Synthesis, X-ray Crystal Structure and Thermal Decomposition Mechanism of [Zn(MCZ)3](NO3)2·H2O (MCZ=Methyl Carbazate)

Um novo complexo de coordenação, [Zn(MCZ) 3 ](NO 3 )2·H 2 O, foi sintetizado através da reação de soluções aquosas de nitrato de zinco(II) e metilcarbazato. O complexo foi caracterizado por espectroscopia IV, análise elementar e por um estudo de difração de raios X. Cristaliza no grupo espacial monoclínico P2 1 /n. O íon metálico central é hexa-coordenado, com geometria octaédrica distorcida e se encontra ligado aos ligantes bidentados MCZ através dos átomos de oxigênio das carbonilas e dos átomos de nitrogênio terminais. Os cátions [Zn(MCZ) 3 ], os anions NO 3 – e as moléculas de água do retículo encontram-se interconectadas por forças eletrostáticas e por ligações de hidrogênio em um arranjo tridimensional. O mecanismo da decomposição térmica foi sugerido pelos estudos de DSC e TG-DTG. O composto [Zn(MCZ) 3 ](NO 3 )2·H 2 O começa a decompor-se a 181,9 °C, e o resíduo final, a 300,0 °C é ZnO.


Introduction
][3][4][5] MCZ molecule consists of a hydrazine group, a carbonyl and a methoxy group, which determine its lively chemical reactivity.For example, it can substitute phosgene to be used as carbonylating reagent, and also can be used as replacer of dimethyl sulfate in methylating reaction. 6In addition, all the hydrazine N and carbonyl O are potential coordination atoms, and the similar structure character to carbohydrazide, which is a widely used ligand in coordination compounds, [7][8][9] determine MCZ a promising coordination ligand.But till now, only a few studies on MCZ coordination compounds have been carried out. 10re the crystal structure and thermal decomposition mechanism of [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O are described.

Infrared spectra of [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O
The complex has been characterized by analytical and spectroscopic data (see experimental).Selected bands from the spectra were tentatively assigned by comparison with previous study of MCZ metal(II) complex. 10The band observed at 3323 cm -1 supports the fact that the H 2 O molecule in the complex is lattice water, of which the bands are around 3400 cm -1 .The bands around 3200 cm -1 were assigned to the stretching vibration of the N-H group, and that at 1686 cm -1 was assigned to the C=O group.Both bands were shifted to lower wavenumber compared to the free ligand, 11 and this was interpreted as the evidence of coordination through the nitrogen atom of the hydrazine group and the carbonyl oxygen atom.Finally, the bands observed in the 1300-700 cm -1 region were assigned to the N-O and C-O stretching vibrations.

Crystal structure of [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O
A single unit cell with the atomic numbering scheme and atom connectivity is shown in Figure 1.There are one [Zn(MCZ) 3 ] 2+ coordination cation, two NO 3 -anions and a lattice H 2 O molecule in the asymmetric unit, and they are linked through electrostatic forces and extensive hydrogen bonds into a 3-D network.
The zinc(II) center is in six-coordinate sites, and is coordinated to three MCZ ligands with bonding through carbonyl O atoms and terminal N atoms of the hydrazine group.This is almost the same coordination mode as observed in the carbohydrazide complexes. 12,13The six coordinating atoms (3N, 3O) form a considerable distorted [ZnN 3 O 3 ] octahedron with the O(1) and N(5) atoms at the apical positions, which is a normal coordination geometry of zinc(II) coordination complex. 14The coordination bonds vary with donor type and position with the Zn-O(5) 2.109(2) Å, Zn-O(1) 2.131(2) Å, Zn-O(3) 2.132(2) Å, Zn-N(1) 2.141(3) Å, Zn-N(5) 2.146(3) Å and Zn-N(3) 2.150(3) Å, so distortion from ideal octahedral geometry is evident.Although there are no closely related octahedral zinc(II) compounds, the Zn-N bond distances are similar to the corresponding values observed in the bis(tripod) zinc(II) complex. 15Whereas, the Zn-O bond distances are a little longer than the typical value in octahedral complexes (2.098 Å). 16 The longer Zn-O bond distances may be attributed to the bidentate coordination of the MCZ ligand and the double bond character of carbonyl group.More   In the asymmetric unit, three five-membered chelating rings, including a zinc(II) cation, are formed (see Figure 1), and all the non-hydrogen atoms of each ring are coplanar with the deviation less than 0.0276 Å.The dihedral angles between the rings are 93.7°,91.3° and 97.8°, leading to minimum steric hindrance.The dihedral angle of the methoxy group outside each chelating plane is less than 10°.The stability of the five-membered chelating rings and minimum steric hindrance contribute to the high thermal stability of the complex, as verified by the DSC study described below.The possibility that there is delocalisation within the MCZ ligand was ruled out by the double bond character of the carbonyl groups of C(1)-O(1), C(3)-O(3) and C(5)-O(5), 1.227(4) Å, 1.223(4) Å and 1.220(4) Å, only a little longer than the normal C=O bond distance of 1.203 Å. 17 One lattice H 2 O molecule and two NO 3 -anions are also located within the asymmetric unit.The coordination cations, NO 3 -anions and lattice H 2 O molecules are linked together through electrostatic forces and intermolecular hydrogen bonds.The hydrogen bond distances and angles are summarized in Table 3.The lattice water oxygen atom, O (13), acts as an acceptor in hydrogen bonds to MCZ ligands through N1 and N4 with distances of 2.991(4) and 3.159(5) Å, and angles of 163.5 and 140.1°.Furthermore, all the O atoms of NO 3 -anions, except O (11), act as acceptors in hydrogen bonds with all the MCZ N atoms as donors with bond distances of 2.922(4)-3.131(5)Å, and angles of 158.6-170.2°.The overall result of the interactions is the formation of a complicated 3-D hydrogen bond network.These extensive hydrogen bonds also make an important contribution to the stability of the complex.

