Synthesis and structure of aroxy-tetra- p-tolylantimony (4-mec 6H 4) 4SbOC 6H 2Br 2-2,6-(t-Bu)-4 Текст научной статьи по специальности «Химические науки»

Химия элементоорганических соединений

DOI: 10.14529/chem160106

SYNTHESIS AND STRUCTURE OF AROXY-TETRA-P-TOLYLANTIMONY ^-MeCa^^SbOCa^B^S-Ct-BuM

P.V. Andreev1, [email protected] V.V. Sharutin2, [email protected] O.K. Sharutin a2, [email protected]

1 Nizhny Novgorod State University, Nizhny Novgorod, Russian Federation,

2 South Ural State University, Chelyabinsk, Russian Federation

Penta-p-tolylantimony interaction with 2,6-dibromo(4-tert-butyl)phenol has led to synthesis of the complex tetra-p-tolylantimony 2,6-dibromo(4-tert-butyl)phenoxide, whose structure has been established by X-ray diffraction. The antimony atom in the molecule (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4 has distorted trigonal-bipyramidal coordination with the aroxy group in axial position. The bond Sb-O is 2.229(2) A, the axial angle CSbO is 176.82(10)°.

Keywords: tetra-p-tolylantimony 2,6-dibromo(4-tert-butyl)phenoxide, synthesis, molecular structure, X-ray analysis.

Introduction

It is well known that in antimony derivatives of the general formula R4SbX the coordination polyhedron of the central atom and the character of its bonding with the electronegative ligand X is determined by the nature of this ligand and the organic radicals R. In the vast majority of R^SbX compounds the antimony atoms have trigonal-bipyramidal coordination in various degrees of distortion. Such compounds are of indisputable interest, as they make it possible to reveal the factors that determine the transition of SbC4 fragment into the tetrahedral structure. The analysis of the published structural data for aroxy-tetraphenylantimony Ph4SbOAr has shown that the distortion of the central atom coordination polyhedron in them increases if in aroxy group there are electron-donating substituents [1-5].

In continuation of the study how the nature of phenol and aryl radicals at the antimony atom influences the geometric characteristics of aroxy-tetraarylantimony molecules we have synthesized and established the structure of new aroxy-tetra-p-tolylantimony: (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4 (1).

Experimental

Synthesis of tetra-p-tolylantimony 2,6-dibromo(4-teri-butyl)phenoxide (1). The mixture of 0.29 g (0.5 mmol) penta-p-tolylantimony, 0.15 g (0.5 mmol) 2,6-dibromo(4-tert-butyl)phenol and 5 mL toluene was allowed to stand for 24 h at room temperature, then it was reduced to 1 mL and cooled. The yield was 0.35 g (87 %) of colorless crystals 1 with m.p. 209 °C. IR spectrum (v, cm-1): 1592, 1299, 1251, 1212, 1189, 1061, 1015, 866, 830, 797, 729, 575, 553, 486. Found, %: C 57.38; H 5.07; Br 20.05. Calculated for C38H39OBr2Sb, %: C 57.50; H 4.92; Br 20.18.

IR spectrum was recorded with the use of the IR spectrometer Bruker Tensor 27 in KBr pellet in the range 4000-400 cm-1.

X-ray diffraction analysis of the complex 1 crystal was performed on the Bruker D8 QUEST automatic four-circle diffractometer (Mo Ka-emission, X = 0.71073 A, graphite monochromator). The data were collected and analyzed, the unit cell parameters were refined, and the absorption correction was applied using the SMART and SAINT-Plus programs [6]. All calculations for structure determination and refinement were performed using the SHELXL/PC programs [7,8]. The structure 1 was determined by the direct method and refined by the least-squares method in the anisotropic approximation for non-hydrogen atoms. The position of hydrogen atoms was refined according to riding model (Driso(H) = 1.2Ueq(C)). The main crystallographic data and refinement results for structure 1 are listed in Table 1, the geometric characteristics of the antimony atom coordination tetrahedron are given in Table 2.

