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DOI: 10.14529/chem160107
SYNTHESIS AND STRUCTURE
OF IODOTRIS(TRYPHENYLSTIBINE)SILVER [(Ph3SbbAgI]
V.V. Sharutin1, vvsharutin@rambler.ru
O.K. Sharutina1, sharutinao@mail.ru
V.S. Senchurin1, senvl@rambler.ru
A.N. Neudachina1, neudachina.a@yandex.ru
P.V. Andreev2, andreev@phys.unn.ru
1 South Ural State University, Chelyabinsk, Russian Federation
2 Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russian Federation
Interaction of silver iodide with triphenylstibine in dimethyl sulfoxide has led to the neutral complex iodotris(triphenylstibine)silver (1), whose structure has been established by X-ray diffraction analysis. The silver atom has distorted tetrahedral coordination. The angles SbAgSb and SbAgI equal 106.501(13)°, 109.644(13)°, 111.099(13)° h 103.063(13)°, 111.594(14)°, 114.337(14)°, the bond lengths Ag-Sb and Ag-I equal 2.7291(4), 2.7326(4), 2.8087(4) h 2.7600(4) Â.
Keywords: iodotris(triphenylstibine)silver, synthesis, structure, X-ray diffraction analysis.
Introduction
Synthesis and structure of molecular complexes of silver that contain the bonds Sb-Ag and Ag-Hal, obtained from silver halide and triphenylstibine in water-alcohol solution, are described in the literature [1-2]. In the present paper the interaction of silver iodide with triphenylstibine in dimethyl sulfoxide has been studied; the characteristic structural features of the obtained Sb-, I-containing silver complex have been investigated.
Experimental
Synthesis of iodotris(triphenylstibine)silver (1). The mixture of 0.529 g (1.50 mmol) triphenylstibine, 0.117 g (0.5 mmol) silver iodide and 10 mL dimethyl sulfoxide was stirred for 1 h at room temperature, the volume was reduced to 0.5 mL, then the mixture was cooled. The yield was 0.520 g (80%) of colorless crystals 1 with decomposition temperature 118 °C. Found, %: C 49.87; H 3.55. Calculated for C54H45SbsAgI, %: C 50.08; H 3.48.
X-ray diffraction analysis of the crystal 1 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-P/hs programs [3]. All calculations for structure determination and refinement were performed using the SHELXL/PC programs [4,5]. 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 the 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.
Table 1
Crystallographic data and the experimental and structure refinement parameters for compound 1
Parameter Value
Empirical formula C54H45SbsAgI
Formula weight 1293.92
T, K 296(2)
Crystal system Monoclinic
Space group P2,/n
a, A 17.7497(6)
Шарутин В.В., Шарутина O.K., Сенчурин В.С. и др. Синтез и строение иодотрис(трифенилстибин)серебра [(Ph3Sb)3AgI]
Table 1 (end)
Parameter Value
b, A 14.4787(4)
c, A 19.6167(7)
a, deg 90.00
P, deg 98.2820(10)
Y, deg 90.00
V, A3 4988.8(3)
Z 4
p(calcd.), g/cm3 1.723
(o, mm1 2.646
F(000) 2488
Crystal size, mm 0.52 x 0.28 x 0.19
28 Range of data collection, deg 3.449 - 27.189
Range of refraction indices -22 < h < 22, -18 < k < 18, -25 < l < 25
Measured reflections 82314
Independent reflections 11060 (Rmt = 0.0294)
Refinement variables 533
GOOF 1.100
R factors for F2 > 2ct(F2) Ri=0.0321, wRj=0.0648
R factors for all reflections Ri=0.0436, wRj=0.0725
Residual electron density (min/max), e/A3 0.824/-0.673
Table 2
Selected bond lengths and bond angles in the structure of compound 1
Bond d, Â Angle ra, deg.
