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DOI: 10.14529/chem150402
SYNTHESIS AND STRUCTURE OF OSMIUM COMPLEX [Ph4PMOsBr6]
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
Tetraphenylphosphonium hexabromoosmate, [Ph4P]2[OsBr6] (I), has been structurally characterized after synthesis by interaction of sodium hexabromoosmate with tetraphenylphosphonium bromide in dimethyl sulfoxide. The phosphorus atoms of [Ph4P]+ cations have distorted tetrahedral coordination geometry (CPC angles are 106.23(11)°-113.23(10)°), the P-C bond lengths are 1.791(2)-1.801(2) A). In octahedral [OsBr6]2- anions the Os-Br bond lengths equal 2.4752(2)-2.5020(3) A, trans-BrOsBr angles are 180°.
Keywords: sodium hexabromoosmate, tetraphenylphosphonium bromide, dimethyl sulfoxide, complex [Ph4P]2[OsBr6], crystal structure, X-ray diffraction analysis.
Introduction
Complexes containing [OsBr6]2- anions are some of the least structurally characterized ionic osmium complexes [1]; among them there is only one complex with phosphonium cations, [Ph3PH]+2[OsBr6]2- [2].
In the present paper the synthesis and structure of osmium complex [Ph4P]+2[OsBr6]2- (1) has been described.
Experimental
Synthesis of [Ph4P]+2[OsBr6]2- (1). A mixture of 0.035 g (0.08 mmol) of tetraphenylphosphonium bromide and 0.030 g (0.04 mmol) of sodium hexabromoosmate was dissolved by stirring in 2 mL of dimethyl sulfoxide. After evaporation of the solvent, formation of dark brown crystals was observed; they were filtered off and dried. 0.046 g (82%) of the complex was obtained, m.p. 320°C. IR (v, cm-1): 3053, 1583, 1482, 1437, 1313, 1186, 1107, 1025, 995, 761, 752, 721, 690, 663, 531, 522. Found, %: C 42.49, H 3.06. Anal. calc. for C48H40P2Br6Os (M = 1348.37), %: C 42.74, H 2.97.
IR-spectrum was recorded on a Bruker Tensor 27 IR spectrometer in KBr pellet.
The X-ray diffraction experiment for crystal 1 was carried out on a Bruker D8 Quest diffractome-ter (Mo K radiation, X = 0.71073 A, graphite monochromator). Data collection, their editing, and refinement of the unit cell parameters, as well as accounting for absorption, were carried out using the SMART and SAINT-Plus programs [3]. All calculations for structure determination and refinement were carried out using the SHELXL/PC program [4]. Structure 1 was determined by the direct method and refined by the least-squares method in anisotropic approximation for non-hydrogen atoms. The main crystallographic data and structure refinement details are given in Table 1. The main bond lengths and bond angles are listed in Table 2.
The full tables of atomic coordinates, bond lengths, and bond angles were deposited with the Cambridge Crystallographic Data Centre (№ 1000138; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Table 1
Crystallographic data, the experimental and structure refinement parameters for compound 1
Parameter Value
Formula C4sH40P2BreOs
M 1348.37
T, K 296(2)
Crystal system Triclinic
Space group P-1
Вестник ЮУрГУ. Серия «Химия». 2015. Т. 7, № 4. С. 13-16
Organometallic chemistry
Table 1 (end)
Parameter Value
a, A 10.2879(4)
b, A 10.5331(4)
c, A 12.1824(5)
a, deg 92.7640(10)
fldeg 99.9850(10)
Y, deg 116.3110(10)
V, A3 1153.68(8)
Z 1
p(calc.), g/cm3 1.941
H, mm 1 8.061
F(000) 644.0
Crystal size, mm 0.32 x 0.26 x 0.13
8 Range of data collection, deg 5.92 - 52.86
Range of refraction indices -12 < h < 12, -13 < k < 13, -15 < l < 15
Measured reflections 36441
Independent reflections 4730 (Rlnt = 0.0245)
Refinement variables 259
GOOF 1.105
R factors for F2> 2ct(F2) Rj = 0.0171, wR2 = 0.0416
R factors for all reflections Rj = 0.0195, wR2 = 0.0426
Residual electron density (min/max), e/A3 0.35/-0.66
Table 2
Selected bond lengths (d) and bond angles (ra) in the structure of compound 1
Bond d, Â Angle m, deg
Os(1)-Br(11) 2.4985(2) Br(11)Os(1)Br1 180.0
Os(1)-Br(1) 2.4986(2) Br(2)Os(1)Br1 91.620(8)
Os(1)-Br(2) 2.4752(2) Br(21)Os(1)Br1 88.380(8)
Os(1)-Br(3) 2.5019(3) C(1)P(1)C31 106.23(11)
Os(1)-Br(31) 2.5020(3) C(1)P(1)C11 109.65(11)
P(1)-C(1) 1.798(2) C(31)P(1)C11 109.57(11)
P(1)-C(31) 1.800(2) C(21)P(1)C1 113.23(10)
P(1)-C(21) 1.791(2) C(21)P(1)C31 108.47(10)
P(1)-C(11) 1.801(2) C(21)P(1)C11 109.60(11)
Symmetry transformation: :-x, 1-y, 1-z
Results and Discussion
It is known that the synthesis of osmium complex [Ph3PH]+2[OsBr6]2~ was carried out by consecutive addition of triphenylphosphine, glacial acetic acid and acetic anhydride to the dichloromethane solution of tetrabutylammonium hexabromoosmate, and heating of the reaction mixture for 3 days at 55-60 °C, with the yield equaling 29% [2].
