Synthesis, crystal structure, physico-chemical characterization of a new hybrid material, (2-hydroxyethyl)piperazine-1,4-diium hexachlorostannate(IV) monohydrate

Accepted Manuscript Synthesis, crystal structure, physico-chemical characterization of a new hybrid material, (2-hydroxyethyl)piperazine-1,4-diium hexachlorostannate(IV) monohydrate S. Belhaj Salah, Pedro Sidónio Pereira da Silva, F. Lefebvre, C. Ben Nasr, S. Ammar, M.L. Mrad PII:

S0022-2860(17)30232-6

DOI:

10.1016/j.molstruc.2017.02.073

Reference:

MOLSTR 23467

To appear in:

Journal of Molecular Structure

Received Date: 23 November 2016 Revised Date:

16 February 2017

Accepted Date: 20 February 2017

Please cite this article as: S.B. Salah, P.S.P. da Silva, F. Lefebvre, C. Ben Nasr, S. Ammar, M.L. Mrad, Synthesis, crystal structure, physico-chemical characterization of a new hybrid material, (2hydroxyethyl)piperazine-1,4-diium hexachlorostannate(IV) monohydrate, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.02.073. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Synthesis, crystal structure, physico-chemical characterization of a new hybrid material, (2hydroxyethyl)piperazine-1,4-diium hexachlorostannate(IV) monohydrate

S. Belhaj Salaha, Pedro Sidónio Pereira da Silvab, F. Lefebvrec, C. Ben Nasra, S. Ammara, M. L. Mrada* a

Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de

b

CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal.

Laboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie

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c

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Bizerte, 7021 Jarzouna, Tunisie

Physique Electronique, 69626Villeurbanne Cedex, France *

Corresponding author: E-mail address: [email protected]

Abstract

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The new organic-inorganic compound [C6H16N2O](SnCl6).H2O was synthesized and single crystals were grown from an aqueous solution through these slow evaporation technique. The atomic arrangement can be described by organic-inorganic layers parallel to the (a, c) plane.

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These layers are connected via hydrogen bonds (O-H…O and C-H…Cl) to build a three dimensional arrangement. The

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C and15N CP-MAS NMR spectra are in agreement with the

X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy

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and Raman scattering. DFT calculations allowed the attribution of the IR bands. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions. X-ray photoelectron spectroscopy analysis (XPS) is a technique for analyzing the surface chemistry of a compound. It was employed to measure the elemental composition and electronic state of the elements within a material. The DSC profile shows endothermic peaks centered at approximately 343, 370 and 552 K. Keywords: Organic-inorganic hybrid; X-ray diffraction; DFT calculations; spectroscopy; Hirshfeld surface, XPS. 1. Introduction 1

ACCEPTED MANUSCRIPT Hybrid compounds based on elements of group 14 (Sn, Pb) with the external configuration ns2(n-1)d10np2 have been extensively investigated in recent years owing to their interesting physical properties [1-4]. These materials have demonstrated potential applications in the development of low cost electronic devices [5-7]. In this complex, both strong and weak intermolecular interactions are present which provide stability and H-bonded supramolecular

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network in the solid state. This behavior can be investigated through the Hirshfeld surface analysis [8] that allows the visualization of different types of interactions present within a crystal structure. As an extension of previous studies on hybrid organic halogenostannate materials [9-12], we have synthesized single crystals of bis-(N-(2hydroxyethyl)piperazine-

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1,4-diium hexachlorostannate) monohydrate, [C6H16N2O] (SnCl6). H2O.

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2. Experimental 2.1.Synthesis of [C6H16N2O] (SnCl6).H2O:

Stannate (IV) tetrachloride (1 mmol, 0.35g) and N-(2-hydroxyethyl)piperazine (4 mmol, 0.49 mL) were dissolved in a concentrated HCl (6M) solution in the presence of ethanol (10 mL) in a stoichiometric ratio. The resulting aqueous solution was then kept at room temperature. After several days colorless parallelepipedic [C6H16N2O] (SnCl6).H2O diffraction analysis.

