1 tetramethylurea adduct

c79 Journal of Organometallic Chemisfry. 228 (1982)C79-C82 Elsevier Sequoia S.A., Lausann e - Printed in The Netherlands

communication

Prelimidry

THE CRYSTAL STRUCTURE OF DICHLORODIMETHYLTIN(N) TETRAMETHYLUREA ADDUCT

l/l

G. VALLE+, Centro di Ricerche sui Biopolimeri de1 CNR, Via Marzolo 1, 35100-Padova S.

(Italy)

CALOGERO,

Istituto di Chimica e Tecnologic dei Radioelementi 35100-Padova (Italy) endU.

de1 CNR, Corso Stati Uniti 4,

RUSSO

lstituto di Chimica Genemle ed Inorganica, Via Loredan 4, 35100-Padova

(Italy)

(Received December 3rd, 1981)

The results of a single crystal X-ray diffraction study of dichlorodimethyltin(IV)l/l tetmmethylurea adduct are reported. The compound is five-coordinated with a distorted trigon& bipyramidal geometry.

In a previous-study, a series of inorganic tin(IV) compounds with general formula SnX, 2L (L = urea or thiourea, X = Cl, Br or I) was described [ 11. The presence of cis-octahedral tin was demonstrated by the crystal structures of SnBr4 - 2(1,3-diethylurea) and SnC14 - 2(1,3diethylthiourea) and extended to the whple series by IR data and calculations of the steric angles on the basis of Zahrobski’s model. We have prepared and characterized a large number of adducts of organotin(IV) halides with urea or thiourea derivatives, and preliminary data on the crystal structure of Me, S&l, tmu (tmu = tetramethylurea) are reported below since to the best of our knowledge this is the first structural determination for a complex containing a urea derivative bonded to our organotin centre. The compound was obtained adding the stoichiometric quantity of tmu to a solution of MezSnClz in methyl ethyl ketone. Addition of pentane gave a white powder, which was filtered off, washed, and dried under vacuum. The elemental analysis agrees with the formula Me,SnCl, - tmu (Found: C, 25.0; l

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TNERMALPARAMETERSWITHESTIMATEDSTANDARD

H(71) H(72) W73)

H(43) H(61) H(W) HG3) HUM H(62) H(63)

H(31) w32) W33) W41) w42)

C(l) C(2) C(3) C(4) C(6) WI C(7) WW W22) W2a)

0.2033(7) 0,1674(B) 0,1669(10) 0,0768(10) 0,2727(10) 0,2864(D) 0,0218(s) 0,0411 0,2082 0,2168 O,lB67 0,0896 0,0836 0.1369 0.0046

0,0632 0.3186 0.3661 0.1977 0.2224 0.3343 0,3113 0.0688 0.9890 0.8466

0.2417(4) 0.2829(6) 0.1422(6) 0.3736(6) 0.3388(6) 0.0013(6) 0.1714(6) 0.2806 0.2730 0.3441 0.1383 0.1449 0,0064 0.4303 0.3463

0,3843 0,4032 0.2894 0.3346 0.8486 0.0232

0.963B 0.2830 0.1766 0.1386

0.9400 0.1273 0.9846 0.0937

0.8199 0.0103 0.0368 0.0236 0.1839 0.8628 0.7969

-0,1917(7) 4,4428(10) 4,4129(10) 4,1310(12) 0,0324(10) 4,1227(10) 0,0892(11) 0,0636 0,442D 0.6919 0.6021 0.4788 0.6629 0,8463

0.24(8) OS3(4) 0,14(6) 0.13(4)

O.OD(3) 0.16(B) 0.16(4) O.lO(3) 0.16(6), 0.26(s) 0.20(e)

0.048(4) 0.077(6) 0.066(6) 0,063(6) 0.064(6) 0,040(4) 0.048(4) 0.16(6) OJO(3) O.OD(3) 0,23(S) 0.12(3) 0.31(8) 0.14(4)

0.043(4) 0,079(6) 0,088(e) 0,074(6) 0,000(7) 0,077(6) 0,047(4)

0.049(4) 0.070(6) 0.061(4) O.lll(8) 0,031(6) 0,071(6) O.OB4(7)

0.004(3) -0.010(6) -0,002(4) 0,006(6) -0,018(6) 0,022(4) 0.016(4)

0.013(3) 4,004(a) 0.040(4) 4,020(6) l-J.O03(4) 4,017(4) 0.019(6) 0.017(6) 4X011(4) 4,011(6) 0,002(a) 0,014(4) 0,002(4) 0.006(3)

0.0461(3) 0.0439(2) 0.0046(Z) 0.0018(2) 0.0014(2) 0,0906(l) 0.1913(l) 0,03B6(1)0.0368(2) Sn 0,3730(2) 0.2129(2)0,081(l)0.063(l)0.063(l)-0.010(l) 0,011(l)-0.013(l) Cl(l) 0,1373(l) Cl(2) -0.0116(l)0.0994(2) 0.2061(2) 0.061(l)0.086(Z)0.073(l) 0.017(l) 0,026(l)-0,004(l) 0.1831(3) 0,2680(6) +.1326(6) 0,050(3)0.069(3)0.046(3) O.OOG(2) O.OlS(2) 0,006(2) O(1) 0.2287(4) 0,1606(6) -0,3372(6) 0,067(4)0,0913(4) 0.046(3)-0.006(3) 0.021(3)-0,009(a) N(1) 0.3174(3) O,lB32(7)4.1090(7) 0.047(3)0.063(4)0.061(4) O.OOl(3) O.OlO(3) 0,003(3) N(2)

