The Structures of Hydrazine Crystal and Its Antibacterial Activities

Transcription

1 Romanian Biotechnological Letters Vol. 17, No.5, 2012 Copyright 2012 University of Bucharest Printed in Romania. All rights reserved ORIGINAL PAPER The Structures of Hydrazine Crystal and Its Antibacterial Activities Abstract Received for publication, January 10, 2012 Accepted, June 11, 2012 FU QIYUN, LU JUNZHONG*, LIN NIN, ZHENG SHAOTONG Department of Laboratory Medicine, the First Huaian Hospital Affiliated to Nanjing Medical University, Huaian , China * Correspondence author. The crystal of 1, 2-bis (ethoxycarbonyl) hydrazine was studied by XRD, FTIR and Raman spectroscopy. The ground-state geometries were optimized at B3LYP/6-31+G (d, p) level. These vibrational wavenumbers were calculated at the same level. The antibacterial activities have been screened for the compound against two bacteria: Staphylococcus aureus and Escherichia coli. Keywords: Hydrazine; IR; Raman; DFT calculations; antibacterial activity Introduction Hydrazine is a chemical raw material with very extensive application. The subhydrazine contains two nucleophilic nitrogen and four replaceable hydrogens, therefore, it can be synthesized into a number of hydrazine derivatives and important pharmaceutical intermediate [1-6]. N, N- disubstituted hydrazine compounds is widely used in the chemical industry, medicine, agriculture, aerospace and utility business and many other areas [7-9]. This gave a great impetus to research the structure of the disubstituted hydrazine and to find the potential valuable structure. The structure of 1, 2-bis (ethoxycarbonyl) hydrazine was studied by XRD, FTIR and Raman spectroscopy. In addition, there is no theoretical study on 1, 2-bis (ethoxycarbonyl) hydrazine before, in order to learn more about the compound, make full use of it and even design important pharmaceuticals, a theoretical study of the vibration properties of the compound by density-functional theory (DFT) was reported. The ground-state geometries were optimized at B3LYP/6-31G (d, p) and the vibration wave numbers were calculated at the same level. At the same time, the antibacterial activities have been screened for the compound against two bacteria: Staphylococcus aureus and Escherichia coli. Experiment The structure of the compound was studied by X-ray single crystal diffraction by the Siemens Smart 1000 instrument using Mo Kα as excitation source. Melting point was measured in WRS-1B digital melting point instrument. Infrared spectra of the compound dispersed in KBr pellet in the range of cm -1 were recorded on an IR-Spectra One (PE). The Raman spectra of powder sample were acquired on with Renishaw RM1000 spectrometer using Nd:YAG laser as excitation source (785 nm) with an output of about 200mW. The spectral regions were cm -1. Antibacterial activity: The bacteriostatic effect of the compound was measured using single filter paper method against S. aureus (Staphylococcus aureus) and E. coli (Escherichia coli). Protein in the beef extract agar medium, laboratory containers and direct diameter of 5.5mm filter paper were sterilized at 121 C for30 min. The medium was dished into the containers as a flat after cooling to about 50 C, then were inoculated with the abovementioned two kinds of bacteria. The sterile filter paper was tiled in the bacterial culture medium respectively, and was marked in a certain concentration of test fluid, cultured at 37 C 7557

2 LU JUNZHONG, FU QIYUN, LIN NIN, ZHENG SHAOTONG for 24h, measure the inhibition zone diameters. Calculations The DFT calculations were employed with the Becke Lee Yang Parr s threeparameter hybrid functional (B3LYP) [10] method in this study. The basic set 6-31+G (d, p) [10] was employed in the B3LYP calculations and the geometry optimizations were performed without symmetry constrain. All calculations were performed with the Gaussian 03W program suit [12]. The assignment of the calculated wave numbers is aided by the animation option of Gauss View 3.0 [13] graphical interface for Gaussian programs, which gives a visual presentation of the shape of the vibration modes. Note that the calculated spectra are all scaled by 0.96, which is close to the recommended value by the NIST database (0.9614) [14] and is comparable to other literature values [15]. Results and discussion The cell diagram of 1, 2-bis (ethoxycarbonyl) hydrazine is shown in Fig. 1, it crystallizes in monoclinic, space group C-2 with a= (18)nm, b= (12)nm, c= (10)nm, α=90, β=97.39, γ=90, Dc=1.325g cm -3, Z=4, F(000)=376, V=0.8832(2)nm 3. The crystallographic data of 1, 2-bis (ethoxycarbonyl) hydrazine was shown in Table 1. Fig. 1. The cell diagram of 1,2-bis(ethoxycarbonyl)hydrazine. Table 1. Crystallographic data of 1, 2-bis (ethoxycarbonyl) hydrazine. Empirical formula C 6 H 12 N 2 O 4 Crystal size/mm Formula weight Temperature/K 292(2) Wavelength/nm Crystal system Monoclinic Space group C2/c a/nm (18) b/nm (12) c/nm (10) α/( ) 90 β/( ) γ/( ) 90 V/nm (2) 7558 Romanian Biotechnological Letters, Vol. 17, No. 5, 2012

