Synthesis and structure of iridium complex [pH 4Sb(DMSO)] +[IrCl 4(DMSO) 2] - Текст научной статьи по специальности «Химические науки»

DOI: 10.14529/chem150410

SYNTHESIS AND STRUCTURE OF IRIDIUM COMPLEX [Ph4Sb(DMSO)]+[IrCl4(DMSO)2]-

V.V. Sharutin, vvsharutin@rambler.ru O.K. Sharutina, sharutinao@mail.ru V.S. Senchurin, senvl@rambler.ru

South Ural State University, Chelyabinsk, Russian Federation

Iridium complex [Ph4Sb(DMSO)]+[IrCl4(DMSO)2r (1) has been synthesized by interaction of tetraphenylstibonium chloride with sodium hexachloroiridate(III) in water. From X-ray diffraction analysis data, two types of crystallographically independent cations [Ph4Sb(DMSO)]+ and anions [IrCl4(DMSO)2]- exist in the crystal. The antimony atoms in cations have distorted trigonal-bipyramidal surroundings with O-dimethyl sulphoxide ligand in axial position (equatorial angles CSbC 113.6(2)°-121.2(2)°, axial angles CSbO 178.33(18)°, 176.47(18)°, bond lengths Sb-Ceq 2.106(6)-2.119(6) A, Sb-Cax 2.126(6), 2.130(6) A, Sb-0 2.545(4), 2.465(4) A). In mononuclear octahedral anions the equatorial positions are occupied by chlorine atoms (angles ClIrCl-trans178.69(7)°-179.56(7)°, SIrS-trans 178.35(7)°, 175.88(7)°; dimethyl sulfoxide ligands are coordinated with iridium atoms through sulfur atoms (Ir-S 2.2958(16)-2.3148(17) A), bond lengths Ir-Cl vary in the range 2.3407(19)-2.3681(17) A. The structural organization in the crystal is determined by interionic hydrogen bonds (H-Cl 2.80-2.94 A and H-Q 2.56-2.71 A).

Keywords: tetraphenylstibonium chloride, sodium hexachloroiridate(III), dimethyl sulfoxide, (dimethylsulfoxido)tetraphenylstibonium bis(dimethylsulfoxido)tetrachloroiridate(III), synthesis, X-ray diffraction analysis, structure.

Introduction

Ionic complex compounds of iridium with anions of the type [IrHal4(<S-DMSO)2]- are described in the literature as single examples [1-4]. Note that both organic cations and tetraorganylphosphonium cations [4] can act as counterions in the crystals of these compounds, at this the structural organization of iridium complexes is determined by the presence of solvent molecules in their structure. In the present paper the synthesis of (dimethylsulfoxido)tetraphenylstibonium Ô7's(dimethylsulfoxido)tetrachloroiridate (III), the characteristic features of its structure are examined.

Results and Discussion

In order to synthesize new iridium complexes we studied the reactions of tetraphenylstibonium chloride with sodium hexachloroiridate(III) in aqueous solution.

It has been found that after addition of sodium hexachloroiridate(III) in water to the aqueous solution of tetraphenylstibonium chloride in equimolar amount, followed by solvent evaporation and recrys-tallization of the solid precipitate from dimethyl sulfoxide, yellow crystals are formed; it is (dimethylsul-foxiodo)tetraphenylstibonium bis(dimethylsulfoxido)tetrachloroiridate(III) [Ph4Sb]+[IrCl4(DMSQ)2]- (1):

1. H2O

Ph4SbCl + NasIrCl6 -— [Ph4Sb(DMSO)]+ [IrCl4(DMSQ)2]- + 3 NaCl

2. DMSQ 1

According to X-ray diffraction analysis, two types of crystallographically independent cations [Ph4Sb(DMSO)]+ and anions [IrCl4(DMSO)2]- coexist in the crystal. The antimony atoms in cations have distorted trigonal-bipyramidal surroundings with O-dimethyl sulphoxide ligand in axial position (equatorial angles CSbC 113.6(2)°-121.2(2)°, axial angles CSbO 178.33(18)°, 176.47(18)°, bond lengths Sb-Ceq 2.106(6)-2.119(6) À, Sb-Cax 2.126(6), 2.130(6) À, Sb-O 2.545(4), 2.465(4) À) (Fig. 1).