Химия элементоорганических соединений

Table 1

Crystallographic data and the experimental and structure refinement parameters for compound 1

Parameter Value

Empirical formula C38H39Br2OSb

Formula weight 793.26

T, K 273(2)

Crystal system Triclinic

Space group PI

a, A 10.7287(17)

b, A 13.0075(18)

c, A 14.446(2)

a, deg 74.905(7)

P, deg 75.639(8)

Y, deg 66.692(7)

V, A3 1763.5(5)

Z 2

p(calcd.), g/cm3 1.494

mm1 3.075

F(000) 792

Crystal size, mm 0.690 x 0.590 x 0.240

Range of refraction indices -13 < h < 13, -14 < k < 16, -18 < l < 18

Measured reflections 19747

Independent reflections 5586 (Rmt = 0.0345)

Refinement variables 402

GOOF 1.031

R factors for F2 > 2ct(F2) Rj=0.0337, wRj=0.0808

R factors for all reflections Ri=0.0498, wRi=0.0870

Residual electron density (min/max), e/A3 0.882/-0.658

Table 2

Selected bond lengths (d) and bond angles (¡a) in the structure of compound 1

Bond d, Â Angle ra, deg

Sb(1)-C(1) 2.114(3) C(1)Sb(1)0(31) 176.82(10)

Sb(1)-C(11) 2.112(3) C(11)Sb(1)C(1) 108.58(12)

Sb(1)-C(21) 2.111(3) C(21)Sb(1)C(1) 126.19(12)

Sb(1)-C(31) 2.174(3) C(1)Sb(1)C(31) 94.38(12)

Sb(1)-O(1) 2.229(2) C(21)Sb(1)C(11) 123.25(12)

O(1)-C(41) 1.320(4) C(1)Sb(1)O(1) 84.75(10)

C(41)O(1)Sb(1) 126.96(19)

The full tables of atomic coordinates, bond lengths, and bond angles were deposited with the Cambridge Crystallographic Data Centre (CCDC 1048264; [email protected]; http: //www.ccdc.cam .ac .uk).

Results and Discussion

Aroxy-tetra-p-tolylantimony 1 has been produced via dearylation of penta-p-tolylantimony by 2,6-dibromo(4-tert-butyl)phenol at mild conditions with 87 % yield:

(4-MeC6H4)5Sb + HOC6H2Br2-2,6-(t-Bu)-4 ^ (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4 + CH3C6H5

1

Compound 1 was crystallized from the toluene solution directly in the process of concentration.

According to X-ray diffraction analysis, in 1 the antimony atom has a distorted trigonal-bipyramidal coordination, trigonality degree t=0.84 [9], with the oxygen atom of the aroxy group in axial position (Fig. 1).

Bulletin of the South Ural State University. Ser. Chemistry.

2016, vol. 8, no. 1, pp. 41-45

Андреев П.В., Шарутин В.В., Шарутинa O.K.

Синтез и строение ароксида тетра-пара-толилсурьмы _(4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4

The atoms of the tert-butyl group C(48)-C(50) are disordered, they displace two positions with the ratio 0.62/0.38. The angle between the positions of the disordered fragment is equal to approximately 62° in relation to the bond C(44)-C(47). The axial angle OSbC equals 176.82(10)°, the sum of the angles CSbC in equatorial plane is equal to 358.0(3)°. The antimony atom deviates from the equatorial plane [C3] towards the axial carbon atom for 0.172 A, which causes departure of the angle values between axial and equatorial bonds from the theoretical value 90°. The angles OSbCeq and CaxSbCeq change within the range 84.62(10)°-86.83(10)° and 93.46(12)°-96.35(12)°, respectively, the bonds Sb-Ceq coincide within the measurement accuracy and equal 2.111(3)-2.114(3) A. The lengths Sb-Cax [2.174(3) A] are longer than equatorial ones, which is typical for trigonal-bipyramidal structures. The length Sb-O equals 2.229(2) A, much higher than the sum of covalent radii of antimony and oxygen atoms (2.07 A [10]).

All observed geometrical parameters for the molecule of compound 1 (decrease of the sum of equatorial angles, significant deviation of the antimony atom from the equatorial plane, approximation of the values for axial and equatorial bonds) point at the tendency of the antimony trigonal-bipyramidal coordination to transform into tetrahedral one [11].

It should be noted that unlike compound 1, tetraphenylantimony picrate (2) is an ionic compound.

