The structure contains two hydrogen bonds 0(1)--0(2), 2.79 ~, and 0(1)--N(1), 2.78 (Figs. 2 and 3). The hydrogen bonds connect the molecules in infinite double layers, almost parallel to the yz plane. These layers are joined to one another by van der Waals forces. The structure does not contain any anomalously short intermolecular contacts.

.

2.

3. 4~

5. 6. 7.

LITERATURE CITED

V. N. Furmal', Ya. K. Futnlnt, V. P~ Barkan, and E.~ Yu. Gudrinietse, Izv. Akad. Nauk Latv. SSR, Sen Khim., 2, 234 (1972). V. N. Yurmal', Ya. K. Putnin', V. M, Ivanov, and E~ Yu. Gudrinietse, Izv. Akad. Nauk Latv. SSR, Ser. Khim., 3, 324 (1973). M. Kurahashi, Chem. Lett., _23 181 (1974). M. Kurahashi, M. Fukuyo, A. Shlmada, and A. Kawase, Bull. Chem. Soc., Jpn., 49, 872 (1976). M. Kurahashi and A. Kawase, Bull. Chem. Soc. Jpn., 49, 1419 (1976). S. K. Apinitis, Izv. Akad. Nauk Latv. SSR, Ser. Khlm., 4, 390 (1977). H. Wunderlich and D. Mootz, Acta Cryst., 27, 1684 (1971).

X-RAY DIFFRACTION STUDY OF THE STRUCTURE OF THE HYDRAZINE

ADDITION COMPOUND OF HYDRAZINIUM TETRAETHYNYLBORATE

N2HsB(C~CH)~'N=H~

A. I. Gusev, D. Yu. Nesterov, A. F. Zhigach, R. A. 8vitsyn, and E. S. Sobolev

UDC 548.737

Ammonium salts of tetraethynylborate were described earlier [i, 2]. The hydrazine ad- dition compound of hydrazinium tetraethynylborate (I) was first obtained by the hydrazinoly- sis of ammonium tetraethynylborate:

(CH3)3NHB(C=CH)~ -t- 2N2H4 ~ N'2H~B(C--~CH)~'N~H4 q- N(CHa)3 (I)

Compound I crystallizes from methanol and melts at 130.0 • 0.2 ~ . Found, %: C 71.52, H 9.46, N 10.08, B 7.82. Calculated for CsNI~N4B, %: C 71.75, H 9.72, N 10.46, B 8.07.

The structure of compound I was studied to determine the position of the hydrazine mole- cule relative to the tetraethynylborate anion.

The studies were carried Out on a syntex four-circle automatic diffractometer; space group P2,/b, a = 9.862, b = 11.758, c = 9.653 ~, y = i06.95 ~ dcalc= 1.097, dmeas = 1.081 g/cm s, Z = 4. The structure was determined by the direct method and refined by the method of least squares in the isotropic approximation from 1247 reflections with I >- 3o (Mo K~ ra- dlation). The H atoms were revealed by a difference synthesis., The final value of R = 0.083. The parameters of all the atoms were refined, and their coordinates are given in Table i.

The structure is made up of B(C=CH)~ anions, hydrazinium cations N2H +, and a hydrazine molecule NzH~, the relative arrangement of which in the unit cell is shown in Fig. i. The bond lengths and valence angles are given in Tables 2 and 3.

The anion has an almost regular tetrahedral configuration; the mean value of the valence angle CBC coincides with the ideal tetrahedral value (109.5~ The lengths of the B--C, C-C, and C--H bonds show good agreement with published data [2]. The cation and the hydrazine molecule are joined to one another by hydrogen bonds N(2)...N(3) and N(4)...N(2"), charac- terized by the following parameters: N(3)...H(8)I.94(5), N(4)...H(9")I.99 A, N(2)H(8)N(3)I70, N(4)H(9")N(2") 172 ~ . Each N atom of the N=H~ molecule forms a hydrogen bond with the N=H~ cation, and each cation in turn forms hydrogen bonds with two N,H5 molecules, related by the center of symmetry 1/2, 1/2, 1/2 (see Fig. I). Thus in the structure it is possible to dis- tinguish associates containing two N2H~ molecules and two NzHs + cations, joined by hydrogen

Translated from Zhurnal Strukturnoi Khimii, Vol. 19, No. i, pp. 180-182, January-Feb- ruary, 1978. Original article submitted March i0, 1977.