We have ascertained that the reaction of sodium hexabromoosmate with tetraphenylphosphonium bromide in dimethyl sulfoxide leads to formation of air-stable dark brown crystals of tetraphenylphos-phonium hexabromoosmate (1), isolated from the reaction mixture with the yield equaling 82 %:
DMSO
2 Ph4PBr + Na2OsBr6 ^ [Ph4P]+2[OsBr6]2- + 2 NaBr
1
Bulletin of the South Ural State University. Ser. Chemistry.
2015, vol. 7, no. 4, pp. 13-16
Sharutin V.V., Sharutina O.K., Senchurin V.S.
Synthesis and structure of osmium complex [Ph4P]2[OsBr6]
According to the X-ray diffraction data, phosphorus atoms in tetraphenylphosphonium cations have slightly distorted tetrahedral coordination geometry: CPC angles lie within the range 106.23(11)°-113.23(10)°, P-C distances are 1.791(2)-1.801(2) À) (Fig. 1).
Fig. 1. Structure of complex 1
In centrosymmetric octahedral [OsBr6]2- anions the Os-Br bond lengths equal 2.4752(2)-2.5020(3) Á, trans--BrOsBr angles are 180°. Two tetraphenylphosphonium cations are bonded with hexabromoos-mate anion by intermolecular H—Br hydrogen bonds (2.90 and 3.01 Á) (Fig. 2).
Fig. 2. The system of hydrogen bonds in the crystal of complex 1
Conclusions
Thus, the osmium complex with the tetrahedral tetraphenylphosphonium cation and the centrosymmetric octahedral Os-,Br-containing [OsBr6]2~ anion has been synthesized and structurally characterized for the first time. Formation of crystal structure occurs due to intermolecular H—Br hydrogen bonds between tetraphenylphosphonium cations and hexabromoosmate anions.
Вестник ЮУрГУ. Серия «Химия». 2015. Т. 7, № 4. С. 13-16
Organometallic chemistry
References
1. Cambridge Crystallografic Database. Release 2015. Cambridge.
2. Robinson P.D., Hinckley C.C., Matusz M., Kibala P.A. Acta Cryst. 1988. Vol. C44. P. 619-621.
3. Bruker (1998). SMART and SAINT-Plus.Versions 5.0.Data Collection and Processing Software for the SMART System.Bruker AXS Inc., Madison, Wisconsin, USA.
4. Bruker (1998). SHELXTL/PC.Versions 5.10. An Integrated System for Solving, Refining and Displaying Crystal Structures From Diffraction Data. Bruker AXS Inc., Madison, Wisconsin, USA.
Received 18 May 2015
УДК У546.97+546.185+547.53.024+548.312.5 DOI: 10.14529/chem150402
СИНТЕЗ И СТРОЕНИЕ КОМПЛЕКСА ОСМИЯ [Ph4P]2[OsBr6]
В.В. Шарутин, О.К. Шарутина, В.С. Сенчурин
Южно-Уральский государственный университет, г. Челябинск
Взаимодействием гексабромоосмата натрия с бромидом тетрафенилфосфония в диметилсульфоксиде синтезирован и структурно охарактеризован гексабромоосмат тетрафенилфосфония [Ph4P]2[OsBr6] (I). Атомы фосфора в катионах [Ph4P]+ имеют искаженную тетраэдрическую координацию (углы СРС 106.23(11)°-113.23(10)°), расстояния P-С составляют 1.791(2)-1.801(2) А). В октаэдрических анионах [OsBr6]2-длины связей Os-Br равны 2.4752(2)-2.5020(3) А, углы транс-BrOsBr составляют 180°.
Ключевые слова: гексабромоосмат натрия, бромид тетрафенилфосфония, диме-тилсульфоксид, комплекс [Ph4P]2[OsBr6], структура, рентгеноструктурный анализ.
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 18 мая 2015 г.
ОБРАЗЕЦ ЦИТИРОВАНИЯ
Sharutin, V.V. Synthesis and structure of osmium complex [Ph4P]2[OsBr6] / V.V. Sharutin, O.K. Sharutina, V.S. Senchurin // Вестник ЮУрГУ. Серия «Химия». -2015. - Т. 7, № 4. - С. 13-16. DOI: 10.14529/chem150402
FOR CITATION
Sharutin V.V., Sharutina O.K., Senchurin V.S. Synthesis and Structure of Osmium Complex [Ph4P]2[OsBr6]. Bulletin of the South Ural State University. Ser. Chemistry. 2015, vol. 7, no. 4, pp. 13-16. DOI: 10.14529/cheml50402
Bulletin of the South Ural State University. Ser. Chemistry.
2015, vol. 7, no. 4, pp. 13-16
