Synthesis and Structure of (4-Acetyl-3-hydroxyphenoxy)tetraphenylantimony

Article abstract of DOI:10.1023/A:1024993400389

Pentaphenylantimony was reacted with 4-acetyl-1,3-dihydroxybenzene in toluene at elevated temperature to obtain (4-acetyl-3-hydroxyphenoxy) tetraphenylantimony in 93% yield. According to X-ray diffraction data, the antimony atom in (4-acetyl-3-hydroxy-phenoxy)tetraphenylantimony has a distorted trigonal-bipyramidal configuration. The Sb-O and Sb-C distances are 2.237(1) and 2.112(1), 2.114(2), 2.118(2), 2.170(2) A, respectively, and the CSbO angle is 177.86(5)°.

Full text of DOI:10.1023/A:1024993400389

0Russian Journal of General Chemistry, Vol. 73, No. 3, 2003, pp. 350 353. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 3, 2003,
pp. 376 379.
Original Russian Text Copyright
2003 by Sharutin, Sharutina, Bondar’, Subacheva, Pakusina, Gerasimenko, Sergienko.
Synthesis and Structure
of (4-Acetyl-3-hydroxyphenoxy)tetraphenylantimony
V. V. Sharutin, O. K. Sharutina, E. A. Bondar’, O. V. Subacheva,
A. P. Pakusina, A. V. Gerasimenko, and S. S. Sergienko
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received February 12, 2001
Abstract Pentaphenylantimony was reacted with 4-acetyl-1,3-dihydroxybenzene in toluene at elevated
temperature to obtain (4-acetyl-3-hydroxyphenoxy)tetraphenylantimony in 93% yield. According to X-ray
diffraction data, the antimony atom in (4-acetyl-3-hydroxy-phenoxy)tetraphenylantimony has a distorted tri-
gonal-bipyramidal configuration. The Sb O and Sb C distances are 2.237(1) and 2.112(1), 2.114(2), 2.118(2),
2.170(2) , respectively, and the CSbO angle is 177.86(5) .
It is known that reactions of pentaarylantimony
with dicarboxylic acids may involve, depending on
the starting reagent ratio, substitution of one or two
carboxyl hydrogen atoms to give derivatives like
Ar4SbOC(O)RC(O)OH or Ar4SbOC(O)RC(O)OSb
Ar4, respectively [1]. No reactions of pentaarylanti-
mony with dihydroxybenzenes have not yet been
reported.
The hydrogen atom of the hydroxy group ortho to
the acetyl group in the starting phenol takes part in
intramolecular hydrogen bonding, and its lability is
decreased. To substitute this hydrogen atom by Ph4Sb
requires more rigid conditions (130 150 C, 2 h).
HO
OH
2Ph5Sb +
C(O)CH3
OSbPh4
We showed that the reaction of pentaphenylanti-
mony with resorcinol (1:1 molar ratio, toluene, 20 C,
12 h) gives (3-hydroxyphenoxy)tertaphenylantimony.
Ph4SbO
2PhH
C(O)CH3
HO
Ph5Sb +
OH
X-ray diffraction data show that the antimony atom
in compound I has a trigonal-bipyramidal coordinaton.
The sum of equatorial bond angles is 356.73 , and the
axial C13SbO1 angle is 177.86(5) . The equatorial
positions are occupied by phenyl substituents. The
angles between them are slightly smallerthan 120
(117.98, 119.04, and 119.71). The axial positions are
occupied by the fourth phenyl substituent and the
aroxy group. The Sb Ce distances [2.112(1), 2.114(2),
and 2.118(2) ] are shorter than Sb Ca [2.170(2) ].
OH
Ph4SbO
PhH
Changing the reagent ratio to 2:1 leads to substitu-
tion of hydrogen in the second hydroxy group. More
rigid conditions are needed in this case, which is
explained by decrease in the lability of the free hydr-
oxyl hydrogen upon introduction of the electron-donor
Ph4Sb substituent into the starting phenol.
