5,

6. 7.

8.

9. 10. 11. 12.

'13.

J. R. Jesson, NMR of Paramagnetic Molecules. Principles and Applications, Academic Press, New York (1973), pp. 1-52. L. D. Landau and E. M. Lifshits, Quantum Mechanics [in Russian], Fizmatgiz, Moscow (1963). S. A. Al' tshuler and B. M. Kozyrev, Electron Paramagnetic Resonance of Compounds of the Elements of the Transition Groups [in Russian], Nauka, Mosco w (1972). N. Bloembergen and L. O. Morgan, J. Chem. Plys., 34, 842 (1961). J. A. Happe and R. L. Ward, J. Chem. Phys., 39, 1211 (1963). W. D. Horroeks, R. C. Taylor, and G. N. La Mar, J. Am. Chem. Soc., 86, 3031 (1964). E. E. Zaev and Yu. N. Molin, Zh. Strukt. Khim., 7, 680 (1966). V. M. Nekipelov, A. N. Shupik, and K. I. Zamaraev, Koord. Khim., 1, 956 (1975). A. V. Kessenikh, A. Ataev, V. M. Agre, and I. A. Krol', in Present-Day Physicochemical Methods for the Study and Analysis of Chemical Reagents and Highly Pure Substances [in Russian], VNII IREA, Moscow (1978), p. 77.

CRYSTAL AND MOLECULAR STRUCTURE

OF THE ADDUCT OF PHENOL WITH 5-METHYL-

1 0- PHENYL- 1 0-OXO- 5,1 0- DIHY'DRO PHENO PHOS PHA ZINE

A. I. Gusev, S. N. Gurkova V. K. B e l ' s k i i , V. E. Z a v o d n i k , and L. A. Y a g o d i n a

UDC 547.241 : 539.2 : 548.7

An x - r ay structural study of the adduct of phenol with 5-methyl-10-phenyl%10-oxo-5,10-dihy- drophenophosphazine has been carr ied out (a =10,567, b = 9.772, c =23.441 A, ~=119.80 ~ space group P21/b; automatic diffractometer, 1410 independent reflections, direct method, R =0.083). The dihydrophenophosphazine molecule is nonplanar (the cent ra l heterocyclic ring has the boat conformation, and the dihedral angle between the planes of the benzene rings is 149.3 ~ and forms a hydrogen bond O. . ,H-O of length 2.68 A with the phenol molecule.

INTRODUCTION

The reaction of phenylmagnesium bromide with 5-methyl-10-chloro-10-oxo-5,10-dihydrophenophospha- zinc gives products of different composition, depending on the reagent ratio. Thus at a ratio of phenylmagne- sium bromideto the chlorophenophosphazine equal to 2 :1 the product is 5-methyl-10-phenyl-10-oxo-5,10-di- hydrophenophosphazine ClsHl~NOP (I) with mp=162.163 ~ [1], whereas at a ratio 3.5:1 the product is an uniden- tified substance II with the composition C25H~2NO2P and mp=112-113 ~ The ultraviolet and mass spectra (at m/e > 100) of compounds I and II are identical.

~H 3 CH~ ~.3

o-/o �9 I ~I iI~

The present paper describes an x - ray diffraction study of crystals of compounds I and II, obtained by reerystal l ization from a mixture of benzene and cyclohexane and from benzene respectively. The lattice param- eters were measured on a "Syntex P~" automatic diffractometer. The crystals of compound I are triclinic, a=12.934, b=12.109, c=10.656 A,~=98.56 , fl%98.48, y=87.44 ~ A~. The crystals of compoundII

~ R are monoclinic, a=10.567, b=9.772, c=23.441 A, -/=119.80 ~ V=2100.5 A , space group P21 b. For four mole-

L. Ya. Karpov Physicochemieal Scientific-Research Institute. Translated from Zhurnal Strukturnoi Khimii, Vol. 20, No. 4, pp. 632-637, July-August, 1979. Original article submitted December 15, 1977; revi- sion submitted December 25, 1978.

