email protected]).
4. Conclusions
Two novel O, N-Containing spiro compounds, 3-((4-chlorophenylamino)methylene)-1,5-dioxaspiro[5.5]undecane-2,4-dione 1 and 3-((2-nitrophenylamino)methylene)-1,5-dioxaspiro[5.5] undecane-2,4-dione 2, have been synthesized and characterized by elemental analysis, IR, UV-Vis and single-crystal X-ray diffraction. In 1, there exist some intra- and intermolecular hydrogen bonds and C–H···π supramolecular interactions; while there are still π···π stacking interactions except for some intra- and intermolecular hydrogen bonds in 2. Two compounds both form a three-dimensional network structure via above intermolecular interactions.
Acknowledgments
This project was supported by the National Natural Science Foundation of China (No. 51541205), the Project of Shandong Province Higher Educational Science and Technology Program (No. J11LC62) and the Development Plan of Science and Technology of Weifang.
Author Contributions
Jinhe Jiang synthesized compound 1 and compound 2. Wulan Zeng conceived and designed the experiments and wrote the paper.
Conflicts of Interest
The authors declare no conflict of interest.
References
- Sundaram, R.; Ganesan, R.; Murugesan, G. In vitro antiplasmodial activity of spiro benzofuran compound from mangrove plant of southern india. Asian Pac. J. Trop. Med. 2012, 5, 358–361. [Google Scholar] [CrossRef]
- Liu, R.D.; Kong, D.L.; Wu, M.S.; Li, G.N.; Li, G.Z. Synthesis, structure and antimicrobial activity of 2-phenyl-4H-spiro[benzo[e][1,4,2] oxa-zaphosphinine-3,3′-indolin]-2′-one 2-oxide. Chin. J. Struct. Chem. 2014, 33, 204–208. [Google Scholar]
- Ding, Y.; Tian, Z.; Zhu, N. Research progress of antibacterial spiro-compounds. Chin. J. Org. Chem. 2010, 30, 1156–1163. [Google Scholar]
- Van Hes, R.; Smit, A.; Kralt, T.; Peters, A. Synthesis and antiviral activities of adamantane spiro compounds. J. Med. Chem. 1972, 15, 132–136. [Google Scholar] [CrossRef]
- Anikina, L.V.; Vikharev, Y.B.; Rozhkova, Y.S.; Shklyaev, V. Synthesis and biological activity of 3-spiro[adamantane-2,3′-isoquinolines]. Pharm. Chem. J. 2013, 46, 707–710. [Google Scholar] [CrossRef]
- Doggett, N.S.; Bailey, D.J.; Qazi, T. Estrogen potentiating activity of two spiro compounds having approximately similar molecular dimensions to stilbestrol. J. Med. Chem. 1977, 20, 318–320. [Google Scholar] [CrossRef] [PubMed]
- Khazir, J.; Singh, P.P.; Reddy, D.M.; Hyder, I.; Shafi, S.; Sawant, S.S.; Chashoo, G.; Mahajan, A.; Alam, M.S.; Saxena, A.K.; et al. Synthesis and anticancer activity of novel spiro-isoxazoline and spiro-isoxazolidine derivatives of a-santonin. Eur. J. Med. Chem. 2013, 63, 279–289. [Google Scholar] [CrossRef] [PubMed]
- Das, S.K.; Bhattacharya, S.; Kundu, A. Rationalized design, synthesis and pharmacological screening of amino acid linked spiro pyrrolldlno oxylndole analogs through environment friendly reaction. J. Adv. Pharm. Technol. Res. 2013, 4, 198–205. [Google Scholar] [PubMed]
- Arya, K.; Rawat, D.H.; Dandia, A.; Sasai, H. Bronsted acidic ionic liquids: Green, efficient and reusable catalyst for synthesis of fluorinated spiro [indole-thiazinones/hiazolidinones] as antihistamic agents. J. Fluor. Chem. 2012, 137, 117–122. [Google Scholar] [CrossRef]
- Yu, B.; Shi, X.J.; Qi, P.P.; Yu, D.Q.; Liu, H.M. Design, synthesis and biological evaluation of novel steroidal spiro-oxindoles as potent antiproliferative agents. J. Steroid Biochem. Mol. Biol. 2014, 141, 121–134. [Google Scholar] [CrossRef] [PubMed]