Note, that among all the structurally characterized
aroxytetraphenyl derivatives of antimony compound I
has the longest Sb O bond [2.237(1) ] and the
shortest O Car bond [1.316(2) ]. The Sb O and
O Car bond lengths in other tetraphenylantimony
phenolates are as follows, : 2.128(3) and 1.333(5)
in (5-ethyl-2-isopropyl-phenoxy); 2.132(6) and
1.41(2) in (2,6-dimethylphenoxy)tetraphenylantimony
[2]; 2.202(3) and 1.321(5) in (4-formylphenoxy)tetra-
phenylantimony; and 2.221(4) and 1.317(6) in tetra-
phenyl(2-nitrophenoxy)antimony [3]. The Sb O and
O Car distances in aroxytetraphenyl derivatives of
It was found that pentaphenylantimony reacts with
4-acetyl-1,3-dihydroxybenzene analogously, i.e. by
way of substitution of the most active hydrogen atom,
to give (4-acetyl-3-hydroxyphenoxy)tetraphenylanti-
mony (I); (toluene, 100 C, 1 h).
OH
Ph4SbO
HO
Ph5Sb +
OH
PhH
C(O)CH3
C(O)CH3
I
1070-3632/03/7303-0350$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS AND STRUCTURE OF (4-ACETYL-3-HYDROXYPHENOXY)TETRAPHENYLANTIMONY 351
C11
C16
C17
C12
C7
C10
C15
C14
C2
C3
C5
C6
C18
C13
C9
C4
C1
C26
C8
Sb
O1
C19
C27
C25
C20
C21
C28
C24
C23
C32
C30
C29
C31
H1
C22
O2
O3
General view of the molecule of (4-acetyl-3-hydroxyphenoxy)tetraphenylantimony.
antimony vary over a wide range and are determined
The C=O stretching absorption bands in the IR
by the electron density on the aroxy group [4]. The
oxygen unshared electron pair interacts with the
benzene -electron system, thereby depleting the
oxygen atom of electron density. This effect is com-
pensated for by electron density shift from the anti-
mony atom, which results in polarization of the Sb O
bond. The above electron interaction shortens the
O Car distance. Electron-acceptor substituents in the
benzene ring favor stronger electron density shift from
oxygen, rendering the Sb O distance longer. Electron-
donor substituents exert the opposite effect. The aroxy
group of compound I both an electron-donor and an
electron-acceptor group. The lengthening of the Sb O
bond and the attendant shortening of the O Car bond
can be explained by prevailing effect of the electron-
acceptor acetyl substituent.
spectra of compounds I and I are observed at 1608
1
and 1600 cm . From that it follows that this bond in
compound II is longer than in I. The C=O bond
length in compound II is probably increased by intra-
molecular interaction between the antimony atom and
the carbonyl oxygen. The same effect is observed in
tetraphenylantimony acylates, where the Sb O=C
distances are shorter than the sum of the van der
Waals radii of antimony and oxygen [6].
EXPRIMENTAL
The IR spectra were measured on a Hitachi-215
spectrometer in Vaselive oil between NaCl plates.
X-ray diffraction analysis was performed on a
Bruker SMART-1000 diffractometer for a balled
single crystal. Data collection was perfomed in groups
of 606 images at 0, 90, and 180 , with -scanning
in 0.3 steps and a dwell time of 10 s. Correction for
absorption was applied. The crystal data and experi-
mental and refinement parameters for structure I were
as follows: empirical formula C32H27O3Sb, molecular
weight 591,29, temperature 293(2) K, MoK radiation
(0.71073 ), space group P1, a 9.454(2), b 9.874(2),
The presence of a potential coordinating center
(carbonyl group) in the aroxyl ligand does not lead to
intermolecular Sb O=C bonding, probably because
of the existence of an O2 H1 O3 intramolecular
hydrogen bond between the carbonyl and hydroxy
groups, with the following parameters: O2 H1
0.92(3) , H1 O3 1.68(3) , and O2H1O3 angle
158(2) . The C31 O3 bond [1.240(2) ] is slightly
longer than the C=O bond in aldehydes and ketones
c 15.168(4)
;
101.454(4) ,
92.332(4) ,
[1.215(5)
1.450(2)
] [5]. The C28 C31 bond length is
104.869(4) ; V 1334.9(6) 3, Z 2, dcalc 1.446 g/cm3,
1
.
