Benzyltrimethylammonium dihydrogen orthophosphate monohydrate

o ganic pape s Ac a C ys . (2005). E61, o1127–o1129 doi:10.1107/S1600536805008755 A. C iado e al. C 10 H 16 N + H 2 PO 4  H 2 Oo1127 Ac a C ys allog aphica Sec ion E S uc u e Repo s Online ISSN 1600-5368 Benzyl ime hylammonium dihyd ogen o hophospha e monohyd a e A. C iado, a Ma ı ´a Jesu ´sDia ´nez, a Ma ı ´a Dolo es Es ada, a *Simeo ´n Pe ´ ez-Ga ido, a M. Belsley b and E. de Ma os Gomes b a Ins i u o de Ciencias de Ma e iales de Se illa and Depa amen o de Fı ´sica de la Ma e ia Condensada, CSIC–Uni e sidad de Se illa, Apa ado 1065, 41080 Se illa, Spain, and b Depa amen o de Fı ´sica, Uni e sidade do Minho, 4709 B aga, Po ugal Co espondence e-mail: [email p o ec ed] Key indica o s Single-c ys al X- ay s udy T= 293 K Mean (C–C) = 0.006 A ˚ R ac o = 0.051 wR ac o = 0.143 Da a- o-pa ame e a io = 11.3 Fo de ails o how hese key indica o s we e au oma ically de i ed om he a icle, see h p://jou nals.iuc .o g/e. #2005 In e na ional Union o C ys allog aphy P in ed in G ea B i ain – all igh s ese ed The i le compound, C 10 H 16 N + H 2 PO 4  H 2 O, c ys allizes in he cen osymme ic space g oup P2 1 /cwi h wo independen molecules in he asymme ic uni . The e o e, nonlinea op ical p ope ies a e absen . The c ys al packing is go e ned by hyd ogen bonds, so ha he phospha e anions a e linked head- o- ail, o ming chains unning pa allel o he adi ec ion. These chains in u n a e in e connec ed by hyd ogen bonds o wa e molecules, o ming hyd ogen-bonded molecula laye s s acked pa allel o he ab plane. Commen Ino ganic sal s o phospho ic acids o m compounds ha exhibi many in e es ing s uc u al p ope ies, such as phase ansi ions, physical p ope ies like e oelec ici y, and op ical nonlinea phenomena like second ha monic gene a ion, as is he case o po assium dihyd ogen o hophospha e (KDP; Rashko ich, 1991). As o o ganic sal s, a gene al syn he ic ou e o ob ain o gano dihyd ogen phospha e c ys als has been de ailed in he li e a u e (Masse & Zyss, 1991). In all hese compounds, he e is an ino ganic hyd ogen-bond sub- ne wo k o med by he dihyd ogen o hophospha e anions. The o ganic ca ion benzyl ime hylammonium (he ea e BTA) is known o o m wi h selenious acid a compound, benzyl ime hylammonium ihyd ogen seleni e, which exhi- bi s s uc u al phase ansi ions (de Ma os Gomes e al., 1995). No o he c ys al s uc u es o BTA sal s wi h o he acid oxoanions ha e been epo ed in he li e a u e. On he o he hand, he s uc u es o he ela ed e ame hylammonium (Ohama e al., 1987) and N-benzylme hylammonium (Elaoud e al., 1998) dihyd ogen o hophospha es ha e been epo ed. In he sea ch o new compounds wi h s uc u al ins abil- i ies and e oelec ici y, he i le compound, (I) (Fig. 1), was syn hesized. The space g oup is cen osymme ic, wi h wo o mula uni s in he asymme ic uni , and he e o e nonlinea op ical p ope ies a e absen in his compound. Di e en ial scanning calo ime y measu emen s pe o med om 93 o 673 K did no show he exis ence o any phase ansi ion. A abou 353 