CRYSTAL STRUCTURE OF 10,10-DIMETHYLPHENOXA(THIA)SILINS O. A. D'yachenko, Yu. A. Sokolova, and L. O. Atovmyan UDC 548.312.5:547.

128

An x-ray crystallographic investigation of 10,10-dimethylphenoxasilin and 10,10dimethylphenothiasilin was undertaken. On the basis of the obtained results and of published data on the structure of related compounds it was shown that the d orbitals of the silicon atom do not take part in the formation of chemical bonds and the transfer of conjugation in the ring. It was observed that the oxygen atom has a "planarizing" effect on the conformation of the series of heterocycles. Electronegative substituents have different kinds of effects on the structure of the molecule. The structure of hetero derivatives of 9,10-dihydroanthracene containing silicon and oxygen or sulfur atoms in the central ring had not been studied Until recently, At the same time, according to the data from a series of investigations, compounds of this type possess certain characteristics which are not only of theoretical but also of practical interest, Thus, a comparative study of the compounds

M = SL,Ge~Srl ./\

by NMR (~H and XSC), UV, IR, CT, and NQR spectroscopy [1-4] has made it possible to regard them as the representatives of aromatic systems of a new type, in which the unshared electron pairs of the nitrogen, oxygen, and sulfur atoms interact with the unoccupied d orbitals of the silidon, germanium, and tin atoms through the T-electronic systems of the aromatic side rings. Here it was established that for the molecules in the ground state the conjugation decreases in the case of an identical element E in the series Si > Ge > Sn and with identical M in the series N > O > S. The enhanced stability of 10,10-dimethylphenoxasilin compared with the corresponding noncyclic compounds to the action of concentrated acids, alkalis, oxidizing agents (potassium permanganate in aqueous pyridine), and reducing agents, (iron filings in the presence of an electrolyte) was also interpreted as evidence for the aromaticity of the heterocycle [5]. There is no doubt that these characterlstic8 of the compounds are a reflection of their molecular structure. Investigation of the kinetics of oxidation, the XSC NMR spectra, and the photoelectron spectra of the 10,10-dimethyl derivatives with M = Si and E = NMe, O, S and M = Ge or Sn and E = S leads to the same conclusion; the main factors responsible both for the rates of the reactions and for the spectroscopic characteristics of the compounds are the changes in the geometry of their molecules [6]. However, all attempts to find a relation between the characteristics and the structure of the compounds were previously doomed to failure on account of the lack of structural investigations. Only recently has definite progress been noticed here; an x-ray crystallographic investigation was undertaken into four derivatives of phenazasilin (M = Si, E = NR) [7-10], phenoxagermin (M = Ge, E = O) [ii], and phenothiagermin (M = Ge, E = S) [12]. In a development of these investigations we have studied the crystal structure of lO,lO-dimethylphenoxasilin (I) and 10,10-dimethylphenothiasilin (II). EXPERIMENTAL Compound (I) crystallizes in the trigonal system: space group P3cl, a = b = 12.452(2), c = 14.379 (3) X, y = 120 ~ , V = 1930.8 ~3, M(CI4H140Si) = 226.35, d c a l c = 1.16 g/cm s, z = 6, Branch of the Institute of Chemical Physics, Academy of Sciences of the USSR. Translated from Zhurnal StrukturnoiKhimii, Vol. 25, No. 4, pp. 83-88, July-August, 1984. Original article submitted December 21, 1982.

