ISSN 0036�0236, Russian Journal of Inorganic Chemistry, 2014, Vol. 59, No. 5, pp. 508–510. © Pleiades Publishing, Ltd., 2014.Original Russian Text © V.V. Sharutin, O.K. Sharutina, V.S. Senchurin, P.P. Mukovoz, 2014, published in Zhurnal Neorganicheskoi Khimii, 2014, Vol. 59, No. 5, pp. 678–680.

508

It is known that β�ketones react with pentapheny�lantimony as H�acids to form chelate complexes,ligands in which are bidentately bonded to the antimonyatom as in similar complexes of transition metals [1]. TheO,O�ligands in structurally characterized complexeswith the general formula Ph4Sb[OC(Ме)CXC(Ме)O](X = Cl [2], Et [3], All [3], Ph [4, 5], SBu [5]) usuallymanifest an anisobidentate character of coordination.The nature of an X substituent at the central carbonatom of a diketonate ligand has been found to not pro�duce any appreciable effect on the distortion of thecoordination polyhedron of the antimony atom, butinduces a redistribution of electron density in the[SbO2C3] six�membered ring to change the strength ofbonds between the ligand and a central atom [6].

1,3,4,6�Tetracarbonyl compounds, which have agreater structural diversity, are of equally great inter�est [7].

In this work, the reaction between pentaphenylan�timony and octanetetraone�2,4,5,7 was studied andthe structure of the synthesized complexPh4Sb[OC(Ме)CHC(O)(O)CCH(Ме)CO]SbPh4 (I)was established by X�ray diffraction for the first time.

EXPERIMENTAL

Synthesis of complex I. A solution of pentapheny�lantimony (0.30 g, 0.59 mmol) and 2,4,5,7�octanetet�raone (0.05 g, 0.295 mol) in toluene (2.5 mL) washeated in an evacuated ampoule on a boiling waterbath for 0.5 h. Thereupon the solution was cooled, andthe solvent was removed. Yellow complex I (0.29 g,96%) with Tdec = 186–188°C was synthesized. To sep�arate crystals suitable for X�ray diffraction analysis,the complex was recrystallized from iso�propanol–chloroform (1 : 1).

For C56H48O4Sb2 anal. calcd. (%): C, 65.34;H, 4.67.

Found (%): C, 65.47; H, 4.78.IR spectrum (ν, cm–1): 3068): 3068, 3051, 3011,

2990, 1955, 1881, 1818, 1579, 1561, 1481, 1430, 1379,1331, 1305, 1265, 1218, 1185, 1156, 1128, 1069, 1021,998, 935, 803, 758, 731, 694, 656, 638, 547, 470, 456.

1H NMR: 1.87 (s, CH3, 6H); 5.93 (s, CH, 2H);7.21–7.48 (m� and p�protons of Ph, 24H); 7.68–7.77(o�protons of Ph, 16H).

13C NMR: 29.75 (CH3); 98.44 (CH); 127.87 (m�Ph); 129.42 (p�Ph); 135.44 (o�Ph); 136.38 (i�Ph);178.44 (C=O).

IR spectrum was recorded on a Bruker Tensor 27 IRspectrometer as KBr pellets.

1H and 13C NMR spectra were recorded on an Agi�lent DD2 400 spectrometer in deuterochloroform anddimethyl sulfoxide at working frequencies of 400 and101 MHz, respectively.

X�ray diffraction analysis of a crystal of complex Iwas performed on a Bruker D8 QUEST diffractometer(MoK

α radiation, λ = 0.71073 Å, graphite monochro�

mator). The collection and edition of data, the refine�ment of unit cell parameters, and the application ofabsorption corrections were performed by theSMART and SAINT�Plus software [8]. All calcula�tions in the structure solution and refinement for com�plex I were performed by the SHELXL/PC software[9]. The structure of complex I was solved by directmethods and refined by the least�square technique inthe anisotropic approximation for non�hydrogenatoms. Selected crystallographic data and results ofstructure refinement for complex I are displayed inTable 1, and selected bond lengths and bond angles arelisted in Table 2.