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crystals were obtained by slow evaporation (yield: 70%) with good quality for single X-ray

H2O

→

[C6H16N2O] (SnCl6). H2O

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C6H14N2O + SnCl4 +2HCl 2.2. Characterization:

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Single crystal X-ray structural analysis A single crystal was carefully selected under a polarizing microscope in order to

perform its structural analysis by X-ray diffraction. Diffraction data were collected on a Bruker APEX2 diffractometer equipped with a CCD area-detector using graphitemonochromatized MoKα radiation (λ=0.71073Ǻ). Intensities were corrected for Lorentz polarization and absorption effects [13]. The structure was solved by direct methods using SHELXS-97 [14] and refined against F2 by full-matrix least-squares methods with anisotropic displacement parameters for all non-hydrogen atoms. All calculations were performed using SHELXS-97 and SHELXL-97 implemented in the WINGX system of programs [15]. The drawings were made with the Diamond [16] and Mercury programs [17].The refinement was 2

ACCEPTED MANUSCRIPT done by full-matrix least squares methods (SHELXL-97 program) and converged to an acceptable final agreement factor. The pertinent experimental details of the structure determination for the new compound are presented in Table 1. All hydrogen atoms were placed at calculated positions. The visualization and exploration of the intermolecular close contacts of the structure was

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achieved by calculating the Hirshfeld surface with the Crystal Explorer software [18]. All the bond lengths to hydrogen were automatically modeled to typical standard neutron values (CH = 1.083 Å, OH = 0,983 Å and N-H = 1.009 Å). In this study, the molecular Hirshfeld surfaces were generated using a standard (high) surface resolution with the 3D dnorm surfaces were displayed by using the standard range 0.5–2.5 Å.

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NMR, IR and Raman

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mapped over a fixed color scale from 0.42 (red) to 1.6 Å (blue). The 2-D finger print plots

The NMR spectra were recorded on a solid-state high-resolution Bruker DSX-500 spectrometer operating at 125.78 MHz for 13C and 50.68 MHz for 15N with a classical 4 mm probe head allowing spinning rates of up to 10 kHz.13C and

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N NMR chemical shifts are

respectively given relative to tetramethylsilane and neat nitromethane (precision 0.5 ppm). The spectra were recorded using cross polarization (CP) from protons (contact time 2 ms) and

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magic angle spinning (MAS). Before recording the spectrum checks were performed to guarantee a sufficient delay between the scans allowing a full relaxation of the protons. The IR spectra were recorded in the 4000-400 cm-1 range with a 1000 Perkin-Elmer FTIR

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spectrometer using samples dispersed in spectroscopically pure KBr pressed into a pellet. The infrared spectrum was calculated with the Gaussian 09 software. All calculations were made

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at the B3LYP/6-31 1++G** level.

The Raman spectrum was recorded between 500 and 100 cm-1 at room temperature

with a LABRAMHR 800 triple monochromatic instrument using a 514.5 nm line spectraphysics argon ion laser.

Calorimetric measurements The differential scanning calorimetric (DSC) measurements were made on a SETARAM DSC131 ks instrument. A powder sample (11.7 mg) was heated from 273 K to 573 K with a ramp rate of 5 K/min under a vacuum atmosphere controlled by Mass Flow Controllers. 3

ACCEPTED MANUSCRIPT XPS measurement XPS spectra were recorded using a K-Alpha (Thermo) apparatus fitted with a monochromatic Al-Kα X-ray source (spot size: 400 µm). The pass energy was set to 200 and 50 eV for the survey and the narrow regions, respectively. Electron and argon flood guns were used to compensate for the static charge build up on the powders. The composition was

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determined using the manufacturer’s sensitivity factors. 3. Results and discussion 3.1. Description of the structure: asymmetric

unit

of

[C6H16N2O](SnCl6).H2O

contains

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The

two

N-(2-

2-

hydroxylethyl)piperazine-1,4-diium dications, two (SnCl6) anions and two water molecules

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(Fig. 1).

