single crystal structure of a layered intercalating phosphate with features of two dimensions and...

Ž .Materials Science and Engineering C 10 1999 67–69www.elsevier.comrlocatermsec

Single crystal structure of a layered intercalating phosphate with featuresof two dimensions and H-bonds

Fa-nian Shi, Chun-ying Duan, Yong-jiang Liu, Xiao-zeng You )

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing UniÕersity, Nanjing 210093, China

Accepted 21 May 1999

Abstract

Ž .Ž .A new organic phosphate of 8-HQDH H PO PH O has been obtained by hydrothermal reaction. The crystal structure was2 4 2˚ ˚ ˚Ž . Ž . Ž . Ž . Ž .determined with data: triclinic, space group P1, as6.541 1 A, bs8.5909 8 A, cs10.769 1 A, as98.734 7 8, bs91.20 1 8,

˚3 yŽ . Ž . Ž .gs97.91 1 8, Vs591.9 1 A , and Zs2. The H PO groups and H O molecules stack into sheets and 8-HQ cations fixed2 4 2

parallelly with each other to form an intercalating compound by H-bonds. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: Organic phosphate; Intercalation; Hydrogen-bond

1. Introduction

Organic phosphates have been widely studied due totheir many uses in various fields such as biomolecular

w xsciences, catalyst, fuel cell, liquid crystal materials 1–5 .Most organic phosphates are formed with co-valency bondsbetween phosphate groups and organic groups, whereasvery few compounds are formed only in the way of

w xH-bonds between the two groups 6 . The formation of thesalt between phosphoric acid and 8-hydroxyquinoline was

w xmentioned in the literature 7 , but the structure remainsunknown.

Ž .Ž .A new intercalating complex of 8-HQDH H PO P2 4ŽH O 8-HQD represents 8-Hydroxy-Quinaldine, C -2 10.H NO. has been synthesized with hydrothermal method,9

and single crystal determination shows H-bonds are theonly force within the molecules and between the molecules.A detailed structural description is presented here.

2. Experimental

All starting materials were reagent grade used as pur-chased. The title compound was synthesized by the hy-drothermal method with the starting materials in an equal

) Corresponding author. Tel.: q86-025-3592969; fax: q86-025-3317761

Ž . Ž .mole ratio of 8-HQD 1.10 g and H PO 85% mixed in3 4

10 ml H O. The mixture was heated at 1808 for 3 days in a2Ž .Teflon-lined autoclave 25 ml . The resulting products

were cooled to room temperature slowly. After filtration,the aqueous solution was allowed to stand in air at roomtemperature. The yellow block single crystals suitable forX-ray structural measurements were obtained by evapora-tion after several weeks.

The elemental analysis was performed on a PE 240Celemental analyzer. The infrared spectrum was recorded ona Fourier Nicolet FT-170 SX spectrophotometer withpressed KBr pellets. The intensity data were collectedusing a Siemens P4 four-circle diffractometer with

˚Ž .monochromatic Mo-Ka ls0.71073 A radiation usingvr2u scan mode with a variable scan speed 4.0–40.08

y1 Ž .min in v at 295 2 K. The data were corrected forLorantz and polarization effects during data reduction us-

w xing XSCANS 8 .The structure was solved by direct method. All non-hy-

drogen atoms were refined anisotropically by full-matrixleast squares. Hydrogen atoms of the ligands were placed

˚in their calculated positions with C–H, 0.96 A, assignedŽfixed isotropic thermal parameters 1.2 times of the atom

.they attached and 1.5 times for the methyl group , andallows to ride on their respective parent atoms. Hydrogenatoms of water molecule were found from the differenceFourier map and refined isotropically. The contributions ofthese hydrogen atoms were included in the structure fac-tors calculations. All analytical expressions of neutral-atom

0928-4931r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.Ž .PII: S0928-4931 99 00113-7

( )F.-n. Shi et al.rMaterials Science and Engineering C 10 1999 67–6968

Table 1Ž .q Ž .yCrystallographic data for C H NO H PO PH O10 10 2 4 2

Formula C H NO P10 14 6

M 275.19Crystal system Triclinic

Space group P1

˚ ˚ ˚Ž . Ž . Ž . Ž . Ž . Ž .a A , b A , c A 6.541 1 , 8.5908 8 , 10.769 1Ž . Ž . Ž . Ž . Ž . Ž .a 8 , b 8 , g 8 98.734 7 , 91.20 1 , 97.91 1

3˚Ž . Ž .Volume A 591.9 1Z 2

y3Ž .D g cm 1.544cŽ .F 000 288

y1Ž . Ž .m Mo-K a cm 74.51Ž .u 8 range 1.92 to 30.00

Reflection collected 3575Ž .Independent reflections 2829 R s0.0134int

T , T 0.2746, 0.3114min max

Data, restraints, parameters 2828, 0, 2202Goodness of fit on F 1.057

w Ž .xR1, wR2 I)2s I 0.0359, 0.1035Ž .all data 0.0386, 0.1067

y3˚Ž . Ž . Ž .D r , D r e A 0.338, y0.377max min2 2 2 2 2 1r25 < < 5 < < w Ž . Ž . xR1s S F y F rS F ,wR2s S w F y F rS w Fo c o o c o

scattering factors and anomalous dispersion correctionswere incorporated. All computations were carried out on aPc-586 computer using the SHELXTL Pc Program Packagew x9 .