582

0022-4766/84/2504-0582508.50

9 1985 Plenum Publishing Corporation

TABLE i. Atomic Coordinates of 10,10-Dimethylphenoxasilin (standard deviations given in parentheses) Atom x y z 3/4 3/4 0,8288(t) 0,9028(2) 0,9598(2) 0,9437(2) 0,8729(2) 0,8t67(2) Amm ~ y z

Si O c(t)
c(2)

c(3)
c(4)

0 0 --0,0789(2y --0,1541(2) --0,2167(2)

--0,2073(3) --0,t352(2) --0,0709(2)

c(5) c(6)

0,4436(I) 0,1875(2) 0,3092(2) 0,3065(2) 0,2054(3) 0,1004(3) 0,0993(2) 0,2028(2)

C(7) H(2) H(3) n(4) H(5) H(71) H(72) H(73)

--o,i141(2) -o,157(3) --0,259(3) -0,244(3) -0329(3) -o,i93(3)

--0,i41(3) --0,067(4)

0,4729(3) 0,375(3) 0,204(3) 0,025(4) 0,026(3) 0,393(3) 0,500(3) o,536(4)

o,o881(2) o,911(2) 1,o15(2) 0,983(2) 0,862(2) o,648(2) 0,727(2) 0,649(3)

TABLE 2. Atomic Coordinates of 10,10-Dimethylphenothiasilin (standard deviations given in parentheses) Atom S Si x y z

0,8405(0)
0,8840(0) 0,8969(t) 0,9207(2)

C(1) C(2)
c(3) c(4)

c(5) c(6) c(9) coo)

C(7) C(8)

0,9651(2) 0,9860(2) 0,9619(i) 0,9168(I) 0,9i02(I) 0,8760(I) 0,7644(i) 0,7485(I) 0,7734(I) 0,8141(I) 0,908(t) t,0t6(t) 0,975(I) 0,918(I) 0,935(i) 0,89i(2)
o,86o(t) 0,906(t) 0,860(2) 0,8t9(t) 0,745(1) 0,720(1) 0,764(t) 0,984(t) 0,83090) 0,8052(t)

o,13oi(i) -o,o755(i) o,1ooi(3) o,1729(4) o,1616(5) 0,0766(5) o,oo51(5)

0,0t6i(4) --0,2248(4)

0,0086(3) --0,0969(2) --0,1994(3)

--0,2tt3(3) --0,i2t9(4) --0,0208(3) --0,0079(3) 0,221(4) 0,203(3)

c(tt) C(t2)

c(13) c(14) H(3) H(4)

n(5) H(2)

H(71) H(72) H(73)

H(81) H(82) H(83) H(~0)

0,066(4) --0,062(3) --0,273(4) o,216(3) --0,282(5) 0,092(3)

o,ot8(4)

0,2970(2) 0,0255(I) 0,2960(6) 0,4124(7) 0,4151(8) 0,3077(6) 0,1964(7) 0,1834(6) --0,0i78(6) --03849(5) 0A374(4) 0,I076(5) 0,1798(5) 0,2878(5) 0,3263(5) 0,2498(4) 0,5i7(6) 0,509(4) 0,324(6) 0,124(4)
0,088(6)

-o,o81(5) -0304(7)
--0,t63(5)

-0,043(5)
--0,268(3) --0,288(4)

H(11) H(12) n(13)

--0,139(3) 0,045(3)

--0;251(6) --0,255(7) 0,024(5) 0,142(7) 0,359(5)

0,417(5)

~(CuKa) = 13.7 cm -I. The intensities of 1023 reflections of the hkO-khl4 type were measured in the range of angles 4 . 1 ~ ~. Compound (II) cryst~llizes in the rhombic system: space group Pbca, a = 30.850(6), b = 11.006(2), c = 7.590(1) A, V = 2577.1 A~, M ( C I , H ~ S S i ) = 242.42, dcalc = 1.25 g/cm s, Z = 8, ~(CuKa) = 27.5 cm -~. The intensities of 1651 reflections of the hk0-hk7 type were measured in the range of angles 2.2~ 0 ~ 67.4 . ~ In both cases the experimental data were obtained on an automatic DAR-UM diffractometer with CuK~ radiation and a graphite monochromator. Absorption was not taken into account. The two structures were determined by direct methods and were refined by the least-square method in anisotropic (nonhydrogen atoms) and isotropic (hydrogen atoms) approximation to R = 0.066 (I) and 0.059 (II). The atomic coordinates of the compounds are given in Tables 1 and 2. The general form of the molecules of (I) and (II), the bond lengths, and the bond angles are shown in Figs. 1 and 2. All the calculations were made by the set of Rentgen-75 [13] and ELLIDS [14] programs on a BESM-6 Computer.

