Physico-Chemical Studies of Tris ( adamantan-1-aminium ) Hexachlorostannate ( IV ) Chloride Monohydrate

Organic–inorganic hybrid materials with the formula (R-NH3)2SnX4, where X = F, Cl, Br or I have been investigated structurally because of their interesting magnetic and electronic properties [1-4]. In contrast, the structural characteristics of compounds with the formula (R-NH3)3SnX6 have not been studied extensively. In the course of investigating compounds with this formula, the title compound, displaying a Abstract


Introduction
Organic-inorganic hybrid materials with the formula (R-NH3)2SnX4, where X = F, Cl, Br or I have been investigated structurally because of their interesting magnetic and electronic properties [1][2][3][4].In contrast, the structural characteristics of compounds with the formula (R-NH3)3SnX6 have not been studied extensively.In the course of investigating compounds with this formula, the title compound, displaying a

Abstract
The structural characteristics of organic ammonium salts of the hexahalogenostannates (IV) with a general formula (R-NH3) 3SnX6 have not yet been studied extensively.In the course of investigating these types of materials, the title compound, a double salt of adamantan-1aminium chloride and hexahalogenostannate (IV), with the formula (C10H18N)3[SnCl6]Cl•H2O, was crystallized.Its asymmetric unit contains three independent cations of protonated adamantan-1-amine, one chloride anion, one Hexachlorostannate (IV) ion and a hydrate water molecule.The atomic arrangement can be described as inorganic SnCl6 2-units isolated from each other by the organic cations, the chloride anions and the cocrystallized water molecules.The compound exhibits bifurcated and simple hydrogenbonding interactions between the ammonium groups, the water molecules and the chlorine atoms, with little variation in the hydrogen-bonding interactions.The 119 Sn, 13 C and 15 N CP-MAS NMR spectra are in agreement with the X-ray structure.

Investigation techniques
The characterization of this coordination compound was carried out using X-ray diffraction, solid state NMR and IR spectroscopy.

X-ray single crystal structural analysis
The intensity data were measured at 100 K on a Bruker AXS SMART APEX CCD diffractometer using graphitemonochromated MoKα radiation with the omega scan technique.The absorption corrections were carried out using the Apex2 software [5].The structure was solved by direct methods using SHELXS and refined by full matrix least squares against F 2 with all reflections using SHELXL [6] and SHELXLE [7].The H-atoms of the water molecules were located from different Fourier maps, while the H-atoms of the ammonium groups were placed in geometrically calculated positions.The drawings were made with Diamond [8].Crystal data and experimental parameters used for the intensity data collection are summarized in Table 1.The low fraction of observed reflexions is due to the lowquality crystal.

Physical measurements
The NMR spectra were recorded on a solidstate high-resolution Bruker DSX-300 spectrometer operating at 75.49 MHz for 13 C and 30.30MHz for 15 N.The 119 Sn NMR spectrum was recorded on a Bruker DRX500 AVANCE spectrometer operating at 186.5 MHz with a classical 4 mm probehead allowing spinning rates up to 10 kHz. 13 C, 15 N and 119 Sn NMR chemical shifts are given relative to tetramethylsilane, nitromethane and Me4Sn, respectively (precision 0. recorded by the use of cross (CP) from protons (contact time 5 ms) and MAS.The delay between two successive scans was optimized to ensure a full relaxation of the proton.The IR spectrum was recorded at r. t with a "Perkin FTIR" spectrophotometer 1000.

X-ray diffraction study
The asymmetric unit of the title compound (Fig. 1) contains six independent adamantan-1-aminium cations, two chloride anions, two Hexachlorostannate (IV) ions and two water molecules.The Sn atom is six-fold coordinated by chloride ions, forming an octahedral arrangement.recorded by the use of cross-polarization (CP) from protons (contact time 5 ms) and MAS.The delay between two successive scans was optimized to ensure a full relaxation of the proton.The IR spectrum was recorded at r. t with a "Perkin-Elmer FTIR" spectrophotometer 1000.
The asymmetric unit of the title compound (Fig. 1) contains six independent aminium cations, two chloride anions, two Hexachlorostannate (IV) ions and two water molecules.The Sn fold coordinated by chloride ions, forming an octahedral arrangement.Fig. 2 shows that the atomic arrangement of the title hybrid compound can be described as inorganic SnCl from each other by the organic cations, the chloride anions and the co water molecules.Multiple hydrogen bonds connect the different entities of the compound to form an infinite three dimensional network.Fig. 2 shows that the structure cohesion is ensured by four types of hydrogen bonds, hexachlorotin anion, cation cation-water and water anion.Atoms H3A3, H1B3 H3A1 and H3B2 of the ammonium groups form bifurcated hydrogen bonds to the acceptor atoms  2 shows that the atomic arrangement of the title hybrid compound can be described as inorganic SnCl6 2-units isolated h other by the organic cations, the chloride anions and the co-crystallized water molecules.Multiple hydrogen bonds connect the different entities of the compound to form an infinite threedimensional network.Fig. 2 2).The H…Cl distances of these hydrogen bonds, varying between 2.57 and 2.92 Å are longer than the ones of simple hydrogen bonds, ranging from 2.27 and 2.56 Å.
Previous studies have shown that, in the [SnCl6] 2-anion, the Sn-Cl bond lengths and Cl-Sn-Cl bond angles are not equal, but vary with the environment around the Cl atom [9].In this complex, the Sn-Cl bond lengths vary between 2.3791( 14) and 2.4694( 14) Å and the Cl-Sn-Cl bond angles range from 88.08(5) to 93.65(5)°, with an average value of 89.97° (Table 3).Owing to these differences in the geometric parameters, the [SnCl6] 2-anion has a slightly distorted octahedral stereochemistry [10].
The examination of the geometric features of the organic entity shows that the organic molecule exhibits a regular spatial configuration with C-C and C-N distances and C-C-C and C-C-N angles quite similar to those found in other adamantan-1aminium compounds [11].

IR spectroscopy
The IR spectrum of crystalline (C10H18N)3[SnCl6]Cl•H2O is shown in Fig. 6.The vibrational modes of this compound were elicited by the comparison of the IR spectra of similar complexes [15,16].The broad bands between 3600 and 2500 cm -1 correspond to the stretching vibrations of (C-H), (N-H) and (O-H) groups [17].
The bands in the 1650-1100 cm -1 region can be attributed to the bending vibrations of the (N-H) and (O-H) groups and to the stretching and bonding modes (C-C), (C-N) and (C-H) [18,19].The bands between 1000 and 600 cm -1 are assigned to the out of plane bending modes γ(C-H), γ(C-C) and γ(N-H) [20].

Figure 1 :Figure 2 :
Figure 1: Asymmetric unit of scheme and thermal ellipsoids at 50 % probability.The dotted lines indicate hydrogen b

Fig. 5
Fig.5shows the15 N CP-MAS NMR spectrum of the title compound.This spectrum exhibits two resonance peaks at -338.6 and -334.6 ppm, with 1: 2 relative intensities.The X-ray structure shows that there are three inequivalent nitrogen