Sharutin V.V., Sharutina O.K., Senchurin V.S.

Synthesis and structure of iridium complex _[Ph4Sb(DMSO)]+[IrCl4(DMSO)2]-

Fig. 1. The structure of compound 1

In mononuclear octahedral anions the equatorial positions are occupied by chlorine atoms (angles ClIrCl-trans 178.69(7)°-179.56(7)°, SIrS-trans 178.35(7)°, 175.88(7)°; dimethyl sulfoxide ligands are coordinated with iridium atoms through sulfur atoms (Ir-S 2.2958(16)—2.3148(17) A), bond lengths Ir-Cl vary in the range 2.3407(19)-2.3681(17) A. The structural organization in the crystal is determined by interionic hydrogen bonds (H-Cl 2.80-2.94 A and H-O 2.56-2.71 A), the strongest ones are shown in Fig. 2. Cations and anions are packed in stacks oriented along crystallographic axis a.

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 [5]. All calculations for structure determination and refinement were performed using the SHELXL/PC programs [6]. 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 main crystallographic data and refinement results for structure 1 are listed in Table 1, the selected bond lengths and bond angles are given in Table 2.

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

Fig. 2. Interionic bonds in the crystal of compound 1

Table 1

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

Parameter Value

Empirical formula C60O6S6a8Sb2Ir2H76

Formula weight 1997.07

T, K 296(2)

Crystal system Triclinic

Space group P-1

a, A 9.5963(6)

b, A 19.2090(14)

c, A 19.5688(14)

a, deg 91.109(3)

P, deg 90.549(2)

Y, deg 90.095(3)

V, A3 3606.4(4)

Z 2

p(calcd.), g/cm3 1.839

|i, mm-1 4.935

F(000) 1944.0

Crystal size, mm 0.11 x 0.18 x 0.24

28 Range of data collection, deg 5.98 — 41.32°

Range of refraction indices -9 < h < 9, -19 < k < 19, -19 < l < 19

Measured reflections 67394

Independent reflections 7363

Rint 0.0325

Sharutin V.V., Sharutina O.K., Senchurin V.S. Synthesis and structure of iridium complex [Ph4Sb(DMSO)]+[Ira4DMSO)2r

Table 1 (end)

Parameter Value

Refinement variables 769

GOOF 1.026

R factors for F2 > 2ct(F2) R1 = 0.0237, wR2 = 0.0533

R factors for all reflections R1 = 0.0286, wR2 = 0.0560

Residual electron density (min/max), e/A3 1.12/-0.93

Table 2

Selected bond lengths and bond angles in the structure of compound 1

Bond d, Â Angle ra, deg

Ir(1)-S(3) 2.2958(16) S(3)Ir(1)S(4) 178.35(7)

Ir(1)-S(4) 2.3002(15) S(3)Ir(1)Cl(3) 90.09(8)

Ir(1)-Cl(3) 2.3407(19) S(3)Ir(1)Cl(4) 87.48(6)

Ir(1)-Cl(4) 2.3529(16) S(3)Ir(1)Cl(5) 92.21(6)

Ir(1)-Cl(5) 2.3500(17) S(3)Ir(1)Cl(6) 90.33(7)

Ir(1)-Cl(6) 2.3681(17) S(4)Ir(1)Cl(3) 91.55(7)

Ir(2)-S(5) 2.311(2) S(4)Ir(1)Cl(4) 92.71(6)

Ir(2)-S(6) 2.3148(17) S(4)Ir(1)Cl(5) 87.62(6)

Ir(2)-Cl(7) 2.3493(18) S(4)Ir(1)Cl(6) 88.03(6)

Ir(2)-Cl(8) 2.3498(17) Cl(3)Ir(1)Cl(4) 90.30(8)

Ir(2)-Cl(9) 2.3546(17) Cl(3)Ir(1)Cl(5) 88.89(8)

Ir(2)-Cl(10) 2.3396(17) Cl(3)Ir(1)Cl(6) 179.56(7)

Sb(1)-O(1) 2.545(4) Cl(4)Ir(1)Cl(6) 89.60(7)

