6,6,6-Trifluoro-3-hexanone-5,5-diolatotriphenylantimony: Synthesis and structure

Article abstract of DOI:10.1134/S0036023608110119

6,6,6-Trifluoro-3-hexanone-5,5-diolatotriphenylantimony, Ph ₃SbO₂C(CF₃)CH₂C(O)CMe₃, was synthesized by reacting triphenylantimony with 6,6,6-trifluoro-2,2- dimethylhexanedione-3,5 in the presence of hydrogen peroxide in diethyl ether. According to X-ray diffraction, the antimony atom in the complex has a distorted octahedral coordination. Sb-C distances are within 2.123(4)-2.131(4) ?. Sb-O(1,2,3) bond lengths are 2.052(2), 2.047(3) and 2.669(2) ?, respectively.

Full text of DOI:10.1134/S0036023608110119

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2008, Vol. 53, No. 11, pp. 1737–1740. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.V. Sharutin, A.P. Pakusina, O. K. Sharutina, T. S. Pochekutova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 11, pp. 1857–1860.
COORDINATION
COMPOUNDS
6,6,6-Trifluoro-3-hexanone-5,5-diolatotriphenylantimony:
Synthesis and Structure
V. V. Sharutina, A. P. Pakusinaa, O. K. Sharutinaa, and T. S. Pochekutovab
a Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
b Razuvaev Institute of Organometallic Compounds, Nizhni Novgorod, Russia
Received July 5, 2007
Abstract—6,6,6-Trifluoro-3-hexanone-5,5-diolatotriphenylantimony, Ph3SbO2C(CF3)CH2C(O)CMe3, was syn-
thesized by reacting triphenylantimony with 6,6,6-trifluoro-2,2-dimethylhexanedione-3,5 in the presence of
hydrogen peroxide in diethyl ether. According to X-ray diffraction, the antimony atom in the complex has a dis-
torted octahedral coordination. Sb–C distances are within 2.123(4)–2.131(4) Å. Sb–O(1,2,3) bond lengths are
2.052(2), 2.047(3) and 2.669(2) Å, respectively.
DOI: 10.1134/S0036023608110119
The synthesis and structure of diolato triarylanti- CCD diffractometer (MoKα radiation, λ = 0.71073 Å,
mony complexes where diolate ligands are fluoro deriv-
atives of butanedione-1,3 and pentanedione-2,4 are
described in [1–4]. In this work, we synthesized 6,6,6-
trifluoro-3-hexanone-5,5-diolatotriphenylantimony
Ph3SbO2C(CF3)CH2C(O)CMe3 (I) from triphenylanti-
mony and 6,6,6-trifluorohexanedione-3,5 in the pres-
ence of hydrogen peroxide and studied its structure.
graphite monochromator).
The structure was solved by a direct method and
refined by the full-matrix least-squares method in the
anisotropic approximation for non-hydrogen atoms
(SHELX-97) [8]. The hydrogen atoms were calculated
geometrically and included into the refinement in the
riding model.
SMART and SAINT Plus software [5] was used in
data collection and editing and the refinement of unit
cell parameters. The SHELXTL/PC program package
[6] was used in all calculations in the structure solution
and refinement.
EXPERIMENTAL
Synthesis of complex I. To a solution of 0.09 g
(0.26 mmol) triphenylantimony in 10 mL of diethyl
ether at 20°ë, added were 0.07 g (0.26 mmol) 6,6,6-tri-
fluorohexanedione-3,5 in 10 mL of diethyl ether and
0.03 mL (0.26 mmol) of 31% aqueous hydrogen perox-
ide. After 24 h, the solvent was removed and the residue
was recrystallized from heptane. Water-colored crystals
were obtained (0.10 g; 59%) with Tm = 113°ë. IR spec-
Selected crystallographic parameters and the results
of structure refinement for complex I are listed in
Table 1, atomic coordinates and thermal parameters are
in Table 2, and selected bond lengths and bond angles
in Table 3.
trum (ν, cm–1): 1685 vs, 1440 m, 1150 vs, 1070 vs,
1000 m.
RESULTS AND DISCUSSION
For ë32ç24é3F3Sb, anal. calcd., %: C, 60.47; H,
3.78.
6,6,6-Trifluorohexanedione-3,5 reacts with triphe-
nylantimony in the presence of tert-butyl hydroperox-
ide in toluene to yield a diolate complex in 85% yield
[1]. We found that this reaction also occurs in the pres-
Found, %: C, 60.05; H, 3.98.