Sb(1)-C(1) 2.132(4) C(1)Sb(1)C(11) 101.16(15)
Sb(1)-C(11) 2.131(4) C(1)Sb(1)C(21) 97.96(16)
Sb(1)-C(21) 2.126(4) C(11)Sb(1)C(21) 101.78(17)
Sb(2)-C(31) 2.128(4) C(1)Sb(1)Ag(1) 122.48(10)
Sb(2)-C(41) 2.129(4) C(11)Sb(1)Ag(1) 117.10(11)
Sb(2)-C(51) 1.140(4) C(21)Sb(1)Ag(1) 112.92(12)
Sb(3)-C(61) 2.137(4) Sb(1)Ag(1)I(1) 111.594(14)
Sb(3)-C(71) 2.143(4) Sb(2)Ag(1)I(1) 114.337(14)
Sb(3)-C(81) 1.125(4) Sb(3)Ag(1)I(1) 103.063(13)
Ag(1)-Sb(1) 2.7291(4) Sb(1)Ag(1)Sb(2) 111.099(13)
Ag(1)-Sb(2) 2.7326(4) Sb(1)Ag(1)Sb(3) 106.501(13)
Ag(1)-Sb(3) 2.8087(4) Sb(2)Ag(1)Sb(3) 109.644(13)
Ag(1)-I(1) 2.7600(4) C(31)Sb(2)Ag(1) 114.86(11)
The full tables of atomic coordinates, bond lengths, and bond angles were deposited with the Cambridge Crystallographic Data Centre (CCDC 1440827; deposit@ccdc.cam.ac.uk; http: //www .ccdc.cam.ac.uk).
Results and Discussion
It is known that mixing aqueous solutions of silver halides with the methanol solution of triphenyls-tibine (1:3 mol) leads to formation of colorless crystals of addition complexes with the general formula [(Ph3Sb)3AgHal] (Hal = Cl, Br, I) [1]. The interaction of silver iodide with triphenylstibine in dimethyl sulfoxide, a strong n-donor solvent, has not been studied previously. The choice of the solvent is due to the fact that in the presence of two n-donor ligands in the reaction mixture, containing silver iodide, competition between them arises together with the possibility of complex formation, in which the coordination sphere of the metal atom would include one of them or both at once.
Вестник ЮУрГУ. Серия «Химия». 2016. Т. 8, № 1. С. 46-50
We have established that at mixing silver iodide with triphenylstibine in dimethyl sulfoxide the sol-ven molecules are not coordinated with the metal atom, so the sole product of the reaction is the molecular complex 1 :
AgI
The structure 1 is proven by the X-ray coordination (Fig. 1).
Fig. 1. The structure of compound 1
The angles SbAgSb and SbAgI equal 106.501(13)°, 109.644(13)°, 111.099(13)° and 103.063(13)°, 111.594(14)°, 114.337(14)°. The bond lengths Ag-Sb and Ag-I equal 2.7291(4), 2.7326(4), 2.8087(4) and 2.7600(4) A, which exceed the sums of the covalent radii of atoms Ag, Sb (2.67 A [6]) and Ag, I (2.58 A [6]). Note that in a similar chlorine-containing complex (Ph3Sb)3AgCl the bond lengths Ag-Sb are smaller (2.720, 2.722, 2.764(4) A) [1]. In the complex of silver iodide with morpholine [AgIC^NO], in which the coordination sphere is formed by nitrogen and three iodine atoms, the lengths Ag-I equal 2.824(6), 2.845(6) and 2.908(6) A [7].
The atoms Sb(1,2,3) are tetracoordinated, at that the angles CSb(1)C (97.96(16)°-101.78(17)°), CSb(2)C (98.20(16)°-102.28(16)°), CSb(3)C (97.22(16)°-99.70(15)°) are less than the ideal values, while CSb(1)Ag (112.92(12)°-122.48(10)°), CSb(2)Ag (114.18(11)°-124.41(12)°), CSb(3)Ag (111.91(11)°-128.03(11)°) are greater than them. The lengths Sb-C (2.125(4)-2.143(4) A) are smaller than in the molecule of free triphenylstibine (2.140(4)-2.168(4) A) [8]).