3 The Structures of Hydrazine Crystal and Its Antibacterial Activities Z 4 Dc/(g cm -3 ) F(000) 376 θ range for data collection 2.80 to Index range -17<=h<=17, -11<=k<=11, - 9<=l<=10 Reflections collected/unique 3727 R(int) Max. and min. transmission and R 1,wR 2 [I>2σ(I)] R1 = , wr2 = R 1,wR 2 (all data) R1 = , wr2 = GOF Largest diff. Peak and hole(e nm -3 ) and The schematic depiction of 1, 2-bis (ethoxycarbonyl) hydrazine and optimized structure are shown in Fig. 2, and the optimized bond lengths, bond angles and dihedral angles are shown in Table 2. From the table it can see that the calculated data are in agreement with those determined by XRD. The bond length of N-N is and Å respectively by calculation and XRD. The N-C bond is 1.385Å by calculation and 0.034Å longer than that of by XRD. The C=O and C-O bond lengths are and 1.346Å by calculation, and they are and 1.334Å by XRD. Fig. 2. The optimized structure of 1,2-bis(ethoxycarbonyl)hydrazine. Table 2. Selected bond lengths (Å), bond angles ( ), dihedral angles ( ) of 1, 2-bis (ethoxycarbonyl) hydrazine. Parameters B3LYP/6-31+G(d, p) XRD R(1,3) (18) R(1,5) (16) R(5,7) (14) R (5,10) (13) R(10,18) (15) R(18,21) (19) A(1,3,6) (9) A(1,3, 4) (10) A(3,6,8) (11) A(8,5,9) (11) A(6,9,11) (9) A(9,11,14) (11) D(1,5,10,18) (10) Romanian Biotechnological Letters, Vol. 17, No. 5,

4 LU JUNZHONG, FU QIYUN, LIN NIN, ZHENG SHAOTONG Table 3. Thermodynamic parameters of 1, 2-bis (ethoxycarbonyl) hydrazine. a Unscaled for 298K and 1 atm. Thermodynamic parameters a B3LYP/6-31+G(d, p) Zero-point vibrational energy (kj mol 1 ) Sum of electronic and zero-point energy (kj mol 1 ) Thermal correction to energy (kj mol 1 ) Entropy (J mol 1 K 1 ) CV (J mol 1 K 1 ) EHOMO (ev) ELUMO (ev) Dipole moment (D) The values of some thermodynamic parameters, of 1, 2-bis (ethoxycarbonyl) hydrazine are listed in Table 3. The zero-point vibrational energy, the sum of electronic and zero-point energy, the thermal correction to energy are 515.9, , kj mol 1 respectively. The entropy, CV, E HOMO, E LUMO and the dipole moment are J mol 1 K 1, J mol 1 K 1, eV, eV, and 1.067D respectively. The FTIR and Raman spectra of 1, 2-bis (ethoxycarbonyl) hydrazine were fully interpreted on the basis of the IR and Raman spectra calculated at B3LYP/6-31+G(d, p) level, and the wave numbers are scaled by the factor of The intensity and assignments are listed in Table 4. Table 4. The calculated wavenumbers (cm -1 ), FTIR and Raman intensity and assignments of the compound. Abbreviation: ν stretching, δ deformation, ρ w wagging, ρ b bending, ρ t twisting, ρ r rocking, ρ s scissoring, γ - torsion, oop out of plane deformation, ip in plane vibrations. as, asymmetric; s, symmetric. a Scaling factor: B3LYP/6 31+G(d,p),0.96. b The absolute IR intensity in KM (mol) 1 ; Raman scattering activity in A4(amu) 1 from B3LYP/6 31+G(d,p) calculation. Calculated Observed Descriptions B3LYP/6- B3LYP/6- IR Raman 31+G(d,p) 31+G(d,p) a intensity b intensity b IR Raman ν as (N H) ν as (C-H) ν as (C-H) (s ν s (C-H) ( ν s (C-H)CH ν as (C5 O7,C ( ρ sc H) ( ρ ras (N-H) ρ rs (N-H) ( ρ bas (C H) ρ bs (C H) ( γ(c H) ( ρ r ( C5-O7,C νs(n N) ( ρ t (C-H) ( ρ t (C-H) ( ν s (C18-O10,C ( ρ t (C-H) ( 871(vs γ(c H) ( 815(w 7560 Romanian Biotechnological Letters, Vol. 17, No. 5, 2012