IR spectrum was recorded as a KBr pellet on an
FSM 1201 Fourier-transform spectrometer.
Single-crystal X-ray diffraction experiment for ence of hydrogen peroxide; in this case, however, the
complex I was carried out on a Bruker SMART-1000 yield of complex I is lower (59%).
CF
3
O
C
CH
Ph Sb
O
O
Ph3Sb + CF3C(O)CH2C(O)CMe3 + H2O2
2
3
C
CMe
3
1737

1738
SHARUTIN et al.
Table 1. Crystal data and the parameters of X-ray diffrac- Table 2. Atomic coordinates (×104) and their isotropic equiva-
tion experiment and structure refinement for complex I
lent thermal parameters (×103) in the structure of complex I
Atom
x
y
z
Ueq, Å2
Parameter
Quantity
Sb
2062.9(2) 2964.3(2) 2298.0(2) 32.35(6)
FW
565.22
298(2)
F(1)
F(2)
F(3)
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(21)
4067(3)
2290(3)
3878(3)
1369(2)
3235(2)
629(3)
4862(3)
4231(3)
2865(3)
3512(2)
4131(2)
5430(2)
4073(4)
4389(4)
5809(4)
6218(3)
7696(4)
8177(5)
7880(6)
8467(5)
2565(3)
2920(4)
2640(5)
2018(5)
1661(4)
1924(4)
3534(3)
4036(4)
4503(4)
4479(4)
3987(4)
3505(4)
1091(4)
509(5)
4429(3)
5593(2)
4577(2)
3884(2)
2677(2)
2253(2)
4576(3)
3708(3)
3733(3)
2808(3)
2552(3)
1791(5)
1966(6)
3574(5)
2368(3)
3234(3)
3274(4)
2437(4)
1572(4)
1529(3)
611(3)
84.9(9)
73.4(9)
76.1(9)
35.8(6)
38.5(6)
41.8(6)
52(1)
T, K
Crystal system
Space group
Trigonal
P1
9.964(3)
a, Å
b, Å
10.521(3)
12.691(4)
83.055(4)
74.233(4)
77.070(4)
1245.3(6)
2
3144(4)
2284(3)
1513(4)
804(4)
c, Å
38.8(8)
40.4(8)
38.2(8)
44.8(9)
85(2)
α, deg
β, deg
γ, deg
V, Å3
Z
304(4)
1565(6)
–896(6)
–222(8)
35(3)
109(2)
98(2)
ρ
calcd, g/cm3
1.507
34.8(8)
48(1)
µ, mm–1
1.154
C(22) –1131(4)
C(23) –2419(5)
C(24) –2600(4)
C(25) –1453(5)
64(1)
F(000)
568
65(1)
Crystal habit (size, mm)
θ range, deg
Index ranges
Prism (0.38 × 0.24 × 0.21)
3.69–28.44
66(1)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
–122(4)
2824(4)
1886(4)
2391(5)
3818(5)
4753(5)
4260(4)
3314(4)
3151(7)
3979(7)
4939(6)
5080(5)
4287(5)
46.8(9)
34.4(8)
44(1)
–13 ≤ h ≤ 13, –14 ≤ k ≤ 14,
–17 ≤ l ≤ 16
–38(3)
Measured reflections
Unique reflections
Reflections with I > 2σ(I)
Refinement variables
GOOF
15037
6022 (Rint = 0.0535)
4670
–1112(3)
–1533(3)
–893(3)
179(3)
55(1)
56(1)
52(1)
43.5(9)
41.4(9)
80(2)
347
2551(3)
3599(4)
3791(5)
2937(5)
1896(4)
1682(3)
1.069
R for F2 > 2σ(F2)
R for all reflections
R1 = 0.0576, wR2 = 0.1394
R1 = 0.0814, wR2 = 0.1576
–1.320/2.300
–692(5)
–1334(5)
–797(4)
428(4)
91(2)
77(2)
64(1)
Residual electron density
(min/max), e/Å3
51(1)
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6,6,6-TRIFLUORO-3-HEXANONE-5,5-DIOLATOTRIPHENYLANTIMONY
1739
Table 3. Selected bond lengths and bond angles in the struc-
ture of complex I
The IR spectrum of complex I contains a strong
absorption band (1685 cm–1) in the region of the
stretching vibrations of carbonyl groups, as the IR spec-
tra of known diolate complexes [1–4].