1.064 mm , F(000) 588;
range 3.12 31.51 ,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003

352
SHARUTIN et al.
Table 1. Bond lengths and angles in structure I
Bond
d,
Bond
d,
Angle
, deg
Angle
, deg
Sb O1
Sb C1
Sb C7
Sb C13
Sb C19
O1 C25
O2 C29
O3 C31
C1 C6
C1 C2
C2 C3
C3 C4
C4 C5
C5 C6
C7 C8
C7 C12
C8 C9
C9 C10
C10 C11
C11 C12
2.237(1)
2.112(1)
2.114(2)
2.170(2)
2.118(2)
1.316(2)
1.359(2)
1.240(2)
1.377(2)
1.380(2)
1.379(2)
1.366(3)
1.365(3)
1.381(2)
1.381(2)
1.382(2)
1.386(2)
1.362(3)
1.371(2)
1.386(2)
C13 C18
C13 C14
C14 C15
C15 C16
C16 C17
C17 C18
C19 C24
C19 C20
C20 C21
C21 C22
C22 C23
C23 C24
C25 C30
C25 C26
C26 C27
C27 C28
C28 C29
C28 C31
C29 C30
C31 C32
1.389(2)
1.393(2)
1.373(2)
1.369(2)
1.378(3)
1.390(2)
1.381(2)
1.383(2)
1.390(3)
1.372(3)
1.367(3)
1.384(2)
1.393(2)
1.415(2)
1.357(2)
1.402(2)
1.417(2)
1.450(2)
1.374(2)
1.500(3)
C1SbC7
117.98(6)
119.04(6)
119.71(6)
97.75(5)
96.03(6)
94.32(6)
84.01(5)
82.05(5)
85.84(5)
177.86(5)
124.35(9)
119.0(1)
121.3(1)
119.6(1)
120.7(2)
119.9(2)
119.8(2)
120.9(2)
119.7(2)
120.1(2)
120.0(2)
117.7(1)
123.8(1)
118.5(1)
121.3(2)
119.3(2)
122.2(1)
118.5(1)
C16C15C14
C15C16C17
C16C17C18
C13C18C17
C8C7C12
120.2(2)
120.0(2)
119.8(2)
120.9(2)
119.4(2)
121.7(1)
118.9(1)
119.8(2)
120.5(2)
119.8(2)
120.4(2)
123.5(1)
119.6(1)
116.9(2)
121.2(2)
122.5(2)
116.3(2)
123.0(2)
120.7(2)
118.0(2)
121.1(2)
121.9(2)
121.2(2)
117.7(2)
121.1(2)
120.1(2)
119.6(2)
120.7(2)
C1SbC19
C7SbC19
C1SbC13
C7SbC13
C19SbC13
C1SbO1
C8C7Sb
C12C7Sb
C7SbO1
C7C8C9
C19SbO1
C13SbO1
C25O1Sb
C6C1C2
C10C9C8
C22C23C24
C19C24C23
O1C25C30
O1C25C26
C30C25C26
C27C26C25
C26C27C28
C27C28C29
C27C28C31
C29C28C31
O2C29C30
C30C29C28
C29C30C25
O3C31C28
O3C31C32
C28C31C32
C19C20C21
C22C21C20
C23C22C21
C6C1Sb
C2C1Sb
C3C2C1
C4C3C2
C5C4C3
C4C5C6
C1C6C5
C9C10C11
C7C12C11
C18C13C14
C18C13Sb
C14C13Sb
C15C14C13
C24C19C20
C24C19Sb
C20C19Sb
13 < h < 13, 14 < k < 14, and 22 < l < 22. We
measured 20915 reflections, 8477 of which were
unique (Rint 0.0352) and 6480 had I > 2 (I). The
extinction coefficient was not refined. Residual elec-
tron density (max/min) 0.300/0.461 e/A3.