K he e is loss o wa e , and mel ing occu s a abou 513 K, ollowed by decomposi ion. Recei ed 16 Feb ua y 2005 Accep ed 18 Ma ch 2005 Online 25 Ma ch 2005 As may be expec ed, he wo P—O dis ances o he OH g oups a e signi ican ly longe han he o he wo P—O dis ances. The bond leng hs in bo h symme y-independen BTA ca ions a e e y simila and also ag ee wi h p e ious wo k (de Ma os Gomes e al., 1995), whe eas he bond angles show a la ge ange as a esul o he in e molecula c ys al packing o ces. The mos in e es ing c ys allog aphic ea u e in hese o ganic sal s is he hyd ogen-bond packing ne wo k. As in he case o 1,1,3,3- e ame hylguanidinium dihyd ogen o hophospha e (C iado e al., 2000), he phospha e anions a e a anged in linea chains (Fig. 2). These chains pa allel o he a di ec ion a e o med by he wo phospha e ions in he asym- me ic uni and all he ansla ionally equi alen ions along he adi ec ion. Each ion is connec ed by wo hyd ogen bonds o each neighbou ing phospha e ion in he chain, so ha al e - na e ions in he chain a e ela ed by a la ice ansla ion aand adjacen ions a e symme ically-independen . In addi ion o his, linea chains ela ed o each o he by a sc ew axis a e in e connec ed by wo wa e molecules, o ming ou hyd ogen bonds (Fig. 3), esul ing in a c ys al packing o hyd ogen-bonded laye s s acked pa allel o he ab plane so ha adjacen laye s a e ela ed by an in e sion cen e and al e na e laye s a e sepa a ed by a la ice pe iod c. Fi e C—HO sho con ac s no depic ed in he Figu es ha e been ound. Expe imen al The p esen compound was syn hesized by mixing equimola amoun s o benzyl ime hylammonium hyd oxide and phospho ic acid in a mixed sol en o wa e and me hanol. The c ys als we e g own by slow e apo a ion and we e o p isma ic habi , colou less and anspa en . C ys al da a C 10 H 16 N + H 2 PO 4  H 2 O M = 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 measu ed by lo a ion in b omobenzene and ace one Mo K adia ion Cell pa ame e s om 25 e lec ions = 7–12 = 0.21 mm 1 T= 293 (2) K P ism, colou less 0.48 0.40 0.28 mm Da a collec ion En a –Nonius CAD-4 di ac ome e !–2scans Abso p ion co ec ion: none 4723 measu ed e lec ions 4723 independen e lec ions 3482 e lec ions wi h I>2(I)  max = 25.0 h=9!9 k=0!15 l=0!29 3 s anda d e lec ions equency: 60 min in ensi y decay: none Re inemen Re inemen on F 2 R[F 2 >2(F 2 )] = 0.051 wR(F 2 ) = 0.143 S= 1.01 4723 e lec ions 419 pa ame e s H a oms ea ed by a mix u e o independen and cons ained e inemen w= 1/[ 2 (F o 2 ) + (0.1215P) 2 + 0.1493P] whe e P=(F o 2 +2F c 2 )/3 (/) max = 0.010  max = 0.49 e A ˚ 3  min =0.58 e A ˚ 3 o ganic pape s o1128 A. C iado e al. C 10 H 16 N + H 2 PO 4  H 2 OAc a C ys . (2005). E61, o1127–o1129 Figu e 2 Molecula packing o (I), iewed along he bdi ec ion, showing he hyd ogen bonds (dashed lines) be ween phospha e ions. Figu e 3 Molecula packing o (I), iewed along he adi ec ion, showing he hyd ogen bonds (dashed lines) in ol ing wa e molecules. Figu e 1 An ORTEPII plo (Johnson, 1976) o (I), showing 30% p obabili y