J Inorg Organomet Polym DOI 10.

1007/s10904-013-9831-z

COMMUNICATION

Crystal Structure and Physicochemical Properties of a New 4,40 -Diammoniumdiphenylether Triphosphate [C12H14N2O]2HP3O102H2O
Saloua Belghith Latifa Ben Hamada Amor Jouini

Received: 23 July 2012 / Accepted: 18 January 2013 Springer Science+Business Media New York 2013

Abstract Crystals of 4,40 -diammoniumdiphenylether triphosphate, [C12H14N2O]2HP3O102H2O (1), were prepared and grown at room temperature. Species 1 crystallizes in the triclinic system with centric space group P1. Its unit cell dimensions are a = 10.487(2), b = 10.766(2), c = , a = 98.53(1), b = 107.55(1), c = 103.31(2), 15.553(2) A 3 and Z = 2. The structure was deterwith V = 1588.8(5) A mined by X-ray data collection on a single-crystal and gives a clear description of hydrogen bonds interconnecting the triphosphoric groups so as to build [(HP3O10)2(H2O)]8innite inorganic chains that extend along the [110] direction. Organic cations, spreading along the [101] direction establish hydrogen bonding connections between the inorganic chains. The IR spectrum for the crystal conrms that most of the vibrational modes are comparable to similar triphosphates. The thermal properties reveal that the compound is stable to 90 C. Keywords Crystal structure Thermal behavior Infrared spectroscopy 4,40 -Diammoniumdiphenylether triphosphate

compounds with acidic triphosphoric anions; e.g. [HP3O104-], [H2P3O103-], [H3P3O102-] and [H4P3O10-], have been reported. Four examples include [C4N2H12]2 HP3O10H2O [1], [3,5-CH3O)2C6H3NH3]3H2P3O10 [2], [2,6-(C6H5)2C6H3NH3]2H3P3O10 [3],[4(CH3O)C6H4CH2 NH3]4 and H2P3O10H4P3O10 [4]. These acidic anions reveal the exibility of their aggregation, via H-bonds, with respect to the organic cations inducing various geometries: chains, ribbons, layers and three-dimensional networks. Many combinations between organic and inorganic components may be achieved to create materials in several areas; e.g. sorbents, catalysts and biotechnological materials [5, 6], because of the nature (molecular, ionic, hydrogen bonding) [7] of the interaction between them. As a contribution to the study of organic triphosphate compounds, we report here the preparation and structural investigation of a new 4,40 -diammoniumdiphenylether triphosphate dihydrate, [C12H14N2O]2HP3O102H2O (1). The thermal behavior (TGA/DTA, DSC) and IR spectrum of 1 were also examined.

2 Experimental 1 Introduction 2.1 Preparation of 1 Oligophosphates are the simplest term for condensed phosphates. Their anions correspond to the general formula [PnO3n?1](n?2)-. The triphosphates (n = 3) were mainly studied with mineral cations. However, several organic
S. Belghith (&) L. B. Hamada A. Jouini partement de chimie, Laboratoire de Chimie du Solide, De des Sciences de Monastir, Universite du centre, 5019 Faculte Monastir, Tunisia e-mail: saloua.belghith@yahoo.fr

Sodium tripolyphosphate Na5P3O10 [8] was prepared by heating a stoichiometric mixture of disodium phosphate, Na2HPO4 (0.2 mol, 6 g), and monosodium phosphate, NaH2PO4 (0.1 mol, 2.53 g) at 200 C under carefully controlled conditions (Eq. 1). 2Na2 HPO4 NaH2 PO4 ! Na5 P3 O10 2H2 O 1

After the preparation and identication of Na5P3O10, the salt was used as a starting material to synthesize the organic