Reaction between Octanetetraone�2,4,5,7and Pentaphenylantimony

V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, and P. P. MukovozNational South Ural State Research University, pr. Lenina 76, Chelyabinsk, 454080 Russia

e�mail: vvsharutin@rambler.ruReceived November 12, 2013

Abstract—Ph4Sb[OC(Me)CHC(O)(O)CCH(Me)CO]SbPh4, a binuclear chelate complex, has been syn�thesized by a reaction between pentaphenylantimony and octanetetraone�2,4,5,7 (2 : 1 mol/mol) in toluene.The Sb(1,2) atoms each have a distorted octahedral coordination, the CSbC and CSbO trans�angles liewithin a range of 158.3(8)°–169.1(9)°, and the Sb–C bond lengths are 2.06(2)–2.25(2) Å. The two six�mem�bered [SbO2C3] chelate rings have the following distances (Å): Sb–O, 2.25(1)–2.29(1); O–C, 1.20(2)–1.32(2); C–C, 1.32(3)–1.53(3).

DOI: 10.1134/S0036023614050155

PHYSICAL METHODS OF INVESTIGATION

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REACTION BETWEEN OCTANETETRAONE�2,4,5,7 509

Full tables of atomic coordinates, bond lengths, andbond angles were deposited with the Cambridge Struc�tural Database (no. 940400; deposit@ccdc.cam.ac.uk;http://www.ccdc.cam.ac.uk).

RESULTS AND DISCUSSION

The reaction between pentaphenylantimony and2,4,5,7�octanetetraone (2 : 1 mol/mol) proceeded intoluene under short�term heating at 100°С with anearly quantitative yield of complex I:

2Ph5Sb + MeC(O)CH2C(O)C(O)CH2C(O)Me → I + 2PhH.

The formation of complex I was also observed at areagent ratio of 1 : 1.

Instead of a broad and intense absorption band at1602 cm–1 which is typical for 1,3�diketones in theenol form with intramolecular H�bonds and observedin the spectrum of the initial tetraketone [10], the IRspectrum of complex I contains two bands at 1579 and1561 cm–1 belonging to the vibrations of C–O andC–C bonds in the antimony�containing chelaterings [11].

According to X�ray diffraction data, a molecule ofcomplex I contains two [SbO2C3] chelate rings (seefigure). The Sb(1) and Sb(2) atoms have a distortedoctahedral coordination. The oxygen atoms of biden�tate ligands, as well as the two carbon atoms of phenylgroups, are located in the equatorial plane of the octa�hedron, and the axial positions are occupied by thecarbon atoms of other two phenyl groups. The axialCSb(1,2)C angles are 159.6(7) and 160.3(7)°, respec�tively. The OSb(1,2)C trans�angles in the equatorialplane are 168.7(7), 170.1(6)° and 166.2(7), 167.3(7)°.The Sb(1) and Sb(2) atoms are, respectively, 0.016 and0.008 Å out of their equatorial planes. The sum of theequatorial angles is 360°.

The [SbО2C3] six�membered chelate rings in amolecule are in trans�positions with respect to theC(84)–C(85) bond. The neighboring [О2C3] moietiesare nearly coplanar (the angle between their planes is1.81°C). The chelate rings are bent along the O–Odiagonals: the planes of the [SbО2] and [О2C3] semi�rings in the Sb(1) and Sb(2) rings form the angles of159.5 and 157.4°, respectively.

The Sb(1,2)–C distances lie within a range of2.06(2)–2.25(2) Å. The diketonates ligand moietiesnearly symmetrically coordinate the antimony atoms:the Sb(1)–O(1,2) and Sb(2)–O(3,4) distances haveclose values (average, 2.255 and 2.255 Å). In this case,the overall strength of ligand bonding in the Sb(1) ringis much higher than in the Sb(2) ring. The O–C bondlengths (1.20–1.32 Å) in the rings indicate their frac�tional orders and the delocalization of electron density.

Hence, octanetetraone�2,4,5,7 dephenylates pen�taphenylantimony to form the complex composed by

Table 1. Crystallographic data and details of the X�ray dif�fraction experiment and structure refinement for complex I

Bulk formula C56H48O4Sb2

Formula weight 1028.44

Symmetry system Triclinic

T, K 295(2)

Space group P1

Unit cell parameters:

a, Å 9.6770(3)

b, Å 10.6281(3)

c, Å 12.5681(4)

α, deg 75.145(1)

β, deg 71.249(1)

γ, deg 78.686(1)

V, Å3 1173.92(4)

Z 1

ρcalcd, g/cm3 1.455

μMo, mm–1 1.196

F(000) 518.0

Crystal size, mm Prism (0.16 × 0.14 × 0.13)

