Benzyltrimethylammonium dihydrogen orthophosphate monohydrate

organic papers Acta Cryst. (2005). E61, o1127–o1129 doi:10.1107/S1600536805008755 A. Criado et al. C 10 H 16 N + H 2 PO 4  H 2 Oo1127 Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Benzyltrimethylammonium dihydrogen orthophosphate monohydrate A. Criado, a Marı ´a Jesu ´sDia ´nez, a Marı ´a Dolores Estrada, a *Simeo ´n Pe ´rez-Garrido, a M. Belsley b and E. de Matos Gomes b a Instituto de Ciencias de Materiales de Sevilla and Departamento de Fı ´sica de la Materia Condensada, CSIC–Universidad de Sevilla, Apartado 1065, 41080 Sevilla, Spain, and b Departamento de Fı ´sica, Universidade do Minho, 4709 Braga, Portugal Correspondence e-mail: [email protected] Key indicators Single-crystal X-ray study T= 293 K Mean (C–C) = 0.006 A ˚ Rfactor = 0.051 wR factor = 0.143 Data-to-parameter ratio = 11.3 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e. #2005 International Union of Crystallography Printed in Great Britain – all rights reserved The title compound, C 10 H 16 N + H 2 PO 4  H 2 O, crystallizes in the centrosymmetric space group P2 1 /cwith two independent molecules in the asymmetric unit. Therefore, nonlinear optical properties are absent. The crystal packing is governed by hydrogen bonds, so that the phosphate anions are linked headto-tail, forming chains running parallel to the adirection. These chains in turn are interconnected by hydrogen bonds to water molecules, forming hydrogen-bonded molecular layers stacked parallel to the ab plane. Comment Inorganic salts of phosphoric acids form compounds that exhibit many interesting structural properties, such as phase transitions, physical properties like ferroelectricity, and optical nonlinear phenomena like second harmonic generation, as is the case for potassium dihydrogen orthophosphate (KDP; Rashkovich, 1991). As for organic salts, a general synthetic route to obtain organo dihydrogen phosphate crystals has been detailed in the literature (Masse & Zyss, 1991). In all these compounds, there is an inorganic hydrogen-bond subnetwork formed by the dihydrogen orthophosphate anions. The organic cation benzyltrimethylammonium (hereafter BTA) is known to form with selenious acid a compound, benzyltrimethylammonium trihydrogen selenite, which exhibits structural phase transitions (de Matos Gomes et al., 1995). No other crystal structures of BTA salts with other acid oxoanions have been reported in the literature. On the other hand, the structures of the related tetramethylammonium (Ohama et al., 1987) and N-benzylmethylammonium (Elaoud et al., 1998) dihydrogen orthophosphates have been reported. In the search for new compounds with structural instabilities and ferroelectricity, the title compound, (I) (Fig. 1), was synthesized. The space group is centrosymmetric, with two formula units in the asymmetric unit, and therefore nonlinear optical properties are absent in this compound. Differential scanning calorimetry measurements performed from 93 to 673 K did not show the existence of any phase transition. At about 353 K there is loss of water, and melting occurs at about 513 K, followed by decomposition. Received 16 February 2005 Accepted 18 March 2005 Online 25 March 2005 As may be expected, the two P—O distances for the OH groups are significantly longer than the other two P—O distances. The bond lengths in both symmetry-independent BTA cations are very similar and also agree with previous work (de Matos Gomes et al., 1995), whereas the bond angles show a larger range as a result of the intermolecular crystal packing forces. The most interesting crystallographic feature in these organic salts is the hydrogen-bond packing network. As in the case of 1,1,3,3-tetramethylguanidinium dihydrogen orthophosphate (Criado et al., 2000), the phosphate anions are arranged in linear chains (Fig. 2). These chains parallel to the a direction are formed by the two phosphate ions in the asymmetric unit and all the translationally equivalent ions along the adirection. Each ion is connected by two hydrogen bonds to each neighbouring phosphate ion in the chain, so that alternate ions in the chain are related by a lattice translation aand adjacent ions are symmetrically-independent. In addition to this, linear chains related to each other by a screw axis are interconnected by two water molecules, forming four hydrogen bonds (Fig. 3), resulting in a crystal packing of hydrogen-bonded layers stacked parallel to the ab plane so that adjacent layers are related by an inversion centre and alternate layers are separated by a lattice period c. Five C—HO short contacts