The atomic arrangement of [C6H16N2O](SnCl6).H2O can be described by organicinorganic layers extending parallel to the (a, c) plane (Fig. 2) at y=0 and y=1/2 (Fig.S1). The cohesion between two consecutive layers is ensured by two types of hydrogen bonds O−H···O(W) and C−H···Cl (Fig. 2). The O−H···O(W) interactions are made by the polar heads

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(OH) of the hydroxyl group and by the oxygen atoms of the water molecules. The C−H···Cl hydrogen bonds are formed between the hydrogen atoms of the organic entities and the chlorine atoms of tin(IV) hexachloride anions. The strength of a hydrogen bond may be interpreted according to the d(D···A) distance [19]. All hydrogen bonds are considered to be

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strong with the exception of the hydrogen bonds of types C-H ... Cl which are considered to be low 3.494 Ǻ < d(A··D) < 3.952 Ǻ (Table 2). In these layers, multiple hydrogen bonds connect the different entities of the structure along the a and b crystallographic axes (Fig. S1).

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So, each (SnCl6)2- anion is connected to its adjacent N-(2-hydroxylethyl)piperazine-1,4-diium cation through the NH2, OH and CH2 groups. Moreover, the water molecules are also involved in the connection between the organic and inorganic molecules via strong hydrogen bonds involving the NH2 polar groups of the organic entities and the chlorine atoms. The two crystallographically independent Sn(IV) ions are hexa-coordinated by six chlorine atoms, forming a slightly distorted octahedron. The Sn-Cl bond lengths vary between 2.3986 (5) and 2.4499 (5) Ǻ for (Sn(1)Cl6)2- and from 2.4153 (6) to 2.4287 (6) Ǻ for (Sn(2)Cl6)2-. The small angles range between 86.540 (18) and 94.09 (2)° for (Sn(1)Cl6)2-and from 87.987 (19) to 91.49 (3)° for (Sn(2)Cl6)2-(Table. 2).The average values of the distortion parameters of the two crystallographically independent anions, (Sn(1)Cl6)2- and (Sn(2)Cl6)2-, are [ID1(Cl-Cl) = 4

ACCEPTED MANUSCRIPT 0.010, ID1(Sn(1)-Cl) = 0.006 and ID1(Cl-Sn(1)-Cl) = 0.015] and [ID2(Cl-Cl) = 0.007, ID2(Sn(2)-Cl) = 0.001 and ID2(Cl-Sn(2)-Cl) = 0.014], respectively. The low values of the distortion indices indicate that the coordination geometry of the metal is a slightly distorted octahedron [20]. The atomic arrangement of [C6H16N2O](SnCl6).H2O contains two independent

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diprotonated [C6H16N2O] 2+cations in order to balance the negative charges of the framework. Their geometrical characteristics are reported in Table 3, N-C, C-C, C-O distances and N-CC, C-N-C, C-C-O angles are in full agreement with those of other compounds containing the same organic cation [21]. Piperazine can have different conformations which are chair, half-

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chair, boat, twist boat and envelope forms [22]. The conformation of the two different piperazine six-membered rings can be described in terms of Cremer and Pople puckering coordinates [23], i.e. evaluating the Q parameters (total puckering amplitude), q2, q3, θ and φ.

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Their calculated values for the N1-C2-C1-N2-C4-C3 ring (I) are Q=0.5696Å, q2=0.0267Å, q3=0.569Å, θ =2.69° and φ =-87.75° and for the N3-C8-C7-N4-C10-C9 ring (II) Q=0.5572Å, q2=0.0215Å, q3=-0.5568Å, θ =177.79° and φ =-78.05° corresponding to the most stable chair conformation (Fig. S2).

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3. 1 .1 Hirshfeld surface

The visualization and exploration of the intermolecular close contacts of a structure is invaluable and can be achieved using the Hirschfield surface. Analysis of intermolecular interactions using Hirschfield surface-based tools represents a major advance in enabling

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supramolecular chemists and crystal engineers to gain insight into crystal packing behavior. The normalized contact distances (dnorm) reveal the close contacts of hydrogen bond donors

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and acceptors, but other close contacts are also evident. In dnorm surfaces, the large circular depressions are the indicators of hydrogen bonding contacts, whereas other visible spots are due to H…H contacts, based on both de and di (where de is the distance from a point on the surface to the nearest nucleus outside the surface, and di is the distance from a point on the surface to the nearest nucleus inside the surface). This enables the identification of the regions of particular importance for intermolecular interactions. The combination of de and di in the form of a two-dimensional (2D) fingerprint plot provides a summary of intermolecular contacts in the crystal (Fig. 3). Fig. 4 shows surfaces that have been mapped over a dnorm range of (-0.542 to 1.403 Ǻ), de (0.5 to 2.5 Ǻ) and di (0.5 to 2.5 Ǻ). The contacts were analyzed with the MoProf Viewer program [24] in terms of chemical species interacting.