3. Results and discussion

The preparation of the single crystal of title compoundhas been tried under ambient temperature and even reflux-ing in aqueous solution, but failed. Hydrothermal reaction

is an effective method for preparation of the single crystalwith good quality.

Ž .The elemental analysis found C, 43.18 43.63 ; H, 5.51Ž . Ž . Ž5.09 ; N, 4.67 5.09 Theoretical data are given in paren-

.theses . The data of IR spectrum are listed as follows:Ž . Ž . Ž .3559.5 O–H , 3226.1 N–H , 1640.45 C5C, C5N ,Ž . Ž .1599.75 C5C, C5N , 1399.5 CH .3

The crystallographic data are listed in Table 1.Ž .yH PO group can be considered as a bridge connecting2 4

Ž .qwith one H O molecule and one 8-HQDH cationic2

group respectively to form a new molecule by the interac-tion of hydrogen bonds. There are five kinds of hydrogenbonds within molecule, of which three are strong H-bondswith the distances between the donors and acceptors vary-

˚ ˚Ž . Ž . Ž . w Ž .ing from 2.697 1 A N–H . . . O to 2.823 2 A O W –Ž .xH . . . O PO . Comparing to the former, the other two are4

very weak H-bonds with the distance between the donors˚Ž .and acceptors C–H . . . O of 3.232 A. The crystal struc-

Ž .Ž .ture of 8-HQDH H PO PH O is shown in Fig. 1. The2 4 2

crystal structure comprises a network of intermolecularhydrogen bonds, with each new molecule involved in eighthydrogen bonds of two different types connected to adja-cent molecules. One type has the kind of O–H . . . O, ofwhich have short hydrogen-bond lengths with the value of

˚Ž . Ž . Ž .O–H . . . O varying from 2.536 2 A minimum to 2.888 2˚ Ž .A maximum and the other has the kind of C–H . . . O, ofwhich have far weaker hydrogen-bonds than those of the

˚Ž . Ž .former with the value varying from 3.373 2 to 3.387 2 A.The crystal structure can be regarded to be composed of

layers parallel to the ac plane, with two such layers perŽ .yunit cell along the b axis. Columns of H PO anions2 4

Žand H O molecules are stacked into a sheet with 8-2.qHQDH cations fixed on the sheet parallelly to eachŽ .other see Fig. 1 . The distance of per adjacent 8-HQD

Fig. 1. The crystal structure of C H NO P along the c axis. H-bonding interactions are shown as dashed lines.10 14 6

( )F.-n. Shi et al.rMaterials Science and Engineering C 10 1999 67–69 69

˚Ž .planes is about 3.2706 6 A, and the intersheet distance islarge enough to hold a molecule as big as 8-HQD

˚Ž Ž .8.5908 8 A from the centers between two adjacent.sheets . The adjacent sheets are also linked by the interac-

tion of hydrogen-bonds to form an infinite network.This complex is very stable in air under ambient tem-

perature by the weak interaction of hydrogen-bonds.

Acknowledgements

This work was supported by a major project from TheState Science and Technology Commission and The Na-tional Nature Science Foundation of China.

References

w x Ž . Ž .1 D. Gani, J. Wilkie, Chem. Soc. Rev. 24 1 1995 55–63.w x2 Y. Kita, T. Kashitani, K. Kishino, K. Nakagawa, Nippon Kagaku

Ž .Kaishi 12 1995 971.w x3 J.T. Wang, R.F. Savinell, J. Wainright, M. Litt, M. Yu, Electrochim.

Ž . Ž .Acta 41 2 1996 193.w x4 S. Oliver, A. Kuperman, N. Coombs, A. Lough, G.A. Ozin, Nature

Ž . Ž .London 378 1995 47.w x5 N. Coombs, D. Khushalani, S. Oliver, G.A. Ozin, G.C. Shen, I.

Ž .Sokolov, H. Yang, J. Chem. Soc. Dalton Trans. 21 1997 3941.w x Ž .6 I. Yoichi, H. Yukiko, Acta Crystallogr. 18 1965 110.w x Ž . Ž .7 J.P. Phillips, Chem. Rev. 56 2 1956 271.w x Ž .8 Siemens, XSCANS version 2.1 , Siemens Analytical X-ray Instru-

ments, Madison, USA, 1994.w x Ž .9 Siemens, SHELXTL vertion 5.0 , Reference Manual, Siemens Indus-

trial Automation, Analytical Instrumentation, USA, 1995.