Changing of the antimony atom coordination polyhedron in the series of tetraarylantimony aroxides can be explained by consideration of the Sb-O bond nature in respect to the phenolate anion basicity, which is determined by electron density redistribution in the aroxy group, depending on the substituent nature in it. The lower is the phenolate anion basicity, the less strong is the coordination bond Sb-O, and the structure of the compound Ar4SbOAr' approaches ionic character to a greater extent. Three nitro groups in 2, with their negative inductive effect, contribute to stabilization of phenolate anion and decrease in its basicity, at that the group Ph4Sb transforms into the stable tetrahedral cation.

Conclusions

To summarize, the distortion of trigonal-bipyramidal configuration of aroxy-tetraarylantimony compounds and the lengthening of the Sb-O bond are both determined by electron acceptor properties of the aroxy group, which strengthen with increasing number of electron acceptor substituents in the aromatic ring.

Химия элементоорганических соединений

References

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2. Sharutin V.V., Sharutina O.K., Osipov P.E., Pushilin M.A., Muslin D.V., Lyapina N.S., Zhidkov V.V., Bel'skij V.K. [Reactions of Pentaarylantimony with Ortho-substituted Phenols]. Zhurn. obshch. himii, 1997, vol. 67, iss. 9, pp. 1528-1530. (in Russ.)

3. Sharutin V.V., Sharutina O.K., Osipov P.E., Vorob'eva E.B., Muslin D.V., Bel'skij V.K. Aroxy-tetraaryl antimony compounds. Synthesis, structure and thermolysis. Russian Journal of General Chemistry, 2000, vol. 70, no. 6, pp. 867-872.

4. Sharutin V.V., Sharutina O.K., Osipov P.E., Platonova T.P., Pakusina A.P., Fukin G.K., Zakha-rov L.N. Synthesis and structure of 2-tert-butylphenoxytetraphenylantimony. Russian Journal of Coordination Chemistry, 2001, vol. 27, no. 7, pp. 483-485.

5. Sharutin V.V., Sharutina O.K., Bondar' E.A., Subacheva O.V., Pakusina A.P., Gerasimen-ko A.V., Sergienko S.S. Synthesis and structure of (4-acetyl-3-hydroxuphenoxy)tetraphenylantimony. Russian Journal of General Chemistry, 2003, vol. 73, no. 3, pp. 350-353. DOI: 10.1023/A: 1024993400389

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8. Sheldrick G.M. A Short History of Shelx. Acta Cryst. A, 2008, vol. 64, pp. 112-122. DOI: 10.1107/S0108767307043930

9. Addison A.W., Rao T.N., Reedijk J., Rijn J., Verschoor G.C. Synthesis, Structure, and Spectroscopic Properties of Copper(II) Compounds Containing Nitrogen-Sulphur Donor Ligands; the Crystal and Molecular Structure of Aqua[1,7-bis(N-methylbenzimidazol-2'-yl)-2,6-dithiaheptane] copper(II) Perchlorate. J. Chem. Soc. Dalton Trans, 1984, no. 7, pp. 1349-1356. DOI: 10.1039/DT9840001349.

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11. Sharutina O.K., Sharutin V.V. Molekulyarnye struktury organicheskikh soedineniy sur'my (V) [The Molecular Structure of Organic Compounds Antimony(V)]. Chelyabinsk, South Ural St. Univ. Publ., 2012, 395 p.

Received 5 November 2015

УДК 546.865+547.53.024+547.563.4+548.312.5 DOI: 10.14529/chem160106

СИНТЕЗ И СТРОЕНИЕ АРОКСИДА ТЕТРА-ПАРА-ТОЛИЛСУРЬМЫ (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4

П.В. Андреев1, В.В. Шарутин2, О.К. Шарутина2

1 Нижегородский государственный университет, г. Нижний Новгород,

2 Южно-Уральский государственный университет, г. Челябинск

Взаимодействием пента-пара-толилсурьмы с 2,6-дибром(4-трет-бутил)фенолом в толуоле синтезирован 2,6-дибром(4-трет-бутил)феноксид тетра-пара-толилсурьмы, строение которого установлено методом РСА. Атом Sb в молекуле (4-MeC6H4)4SbOC<5H2Br2-2,6-(t-Bu)-4 имеет искаженную тригонально-бипирамидальную

Bulletin of the South Ural State University. Ser. Chemistry.

2016, vol. 8, no. 1, pp. 41-45

Андреев П.В., Шарутин В.В., Шарутинa O.K.