5 The Structures of Hydrazine Crystal and Its Antibacterial Activities γ(c H) ( 795(w ρ w (N-H) ( 670(w ρ r ske ( 598(m δske ( 466(w ρ s ske ( 431(w Fig. 3 shows the observed FTIR and calculated IR spectra of 1, 2-bis (ethoxycarbonyl) hydrazine at B3LYP/6-31+G (d, p) level. Fig. 4 shows the observed and calculated Raman spectra of the compound at that level. These figures showed that the agreement between the experimental and scaled theoretical frequencies is quite good in general. The weak band at around 3415cm -1 is associated with the asymmetric stretching vibrations of N-H, and the calculated band is at 3485cm -1. The bands near 3000cm -1 can be attributed to the C-H stretching vibrations, and these can be seen from the theoretical results. The asymmetric stretching vibration of C-H are at 3043, 2988cm -1 in FTIR spectra with media strong bands and 2980cm -1 in Raman spectra with a strong band, while they are at 3025 and 3004 in calculated spectra. The stretching vibration of C-H are at 2940, 2912cm -1 in FTIR spectra with media strong and weak bands and 2934cm -1 in Raman spectra with a weak band, while they are at 2964 and 2962cm -1 in calculated spectra. The very strong band at 1698cm -1 in FTIR spectra and media strong band at 1708cm -1 in Raman spectra is attributed to the C5-O7 and C6-C8 stretching vibration, and the calculated band is at 1721cm -1. Fig. 3. The FTIR and unscaled IR spectra of 1,2-bis(ethoxycarbonyl)hydrazine at B3LYP/6-31+G(d,p) level. Romanian Biotechnological Letters, Vol. 17, No. 5,

6 LU JUNZHONG, FU QIYUN, LIN NIN, ZHENG SHAOTONG Fig. 4. The Raman and unscaled Raman spectra of 1,2-bis(ethoxycarbonyl)hydrazine at B3LYP/6-31+G(d,p) level. The media strong bands both at 1448cm -1 in FTIR spectra and Raman spectra are attributed to the scissors vibration of C-H which was found at 1451cm -1 in calculated spectra. The bands of asymmetric and symmetric rocking of N-H are at 1485 and 1450cm -1 respectively of the calculation, and these bands are observed at 1425 and 1388cm -1 in FTIR spectra and 1401cm -1 in Raman spectra as weak bands. The weak band at 1374cm -1 in FTIR spectra is attributed to the asymmetric bending of C-H, and the band of C-H symmetric bending is observed at 1336cm -1 in FTIR spectra and 1334cm -1 in Raman spectra. The very strong band at 1254cm -1 in FTIR spectra and weak band at 1294cm -1 in Raman spectra are corresponding to the torsion of C-H, and the mode is computed at 1279cm -1. The very strong band at 1240cm -1 in FTIR spectra and 1265cm -1 in the calculation spectra are attributed to the rocking of C5-C7 and C6-C8. The weak band at 1197cm -1 in Raman spectra are attributed to the N-N stretching, and it is found at 1201cm -1 in the calculation spectra. The torsion of C-H is observed at 1150, 1607, 891cm -1 in FTIR spectra and 1150, 1070, 871cm -1 in Raman spectra, and it is computed at 1148, 1072, 847cm -1. The bands at 1607 and 847cm -1 are very strong. The media strong band at 1025cm -1 in FTIR spectra and 1035cm -1 in Raman spectra is attributed to the symmetric stretching of C18-O10 and C11-O9 which calculated at 1034cm -1. The media strong bands at 780, 757cm -1 in FTIR spectra and weak bands at 815, 795cm -1 in Raman spectra are corresponding to the torsion of C-H, which are calculated at 772 and 763cm -1. The out of plane wagging of N-H is computed at 662cm -1 and is observed at 671cm -1 with a media strong band in FTIR spectra and 670cm -1 with a weak band in Raman spectra. The media strong bands at 595cm -1 in FTIR spectra and 598cm -1 in Raman spectra are attributed to the rocking of the skeleton, and it is calculated at 761cm -1. The weak bands at 453cm -1 in FTIR spectra and 466cm -1 in Raman spectra are attributed to the deformation of the skeleton, and it is calculated at 445cm -1. The scissoring of the skeleton is calculated at 407cm -1 and is observed at 416cm -1 in FTIR spectra and 431cm -1 in Raman spectra Romanian Biotechnological Letters, Vol. 17, No. 5, 2012