583

M5

H5 v

(~

~5

05'.,-.~.119(2) 'f'~

c~,

I ...... ,

" c"

H3~.~ r - ~

(.~b,

_.LU'!,~I15,B(2) / Z . . ' ~

H?(~

111~

2~(.1!

6 H2'

Fig. I. The bond lengths (~) and bond angles (deg) in the molecule of 10,10-dimethylphenoxasilin.

C6-SL-CB 110,8 C7-S%~C9 !10,6 SL-C7-H72 1!1

H2

H71 - C 7 - N 7 5 SL-C8-N83 HB1-Cg-H 82

108 109 112. 116, C13 ~.59()/

H12 ~, 120~1, 06 118 20~4T c 12

L ~'zl c11flL~l,~

11,371

145

115 125 C'Zf / ~ L 1.4n1 ""~V 1221,376~ f l ~ l ~ , ~ ~ ' 115,9 ~ 122,5 25,7 1~.399 C6 116,7~ ~ , 9

107(I

1~598 121,1

!'014 " -:1,8

117 0~ 1~598 117,5~ ~119,5

H4

"010 1~08 H10

86'2

122-

I 9,2Y.~) 115 5 I.~00

110,9 H71(~ 1~866 863 H8I 0' 9 8 ~ , UO ~1 10'7 ~ 3 , j '~ 3 ~ ~="~ . 7 i:13

B72

L~H82

Fig. 2. Bond l e n g t h s (~) and bond a n g l e s (deg) in the molecule of lO,lO-dimethylphenothiasilin. Mean standa[d deviations: A (S-C , Si C) = 0.004, &(C--C) = 0.007, A(C--H) = 0.06 A, A(CSC, CSiC) = 0.2, A(SCC, SiCC) = 0.3, A(CCC) = 0.5, A(SiCH, CCH) = 3 ~ . DISCUSSION OF RESULTS On the basis of the investigation it was shown that the molecule of (I) has a crystallographic C2 symmetry. The twofold rotation axis passes through the Si and 0 atoms. The tricyclic system is close to planar; the dihedral angle ~ between the planes of the benzene rings is 175.6 ~ The maximum p[ojection of the atoms of the heterocycle from the average plane is not greater than 0.02 A. The tetrahedral configuration of the bonds at the Si atom deviates from the ideal mainly on account of the bond angles, which have values between 100.3 (i) and 112.4 (i) ~ The range of variation in the S i C bond lengths 1.845(1)--1.861(3) A is due to the different states of hybridization of the C atoms. The tricyclic system of (II) deviates substantially from planar (~ = 148.0~ The heterocycle has a boat conformation. The Si and S atoms project from the average plane passing

584

Structural Parameters of the Tricyclic System of Some Hetero Derivatives of the DihydroanthraTABLE 3 . cene Type

R( \R 1
Compound
E 0
Me

. Bond lengths, ,A

Angles, deg

Refer-

No,

I S

Si

H H Et Et EI Br It Br H

1,845d)
i,38i(2) i,767(4) i,408(3) t ,406(3) i,42(2) i,4t4(4) t,417(4)

i,388(3) 1,399(6) ,403(3) i,4i8(3) i,39(2) t,408(4) 1,409(4) 1,41(2) t,390(7) loi,i(t) 99,8(1) 98,7(6) 99,5(2) 99,6(2) I05,4(3) ~02,7(2) 1o4,6(2)

loo,3(i)

125,4(4) 1o7,1(2) 124,5(2) t2t,3(2) 12o0) t22,9(3) t.22,8(3) i27(t) 1o6,6(3)

i2i,9(2) 121,0(3) i19,4(2) it5,8(2)

