Synthesis and Crystal Structures of Two Novel O, N-containing Spiro Compounds

Two novel O, N-containing spiro compounds, C 16 H 16 ClNO 4 (1) and C 16 H 16 N 2 O 6 (2), were prepared by reactions of monosubstituted benzenamine (substituent = –NO 2 , –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. 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.


Spectroscopic Properties
The IR spectra of the two compounds show a little difference.The broad bands at 3231 cm 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].
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].

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.

Preparation of Two Spiro Compounds
The synthetic route is shown in Scheme 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.

Preparation of Two Spiro Compounds
The synthetic route is shown in Scheme 1.
Crystals 2016, 6, 69 4 of 7 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].

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.

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.

Crystallography
The structure of the two compounds were solved by direct methods and refined by full-matrix least-squares techniques on F 2 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 = 0.93-0.97Å 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

Figure 1 .
Figure 1.The molecular structures of 1 and 2 with atomic numbering scheme.Figure 1.The molecular structures of 1 and 2 with atomic numbering scheme.

Figure 2 .
Figure 2. The packing arrangement in a unit cell of 1 and 2.

´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.

Table 2 .
Intra-and intermolecular interaction distances and aromatic-aromatic interactions in 1 and 2.

Table 2 .
Intra-and intermolecular interaction distances and aromatic-aromatic interactions in 1 and 2.