- Zhang, P.; Meng, J.B.; Matsuura, T.; Wang, Y.M. DNA modification with photochromic spiro compounds. Chin. Chem. Lett. 2002, 13, 299–302. [Google Scholar]
- Crossley, D.L.; Gabbutt, C.D.; Mark Heron, B.; Kay, P.; Mogstad, M. Synthesis and photochromic properties of spiro[naphthopyra-7′H-benzocyclohepta-5′,8′-dienes]. Dyes Pigment. 2012, 95, 62–68. [Google Scholar] [CrossRef]
- Jiang, Y.; Xue, S.; Li, Z.; Deng, J.; Mi, A.; Chan, A.S.C. Asymmetric hydroformylation of styrene catalyzed by chiral spiro diphosphite-rhodium(I) complexes. Tetra. Asymm. 1998, 9, 3185–3189. [Google Scholar] [CrossRef]
- Chu, Z.Z.; Wang, D.; Zhang, C.; Wang, F.Z.; Wu, H.W.; Lv, Z.B.; Hou, S.C.; Fan, X.; Zou, D.H. Synthesis of spiro[fluorene-9,9′-xanthene] derivatives and their application as hole-transporting materials for organic light-emitting devices. Synth. Met. 2012, 162, 614–620. [Google Scholar] [CrossRef]
- Zeng, W.L.; Li, Y.F.; Guo, H.M. Syntheses and Crystal Structures of 1,5-dioxaspiro[5.5]undecane-2,4-dione Derivatives. J. Chem. Crystallogr. 2013, 43, 223–227. [Google Scholar] [CrossRef]
- Zeng, W.L.; Meng, Q.G.; Guo, H.M.; Zhang, L.; Jian, F.F. Syntheses and crystal structures of two novel spiro compounds containing 1,5-Dioxaspiro[5.5]undecane-2,4-dione. Chin. J. Struct. Chem. 2010, 29, 696–699. [Google Scholar]
- Zeng, W.L.; Cai, X.; Guo, H.M. Synthesis, experimental and theoretical characterization of 3-(4-(dimethylamino)benzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione. Chin. J. Struct. Chem. 2013, 32, 1603–1610. [Google Scholar]
- Cremer, D.J.; Pople, A. A general definition of ring puckering coordinates. J. Am. Chem. Soc. 1975, 97, 1354–1358. [Google Scholar] [CrossRef]
- Özdemir, M.; Sönmez, M.; Sen, F.; Dincer, M.; Özdemir, N. A novel one-pot synthesis heterocyclic compound (4-benzoyl-5-phenyl-2(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c] pyrimidin-7 (6H)-one): Structural (X-ray and DFT) and spectroscopic (FI-IR, NMR, UV-Vis and Mass) characterization studies. Spectrochim. Acta Part A 2015, 137, 1304–1314. [Google Scholar] [CrossRef] [PubMed]
- Sheldrick, G.M. A short history of SHELX. Acta Cryst. 2008, A64, 112–122. [Google Scholar] [CrossRef] [PubMed]
- SMART and SAINT. Area Detector Control and Integration Software; Siemens Analytical X-Ray Systems Inc.: Madison, WI, USA, 1996. [Google Scholar]
Figure 1.
The molecular structures of 1 and 2 with atomic numbering scheme.
Figure 2.
The packing arrangement in a unit cell of 1 and 2.
Figure 3.
UV-Vis spectra of 1 and 2.
Scheme 1.
Synthesis of two spiro compounds.
| Selected Bond Lengths for 1 | Selected Bond Lengths for 2 | ||
| C(11)–N(1) | 1.422(6) | N(2)–C(7) | 1.3248(18) |
| N(1)–C(10) | 1.308(7) | N(2)–C(1) | 1.4023(18) |
| C(10)–C(8) | 1.371(7) | C(9)–C(7) | 1.366(2) |
| C(8)–C(9) | 1.437(8) | C(8)–C(9) | 1.445(2) |
| C(8)–C(7) | 1.448(6) | C(9)–C(10) | 1.456(2) |
| Cl(1)–C(14) | 1.735(5) | C(2)–N(1) | 1.4634(19) |
| Selected Bond Angles for 1 | Selected Bond Angles for 2 | ||
| C(10)–N(1)–C(11) | 124.4(4) | C(7)–N(2)–C(1) | 125.57(12) |
| N(1)–C(10)–C(8) | 127.0(5) | N(2)–C(7)–C(9) | 125.05(14) |
| C(16)–C(11)–C(12) | 119.3(5) | C(7)–C(9)–C(10) | 117.25(14) |
| C(16)–C(11)–N(1) | 119.3(4) | C(8)–C(9)–C(10) | 120.39(14) |
| C(10)–C(8)–C(9) | 116.7(4) | C(6)–C(1)–C(2) | 116.79(13) |
| C(10)–C(8)–C(7) | 122.4(5) | C(6)–C(1)–N(2) | 121.34(13) |
| C(9)–C(8)–C(7) | 119.6(5) | C(2)–C(1)–N(2) | 121.87(12) |
Table 2.