Reaction of pentaphenylantimony with 4-acetyl-
1,3-dihydroxybenzene (molar ratio 1:1). A mixture
of 1.00 g of pentaphenylantimony, 0.30 g of 4-acetyl-
1,3-dihydroxybenzene, and 10 ml of toluene was
heated at 100 C for 1 h. The solvent was removed,
and the residue was crystallized from toluene
heptane (1:1) to obtain 1.05 g (92%) of pinkish
crystals, mp 194 195 C. IR spectrum, , cm : 1800 s,
1745 m, 1330 s, 1275 v.s, 1220 m, 1180 s, 1120 s,
1060 s.
The structure was solved by the direct method and
refined by the least-squares procedure anisotropically
for non-hydrogen atoms [330 variables, GOOF 0.889,
R1 0.0291 and R2 0.0578 for F2 > 4 (F2) and R1
0.0436 and R2 0.0611 for all reflections]. The H1
atom was located by difference synthesis and refined
isotropically. The other H atoms were placed in
geometrically calculated positions and refined by the
rider model.
1
The reaction of pentaphenylantimony with re-
sorcinol was carried out analogously. Crystals of
(3-hydroxyphenoxy)tetraphenylantimony (67%) were
obtained, mp 159 C.
Data collection and edition, as well as refinement
of unit cell parameters were carried out using the
SMART and SAINT Plus programs [7]. All structural
calculations were carried out using the SHELXTL/PC
program package [8].
Reaction of pentaphenylantimony with 4-acetyl-
1,3-dihydroxybenzene (molar ratio 2:1). A mixture
of 3.00 g of pentaphenylantimony, 0.44 g of 4-acetyl-
1,3-dihydroxybenzene, and 15 ml of toluene were
heated at 130 150 C for 2 h. The reaction mixture
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003

SYNTHESIS AND STRUCTURE OF (4-ACETYL-3-HYDROXYPHENOXY)TETRAPHENYLANTIMONY 353
Table 2. Atomic coordinates and isotropic equivalent
thermal parameters ( 105 for Sb and 104 for the rest
atoms) in structure I
was cooled to room temperature to form yellow
crystals which were filtered off and dried to obtain
2.45 g (84%) of yellow crystals, mp 123 131 C. IR
1
spectrum, , cm : 1600 s, 1290 v.s, 1150 s, 1060 s.
Atom
x
y
z
Ueq
ACKNOWLEDGMENTS
Sb
1766(1)
1161(1)
4679(1)
4883(2)
758(2)
1679(2)
2022(2)
1469(2)
565(2)
23777(1)
2562(1)
16(2)
1905(2)
160(1)
21601(1)
3452(1)
2686(1)
3584(1)
2144(1)
2754(1)
2785(1)
2194(1)
1584(2)
1553(1)
3028(1)
3727(1)
4265(1)
4126(1)
3445(1)
2885(1)
929(1)
618(1)
153(1)
640(1)
351(1)
438(1)
1688(1)
848(1)
3727(3)
494(3)
695(4)
819(4)
377(3)
524(4)
614(5)
648(5)
808(6)
620(5)
399(3)
558(5)
667(5)
614(5)
584(5)
493(4)
408(4)
497(4)
605(5)
653(5)
659(6)
533(4)
425(4)
568(5)
718(6)
719(6)
656(5)
540(5)
423(4)
508(4)
517(4)
436(4)
458(4)
476(4)
557(5)
744(6)
114(9)
O1
The authors express their gratitude to the Russian
Fundation for Basic Research for providing access to
the Cambridge Structural Database (project no. 99-07-
90133).
O2
O3
C1
C2
361(2)
C3
1794(2)
2718(2)
2214(2)
778(2)
C4
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C5
C6
202(2)
1218(2)
433(2)
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4782(2)
5643(2)
5398(2)
4299(2)
3454(2)
2275(2)
3534(2)
3543(2)
2299(2)
1036(2)
1029(2)
3312(2)
2681(2)
3202(2)
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5041(2)
4498(2)
1626(2)
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C11
C12
C13
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C15
C16
C17
C18
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003