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ACCEPTED MANUSCRIPT Overall, Cl…H and H…H intermolecular interactions are the most abundant in the crystal packing (58.5% and 18.6% respectively). There are twenty three H…Cl hydrogen bonds in the crystal structure (Table 2, Fig.5.a). The H…H contacts are the second most frequent interactions due to the abundance of hydrogen on the molecular surface (Fig.5.b). It is evident that van der Waals forces exert an important influence on the stabilization of the

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packing in the crystal structure. Other intermolecular interactions such as O-H (11.2%) (Fig.5.c), Cl-Cl (2.8%) (Fig.5.d), N-H (1.7%) and Sn-Cl (0.9%) (Fig.5.e) (Fig.5.f) contribute less to the Hirshfeld surfaces.

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3. 1. 2Molecular electrostatic potential

The electrostatic potential was determined with the Avogadro 1.0.0 software package [25]. Figure S3 shows that a positive electrostatic potential is localized over the organic

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cation, while the (SnCl6)2- part is more electronegative. According to these results, we can say that there is a global electrostatic attraction between the (SnCl6)2- anions and the organic cations which adds up to the favorable H…Cl hydrogen bonding. 3.2. NMR spectroscopy: 13

C CP-MAS-NMR spectrum of crystalline [C6H16N2O](SnCl6).H2O shown in

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The

Figure S4, exhibits at least eleven resonances. This result proves the presence of two independent

crystallographic

N-(2-hydroxylethyl)piperazine-1,4-diiumcations

in

the

The

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asymmetric unit, in agreement with the X-ray diffraction data. N CP–MAS NMR spectrum of the title compound (Fig. S5) is also in good

agreement with the single crystal X-ray diffraction data. Indeed, it exhibits four well-defined

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resonances at -362.8, -360.8, -359.1 and -358 ppm corresponding to the four crystallographically independent nitrogen atoms, confirming the presence of two organic entities in the asymmetric unit as revealed by the structural study. 3.3. Infrared Spectroscopy: FT-IR spectroscopy was used to verify the functional groups present in the crystal, and to investigate their vibrational behavior in the solid state. The IR spectrum of the title crystalline complex is shown in Fig.6. The assignment of the different bands can be made by comparing them to those of similar materials and to the literature [22, 26]. The highfrequency domain is assigned to the N–H, O–H and C–H stretching modes, combination

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ACCEPTED MANUSCRIPT bands and harmonics, while the lower one corresponds to the bending and to the external modes. However, the strong peaks located at 3521 and 3448 cm-1 are attributed to the stretching modes of NH2 and OH of the crystallization water molecule. The 3125–2745 cm-1 region is characteristic of stretching vibrations of NH+, C–H and CH2. The weak peak at 1620 cm-1 and the strong one at 1589 cm-1 are assigned to the OH bending modes of the hydroxyl

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group and water molecule, respectively. The peaks appearing in the 1457–1341 cm-1 range can be assigned to the N–H bending mode of NH2+ and NH+ groups. The bands observed at 1257, 1063 and 1000 cm-1 correspond to the stretching vibrations of (C–N), (C–C), (C–O) and δ(C–H), respectively. IR bands observed in the 910–580 cm-1 field are assigned to the rocking

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deformations ρ(NH2) and to the bending modes δ(C–C), δ(C–N) and δ(C–C–N).

DFT calculations showed that the inorganic entities lead to vibrations below 500 cm-1

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which were not observed experimentally under our conditions. Hence we only focused on the vibrations of N-(2-hydroxyethyl)piperazine-1,4-diium. The calculation of the frequencies was made from the geometry obtained after optimization of the proton positions. The resulting IR spectrum between 500 and 4000 cm-1 is shown in Fig. S6. A close agreement between the experimental and theoretical wave numbers is mostly achieved in the fingerprint region as shown in Fig.7. Thus, the precision is sufficient to assign the experimental frequencies and to

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confirm the attributions proposed above.