7 The Structures of Hydrazine Crystal and Its Antibacterial Activities The results of antibacterial activity were shown in Table 5. It shows that the compound has certain antibacterial activity against the two kinds of strains. The antibacterial activity of S. aureus and E. coli increased as the concentration increasing. The diameter inhibition zone of E. coli at the concentration of 1.5 mmol L -1 is 10.1 mm, and it is 0.8 mm bigger than that of S. aureus. So the antibacterial activity of the compound against E. coli is higher than S. aureus. Table 5. Antibacterial activities of 1, 2-bis (ethoxycarbonyl) hydrazine. Concentration(mmol L -1 ) Diameter inhibition zone/mm S. aureus E. coli Conclusions The structure of 1, 2-bis (ethoxycarbonyl) hydrazine crystal was verified by XRD, FTIR and Raman spectroscopy. The ground-state geometries were optimized at B3LYP/6-31G (d, p) level. The vibrational wave numbers were calculated at the same level. It was found that the calculated spectra are in agreement with the experimental data. The antibacterial activities have been screened for the compound against two bacteria: Staphylococcus aureus and Escherichia coli, resulting that the antibacterial activity of the compound against E. coli is higher than that against S. aureus. References 1. TOMEI EJ. Explosive Equivalence Liquid Propellants. 1998(01). 2. KATRITZKY AR., RESS CW. Comprehensive Heterocyclic Chemistry; Pergamon Press: Oxford. 5(1984), KANIA RS. Indazole Compound and Phharnacdutical Compsitions for Inhibiting Protein Kinases, and Mehtod for Their Use YASUSHI M. Photochromic Titanium Oxide Gel and Glass Part. Japan COREY EJ., SACHDEV HS., GOUGOUTAS JZ., Saenger W. Studies on the symmetric synthesis of alphaamino acids. II. New systems for highly specific asymmetric synthesis with conservation of the Chiral reagent. J. Am. Chem.Soc. 92(8) (1970), ENDER D. Asymmetric Synthesis BROOKS G., BURGESS W., COLTHRUST D. The Identification of Novel Mutilin 14-Carbonates. Bioorg. Med. Chem, Lett. 9(5) (2001), TOSHIO N., TAKASHI M. Heterocyclic Imino Compounds and Fungilides and Insecticides for Agricultural and Horticultural Use WELLA AG. Preparation of 2,5-Diamino-benzaldehyde-derivates and Their Usage in Hair Dyes BECKE AD. Density functional thermochemistry. III. The role of exact exchange J. Chem. Phys. 98, (1993), HEHRE WJ., RADOM L., SCHLEYER PVR. Ab Initio Molecular Orbital Theory, Wiley, New York, FRISCH MJ., TRUCKS GW., SCHLEGEL HB., et al. Gaussian03 Revision C. 02, Gaussian Inc., Wallingford, CT, 2004 (page 7 of 198). 13. GaussView 3.0, Gaussian Inc., Garnegieoffice. Park. Pittsburgh. PA, USA. 14. POLFER NC., PARIZS B., SNOEK LC. Infrared Fingerprint Spectroscopy and Theoretical Studies of Potassium Ion Tagged Amino Acids and Peptides in the Gas Phase. J. Am. Chem. Soc. 127(2005), KAPOTA C., LEMAIRE J., OHANESSIAN G. Vibrational Signature of Charge Solvation vs. Salt Bridge Isomers of Sodiated Amino Acids in the Gas Phase. J. Am. Chem. Soc. 126(2004), Romanian Biotechnological Letters, Vol. 17, No. 5,