Intra- and intermolecular interaction distances and aromatic-aromatic interactions in 1 and 2.
| D–H···A | Symmetry | D–H (Å) | H···A (Å) | D···A (Å) | ∠D–H···A (°) |
|---|---|---|---|---|---|
| N(1)–H(1A)···O(2) 1 | intra | 0.86 | 2.168 | 2.783(6) | 128.3 |
| N(1)–H(1A)···O(2) 1 | −2−x, 1−y, 1−z | 0.86 | 2.539 | 3.311(7) | 149.8 |
| C(10)–H(10A)···O(1) 1 | intra | 0.93 | 2.420 | 2.767(7) | 102.0 |
| C(10)–H(10A)···O(1) 1 | −1−x, −y, 1−z | 0.93 | 2.550 | 3.469(7) | 169.7 |
| C(12)–H(12A)···O(1) 1 | −1−x, −y, 1−z | 0.93 | 2.346 | 3.188(7) | 150.4 |
| C(16)–H(16A)···O(2) 1 | −2−x, 1−y, 1−z | 0.93 | 2.463 | 3.291(7) | 148.3 |
| C(5)–H(5B)···Cg(3) a 1 | −2−x, −y, 1−z | 0.97 | 3.254 | 3.790 | 116.6 |
| N(2)–H(2A)···O(2) 2 | intra | 0.86 | 2.041 | 2.6809(19) | 130.6 |
| N(2)–H(2A)···O(4) 2 | intra | 0.86 | 2.103 | 2.7429(17) | 130.8 |
| N(2)–H(2A)···N(1) 2 | intra | 0.86 | 2.582 | 2.911(2) | 125.2 |
| C(2)–H(7A)···O(3) 2 | intra | 0.93 | 2.462 | 2.798(2) | 101.4 |
| C(4)–H(4A)···O(1) 2 | x, 5/2−y, −1/2+z | 0.93 | 2.589 | 3.368(2) | 141.7 |
| C(14)–H(4A)···O(3) 2 | 1−x, 1−y, −z | 0.97 | 2.562 | 3.465(3) | 154.9 |
| Ring | Symmetry | Dihedral angels (°) | π···π (Å) | Centroid to centroid distances (Å) | |
| Cg(2)···Cg(2) b 2 | 2−x, −y, −z | 0 | 3.701 | 3.465 | |
a Cg(3) ring denotes phenyl ring of compound 1: C(11)–C(16); b Cg(2) ring denotes phenyl ring of compound 2: C(1)–C(6).
| Compounds | 1 | 2 |
|---|---|---|
| Empirical formula | C16H16ClNO4 | C16H16N2O6 |
| Color/shape | yellow/block | yellow/block |
| Formula weight | 321.75 | 332.31 |
| Crystal system | triclinic | monoclinic |
| Space group | P-1 | P21/c |
| Unit cell dimensions | a = 5.9448(12) Å α = 100.28(3)° | a = 12.472(3) Å α = 90° |
| b = 9.782(2) Å β = 100.66(3)° | b = 11.856(2) Å β = 99.83(3)° | |
| c = 13.480(3) Å γ = 97.83(3)° | c = 10.643(2) Å γ = 90° | |
| Volume | 746.3(3) Å3 | 1550.7(5) Å3 |
| Z | 2 | 4 |
| Density (calculated) | 1.432 g·cm−3 | 1.423 g·cm−3 |
| Absorption coefficient | 0.274 mm−1 | 0.110 mm−1 |
| F(000) | 336 | 696 |
| Crystal size | 0.15 × 0.10 × 0.08 mm3 | 0.25 × 0.22 × 0.12 mm3 |
| Theta range for data collection | 3.15°–25.25° | 3.25°–27.48° |
| Limiting indices | −6 ≤ h ≤ 7, −11 ≤ k ≤ 11, −16 ≤ l ≤ 1 | −16 ≤ h ≤ 16, −15 ≤ k ≤ 15, −13 ≤ l ≤ 13 |
| Reflections collected | 6027 | 14428 |
| Independent reflections (Rint) | 2701 (0.0497) | 3552 (0.0379) |
| Reflections observed (I > 2σ(I)) | 1007 | 2471 |
| Refinement method | Full-matrix least-squares on F2 | Full-matrix least-squares on F2 |
| Data/restraints/parameters | 2701/0/199 | 3552/0/217 |
| Goodness-of-fit on F2 | 1.041 | 1.059 |
| R1/wR2 (I > 2σ(I)) R1/wR2 (all data) | 0.0544 / 0.1538 0.1661 / 0.2587 | 0.0444 / 0.1187 0.0677 / 0.1345 |
| Largest diff. peak and hole | 0.421 and −0.359 e Å−3 | 0.273 and −0.227 e Å−3 |
© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
MDPI and ACS Style
Zeng, W.; Jiang, J. Synthesis and Crystal Structures of Two Novel O, N-Containing Spiro Compounds. Crystals 2016, 6, 69. https://doi.org/10.3390/cryst6060069
AMA Style
Zeng W, Jiang J. Synthesis and Crystal Structures of Two Novel O, N-Containing Spiro Compounds. Crystals. 2016; 6(6):69. https://doi.org/10.3390/cryst6060069
Chicago/Turabian StyleZeng, Wulan, and Jinhe Jiang. 2016. "Synthesis and Crystal Structures of Two Novel O, N-Containing Spiro Compounds" Crystals 6, no. 6: 69. https://doi.org/10.3390/cryst6060069
Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.