3.4. Raman spectroscopy of [C6H16N2O](SnCl6).H2O: The Raman spectrum of the title compound observed below 500 cm-1 is illustrated in

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Fig. 8. An attempt to assign the Raman bands appearing in this range was done by comparison with previous research works reporting similar compounds containing the isolated SnCl6

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octahedron [27-32]. In fact, the strong band observed in the Raman spectrum at 314 cm-1 is assigned to the (Sn–Cl) asymmetric stretching (ν1(Sn–Cl)). The symmetric stretching (ν2(Sn– Cl)) vibration appears as a shoulder band at 251 cm-1.The frequency of the bending vibration in the ν5(Cl-Sn-Cl) plane is located at 231 cm-1. The weak band located at 155 cm-1 in the raman spectrum is attributed to the bending vibration out of the ν6(Cl-Sn-Cl) plane. 3. 5 Quantum mechanical study: Quantum chemical calculation was performed from the crystal data with DFT method at the B3LYP/6-31+G* level except for tin for which the LANL2DZ pseudopotential was used. The highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital 7

ACCEPTED MANUSCRIPT (LUMO) of the molecule are displayed in Fig 9. Clearly the HOMOs are localized on the inorganic part of the crystal, while the LUMOs are located on the organic cation. The gap value between the LUMO and the HOMO is 0.82 eV, which is relatively small, agreeing with that reported for an other similar hybrid compound [33].

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3.6. XPS analysis: [C6H16N2O](SnCl6).H2O was dried and characterized by XPS. The surface chemical composition is reported in Table S1. The main peaks are O1s, Sn3d, N1s, C1s and Cl2p centered at 530, 486.7, 400.3, 285.0, and 199.8 eV respectively (Fig. 10). In addition, the

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survey spectrum for this crystal exhibits an N1s peak (400eV) assigned to the (C6H16N2O) cation. Interestingly, the high resolution N1s spectrum of the title compound (Fig. 11.a) is fitted with two components centered at 399.6 eV and 401.8 eV. Whilst the latter is assigned to

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the quaternized form of the ligand H2N+(CH2)2, the former could be due to a free amine of the HN(CH2)2 type, resulting from a deprotonation of the quaternized ion. Indeed, an energy of 399.6 eV is consistent with nitrogen in amines [34].

The oxidation states of Sn were further confirmed by examination of the binding energy position of the Sn3 doublet. The Sn3d XP spectrum in Figure 11.b present two peaks

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at 487 eV (Sn3d5/2) and 495.4 eV (Sn3d3/2); the position of the main Sn3d5/2 is in line with Sn in the oxidation state IV [35, 36]. All these results confirm the valence sum calculations of this compound.

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3.7. DSC analysis: A differential

scanning

calorimetric

study was

performed

by heating a

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[C6H16N2O](SnCl6).H2O sample from 300 to 573 K. The DSC profile reported in Fig. 12 illustrates the existence of three distinct thermal anomalies at T1 = 343, T2=370 and T3=552 K. The first anomaly located at T1= 343 K may be due to a phase transition, the second one observed at T2= 370 K can be assigned to departure of the water molecules. To explain that, the sample powder is heated to 423 K and analyzed by infrared spectroscopy. The IR spectrum shows the disappearance of the bands allocated to stretching and vibrations of the water molecules (Fig.6). After dehydration, the anhydrous compound decomposes at 552 K and followed by degradation of the organic part. The enthalpy values for the last two anomalies determined from the peak area are respectively ∆H2= 63.703 J.g-1 for T2= 370 K and ∆H3= 253.721 J.g-1 for T3= 552 K.

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ACCEPTED MANUSCRIPT Supplementary data Supplementary crystallographic data for this article in CIF format are available at the Electronic Supplementary Publication from Cambridge Crystallographic Data Centre (CCDC1434706).