It is notable that the molecular and crystal structure of complex 1 was discussed previously in [1], but the experiment was carried out imperfectly.
Conclusions
Hence, the interaction of silver iodide with triphenylstibine in dimethyl sulfoxide solution leads to formation of iodotris(triphenylstibine)silver; dimethyl sulfoxide does not exhibit the properties of a li-gand capable of coordination with the silver cation.
+ 3 Ph3Sb ^ [(Ph3Sb)sAgI].
1
diffraction method. The silver atom in 1 has distorted tetrahedral
Шарутин В.В., Шарутинa O.K., Сенчурин В.С. и др.
Синтез и строение иодотрис(трифенилстибин)серебра [(Ph3Sb)3AgI]
References
1. Effendy, Kildea J.D., White A.H. Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXVIII. Synthesis and Structural Systematics of Some 1 : 3 Adducts of Silver(I) Compounds with Tri-phenylstibine, [^Sb^AgX], X = Cl, I, SCN, NCS, CN, ONO2. Aust. J. Chem. 1997, vol. 50, no. 6, pp. 587-604. DOI: 10.1071/C96035.
2. Bowmaker G.A., Effendy, Silva E.N., White A.H. Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXIIf Synthesis, Spectroscopy and Structural Systematics of Some 1 : 2 Binuclear Complexes of Silver(I) Halides with Triphenylstibine, [(Ph3Sb)2Ag(^-X)2Ag(SbPh3)2], X = Cl, Br, I. Aust. J. Chem. 1997, vol. 50, no. 6, pp. 641-651. DOI: 10.1071/C96038.
3. Bruker (2000) SMART. Bruker Molecular Analysis Research Tool, Versions 5.625 Bruker AXS, Madison, Wisconsin, USA.
4. Bruker (2000) SAINTPlus Data Reduction and Correction Program Versions 6.02a, Bruker AXS, Madison, Wisconsin, USA.
5. Sheldrick G.M. A Short History of Shelx. Acta Cryst. 2008, vol. A64, no. 1, pp. 112-122. DOI: 10.1107/S0108767307043930.
6. Bacanov S.S. Atomic Radii of the Elements [Atomnye radiusy jelementov]. Zhurn. Neorgan. Himii [Russian Journal of Inorganic Chemistry], 1991, vol. 36, no. 12, pp. 3015-3037. (in Russ.)
7. Ansell G. B. Crystal Structure of 1:1 Complex between Silver Iodide and Morpholine. J. Chem. Soc., Perkin Trans., II. 1976, no. 1, pp. 104-106. DOI: 10.1039/P29760000104.
8. Sobolev A.N., Romm I.P., Belskii V.K., Gur'yanova E.N. Structure Analysis of Triaryl Derivatives of the Group V Elements. Crystal and Molecular Strycture of Tri-p-tolylantimony, C2iH2iSb. J. Organomet. Chem., 1979, vol. 179, no. 2, pp. 153-157. DOI: 10.1016/S0022-328X(00)95217-3.
Received 12 December 2015
УДК 546.865+547.53.024+547.563.4+548.312.5 DOI: 10.14529/chem160107
СИНТЕЗ И СТРОЕНИЕ ИОДОТРИС(ТРИФЕНИЛСТИБИН)СЕРЕБРА [(PhaSbbAgI]
В.В. Шарутин1, О.К. Шарутина1, В.С. Сенчурин1, А.Н. Неудачина1, П.В. Андреев2
1 Южно-Уральский государственный университет, г. Челябинск,
2 Нижегородский государственный университет, г. Нижний Новгород
Взаимодействием иодида серебра с трифенилстибином в диметилсульфоксиде синтезирован нейтральный комплекс иодотрис(трифенилстибин)серебро (1), строение которого установлено методом РСА. Атом Ag имеет искаженную тетрагональную координацию. Углы SbAgSb и SbAgI составляют 106,501(13)°, 109,644(13)°, 111,099(13)° и 103,063(13)°, 111,594(14)°, 114,337(14)°, длины связей Ag-Sb и Ag-I равны 2,7291(4); 2,7326(4); 2,8087(4) и 2,7600(4) Ä.