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triphosphate. Single crystals of 1 were prepared in two steps; (i) An aqueous solution of triphosphoric acid is rst obtained by passing a solution of Na5P3O10 (4.13 g) through an ion exchange resin (Amberlite IR 120). (ii) 4,40 diaminodiphenylether (4 g) was added to the solution (Eq. 2). H5 P3 O10 2C12 H12 N2 O !C12 H14 N2 O2 HP3 O10 2H2 O 2 When most of the solvent (pH = 2) was evaporated, prismatic crystals appear. The crystals were pure and stable under normal conditions of temperature and humidity. 2.2 X-ray Structure Determination of 1 X-ray intensity data were collected on a Nonius-Mach 3 diffractometer using monochromatic MoKa radiation. The results are summarized in Table 1. The structure was solved by direct method using the SHELXS-97 programs, which allows the location of the P3O10 groups. The remaining non-hydrogen atoms were found by the successive difference Fourier maps using the SHELXL-97 programs [9]. In the nal least-squares renement of atomic parameters with isotropic thermal factors of
H2 O

H-atoms, R decreased to 3.61 % (Rw = 9.34 %) for 1. It should be noted that one H-atom of O(W2) was not included in the renement since its corresponding O-atom has a higher thermal coefcient. 2.3 Thermal Behavior of 1 A Setaram TGDTA92 and a DSC1 star system Mettler Toledo thermoanalyser were used to perform thermal treatment on 1. The TGDTA experiments were carried out with 16.6 mg samples in an open alumina crucible. The DSC analyses were made with 7.4 mg (on heating) and 7.5 mg (on heating and cooling) samples sealed in aluminum DSC crucibles. In both techniques, the samples were heated in air at a heating rate of 5 C min-1. 2.4 Infrared Spectroscopy The IR spectrum of 1 was recorded at room temperature with a Biored FTS 6000 FTIR spectrometer from 4,000 to 400 cm-1 with a resolution of *4 cm-1. Thin transparent pellets were made by compacting an intimate mixture obtained by shaking 2 mg of the samples in 100 mg of KBr.

3 Results and Discussion

Table 1 Crystallographic data and renement details for 1 Empirical formula Formula weight (g mol-1) Temperature (K) ) Wavelength (A Space group Unit cell dimension ) a (A ) b (A c (A) a () b ( ) c () 3) Cell volume (A Z Absorption coefcient (mm-1) Crystal size (mm3) h range for data collection () Reections (collected/unique) Parameters Goodness-of-t R indices [I [ 2r(I)] R indices (all data) -3) Dqmax/Dqmin (e.A [C12H14N2O]2HP3O102H2O 694.45 293 0.71073 P1(2) 10.487(2) 10.766(2) 15.553(2) 98.53(1) 107.55(1) 103.31(2) 1588.8(5) 2 0.260 0,43 9 0,41 9 0,18 225 6254/5522 [R(int) = 0.0194] 543 1.015 R1 = 0.0361, wR2 = 0.0934 R1 = 0.0594, wR2 = 0.1047 0.294/-0.278

3.1 Structure Description of 1 The asymmetric unit of 1 contains two organic cations, one monohydrogentriphosphate anion and two water molecules. The atomic arrangement can be described as inorganic chains built by HP3O104- anions and one water molecule. In such a chain, two HP3O104- anions are linked together by strong OHO hydrogen bonds to form H2P6O208- cyclic units. An OD(donor)OA(acceptor) is the same order of magnitude as distance of 2.553(3) A the PO4 tetrahedron. Each one of these units is connected by (OW1) to its two neighbours by hydrogen bonds, , to form innite chains ODLOA = 2.829(4)2.890(4) A parallel to the [110] direction (Fig. 1). The HP3O104- anion has no internal symmetry; therefore, it is built from three independent PO4 tetrahedrons. Nevertheless some of the known triphosphate anions with mineral cations have a twofold internal symmetry, their central phosphorous being located on a twofold axis [1014]. There are three different types of PO distances inside the PO4 tetrahedron; i.e. the ] corresponds to the longest [1.607(2) and 1.631(2) A ] bridging oxygen atoms. The intermediate [1.554(2) A corresponds to the POH bonding and the shortest, which and 1.512(2) A (relative to the is between 1.480(2) A external O-atoms). Despite these differences, the average