0022-4766/79/2004-0537 $07.50 �9 1980 Plenum Publishing Corporation 537

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cules of C19H~NOP in the unit cell , the calculated densi t ies are 0.969 for compound II and 1.247 g /cm 3 for com- pound I, the la t ter p rac t i ca l ly coinciding with the density 1.260 g /cm 3 calculated for 5 -me thy l -10 -pheny l -5 ,10 - dihydrophenophosphazine (III), the s t ruc tu re of which has been studied [2]. The value of 0.969 g /cm 3 is too smal l for compounds of this type, however , so that we assumed that the c ry s t a l s of compound II contain solvate molecules , which does not contradic t the d i f ference in the composi t ions of compounds I and II (see above). To ve r i fy this assumpt ion , and also to es tab l i sh the s t e r e o c h e m i s t r y of the molecule of compound I we c a r r i e d out a complete x - r a y s t ruc tu ra l s tudy of the c rys t a l s of compound II,

S T R U C T U R E D E T E R M I N A T I O N

The intensi t ies of 1410 ref lec t ions w i th I - 3 r were measu red on a f o u r - c i r c l e "Syntex 1~" d i f f r ac tome te r ( x Mo, graphi te monochromator , 0~-scanning, 20 max =46~ The c ry s t a l gradual ly decomposed under the influ- ence of x - r a y s , and towards the end of the record ing the in tensi t ies of the th ree s tandard ref lec t ions dec rea sed by~10%; this was taken into account in the reca lcu la t ion of the in tens i t ies to s t ruc tu re fac tors . No allowance was made for absorpt ion.

The s t ruc tu re was de te rmined by the d i rec t method using the p r o g r a m s "Rentgen-70" [3]. All a toms other than hydrogen were detected. The calculat ion at this s tage c l ea r ly revea led the p r e sence of a solvate molecule of phenol, which may be fo rmed at the stage involving the hydro lys i s of the reac t ion mixture , by the oxidation of unreac ted phenylmagnes ium bromide . The re f inement was ca r r i ed out by the method of leas t squa res in the i so t rop ic approximat ion as fa r as R =0.121. A di f ference s e r i e s was then cons t ruc ted and r e - vealed all the H atoms. Finally, a re f inement cycle was ca r r i ed out, including the H a toms, in the i so t ropic approximat ion as fa r as R=0.083.

Table 1 gives the coordinates and t e m p e r a t u r e fac tors of the a toms other than hydrogen, Table 2 gives the ref ined coordinates of the H a toms , and Table 3 gives the pr inc ipa l bond lengths and valence angles. The number ing of the atoms and the a r r a n g e m e n t of the molecules in the unit cel l a re shown in Fig. 1.

The C - H bond lengths lie in the range 0.75-1.09 A (average 0.94 A).

The angles between the plane C(5), C(11), and C(17) and the planes of the benzene r ings C(5)...C(10) (A), C(11)...C(16) (B), and C(17)...C(22) (C) are 60.5, 64.5, and 38 .7 respec t ive ly . The dihedral angle between the planes A and C is 80.3 ~ and that between the planes B and C is 87.7 ~.

D I S C U S S I O N O F R E S U L T S

Compound II is the adduct C~gHIGNOP. C6H5OH. CigHI6NOP is the P-oxide of 5 -me thy l -10 -pheny l -5 ,10 - dihydrophenophosphazine (liD, the s t ruc tu re of which was de te rmined e a r l i e r [2]. As in compound III, the cent ra l he te rocyc l i c r ing in C19H16NOP is bent along the line P . . . N and has the boat conformat ion; the bulky Ph sub- st i tuent C occupies an axial posit ion, and the oxygen a tom O(3) occupies an equator ia l posit ion, which in com- pound III is occupied by the unshared pa i r of e lec t rons of the phosphorus atom.

The dihedral angle between the planes of the phenyl r ings A and B is 149.3 ~ (145.1 ~ in compound III).

Compar i son of compounds II and III shows a dist inct d i f ference in the P - C bond lengths and CPC va- lence angles. The average values are 1.777 A and 108.2 ~ for compound II, and 1.818 ,~ and 100.0 ~ for compound III. A s i m i l a r d i f ference may be obse rved by compar ing the s t r u c t u r e s of t r iphenylphosphine oxide [4] (1.792 A and 106.5 ~ and tr iphenylphosphine [5] (1.828 A and 103.0~). This d i f ference in the geome t r i c p a r a m e t e r s in the cor responding compounds OPR 3 and PR 3 is due to the di f ference in the hybr idizat ion of the phosphorus atom.