Bond
d, Å
Angle
ω, deg
According to X-ray diffraction, an antimony atom in
crystals of complex I is bonded with three phenyl
groups and with the diketonate ligand via two oxygen
atoms (figure). The Sb...O(3) distance (2.669(2) Å) is
far smaller than the sum of the van der Waals radii of Sb
and O atoms (3.70 Å [7]). This points to the donor–
acceptor interaction of the carbonyl oxygen atom O(3)
with the central atom, whose coordination number
increases to six. A distorted octahedron, which can fit
the coordination polyhedron around the antimony atom
in complex I, has the O(3) carbonyl oxygen atom and
the C(41) phenyl atom in axial positions (the angle
O(3)SbC(41) is 170.5(1)°) and the O(1) and O(2)
diolate atoms and the C(21)and C(31) phenyl atoms in
equatorial positions (the angle sum in the equatorial
plane is 348.7(1)°). The C(21)C(31)O(1)O(2) fragment
is planar. The antimony atom is displaced from this
plane toward the C(41) atom. The C(41)SbC(21),
C(41)SbC(31), C(41)SbO(1), and C(41)SbO(2) bond
angles are, respectively, 103.7(1), 105.6(1), 99.5(1),
and 100.4(1)°; that is, they exceed 90°, which is
characteristic of a regular octahedron. A similar dis-
torted octahedral coordination of an antimony(V)
atom, with close angles, was observed for 5,5,5-tri-
fluoro-2-pentanone-4,4-diolatotriphenylantimony
Ph3SbO2C(CF3)CH2C(O)Me (II) [1], 5,5,5-trifluoro-2-
pentatanone-4,4-diolato-tris(p-chlorophenyl)antimony (p-
ClC6H4)3SbO2C(CF3)CH2C(O)Me (III) [2], and 4,4,4-trif-
luoro-1-phenyl-1-butanone-3,3-diolato-tris(p-tolyl)anti-
mony (p-MeC6H4)3SbO2C(CF3)CH2C(O)Ph (IV) [3, 4].
Sb–O(2)
2.047(3)
2.052(2)
2.123(4)
2.129(3)
2.131(4)
2.551(4)
2.669(2)
1.335(5)
1.345(4)
1.317(5)
1.396(4)
1.408(4)
1.219(5)
1.534(5)
1.519(5)
1.502(5)
O(2)SbO(1)
65.98(9)
100.4(1)
99.5(1)
Sb–O(1)
O(2)SbC(41)
O(1)SbC(41)
O(2)SbC(31)
O(1)SbC(31)
C(41)SbC(31)
O(2)SbC(21)
O(1)SbC(21)
C(41)SbC(21)
C(31)SbC(21)
O(2)SbO(3)
Sb–C(41)
Sb–C(31)
Sb–C(21)
Sb–C(2)
88.8(1)
147.2(1)
105.6(1)
149.1(1)
91.1(1)
Sb–O(3)
F(1)–C(1)
F(2)–C(1)
F(3)–C(1)
O(1)–C(2)
O(2)–C(2)
O(3)–C(4)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
103.7(1)
102.8(1)
71.75(9)
ever, the C(4)–C(5) distance in complex I (1.546(5) Å)
far exceeds the average value (1.511 Å).
The Sb–C(Ph) bond lengths in complex I (2.123(4),
2.129(3), and 2.131(4) Å; Table 3) are close to the
respective bond lengths: Sb–C(Ph) (2.117–2.137 Å) in
complex Sb–C(p-ClC6H4) (2.107–2.142 Å) in complex
III, and Sb–C(p-åÂC6H4) (2.113–2.137 Å) in complex
IV. Distances from the antimony atom to diolate oxy-
gen atoms (Sb–O(1,2), 2.052(2) and 2.047(3) Å) are
equalized, as in complex III (2.032 and 2.036 Å) and
complex IV (2.042 and 2.051 Å). In complex II, these
bonds are noticeably differentiated (2.029 and 2.058 Å).
In all compounds, Sb–O bond lengths do not exceed the
sum of the covalent radii of Sb and O atoms (2.07 Å
[7]). The C(2)–O(1) and C(2)–O(2) distances in com-
plex I are also close to each other (1.396(4) and
1.408(4) Å) and are smaller than the average é–ë(sp3)
bond length, which is 1.426 Å [8]. The respective bond
lengths in complexes II, III, and IV are 1.397, 1.405;
1.403, 1.432; and 1.398, 1.405 Å.