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-. Fig. 1 Innite chains of HP3O4 10 2H2O viewed down the crystallographic c axis

Fig. 2 Projection along the b axis of the atomic arrangement in 1

) and OPO angles values for the PO distances (1.538 A (109.28) (Table 2) indicate that the PO4 regular a tetrahedron. Organic cations, inducing NHO hydrogen bonds, are oriented along [101] direction to ensure structural stability (Fig. 2). The two types of hydrogen bonds, OHO and NHO, contribute to the cohesion in the network of 1. Figure 3 shows the hydrogen bonds in an asymmetric unit of 1. Moreover, the four aromatic rings built up by the six carbon atoms, C1 ? C6 (AR1), C7 ? C12 (AR2), C13 ? C18 (AR3) and C19 ? C24 (AR4), are relatively planar with r.m.s. deviations of the six C-atoms of each (AR1), ring from their restraint planes of 0.0058 A
) and bond angles () in the Table 2 Main interatomic distances (A PO4 tetrahedra of 1 P(1) O(E11) O(E12) O(E13) O(L12) P(2) O(E21) O(E22) O(L12) O(L23) P(3) O(E31) O(E32) O(E33) O(L23) P(1)P(2) P(2)P(3) O(E11) 1.490(2) 2.461(1) 2.562(3) 2.536(3) O(E21) 1.483(2) 2.537(3) 2.515(3) 2.485(3) O(E31) 1.504(2) 2.526(3) 2.504(3) 2.446(3) 2.934(1) 2.916(1) O(E12) 107.87(10) 1.554(2) 2.519(3) 2.517(3) O(E22) 117.82(10) 1.480(2) 2.526(3) 2.538(3) O(E32) 114.22(11) 1.505(2) 2.519(2) 2.517(3) O(E13) 118.14(10) 111.29(10) 1.497(2) 2.436(3) O(L12) 109.02(9) 110.01(10) 1.605(2) 2.431(2) O(E33) 112.28(10) 113.26(10) 1.512(2) 2.524(3) O(L12) 109.91(9) 105.53(10) 103.37(9) 1.607(2) O(L23) 107.86(9) 111.42(9) 99.04(9) 1.591(2) O(L23) 102.53(9) 106.70(9) 106.81(9) 1.631(2) 132.0(2) 129.6(2) 112(2)

(AR2), 0.0033 A (AR3) and 0.0116 A (AR4). 0.0027 A Their dihedral angles \AR1, AR2; \AR1, AR3,\AR1, AR4, \AR2, AR3, \AR2, AR4 and \AR3, AR4 being, respectively, 65.24(2), 36.38(1), 46.58(2), 80.74(2), 43.23(1)and 80.49(2), and indicate that these two independent organic cations do not have the same orientation within this crystal structure; their behaviour is rather different. Indeed, the central O-atom of one of is disordered and must be described as two fragments with occupancy rates of O(2A)0.57 O(2B)0.43 (Fig. 4), with dO(2A)O(2B) = . 0.989(9) A

P(1)O(L12)P(2) P(2)O(L23)P(3) P(1)O(E12)H12

Fig. 3 Hydrogen bonds in an asymmetric unit of 1

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Fig. 4 Representation of the organic cations in 1