0022-4766/78/1901-0161507.50 �9 1978 Plenum Publishing Corporation 161

TABLE i. Coordinates of the Atoms and Tem- perature Factors Biso, ~2

Atom x u z Biso, ~2

B C(t) C(2) C(3) c(4) c(5) c(6) c(7) c(8)

N(2) N(3) N(4) H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(t3)

0,2308(4) 0~1242(4) 0,0426(5) 0,3880(6) o,5o65(5) 0,t867(6) 0,1496(5) o,2163(6) 0,2064(4) 0,t896(5) 0,2726(4) 0,3625(5) 0,4878(5)

--0,009(8), 0,6i4(14) o,i07(5) 0,t98(8) 0,127(7) 0384(8)

0,26t2(3) 0,i676(3) 0,0972(4) 0,2577(4) 0,2543(5) 0,2275(3) 0,2023(4) 0,3900(4) 0,4855(5). 0,3346(4) o,4549(3) o,5tlo(4) 0,4885(4) o,o61(5) 0,25100) o,174(4) 0,554(6) 0,327(6) 0,315(6)

o,oo4i(5) --0,0945(4) --0,1642(5) --0,0t96(4) --0,0339(6)

0,1599(4) 0,2749(5)

--0,0297(5) --0,0565(6)

0,6000(4) 0,5762(4) 0,2959(5) 0,2469(5)

--0,2t8(6) -o,o5i04)

0,350(6) --0,077(9)

0,567(8) 0,692(8)

0,253(5) 0,5i5(4) 0,300(6) 0,464(4) 0,349(5) 0,473(4) 0,288(t0) 0,501(9) 0,395(5) 0,576(4) 0,463(10) 0,406(8) 0,5i2(7) 0,534(6)

0,597(5) 0,483(6) 0,622(5) 0,234(10) 0,302(5) 0,226(10) o,168(8)

2,33(7) 2,43(7) 3,8t(9) 2,83(7) 4,70(t0) 2,40(7) 3,74(9) 2,74(7) 4,13(9) 4,05(8) 3,32(8) 4,25(8) 4,80(9) .3(1) 14(4) 2(t) 7(2) 5(t) 5(t) 2(I) 2(1) t(t) 9(2) t,(t) 8(2) 5(2)

TABLE 2. Bond Lengths d,

Angle a d Angle

1,597(6) N(I)--N(2) t,580(7) N(3)--N(4) 1,584(6) N(1)--H(5) 1,596(7) N(t)--H(6) t,181(6) N(2)--H(7) t,t89(8) N(2)--H(8) t,i79(6) N(2)--H(9) t,t84(7) N(3)--H(t0: 0,77(6) N(3)--H(lt) t,08(t5) N(4)--H(t2) 0,86(5) N(4)--H(t3) 0,85(8)

B--C0) B--C(3) B--C(5) B--C(7) C(t)--C(2) C(3)--C(4) c(5)-c(6) C(7)--C(8) C(2)--H(I) C(4)--H(2) C(6)--H(3) C(8)--H(4)

t,431(6) 1,4t8(7) 0,67(7) 0,92(7) o,s1(5) 0,94(5) 0,85(5) o,93(1o) 0,74(4) 0,95(9) 0,92(7)

TABLE 3. Valence Angles ~ (deg)

Angle ~ Angle s Angle

C(I)BC(5) C(t)BC(3) C(t)BC(7) C(5) BC(3) C(5)BC(7) C(3)BC(7) BC(I)C(2) BC(3)C(4) BC(5)C(6) BC(7)C(8)

t08,4(2) tt0,4(3) 108,1(3) 109,3(3) 109,7(3) flo,8(4) 178,2(4) t78,3(4) 177,9(4) t79,t(4)

C(1)C(2)H(1) C(3)C(4)H(2) C(5)C(6)H(3) C(7)C(8)H(4) N(2)N(t)H(5) N(2)N(t)H(6) H(5)N(I)H(6) N(I)N(2)H(7) N(I)N(2)H(8) -N(1)N(2)H(9)

t7o(4) 178(3) t68(5) 16t(5) to7(4)

�9 tt2(4) 115(5) t27(3) lO9(2) 112(3)

H(7)N(2)H(8) H(7)N(2)H(9) H(8)N(2)H(9) N(4)N(3)H(10) N(4)N(3)H(it) H(10)N(3)H(tt) N(3)N(4)H(12) N(2)N(4)H(t3) H(12)N(4)H(13)

105(4) 94(4)

to5(3) t17(6) 94(4)

to5(6) 1o6(5) io5(4) tt1(6)

162

;/,~

t-I 5

TI ~41 ,

hi2

H4 H'I,

Fig. 1

~ - . 1 1 I,I

bonds. The arrangement of the atoms H(8) and H(9") is such that they bring the coordination of the atoms N(3) and N(4) up to tetrahedral, and the corresponding angles are N(2)N(3)H(8) 119, H(8)N(3)H(10) 113, H(8)N(3)H(II) 109, N(3)N(4)H(9") 116, H(9")N(4)H(12) 108, and H(13)N(4)H(9") Ii0 ~ .

Thereare also several shortened contacts between the anion and the hydrogen atoms of the cation.

LITERATURE CITED

i. A.F. Zhigach, R. A. Svltsyn, E. S. Sobolev, and I. V. Persianova, Dokl. Akad. Nauk SSSR, 196, 1349 (1971).

2. A.I. Gusev, M. G. Los', A. F. Zhigach, R. A. Svltsyn, and E. S. Sobolev, Zh. Strukt. Khlm., 17, 537 (1976).

163