displacemen ellipsoids. H a oms a e shown as sphe es o a bi a y adii. Table 1 Selec ed geome ic pa ame e s (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 Hyd ogen-bonding geome y (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 i 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 0.99 (4) 2.41 (5) 3.388 (4) 173 (4) C8—H8CO2 i 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 ii 0.96 (4) 2.43 (3) 3.359 (4) 162 (3) Symme y codes: (i) 1 x;y1 2;1 2z; (ii) 1 x;1 2þy;1 2z; (iii) 1 þx;y;z; (i ) x1;y;z; ( ) 1 þx;1 2y;1 2þz; ( i) 2 x;y1 2;1 2z; ( ii) 2 x;1 2þy;1 2z. C-bound H a oms we e e ined eely [C—H = 0.79 (5)–1.06 (5) A ˚]. Wa e H a oms we e also e ined eely. H-a om bond leng hs and angles in he phospha e ion we e cons ained in he e inemen [O— H dis ances gi en in Table 2; U iso (H)=1.5U eq (C)] so ha only he o sion angles o he OH g oups ha e been allowed o e ine. Da a collec ion: CAD-4 So wa e (En a –Nonius, 1989); cell e inemen : SET4 (de Boe & Duissenbe g, 1984) and CELDIM (Re ing, 1989); da a educ ion: XRAY76 Sys em (S ewa e al., 1976); p og am(s) used o sol e s uc u e: SIR92 (Al oma e e al., 1994); p og am(s) used o e ine s uc u e: SHELXL93 (Sheld ick, 1993); molecula g aphics: PLATON (Spek, 2003); so wa e used o p epa e ma e ial o publica ion: PARST (Na delli, 1995) and PARSTCIF (Na delli, 1991). This wo k was suppo ed by he Spanish CICYT p ojec BFM2002-03327 and FEDER unds. Re e ences Al oma e, A., Casca ano, G., Giaco azzo, C., Guaglia di, A., Bu la, M. C., Polido i, G. & Camalli, M. (1994). J. Appl. C ys . 27, 435. Boe , J. L. de & Duissenbe g, A. J. M. (1984). Ac a C ys . A40, C-410. C iado, A. Dia ´nez, M. J., Pe ´ ez-Ga ido, S., Fe nandes, I. M. L., Belsley, M. & de Ma os Gomes, E. (2000). Ac a C ys . C56, 888–889. Elaoud, Z., Kamoun, S., Jaud, J. & Mhi i, T. (1998). J. Chem. C ys . 28, 313– 315. En a –Nonius (1989). CAD-4 So wa e. Ve sion 5.0. En a –Nonius, Del , The Ne he lands. Johnson, C. K. (1976). ORTEPII. Repo ORNL-5138. Oak Ridge Na ional Labo a o y, Tennessee, USA. Masse, R. & Zyss, J. (1991). Mol. Eng. 1, 141–152. Ma os Gomes, E. de, Ma os Beja, A., Paixao, J. A., Al e da Veiga, L., Ramos Sil a, R., Ma in-Gil, J. & Ma in-Gil, F. J. (1995). Z. K is allog . 210, 929– 933. Na delli, M. (1995). J. Appl. C ys . 28, 659. Na delli, M. (1991). PARSTCIF. Uni e si y o Pa ma, I aly. Ohama, N., Machida, M., Nakamu a, T. & Kuni uji, Y. (1987). Ac a C ys . C43, 962–964. Rashko ich, L. N. (1991). KDP-Family Single C ys als. B is ol: IOP Publishing. Re ing, S. (1989). CELDIM in CAD-4 So wa e. Ve sion 5.0. En a –Nonius, Del , The Ne he lands. Sheld ick, G. M. (1993). SHELXL93. Uni e si y o Go ¨ ingen, Ge many. Spek, A. L. (2003). J. Appl. C ys . 36, 7–13. S ewa , J. M., Machin, P. A., Dickinson, C. W., Ammon, H. L., Heck, H. & Flack, H. (1976). XRAY76 Sys em. Technical Repo TR-446. Compu e Science Cen e , Uni e si y o Ma yland, College Pa k, Ma yland, USA. o ganic pape s Ac a C ys . (2005). E61, o1127–o1129 A. C iado e al. C 10 H 16 N + H 2 PO 4  H 2 Oo1129