This

data

can

be

obtained

free

of

charge

via

http://www.ccdc.cam.ac.uk/conts/retrieving.html, from the Cambridge Crystallographic Data

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Centre, 12 Union Rood, Cambridge CB2 1EZ, UK (Fax: (international): +44 1223/336 033; e-

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mail: deposit@ ccdc.cam.ac.uk).

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Acknowledgements: We would like to acknowledge the support provided by the Secretary of State for Scientific

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Research and Technology of Tunisia.

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ACCEPTED MANUSCRIPT Figure captions

Fig. 1

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View of the asymmetric unit in the crystal structure of the title compound showing the atomnumbering scheme and displacement ellipsoids drawn at the 50% probability level. Fig. 2

Hydrogen bonds are denoted by dotted lines.

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Fig. 3

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Projection along the b-axis showing the organic-inorganic layers in the title compound crystal.

Hirshfeld surfaces mapped with dnorm, di and de for [C6H16N2O](SnCl6).H2O. Fig. 4

Hirshfeld surface (a) and 2D fingerprint map (b) 98.7 % for [C6H16N2O](SnCl6).H2O

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Fig. 5

Fingerprint plots of major contacts in [C6H16N2O](SnCl6).H2O

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Fig. 6.

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Infrared absorption spectrum of [C6H16N2O](SnCl6).H2O. Fig. 7

Comparison between experimental and calculated IR frequencies of [C6H16N2O](SnCl6).H2O. Fig. 8

Raman spectrum of the title compound in the [500-100] cm-1range. Fig. 9 Frontier molecular orbitals (HOMO and LUMO) of [C6H16N2O](SnCl6).H2O. Fig. 10

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ACCEPTED MANUSCRIPT XPS survey scans of [C6H16N2O](SnCl6).H2O. Fig. 11. a N1s narrow region of [C6H16N2O](SnCl6).H2O.

High-resolution Sn3d of [C6H16N2O](SnCl6).H2O. Fig. 12

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TE D

M AN U

SC

DSC thermogram of [C6H16N2O](SnCl6).H2O.

RI PT

Fig. 11.b

14

M AN U

SC

RI PT

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AC C

EP

TE D

Fig. 1

Fig. 2

15

AC C

EP

TE D

M AN U

Fig.3

SC

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Fig.4

16

(b) H…H: 18.6%

(c) O…H/H…O:11.2%

M AN U

(a) H…Cl/Cl…H:58.5%

SC

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ACCEPTED MANUSCRIPT

EP

TE D

0

AC C

(d) Cl…Cl:2.8%

(e) N…H:1.1%

(d) Sn…Cl:0.9%

Fig. 5

17

TE D

M AN U

SC

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AC C

EP

Fig. 6

18

M AN U

SC

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AC C

EP

TE D

Fig. 7

Fig. 8

19

AC C

EP

TE D

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SC

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Fig. 9

20

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SC

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Fig.10

TE D

EP

8k

AC C

I(cps)

(d)

N-N+

N1s

4k

394

396

398

400

402

404

406

408

Binding energy (eV)

Fig. 11.a

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ACCEPTED MANUSCRIPT 50k

(h)

SnSn3d 3d5/2 40k

Sn 3d3/2

RI PT

I(cps)

30k

20k

10k

482

484

486

488

490

492

494

496

498

500

M AN U

Binding energy (eV)

SC

480

AC C

EP

TE D

Fig. 11.b

Fig. 12

22

ACCEPTED MANUSCRIPT Table.1. Crystal data and structure refinement for [C6H16N2O](SnCl6).H2O crystal.

[C6H16N2O](SnCl6).H2O

Color/shape

colorless

crystal system

monoclinic

Space group

P21/c

Température (°C)

25

a (Å)

10.3644(3)

b (Å)

11.7188(3)

c (Å)

27.4621(8)

β (deg)

99.9399(13)

Formula units/unit cell Dx (Mg m−3) Diffractomètre/scan Radiation, graphite

SC

M AN U

Cell volume (Å3)

RI PT

Compound

3285.43(16) 4

1.947

Buker APEX2 CCD area-detector Mo-Kα (λ=0.71073 Å)

TE D

monochromator

0.55×0.53×0.46 2.52

Unique reflections

3093

θ range (deg)

2.0 ⩽θ⩽ 28.0

Reflections with I>2σ(I) a

7260

AC C

µcalc (mm−1)