125,1(2) i23,8(3) 122,5(2) t2t,1(2)

175,6 148,0 157;3 t.38,8 9 8

II

Si

Me Ph Ph Me Me
>) )>

i,863(4) t,85o(2) t,857(2) 1,86(t) 1,853(3) 1,848(3), 1,89(1)

III
N

Si N N N

IV

Si

Si

li8(f)
ti7,5(2)

i21(1) 12i,5(3)

140,9 i43,9

7 i0

VI

si

c7:{1aN
H tt

1i7,6(2)
1i6,0(4) i20,f(4)

12i,8(3) 126(i) 123,4(5)

147,4 i70,5 i43,6

))

"VII S Me

Ge

CI

1,37(I) 1,774(3)

it i2

Ge

1,933(7)

k.n 09

TABLE 4.

Geometry of the Molecules

"v CH2 S S SiMe 2

(z, deg

Referenee

x
0

Y SiM% GeM% GeC12 0

c~, deg

Referenee

CH2 S 0
SiM%

145,0
128,1

16
t7

GeM%

138,4
'155,5

18
19

0 0

i75,6 the present work 20 15i,6 ii 170,5 21 175,9

o

through the carbon atoms of the heterocycle by 0.51 and 0.49 A, respectively. The tetrahedral configuration of the silicon bonds deviates from the ideal to a lesser degree than with (I); the Si C bonds are practically identical [1.860(4)--1.864(4) ~], and the angles vary in a narrower range [104.6(2)--110.9(2)~ The obtained data are given in Table 3 together with published structural parameters of related compounds. Their analysis makes it possible to come to the following conclusions. The structural indications of an aromatic system (a planar ring structure and the absence of alternant bonds) are not realized to the full extent in any of the investigated compounds. The heterocycles are close to planar in (I) and (VII), but the length of the endocyclic S i C bond in (I) coincides within the error limits with the size of the analogous bonds in the remaining less planar heterocycles and hardly differs at all from the value of 1.84 ~ calculated by means of the Schomaker--Stevenson equation [15] for an ordinary S i C bond with allowance for the sp ~ hybridization of the C atom. The nonplanar structure of the tricyclic systems (1-VIII) together with the absence of shortened S i C bonds and the elongated C-C bonds, expected in the case of the formation of an aromatic system, indicates that the d orbitals of the Si atom do not participate in the formation of chemical bonds and in the transfer of conjuration in the ring. In our opinion the shortening of the Ge--C bonds in (VII) to 1.89(1) A i s due to the increase in the fraction of the ionic component of the Ge-C bond on account of the presence of the electronegative CI substituents at the Ge atom. Comparison of the angles e in the molecules of (I) and (VIII) demonstrates the clear "planarizing" effect of the oxygen atoms. A similar effect appears in the structures of the oxygen derivatives of dihydroanthracene (Table 4) and four-membered heterocycles; azetidine [22], thietane [23], and silacyclobutane [24] are characterized by a folded conformation, whereas oxetane [25] is planar. The planarizing effect of the 0 atom makes it possible to explain to some degree why the oxygen-containing azobenzene complexes have the trans structure unlike the cis structure of their analogs, i.e., the sulfur-containing complexes [26]. Evidently, the inclusion of the 0 atom in the metal ring leads to such flattening and to the steplike conformation of the molecule as a whole that the realization of the cis structure becomes impossible on account of steric hindrances arising between the phenyl substituents. Comparison of the phenazasilins (III-VI) shows what an appreciable effect the substituents R~, R2, and R3 have on the structure of the molecule. Here a special role is played by electronegative substituents, which have the strongest effect. Its character depends to a significant degree on the position of the substituent in the molecule. Thus, whereas the presence of Rs = Br increases the departure from planarity in the tricyclic system of (IV) by 18.5 ~ in comparison with (III), the presence of electronegative substituents Rt = CI at the Ge atom in (VII) leads to a substantial shortening of the Ge--C bonds in comparison with their normal values [e.g., see (VIII)]. The authors convey their gratitude to V. F. Traven' for providing the crystals. LITERATURE CITED~ i. 2. 3. 4. V . O . Reikhsfel'd, A. N. Egorochkin, V. A. Kuznetsov, et al., Dokl. Akad. Nauk SSSR, 253, 361 (1980). V. O. Reikhsfel'd, A. N. Egoroehkin, V. A. Kuznetsov, et al., Zh. Obshch. Khim., 50,