Ключевые слова: иодотрис(трифенилстибин)серебро, синтез, строение, рентге-ноструктурный анализ.
Литература
1. Effendy. Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXVIII. Synthesis and Structural Systematics of Some 1 : 3 Adducts of Silver(I) Compounds with Triphenylstibine, [(Ph3Sb)3AgX], X = Cl, I, SCN, NCS, CN, ONO2 / Effendy, J.D. Kildea, A.H. White // Aust. J. Chem. - 1997. - V. 50, № 6. - P.587-604.
Вестник ЮУрГУ. Серия «Химия». 2016. Т. 8, № 1. С. 46-50
2. Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXIIf Synthesis, Spectroscopy and Structural Systematics of Some 1 : 2 Binuclear Complexes of Silver(I) Halides with Triphenylstibine, [(Ph3Sb)2Ag(^-X)2Ag(SbPh3)2], X = Cl, Br, I / G.A. Bowmaker, Effendy, E.N. Silva et al. // Aust. J. Chem. - 1997. - V. 50, № 6. - P. 641-651.
3. Bruker (2000) SMART. Bruker Molecular Analysis Research Tool, Versions 5.625 Bruker AXS, Madison, Wisconsin, USA.
4. Bruker (2000) SAINTPlus Data Reduction and Correction Program Versions 6.02a, Bruker AXS, Madison, Wisconsin, USA.
5. Sheldrick, G.M. A Short History of Shelx / G.M. Sheldrick // Acta Cryst. - 2008. - V. A64, № 1. - P. 112-122.
6. Бацанов, С.С. Атомные радиусы элементов / С.С. Бацанов // Журн. неорган. химии. - 1991. - Т. 36, вып. 12. - С. 3015-3037.
7. Ansell, G.B. Crystal Structure of 1:1 Complex between Silver Iodide and Morpholine / G.B. An-sell // J. Chem. Soc., Perkin Trans., II. - 1976. - № 1. - P. 104-106.
8. Structure Analysis of Triaryl Derivatives of the Group V Elements. Crystal and Molecular Stryc-ture of Tri-p-tolylantimony, C2iH2iSb / A.N. Sobolev, I.P. Romm, V.K. Belskii et al. // J. Organomet. Chem. - 1979. - V. 179, № 2. - P. 153-157.
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, доцент, кафедра органической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: senvl@rambler.ru
Неудачина Анастасия Николаевна - студент, кафедра органической химии, ЮжноУральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: neudachina.a@yandex.ru
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: andreev@phys.unn.ru
Поступила в редакцию 12 декабря 2015 г.
ОБРАЗЕЦ ЦИТИРОВАНИЯ
Synthesis and structure of iodotris-(tryphenylstibine)silver [(Ph3Sb)3AgI] / V.V. Sharutin, O.K. Sharutina, V.S. Senchurin et al. // Вестник ЮУрГУ. Серия «Химия». - 2016. - Т. 8, № 1. - С. 46-50. DOI: 10.14529/chem160107
FOR CITATION
Sharutin V.V., Sharutina O.K., Senchurin V.S., Neudachina A.N., Andreev P.V. Synthesis and structure of iodotris(tryphenylstibine)silver [(Ph3Sb)3AgI]. Bulletin of the South Ural State University. Ser. Chemistry. 2016, vol. 8, no. 1, pp. 46-50. DOI: 10.14529/chem160107