θ, deg 3.57–26.45

Index ranges –11 ≤ h ≤ 12, –13 ≤ k ≤ 11, –13 ≤ l ≤ 15

Measured reflections 4334

Independent reflection 3724

Rint 0.0441

Refined parameters 561

GOOF 1.049

R factors for F2 > 2σ(F2) R1 = 0.0297, wR2 = 0.0404

R factors for all reflections R1 = 0.0592, wR2 = 0.0630

Residual electron density (max/min), e/Å3

0.340/–0.254

Table 2. Selected bond lengths and bond angles in thestructure of complex I

Bond d, Å Angle ω, deg

Sb(1)–C(31) 2.25(2) C(21)Sb(1)O(1) 168.7(7)

Sb(1)–C(1) 2.23(2) C(1)Sb(1)O(2) 170.1(6)

Sb(1)–C(11) 2.16(2) C(31)Sb(1)C(11) 159.6(7)

Sb(1)–C(21) 2.12(2) O(1)Sb(1)O(2) 81.4(6)

Sb(1)–O(1) 2.26(2) C(7)Sb(2)O(4) 166.2(7)

Sb(1)–O(2) 2.25(1) C(51)Sb(2)O(3) 167.3(7)

Sb(2)–C(41) 2.14(2) C(41)Sb(2)C(61) 160.3(7)

Sb(2)–C(61) 2.06(2) O(4)Sb(2)O(3) 77.7(6)

Sb(2)–C(51) 2.19(2) Sb(1)O(1)C(82) 123(1)

Sb(2)–C(71) 2.11(2) Sb(1)O(2)C(84) 126(1)

Sb(2)–O(4) 2.26(1) Sb(2)O(3)C(87) 132(1)

Sb(2)–O(3) 2.29(2) Sb(2)O(4)C(85) 128(1)

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SHARUTIN et al.

two six�membered chelate rings, and the denticity ofthe tetraketone is 4.

REFERENCES

1. V. V. Sharutin, O. K. Sharutina, O. P. Zadachina, et al.,Zh. Obshch. Khim. 70, 746 (2000).

2. V. V. Sharutin, O. K. Sharutina, O. P. Zadachina, et al.,Zh. Obshch. Khim. 70, 1672 (2000).

3. V. V. Sharutin, O. K. Sharutina, O. P. Zadachina, et al.,Koord. Khim. 29, 8 (2003).

4. V. V. Sharutin, A. P. Pakusina, O. K. Sharutina, et al.,Butlerov. Soobshch, No. 1, 34 (2003).

5. V. V. Sharutin, A. P. Pakusina, I. V. Egorova, et al.,Koord. Khim. 34, 267 (2008).

6. V. V. Sharutin and O. K. Sharutina, Vestn. Yuzhno�Ural’sk. Gos. Univ., No. 2, 4 (2013).

7. O. G. Karmanova, V. O. Koz’minykh, P. P. Mukovoz,et al., Vestn. Yuzhno�Ural’sk. Gos. Univ., No. 24, 39(2012).

8. SMART and SAINT�Plus: Data Collection and Pro�cessing Software for the SMART System. Versions 5.0.(Bruker, 1998).

9. SHELXTL/PC: An Integrated System for Solving,Refining and Displaying Crystal Structures from Dif�fraction Data. Versions 5.10. (Bruker, 1998).

10. E. Pretsch, P. Buhlmann, and C. Affolter, StructureDetermination of Organic Compounds. Tables of SpectralData (Springer, 2000; Mir, Moscow, 2009).

11. H. A. Meinema and I. G. Noltes, J. Organomet. Chem.16, 257 (1969).

Translated by E. Glushachenkova

C(44)

C(43)

C(42)

C(41)

C(56)C(71)C(76)C(74)

C(73) C(72)C(54)

C(53)

C(62)

C(63)

C(64)

C(65)

C(66)

C(61)

C(52)

Sb(2)

O(3)

C(45)

C(46)

C(88)

C(86)

O(4)

C(85)

C(84)

C(83)

O(2)

Sb(1)

C(32) C(31)

C(33)

C(34)

C(35)

C(36)

C(25)

C(24)C(6) C(2) C(3) C(4)

C(5)C(1)C(23)

C(11)

C(12)

C(13)

C(14)

C(15)

C(16)

C(82)

O(1)

C(81)

Structure of complex I.