EP

Max, Crystal dimensions (mm)

Range of h, k, l

[-12,13]; [-14,15];[-36,35]

F(000)

1888

Weight

1/[σ2(Fo2)+(0.0213P)2+0.168P], where P=max[(Fo2,o)+2Fc2]/3

R=∑||Fo−Fc||/∑|Fo|

0.022

Rw

0.046

Goodness-of-fit on F2

1.19

Computer programs

SHELXS [15], SHELXL [14]

23

ACCEPTED MANUSCRIPT

Table.2.Main interatomic distances (Å) and bond angles (°) of atoms involved in hydrogen

d(D-H)

d(H…A)

d (D...A)

N2-H2B…Clii

0.89

2.42

3.2319 (19)

151

C8-H8B…Cl1

0.97

2.99

3.952 (2)

173

C10-H10A…Cl2vi

0.97

2.81

3.512 (2)

130

C3-H3B…Cl3

0.97

2.79

3.494 (2)

130

N4-H4D…Cl3iv

0.89

2.67

3.2460 (17)

123

C7-H7B…Cl3

0.97

2.81

3.502 (2)

129

N1-H1…Cl4

0.98

2.45

3.3706 (17)

156

C1-H1B…Cl4

0.97

2.83

3.620 (2)

139

C4-H4A…Cl4

0.97

2.92

3.706 (2)

139

C2-H2D…Cl5i

0.97

2.82

3.553 (19)

134

M AN U

TE D

DHA

RI PT

D-H…. A

SC

bonds (e.s.d. are given in parentheses).

O1W-H1WB…Cl6

0.74 (3)

2.55 (3)

3.2903 (19)

177 (4)

O2W-H2WA…Cl6

0.78 (3)

2.64 (3)

3.334 (2)

148 (3)

0.97

2.72

3.663 (2)

166

EP

C6-H6A…Cl7iii

0.97

2.77

3.532 (2)

136

C8-H8A…Cl8iv

0.97

2.98

3.864 (2)

153

C11-H11A…Cl8vii

0.97

2.79

3.673 (2)

152

O1W-H1WA…Cl8

0.70 (3)

2.84 (3)

3.3581 (19)

132 (3)

N3-H3…Cl9v

0.98

2.44

3.3667 (18)

157

C10-H10B…Cl9v

0.97

2.93

3.712 (2)

139

C8-H8A…Cl10iv

0.97

2.86

3.601 (2)

134

0.70 (3)

2.88 (3)

3.445 (2)

139 (3)

0.97

2.73

3.597 (2)

150

AC C

C10-H10B…Cl7v

O1W-H1W…Cl10 C4-H4B…Cl11iv

24

ACCEPTED MANUSCRIPT 0.97

2.97

3.655 (2)

129

C1-H1A…Cl12iii

0.97

2.97

3.694 (2)

132

O2-H2…Cl12vii

0.82

2.57

3.300 (2)

149

N2-H2A…O2Wi

0.89

2.02

2.828 (3)

151

O1-H1C…O1Wiii

0.82

2.12

2.926 (3)

169

N4-H4C…O1Wiv

0.89

2.02

2.895 (3)

167

N4-H4D…O1iv

0.89

2.19

2.919 (2)

139

C12-H12A…Cl8iv

0.97

2.95

3.838 (3)

154

C6-H6B…Cl9i

0.97

2.87

SC

RI PT

C12-H12B…Cl11vii

3.779 (2)

157

Symmetry codes: (i) x+1, y, z; (ii) –x+1, -y+1, -z; (iii) –x+1, y-1/2, -z+1/2; (iv) –x+1,

M AN U

y+1/2, -z+1/2; (v) –x, y+1/2, -z+1/2; (vi) x, y+1, z; (vii) x, -y+3/2, z-1/2.