a

The molecule of compound II contains two dis tances between the benzene r ings sho r t e r than 3.6 A: C(18 ) . . .C (5 ) 3.10 and C(22)...C(11) 3.54 A. These contacts involve the a toms of the r ing C, and this explains the i nc rea se in the length of the P - C ( 1 7 ) bond to 1.796 A. An analogous i nc r ea se in the length of an exocycl ic P - C bond was also found in compound III [21.*

The phenol molecule f o r m s a hydrogen bond 0 (4 ) -H(4 ) . . . 0 (3 ) with the 5 -me thy l -10 -pheny l -10 -oxo-5 , 10-dihydrophenophosphazine molecule (see Fig. 1). This bond is fa i r ly s t rong, as indicated by the shor t d i s - t ances 0 ( 4 ) . . . O ( 3 ) 2.68 A, the marked dec rea se in the dis tance H ( 4 ) . . . 0 ( 3 ) 1.75 A compared with the sum of

o

the van der Wools radi i 2.57 A, and the la rge value of the angle O(4)H(4)O(3) 155 ~

* In [2] it was repor ted e r roneous ly that the molecule of compound III has th ree shor t d is tances between the benzene r ings; in fact , the re two suchd i s t ances : c ( i6 ) . .C(8) 3.30 and C ( 2 0 ) . . . C ( 9 ) 3.08 ,~ (numbering of the a toms according to [2]).

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The strength of the hydrogen bond ensures that compound II has a comparatively high stability. Thus rupture of the hydrogen bond and liberation of phenol take place only on heating to 160 ~ in a vacuum (2 mm ttg).

The formation of a hydrogen bond involving the phosphine oxide group is often observed in solution, but it is comparatively rarely studied by x-ray structural analysis, because of the difficulty of obtaining crystals.

/ The hydrogen bond 0 - - H . . . 0 = P ' ~ has been studied in only five papers [6-10]. In the adduct (CH~C~H4NH)3-

P(O)- C2HsOH [6], weak hydrogen~bonds involving ethanol (O. . .O 2.76 A) were detected. In 1-oxo-l-benzyl-2- phenyl-3-hydroxy-4,5-dimethylphosphol-2-ene [7], the hydrogen bond involving the hydroxyl group of a neigh- boring molecule is stronger than that in compound II (O . . .O 2.595 A, O . . . H 1.590 A). In the molecular com- plex formed by triphenylphosphine oxide with trichloroacetic acid, the hydrogen bond between the carboxyl and phosphoryl groups is even stronger (O . . .O 2.496, H . . . O 1.52 A [8]).

The authors thank A. I. Bokanov for discussion of the results obtained.

I.

2.

3.

4. 5. 6. 7. 8.

9.

10.

LITERATURE CITED

L. A. Yagodina, A. B. Kudryavtsev, E. N. Karpova, A. I. Bokanov, and B. I. Stepanov, Paper deposited at VINITI, July 30, 1975, 11o. 2329-75. Dep. (Ref. Zh. Khim., 21Zh346, 1975). S. N. Gurkova, A. I. 'Gusev, V. N. Sharapov, L. A. Yagodina, A. I. Bokanov, and B. I. Stepanov, Zh. Strukt. Khim., 18, 62 (1977). B. L. Tarnopol'skii, V. I. Andrianov, and Z. Sh. Safina, Description of and Instructions for the Set Rentgen-70. Rotaprint of the Branch of the Inst. of Chem. Phys., Acad. of Sciences of the USSR [in Russian] (1972). G. Ruban and V. Zabel, Cryst. Struct. Commun., 5, 671 (1976). J. J. DaVy, J. Chem. Soc., 3799 (1964). T. S. Cameron, M. G. Magee, and S. McLean, Z. Naturforsch., B31, 1295 (1976). D. Helm, D.M. Washecheck, J. E. Burks, and S. E. Ealick, Acta Cryst., B32, 659 (1976). L. Goli~ and V. Kau~ic, Cryst. Struct. Commun., 5, 319 (1976). G. P. Declercq, G. Germain, J. P. Putzeys, M. Van, and M. Meersshe, Cryst. Struct. Commun., 3, 579 (1974). A. E. Kalinin, V. G. Andrianov, and Yu. T. Struchkov, Zh. Strukt. Khim., 17, 153 (1976).

541