1095 (1980).
I . E . Saratov, I. P. Yakovlev, V. O. Reikhsfel'd, and F. P. Egorochkln, Zh. Obshch, Khim., 5-0, 1359 (1980). I . E . Saratov, I. P. Yakovlev, V. O. Reikhsfel'd, and V. I. Zakharov, Zh, Obshch. Khim,,

50, 1090 (1980).

586

5. 6. 7. 8. 9. i0. ii. 12. 13.

14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26,

V. F. Traven', V. B. Knyazhevskaya, Yu. M. Eismont, et al., Zh. Obshch. Khim.~ 51, 99 (1981). A. Ricci, D. Pietropaolo, G. Distefano, et al., J. Chem. Sot., Perkin Trans. II, 1977, 689. W. F. Paton, E. R. Corey, J. Y. Corey and M. D. Glick, Acta Crystallogr., B33, 226 (1977). A. B. Zolotoi, O. A. D'yachenko, L. O. Atovmyan, et al., Zh. Strukt, Khim., 21, 134 (1980). A. B. Zolotoy (Zolotoi), O. A. D'yachenko, L. O, Atovmyan, et al., J. Organomet. Chem,, 190, 267 (1980). T. Debaerdemaeker and U. Thewalt, Cryst. Struct. Commun., 1981, 1419. A. I. Udel'nov, V. E. Shklover, N. G. Bokii, et al., Zh, Strukt. Khim., 15, 83 (1974), G. D. Andreetti, G. Bocelli, P. Domiano, and P. Sgarabotto, J. Organomet. Chem., 179, 7 (1979). V. I. Andrianov, Zh. Sh. Safina, and B. L. Tarnopol'skii, Rentgen-75. Automated System of Programs for the Interpretation of Crystal Structures [in Russian], Chernogolovka (1975). A. N. Chekhlov, Kristallografiya, 26, 596 (1981). V. Schomaker and D. P. Stevenson, J. Am. Chem. Soc., 63, 37 (1941). W. G. Ferrier and J. Iball, Chem. Ind., 1954, 1296o I. Rowe and B. Post, Acta Crystallogr., ii, 372 (1958), S. Hosoya, Acta Crystallogr., 20, 429 (1966). O. A. D'yachenko, L. O. Atovmyan, S. V. Soboleva, et al., Zh. Strukt. Khim., 1-5, 667 (1974). O. A. D'yachenko, S. V. Soboleva, and L. O. Atovmyan, Zh. Strukt. Khim., 17~ 496 (1976). A. W. Cordes and C. K. Fair, Acta Crystallogr., B30, 1621 (1974). L. V. Vilkov, A. V. Golubinskii, V. S. Mastryukov, et al., Modern Problems of Physical Chemistry [in Russian], Izd. MGU, Moscow (1979), p. Ii. L. Karakida and K. Kuchitsu, Bull. Chem. Soc. Jpn., 48, 1691 (1975). V. S. Mastryukov, O. V. Dorofeeva, L. V. Vilkov, et al., Zh. Strukt. Khim., 16, 473 (1975). R. A. Creswell, Mol. Phys., 30, 217 (1975). O. A. D'yachenko, L. O. Atovmyan, S. M, Aldoshin, and V. V. Tkachev, Zh. Strukt. Khim.~ 19, 892 (1978).

587