Синтез и строение ароксида тетра-пара-толилсурьмы _(4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4

координацию с ароксигруппой в аксиальном положении. Связь Sb-O равна 2.229(2) А, аксиальный угол CSbO составляет 176.82(10)°.

Ключевые слова: 2,6-дибром(4-трет-бутил)феноксид тетра-пара-толилсурьмы, синтез, молекулярная структура, рентгеноструктурный анализ.

Литература

1. Синтез, строение и термическое разложение арокситетрафенилстиборанов / В.В. Шарутин, В.В. Жидков, Д.В. Муслин и др. // Изв. АН СССР. Сер. хим. - 1995. - № 5. - С. 958-963.

2. Реакции пентаарилсурьмы с орто-замещенными фенолами / В.В. Шарутин, О.К. Шарутина, П.Е. Осипов и др. // Журн. общ. химии. - 1997. - Т. 67. - № 9. - С. 1528-1530.

3. Арокситетраарильные соединения сурьмы. Синтез, строение и термическое разложение / В.В. Шарутин, О.К. Шарутина, П.Е. Осипов и др. // Журн. общ. химии. - 2000. - Т. 70, № 6.

- С. 931-936.

4. Синтез и строение 2-третбутилфенокситетрафенилсурьмы / В.В. Шарутин, О.К. Шарутина, П.Е. Осипов и др. // Коорд. химия. - 2001. - Т. 27, № 7. - С. 518-520.

5. Синтез и строение 3-гидокси-4-ацетилфенокситетрафенилсурьмы / В.В. Шарутин, О.К. Шарутина, Е.А. Бондарь и др. // Журн. общ. химии. - 2003. - Т. 73, № 3. - С. 376-379.

6. Bruker (2000) SMART. Bruker Molecular Analysis Research Tool, Versions 5.625 Bruker AXS, Madison, Wisconsin, USA.

7. Bruker (2000) SAINTPlus Data Reduction and Correction Program Versions 6.02a, Bruker AXS, Madison, Wisconsin, USA.

8. Sheldrick, G.M. A Short History of Shelx / G.M. Sheldrick // Acta Cryst. A. - 2008. - V. 64. -P.112-122.

9. Synthesis, Structure, and Spectroscopic Properties of Copper(II) Compounds Containing Nitrogen-Sulphur Donor Ligands; the Crystal and Molecular Structure of Aqua[1,7-bis(Af-methylbenzimidazol-2'-yl)-2,6-dithiaheptane]copper(II) Perchlorate / A.W. Addison, T.N. Rao, J. Ree-dijk et al. // J. Chem. Soc. Dalton Trans. - 1984. - № 7. - Р. 1349-1356.

10. Бацанов, С.С. Атомные радиусы элементов / С.С. Бацанов // Журн. неорган. химии. - 1991.

- Т. 36, вып. 12. - С. 3015-3037.

11. Шарутина, О.К. Молекулярные структуры органических соединений сурьмы (V) / О.К. Шарутина, В.В. Шарутин. - Челябинск: Издательский центр ЮУрГУ, 2012. - 395 с.

Андреев Павел Валерьевич - аспирант, младший научный сотрудник НИЛ кафедры кристаллографии и экспериментальной физики. Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Н. Новгород, пр. Гагарина, 23А. E-mail: [email protected].

Шарутин Владимир Викторович - доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: [email protected].

Шарутина Ольга Константиновна - доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: [email protected].

Поступила в редакцию 5 ноября 2015 г.

ОБРАЗЕЦ ЦИТИРОВАНИЯ

Andreev, P.V. Synthesis and structure of aroxy-tetra-p-tolylantimony (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4 / P.V. Andreev, V.V. Sharutin, O.K. Sharutina // Вестник ЮУрГУ. Серия «Химия». - 2016. - Т. 8, № 1. - С. 41-45. DOI: 10.14529/chem160106

FOR CITATION

Andreev P.V., Sharutin V.V., Sharutina O.K. Synthesis and structure of aroxy-tetra-p-tolylantimony (4-MeC6H4)4SbOC6H2Br2-2,6-(t-Bu)-4. Bulletin of the South Ural State University. Ser. Chemistry. 2016, vol. 8, no. 1, pp. 41-45. DOI: 10.14529/chem160106