Fig. 6 DSC thermogram of 1

3.2 Thermal Behaviour The TGDTA thermogram of 1 (Fig. 5) was obtained on ground samples. The TG curve shows that this compound is stable to 90 C. The removal of the two water molecules (weight loss = 0.3 mg) from 94 to 170 C is related to the endothermic DTA peak with maximum elimination at 119 C. This dehydration occurs in a large temperature domain and indicates the presence of two types of water molecules. Indeed, the structural resolution shows that one water molecule is less restrained in the atomic arrangement. The exothermic peak at 150 C is probably due to the enhanced partial pressure of water vapour. Furthermore the DTA curve reveals two endothermic peaks at 194 and 220 C and indicates the presence of two phase transitions since the TG curve does not show any weight loss. With a further increase in temperature, the sample decomposes (230350 C) with maximum evolution of ammonia at 268 C. Ammonia is indicated by its odor. Indeed the TG curve shows a rather substantial and continuous weight loss during the second phase transition. The base line, as shown in the DTA curve, is gently sloping downward and its slope may change with temperature. Such a premonitory

Fig. 7 Cycle of heating and cooling of 1

phenomenon is associated with an increase of atomic motions; in particular the increase of disorder when the decomposition is approached. On the other hand, the DSC thermogram for ground samples (Fig. 6) exhibits the same thermal behaviour as the DTA. Nevertheless, endothermic effects are somewhat shifted to lower temperature since the two techniques (TG DTA and DSC) have different sensitivities. The rst endotherm corresponds to dehydration with DHde-1 hyd = 32.4 kJ mol ; the two following endotherms at 188 and 216 C have DH(P.T1) = 8.3 kJ mol-1 and -1 DH(P.T2) = 0.95 kJ mol , respectively, and are related to two phase transitions. A cycle of heating and cooling, with equal rate (5 C min-1) from room temperature to 223 C (Fig. 7) conrms the presence of the phase transitions. Nevertheless, the absence of exothermic peaks on cooling indicates that the transformation is irreversible. 3.3 IR Spectroscopic Investigation The IR spectrum of crystalline 4,40 -diammoniumdiphenylether triphosphate is shown in Fig. 8. Representative and characteristic vibrational modes for the compound are

Fig. 5 TG-DTA thermogram of 1

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organic entities. The gap between the average planes of the and mineral and the organic cations is approximately 7.8 A correspond to half the c parameter. 1 is stable to 90 C and then undergoes a dehydration and degradation of the organic entity. The thermal behavior of 1 reveals two-phase transitions; thermodynamic properties were deduced from the calorimetry. The same thermal behaviour was conrmed by the DSC. The energies of the crystals vibration modes were assigned on the basis of the characteristic vibrations of the POP, PO2 and PO3 groups.

5 Supporting Data
Fig. 8 IR Spectrum of 1

compared to similar triphosphates [14]; i.e. (O3POPO2 OPO3). The assignments are as follows: The stretching vibrations of PO2 central group are observed between 1300 and 1100 cm-1. Those between 1260 and 990 cm-1 correspond to the stretching vibrations of PO3 terminal groups. Those ranging from 670 to 960 cm-1 correspond to the stretching POP modes [15, 16]. The bending vibrations of PO3 terminal groups are from 600 to 400 cm-1. Supplementary frequencies in the m(PO3) domain are attributed to the bending modes, d(CaryH) and d(CaryCary) [17]. Bands from 1600 to 1200 cm-1 correspond to the bending vibrations of NH and OH groups. The valence vibrations of CC and CN groups occur in this same region. Bands from 3600 to 2300 cm-1 are attributed to the stretching of the organic and hydroxyl groups, m(NH), m(CH) and m(OH) of H2O and POH groups.

Crystallographic data for the structural analysis have been deposited at the Cambridge Crystallographic Data Centre, CCDC No 818074. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 IEZ, UK(fax: ?44-1226336033; e-mail: deposit@ccdc.cam.ac.uk).

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4 Conclusions Compound 1 was prepared as a single crystal at room temperature. The physicochemical characterization of 1 using TG-DTA, DSC and IR are reported. The atomic arrangement in 1 is described by chains of HP3O104- groups and water molecules that are parallel to the [110] direction. The interlayer spacing is occupied by the organic entities extended along the [101] direction and assembled as inorganic chains giving rise to a three-dimensional network, which can be designed by an alternative localization of mineral and

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