Thermal decomposition mechanism of [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O
In order to investigate the thermal decomposition of [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O, the DSC and TG experiments were carried out.The DSC and TG-DTG curves are shown in Figures 3 and 4, respectively.The infrared spectra of the solid residues at different temperatures were used to determine their compositions, see Figure 5.Under linear   heating rate under N 2 atmosphere, the complex is stable up to 181.9 °C, when the first endothermic process starts, with a change of enthalpy of 67.75 kJ mol -1 , and peak temperature of 185.8 °C.Corresponding to this endothermic process, there is a weight loss of 46.09% of the initial weight in the temperature range of 153.9-199.4°C on the TG curve (see Figure 4).The dehydration process and the cleavage of the chelating rings and NO 3 are confirmed from the disappearance of the absorbance bands at 3323, 2979, 2860, 1547, 1309, 1213 and 1018 cm -1 in the FT-IR spectrum of the residue at 210 °C.New bands at 3277, 1671, 1628, 1541, 1379, 1112 and 1029 cm -1 prove the existence of [-CO-NH-] polymer and Zn(RCO 2 ) 2 in the solid residue. 11The nature of the gases formed was not established, however, the studies showed clearly that dehydration and decomposition of the chelating rings occur in one weight loss process, which is a peculiar decomposition mechanism compared with other lattice water containing complexes. 10he further decomposition occurs in the range of 263.5-278.6 °C, and two intense and separate exothermic peaks can be seen on the DSC curve.The peak temperature of the first exothermic process is 265.3 °C with a change of enthalpy of 82.07 kJ mol -1 , and that for the second one is 273.4 °C with 101.31 kJ mol -1 .These two exothermic processes are accompanied by a weight loss of 37.32% on the TG curve.The [-CO-NH-] polymer and Zn(RCO 2 ) 2 decomposed completely in the process.The weight of the final residue is 16.59% of the initial weight, coinciding with the calculating value of ZnO, 16.75%.The bands at 1375, 1093 and 626 cm -1 in the FT-IR spectrum of the final residue at 300 °C also prove the final residue is ZnO. 18ased on the experimental and calculated results, the thermal decomposition mechanism of [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O is proposed as follows: [Zn(MCZ) 3 ](NO 3 ) 2 •H 2 O → [-CO-NH-] polymer + Zn(RCO 2 ) 2 + gas products → ZnO + gas products

Materials
The zinc(II) nitrate of analytical grade was commercially available and used as received.Methyl carbazate (MCZ) was prepared according to literature methods.

Physical techniques
C, H, N were determined using a Flash EA 1112 fullautomatic microanalyser.Infrared spectra were recorded on a Bruker Equinox 55 infrared spectrometer as KBr microdiscs in the range of 4000-500 cm -1 with the resolution of 4 cm -1 .Differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) were carried out on Pyris-1 differential scanning calorimeter and thermogravimeter, respectively, using dry nitrogen as atmosphere with flowing speed of 20 mL min -1 .The solid sample was sealed in aluminum pans for DSC and held in platinum pans for TG with heat rate of 10 °C min -1 .Indium and zinc were used for temperature and heat flow for the DSC instrument.For the TG instrument, Nickel and Iron were used for temperature calibration, and a 100 mg poise was used for weight calibration.

X-ray data collection and structure refinement
X-ray diffraction data were collected with graphite monochromated Kα radiation (λ = 0.71073 Å) on a Siemens P4 full automatic four-circle diffractometer using ω scans at 295(2) K. Details of data collection, refinement and crystal data are summarized in Table 1.Lorentzpolarisation and empirical absorption corrections were applied to the data of both crystal data and structure refinement parameters.The structure was solved by the direct methods routine of SHELXS-97 in the space group P2 1 /n, and subsequent difference-Fourier map revealed the positions of the remaining non-hydrogen atoms. 19All hydrogen atoms were located at their geometrical idealized positions and their positions were refined with bond distances restraints.All esds (except the esd in the dihedral angle between two l.s.planes) are estimated using the full covariance matrix.The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry.An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s.planes.All nonhydrogen atoms were refined anisotropically using a fullmatrix least-squares procedure on F 2 using SHELXL 97. 20inal R 1 and wR 2 are and 0.1014 with goodness-offit on F of 1.058.The maximum and minimum residual peaks in the final difference-Fourier map are 0.492 and -0.441 e•Å -3 .The selected bond distances and angles are listed in Table 2.