not depicted in the Figures have been found. Experimental The present compound was synthesized by mixing equimolar amounts of benzyltrimethylammonium hydroxide and phosphoric acid in a mixed solvent of water and methanol. The crystals were grown by slow evaporation and were of prismatic habit, colourless and transparent. Crystal data C 10 H 16 N + H 2 PO 4  H 2 O M r = 265.24 Monoclinic, P21=c a= 8.295 (2) A ˚ b= 13.178 (7) A ˚ c= 24.714 (4) A ˚ = 95.412 (1) V= 2689.5 (16) A ˚ 3 Z=8 D x = 1.310 Mg m 3 D m =1.30Mgm 3 D m measured by flotation in bromobenzene and acetone Mo Kradiation Cell parameters from 25 reflections = 7–12 = 0.21 mm 1 T= 293 (2) K Prism, colourless 0.48 0.40 0.28 mm Data collection Enraf–Nonius CAD-4 diffractometer !–2scans Absorption correction: none 4723 measured reflections 4723 independent reflections 3482 reflections with I>2(I)  max = 25.0 h=9!9 k=0!15 l=0!29 3 standard reflections frequency: 60 min intensity decay: none Refinement Refinement on F 2 R[F 2 >2(F 2 )] = 0.051 wR(F 2 ) = 0.143 S= 1.01 4723 reflections 419 parameters H atoms treated by a mixture of independent and constrained refinement w= 1/[ 2 (F o 2 ) + (0.1215P) 2 + 0.1493P] where P=(F o 2 +2F c 2 )/3 (/) max = 0.010  max = 0.49 e A ˚ 3  min =0.58 e A ˚ 3 organic papers o1128 A. Criado et al. C 10 H 16 N + H 2 PO 4  H 2 OActa Cryst. (2005). E61, o1127–o1129 Figure 2 Molecular packing of (I), viewed along the bdirection, showing the hydrogen bonds (dashed lines) between phosphate ions. Figure 3 Molecular packing of (I), viewed along the adirection, showing the hydrogen bonds (dashed lines) involving water molecules. Figure 1 An ORTEPII plot (Johnson, 1976) of (I), showing 30% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radii. Table 1 Selected geometric parameters (A ˚,). P—O1 1.492 (2) P—O3 1.492 (2) P—O2 1.556 (2) P—O4 1.560 (2) N—C10 1.488 (4) N—C8 1.490 (4) N—C9 1.497 (4) N—C7 1.524 (4) P1—O31 1.494 (2) P1—O11 1.494 (2) P1—O41 1.569 (2) P1—O21 1.571 (2) N1—C91 1.487 (4) N1—C81 1.504 (4) N1—C71 1.522 (4) O1—P—O3 116.4 (1) O1—P—O2 108.2 (1) O3—P—O2 108.6 (1) O1—P—O4 109.6 (1) O3—P—O4 106.0 (2) O2—P—O4 107.7 (2) C10—N—C8 109.6 (3) C10—N—C9 108.1 (3) C8—N—C9 108.2 (3) C10—N—C7 111.7 (3) C8—N—C7 110.7 (2) C9—N—C7 108.4 (2) C1—C7—N 113.8 (2) O31—P1—O11 117.9 (1) O31—P1—O41 107.8 (1) O11—P1—O41 109.7 (1) O31—P1—O21 108.2 (1) O11—P1—O21 106.5 (1) O41—P1—O21 106.0 (2) C101—N1—C91 109.3 (3) C101—N1—C81 108.2 (3) C91—N1—C81 108.8 (3) C101—N1—C71 110.5 (3) C91—N1—C71 112.2 (3) C81—N1—C71 107.7 (2) C11—C71—N1 115.6 (2) Table 2 Hydrogen-bonding geometry (A ˚,). D—HAD—H HADAD—HA O5—H5AO1 0.80 (5) 2.02 (5) 2.807 (3) 168 (5) O5—H5BO11 i 0.86 (5) 2.03 (5) 2.870 (3) 170 (4) O51—H51AO31 0.79 (5) 2.05 (5) 2.826 (4) 177 (5) O51—H51BO3 ii 0.79 (5) 2.08 (5) 2.860 (4) 171 (5) O2—H2O31 0.82 1.82 2.629 (3) 168 O4—H4O11 iii 0.83 1.86 2.566 (3) 143 O21—H21O3 0.82 1.77 2.582 (3) 170 O41—H41O1 iv 0.82 1.79 2.579 (3) 159 C8—H8BO21 iii 0.90 (4) 2.43 (5) 3.311 (5) 168 (4) C4—H4AO31 v 0.99 (4) 2.41 (5) 3.388 (4) 173 (4) C8—H8CO2 vi 0.95 (5) 2.53 (5) 3.467 (5) 169 (4) C81—H81BO3 ii 0.95 (5) 2.43 (4) 3.372 (5) 174 (4) C71—H71BO5 vii 0.96 (4) 2.43 (3) 3.359 (4) 162 (3) Symmetry codes: (i) 1 x;y1 2;1 2z; (ii) 1 x;1 2þy;1 2z; (iii) 1 þx;y;z; (iv) x1;y;z; (v) 1 þx;1 2y;1 2þz; (vi) 2 x;y1 2;1 2z; (vii) 2 x;1 2þy;1 2z. C-bound H atoms were refined freely [C—H = 0.79 (5)–1.06 (5) A ˚]. Water H atoms were also refined freely. H-atom bond lengths and angles in the phosphate ion were constrained in the refinement [O— H distances given in Table 2; U iso (H)=1.5U eq (C)] so that only the torsion angles of the OH groups have been allowed to refine. Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: SET4 (de Boer & Duissenberg, 1984) and CELDIM (Retting, 1989); data reduction: XRAY76 System (Stewart et al., 1976); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PARST (Nardelli, 1995) and PARSTCIF (Nardelli, 1991). This work was supported by the Spanish CICYT project BFM2002-03327 and FEDER funds. References Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Boer, J. L. de & Duissenberg, A. J. M. (1984). Acta Cryst. A40, C-410. Criado, A. 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SHELXL93. University of Go ¨ttingen, Germany. Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Stewart, J. M., Machin, P. A., Dickinson, C. W., Ammon, H. L., Heck, H. & Flack, H. (1976). XRAY76 System. Technical Report TR-446. Computer Science Center, University of Maryland, College Park, Maryland, USA. organic papers Acta Cryst. (2005). E61, o1127–o1129 A. Criado et al. C 10 H 16 N + H 2 PO 4  H 2 Oo1129