Sb(1)-C(1) 2.117(6) Cl(5)Ir(1)Cl(4) 179.14(7)

Sb(1)-C(11) 2.106(6) Cl(5)Ir(1)Cl(6) 91.20(8)

Sb(1)-C(21) 2.106(6) S(5)Ir(2)S(6) 175.88(7)

Sb(1)-C(31) 2.126(6) S(5)Ir(2)Cl(10) 91.53(8)

Sb(2)-O(2) 2.465(4) Cl(7)Ir(2)Cl(9) 179.22(7)

Sb(2)-C(51) 2.106(6) Cl(10)Ir(2)Cl(8) 178.69(7)

Sb(2)-C(71) 2.130(6) Cl(10)Ir(2)Cl(9) 90.30(8)

Sb(2)-C(41) 2.111(6) C(1)Sb(1)O(1) 77.93(19)

Sb(2)-C(61) 2.119(6) C(1)Sb(1)C(31) 100.4(2)

O(4)-S(4) 1.459(5) C(11)Sb(1)O(1) 78.92(18)

O(6)-S(6) 1.464(5) C(11)Sb(1)C(1) 116.7(2)

S(1)-O(1) 1.457(5) C(11)Sb(1)C(21) 113.6(2)

S(1)-C(38) 1.739(10) C(11)Sb(1)C(31) 102.2(2)

S(1)-C(37) 1.785(11) C(21)Sb(1)O(1) 80.45(19)

S(2)-O(2) 1.517(4) C(21)Sb(1)C(1) 119.2(2)

S(2)-C(77) 1.763(8) C(21)Sb(1)C(31) 100.2(2)

S(2)-C(78) 1.753(9) C(31)Sb(1)O(1) 178.33(18)

S(3)-O(3) 1.450(5) C(51)Sb(2)O(2) 82.50(18)

S(3)-C(84) 1.779(9) C(51)Sb(2)C(71) 98.7(2)

S(3)-C(83) 1.758(8) C(51)Sb(2)C(41) 114.4(2)

S(4)-C(81) 1.764(6) C(51)Sb(2)C(61) 121.2(2)

S(4)-C(82) 1.769(7) C(71)Sb(2)O(2) 176.47(18)

S(5)-C(86) 1.676(11) C(41)Sb(2)O(2) 83.41(18)

S(5)-O(5) 1.477(6) C(41)Sb(2)C(71) 99.0(2)

S(5)-C(85) 1.678(11) C(41)Sb(2)C(61) 117.3(2)

S(6)-C(88) 1.765(7) C(61)Sb(2)O(2) 77.58(18)

S(6)-C(87) 1.770(7) C(61)Sb(2)C(71) 99.0(2)

Conclusion

The structure of iridium complex [Ph4Sb(DMSO)]+[IrCl4(DMSO)2]-, obtained from tetraphenylsti-bonium chloride and sodium hexachloroiridate (III) in water, followed by recrystallization from dimethyl sulfoxide, has been established by X-ray diffraction analysis.

References

1. Haddad Y.M.Y., Henbest H.B., Trocha-Grimshaw J. Aspects of Catalysis. Part II. Dimethyl Sul-phoxide Complexes of Iridium(III) Including Hydrides. Journal of the Chemical Society, Perkin Transactions 1, 1974, pp. 592-595.

2. Messori L., Marcon G., Orioli P, Fontani M., Zanello P., Bergamoc A., Savac G., Murad P. Molecular Structure, Solution Chemistry and Biological Properties of the Novel [ImH][trans-IrCl4(Im)(DMSO)], (I) and of the Orange Form of 4 [(DMSO)2H][trans-IrCl4(DMSO)2], (II). Journal of Inorganic Biochemistry, 2003, vol. 95, iss. 1, pp. 37-46.