Atom

FINALFRACTIONALATOMlC CO~ORDINATESAND DEVIATIONS INPARENTHESES

TABLE1

cm

H, 5.5; Cl, 21.2; N, 8.4. C,H1&lZN20Sn calcd.: C, 25.0; H, 5.4; Cl, 21.1; N, 8.3%). Crystals suitable for X-ray study were obtained by slow evaporation of the ketone_ The crystaIs are monoclinic with a = 16.241(g), b = 9.624(6), c = S-659(5) K p = 96_8(3)“, 2 = 4; U = 1344.0 A3, Do and& = 1.64 and 1.66 g cms3, F(OOO) = 664, space group P21 /n. Intensity data were collected using a Philips PW 1100 four-circle diffractometer in the range 4 <28 <50° with MO-K, radiation. Using the criterion I> 3 a(l), 2036 of the 2687 recorded intensities were independent and observable. Lorentz and polarization corrections were apphed. The structure was solved using a three-dimensional PattersonFourier synthesis. A full-matrix least-squares refinement on F was computed and the function ZW[ IF01 - IF,]] 2 in which w = 1 was minimized. The SHELX program [ 21 and the usual scattering factors [S] were used. The non-hydrogen atoms were refined anisotropicahy. The positions of the hydrogen atoms were located from a difference Fourier map but not refined. The final R value is 0.038. Fractional atomic coordinates are reported in Table 1. Tables of observed and calculated structure factors can be obtained from the authors_ The crystal structure is shown in Fig_ 1. The tin atom has a distorted trigonal bipyramidal geometry with the urea oxygen and one chlorine atom in the axial positions. This geometry is similar to that in Me,SnCl, - salicylaldehyde, which contains an axial carbonyl oxygen [4]. The IR spectrum of our compound is consistent with an O-bonded tmu. Its v(CN) band is found as a shoulder at ca. 1540 cm-’ with a positive shift of 35 cm-l from the free tmu, while the v(C0) is at 1554 with a negative shift of ca. 90 cm-’ _ The distortion in the

00000 Sn Cl

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C82

TABLE2 BONDDISTANCES(~)ANDANGLES(o)WITHESTIMATEDSTANDARDDEVIATIONSIN PARENTHESES

Srl
2.372<2) 2.49?(2) 2.100(7) 2.10?(7) 2.367(4) l-269(7)

C
1.335(S) l-465(9) 1.479(9) 1.356(8) 1.47(l) 1.45(l)


94.4(l) 104_5(3) 89.4(l) 107.2(3) 95.2(2) 176.2(l) 92.7(2) 83.3<3) 146.6(3) 86.7(3)

Sn-o(lFC(l) o(l)--C C(lFN(l)--c(2) C(2l-N(l)--c(3> C<3)_N(l)--c N(l)--C(l)--O(l)

132.6(4) 120.8(6) 120-l(6) 114.8(7) 123.4(7) 119.6<6) 123.5(6) 115.6(6) 117.7<6) 119.6<6) -

equatorial positions is large (cf. Table 2), while the 0-Sri-Cl angle is nearly regular. The tin atom is displaced by 0.15 A from the equatorial plane towards the axial chlorine atom, even if this Sri-Cl bond length is larger (by 0.12 A) than the equatorial ones. The two Sn-C(Me) bond distances are equal and in good agreement with the literature range of values [5]. The v,(Sn-C) and p,(Sn-C) absorptions, 568 and 518 cm-‘, respectively, are practically uneffected by coordination of the tmu ligand. As for Me, SnCl, - salicylaldehyde, our compound is present as discretemolecules, while some association between neighbouring molecules has been suggested for the related Me, SnCl, [6]. The structural difference between our compound and Me, SnCl, is illustrated by the spadings Sn- 0- Sn (4.71 and 4.2 A respectively) and Sno - Cl (3.66 and ca. 4.2 A vs. 3.54 A in Me, SnCI, )_ This confirmes [ 43 that the distortion of the C-Sri--angles is due to a large tin 5s orbital contribution to the Sri--- bond [7] and not to association [6]_ l

Acknowledgements. Partial financial support by NATO RG 157.80 is acknowledged_ One of us (U-R,) is grateful to the CNR (Rome) and to the ICTR-CNR of Padua for support.

References S. Calogero. U. Russo, G. Valle, P.W.C. Barnard and J.D. Donaldson. Inorg. Cbim. Acta, in press. G. Shcldxick.SHELX76Systemof computing~m~.UnivessitY ofCaxnbrid~.1976_ htemational Tables forX-ray CrystaUogra~h~. 2ndEdn..KynochRess.Birmingham.l974.~ol. 4. D_~gham.LDouefr.M.J.Frazer.M. McPartlina~dJ.D. Matthews.J.Orgsnometal_Chem.. 90(1975)C23. J.A.Zl&iets.J.J.Zucke~~an,inS.J. Lippad