The C(4)–O(3) bond length (1.219(5) Å) in the car-
bonyl group of complex I, as the relevant distances in
complexes II (1.230 Å), III (1.214 Å), and IV (1.228 Å),
is close to the length of ë=é double bonds in ketones
(1.210 Å [8]). Thus, the involvement of the carbonyl
oxygen atom in the intermolecular interaction with the
central atom does not considerably affect the bond
…
length in the carbonyl group. The observed Sb O=C
distances in complexes I, II, III, and IV are 2.669,
2.705, 2.534, and 2.568 Å, respectively; therefore, we
can state the absence of the expected correlation
between the strength of the intermolecular contact and
the C=O bond length.
A certain role in generating the intermolecular con-
…
tact Sb O=C is played by electronic factors, in partic-
ular, the nature of substituents at the antimony atom and
the donor properties of the extra coordinated fragment.
…
In the diketonate group of complex I, distances
C(1)–C(2) (1.534(5) Å), ë(2)–ë(3) (1.519(5) Å), and
C(3)–C(4) (1.502(5) Å) are close to the average lengths
The shortest Sb O=C distance (2.534 Å) in complex
III can be assigned to enhancement of the acceptor
properties of the antimony atom as a result of the nega-
of C(sp3)–C(sp3) and C(sp3)–C(sp2) bonds in organic tive inductive effect of chlorine atoms in aryl groups.
compounds (1.530 and 1.511 Å, respectively) [8]. How- The strengthening of this contact in complex I relative
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 11 2008

1740
SHARUTIN et al.
F(2)
F(1)
F(3)
C(1)
C(2)
C(43)
C(42)
C(41)
C(3)
C(8)
O(1)
C(44)
C(45)
O(2)
C(4)
O(3)
C(5)
C(46)
C(22)
C(6)
Sb
C(31)
C(36)
C(35)
C(21)
C(7)
C(23)
C(32)
C(34)
C(26)
C(24)
C(33)
C(25)
Molecular structure of 6,6,6-trifluoro-3-hexanone-5,5-diolatotriphenylantimony.
to complex II likely arises from the positive inductive Academy of Sciences, Vladivostok) for the X-ray diffrac-
tion analysis of complex I.
effect of the tert-butyl radical and the associated
enhancement of the donor properties of the carbonyl
oxygen atom.
REFERENCES
Molecules of complex I in crystals are associated
into centrosymmetric dimers via weak hydrogen bonds
between the O(1) and H(3A)C(3) atoms of neighboring
1. A. V. Gushchin, R. I. Usyatinsky, G. K. Fukin, and
V. A. Dodonov, Main Group Chem. 2, 187 (1998).
2. F. Ebina, A. Ouchi, Y. Yoshino, et al., Acta Crystallogr.
33 B (10), 3252 (1977).
…
molecules. The O H distance (2.61 Å) is slightly
3. F. Ebina, A. Uehiro, Y. Yoshino, et al., J. Chem. Soc.,
smaller than the sum of the van der Waals radii of O and
Chem. Commun., No. 7, 245 (1976).
H atoms (2.70 Å [7]), but far larger than the typical
4. F. Ebina, A. Ouchi, Y. Yoshino, et al., Acta Crystallogr.
34 B (5), 1512 (1978).
5. SMART and SAINT-Plus. Versions 5.0. Data Collection
and Processing Software for the SMART System (Bruker
AXS, Madison (WI, USA), 1998).
6. SHELXTL/PC. Versions 5.10. An Integrated System for
Solving, Refining, and Displaying Crystal Structures
from Diffraction Data (Bruker AXS, Madison (WI,
USA), 1998).
…
length of strong hydrogen bonds é ç–ë (less than
…
2.1 Å). Angle O(1) H(3A)–C(3) in complex I (171°)
is close to 180°. Notably, similar pseudodimers exist in
crystals of complex II, whereas complexes III and IV
in crystals are monomeric.
ACKNOWLEDGMENTS
7. S. S. Batsanov, Zh. Neorg. Khim. 36 (12), 3015 (1991).
The authors thank A.V. Gerasimenko and M. A. Push-
ilin (Institute of Chemistry, Far-East Division, Russian
8. F. Allen, O., Kennard, D. G. Watson, et al., J. Chem.
Soc., Perkin Trans. II, No. 12, Part 2, S1 (1987).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 11 2008