3. Albertí F.M., Fiol J.J., García-Raso A., Torres M., Terrón A., Barceló-Oliver M., Prieto M.J., Moreno V., Molins E. Ruthenium(III) and Iridium(III) Complexes with Nicotine. Polyhedron, 2010, vol. 29, iss. 1, pp. 34-41. DOI: 10.1016/j.poly.2009.05.082

4. Sharutin V.V., Sharutina O.K., Senchurin V.S., Somov N.V. [Synthesis and Structure of Iridium Complexes [Ph3PR][trans-IrCl4(DMSO)2]. Russian Journal of General Chemistry, 2015, vol. 85, no. 3, pp. 634-639. DOI: 10.1134/S1070363215030184

5. SMART and SAINT-Plus. Versions 5.0. Data Collection and Processing Software for the SMART System. - Bruker AXS Inc. - 1998. - Madison, Wisconsin, USA.

6. SHELXTL/PC. Versions 5.10. An Integrated System for Solving, Refining and Displaying Crystal Structures From Diffraction Data. - Bruker AXS Inc. -1998. - Madison, Wisconsin, USA.

Received 10 September 2015

УДК 547.243; 546.9; 548.312.2 DOI: 10.14529/chem150410

СИНТЕЗ И СТРОЕНИЕ КОМПЛЕКСА ИРИДИЯ

[Ph4Sb(DMSO)nirCU(DMSOhr

В.В. Шарутин, О.К. Шарутина, В.С. Сенчурин

Южно-Уральский государственный университет, г. Челябинск

Взаимодействием хлорида тетрафенилстибония с гексахлороиридатом(Ш) натрия в воде синтезирован комплекс иридия [Ph4Sb(DMSO)]+[IrCl4(DMSO)2]- (1). По данным РСА в кристалле присутствуют по два типа кристаллографически независимых катионов [Ph4Sb(DMSO)]+ и анионов [IrCl4(DMSO)2]-. Атомы сурьмы в катионах имеют искаженное тригонально-бипирамидальное окружение с аксиально расположенным О-диметилсульфоксидным лигандом, (экваториальные углы CSbC 113.6(2)°-121.2(2)°, аксиальные углы CSbO 178.33(18)°, 176.47(18)°, длины связей Sb-Сжв 2.106(6)-2.119(6) А, Sb-Q^ 2.126(6), 2.130(6) А, Sb-О 2.545(4), 2.465(4) А). В моноядерных октаэдрических анионах экваториальные положения занимают атомы хлора (углы ClIrCl-транс 178.69(7)°-179.56(7)°, SirS-транс 178.35(7)°, 175.88(7)°; диметилсульфоксидные ли-ганды координируются с атомами Ir посредством атомов серы (Ir-S 2.2958(16)-2.3148(17) А), длины связей Ir-Cl изменяются в интервалах 2.3407(19)-2.3681(17) А. Структурная организация в кристалле обусловлена межионными водородными связями (H-Cl 2.80-2.94 А и H-O 2.56-2.71 А).

Ключевые слова: хлорид тетрафенилстибония, гексахлороиридат(Ш) натрия, диметилсульфоксид, бис(диметилсульфоксидо)тетрахлороиридат(Ш) (диметилсуль-фоксидо)тетрафенилстибония, синтез, рентгеноструктурный анализ, строение.

Sharutin V.V., Sharutina O.K., Senchurin V.S.

Synthesis and structure of iridium complex _[Ph4Sb(DMSO)]+[IrCl4(DMSO)2]-

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: vvsharutin@rambler.ru

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: sharutinao@mail.ru

Сенчурин Владислав Станиславович - кандидат химических наук, кафедра органической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: senvl@rambler.ru

Поступила в редакцию 10 сентября 2015 г.

ОБРАЗЕЦ ЦИТИРОВАНИЯ

Sharutin, V.V. Synthesis and structure of iridium complex [Ph4Sb(DMSO)]+[Ira4(DMSO)2r / V.V. Sharutin, O.K. Sharutina, V.S. Senchurin // Вестник ЮУрГУ. Серия «Химия». - 2015. - Т. 7, № 4. - С. 80-85. DOI: 10.14529/chem150410

FOR CITATION

Sharutin V.V., Sharutina O.K., Senchurin V.S. Synthesis and Structure of Iridium Complex [Ph4Sb(DMSO)]+[IrCl4(DMSO)2]-. Bulletin of the South Ural State University. Ser. Chemistry. 2015, vol. 7, no. 4, pp. 80-85. DOI: 10.14529/chem150410