Table 3: Selected bond distances [Å] and angles [°] in [C6H16N2O](SnCl6).H2O . Angles(°)

C1-C2 C3-C4 C5-C6

C1-N2-C4

111.34 (16)

1.505 (3)

N2-C1-C2

110.91 (17)

1.500 (3)

N1-C2-C1

112.11 (16)

1.500 (2)

N1-C3-C4

110.94 (17)

AC C

N1-C2

1.502 (3)

EP

[C6H16N2O] (I)

TE D

Distances (Å)

N1-C3

1.501 (3)

N1-C5-C6

111.80 (17)

N1-C5

1.501 (3)

C5-N1-C2

111.69 (16)

N2-C1

1.477 (3)

C5-N1-C3

111.12 (16)

N2-C1

1.486 (3)

C2-N1-C3

109.42 (15)

O1-C6

1.423 (3)

O1-C6-C5

108.27 (18)

N2-C4-C3

110.04 (18)

[C6H16N2O] (II)

25

ACCEPTED MANUSCRIPT 1.504 (3)

C12-N3-C8

112.31 (17)

C8-N3

1.500 (2)

C12-N3-C9

110.12 (16)

N3-C9

1.500 (2)

C8-N3-C9

109.89 (15)

C9-C10

1.501 (3)

C7-N4-C10

111.11 (15)

C10-N4

1.486 (3)

N4-C7-C8

111.55 (17)

N4-C7

1.484 (2)

N3-C8-C7

112.25 (16)

N3-C12

1.494 (3)

N3-C9-C10

111.62 (16)

C11-C12

1.500 (4)

N4-C10-C9

110.66 (17)

O2-C11

1.398 (4)

O2-C11-C12

SC 110.2 (2) 111.2 (2)

M AN U

N3-C12-C11

RI PT

C7-C8

Octahedron SnCl6(I)

2.3986 (5) Cl4—Sn1—Cl5

89.528 (19)

Sn1-Cl5

2.4085 (5) Cl4—Sn1—Cl2

90.97 (2)

2.4137 (5) Cl5—Sn1—Cl2

94.09(2)

2.4260 (5) Cl4—Sn1—Cl6

178.65 (2)

2.4417 (5) Cl5—Sn1—Cl6

90.55 (2)

2.4499 (5) Cl2—Sn1—Cl6

87.68 (2)

Cl4—Sn1—Cl1

91.24 (2)

Cl5—Sn1—Cl1

89.74 (2)

Cl2—Sn1—Cl1

175.59 (2)

Cl6—Sn1—Cl1

90.11 (2)

Cl4—Sn1—Cl3

91.211 (18)

Cl5—Sn1—Cl3

176.226 (19)

Cl6—Sn1—C3

88.802 (19)

Cl1—Sn1—Cl3

86.540 (18)

Sn1-Cl6 Sn1-Cl

AC C

Sn1-Cl3

EP

Sn1-Cl2

TE D

Sn1-Cl4

26

ACCEPTED MANUSCRIPT Cl2—Sn1—Cl3

89.595 (18)

Octahedron SnCl6(II) 2.4153 (6) Cl11—Sn2—Cl9

90.53

Sn2-Cl9

2.4162 (5) Cl11—Sn2—Cl8

90.69 (2)

Sn2-Cl8

2.4185 (5) Cl9—Sn2—Cl8

178.71 (2)

Sn2-Cl10

2.4232(6)

Sn2-Cl7

2.4255 (6)

Sn2-Cl12

2.4287 (6)

RI PT

Sn2-Cl11

91.49 (3)

Cl9—Sn2—Cl10

89.00 (2)

Cl8—Sn2—Cl10

90.55 (2)

Cl11—Sn2—Cl7

178.28 (2)

Cl8—Sn2—Cl7

SC

Cl11—Sn2—C10

Cl10—Sn2—Cl7

89.63 (3)

Cl11—Sn2—Cl12

89.93 (3)

Cl9—Sn2—Cl12

89.08 (2)

Cl8—Sn2—Cl12

91.342 (19)

Cl10—Sn2—Cl12

177.62 (2)

Cl7—Sn2—Cl12

89.00 (2)

90.802 (19) 87.987 (19)

AC C

EP

TE D

M AN U

Cl9—Sn2—Cl7

27

ACCEPTED MANUSCRIPT Highlights The atomic arrangement can be described by thick organic-inorganic layers. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. DFT calculations allowed the attribution of the IR bands. The 3D Hirshfield surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions.

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• • • •

AC C

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•