Synthesis and structure of triarylantimony dioximates

Article abstract of DOI:10.1007/s11176-005-0041-4

The reaction of triphenylantimony, hydrogen peroxide and 5-bromo-2-hydroxybenzaldoxime in a 1:1:2 molar ratio in ether gives triphenylantimony bis(5-bromo-2-hydroxybenzaldoximate). The reaction of penta-p-tolylantimony with the same oxime in toluene yields tri-p-tolylantimony bis(cyclohexanone oximate). According to X-ray data, the Sb atoms in the products have a distorted trigonal bipyramidal coordination with the oximate ligands in axial positions. In triphenylantimony bis(5-bromo-2- hydroxybenzaldoximate), the O-Sb-O angle is 175.49(6)°, and the interatomic distances are as follows, A: Sb-C 2.095-2.103; Sb-O 2.069(2) and 2.083(2); and Sb...N (intermolecular) 2.896(2) and 2.832(2). The respective geometric parameters of tri-p-tolylantimony bis(cyclohexanone oximate) are 174.25(6)°; 2.107-2.117; 2.049(2) and 2.057(2); and 2.890(2) and 2.861(2) A. 2004 MAIK Nauka/Interperiodica .

Full text of DOI:10.1007/s11176-005-0041-4

Russian Journal of General Chemistry, Vol. 74, No. 10, 2004, pp. 1485 1491. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 10, 2004,
pp. 1600 1607.
Original Russian Text Copyright
2004 by Sharutin, Molokova, Sharutina, Gerasimenko, Pushilin.
Synthesis and Structure of Triarylantimony Dioximates
V. V. Sharutin, O. V. Molokova,
O. K. Sharutina, A. V. Gerasimenko, and M. A. Pushilin
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received December 4, 2002
Abstract The reaction of triphenylantimony, hydrogen peroxide and 5-bromo-2-hydroxybenzaldoxime in a
1: 1: 2 molar ratio in ether gives triphenylantimony bis(5-bromo-2-hydroxybenzaldoximate). The reaction of
penta-p-tolylantimony with the same oxime in toluene yields tri-p-tolylantimony bis(cyclohexanone oximate).
According to X-ray data, the Sb atoms in the products have a distorted trigonal bipyramidal coordination with
the oximate ligands in axial positions. In triphenylantimony bis(5-bromo-2-hydroxybenzaldoximate), the
O Sb O angle is 175.49(6) , and the interatomic distances are as follows, : Sb C 2.095 2.103; Sb O
2.069(2) and 2.083(2); and Sb N (intermolecular) 2.896(2) and 2.832(2). The respective geometric param-
eters of tri-p-tolylantimony bis(cyclohexanone oximate) are 174.25(6) ; 2.107 2.117; 2.049(2) and 2.057(2);
and 2.890(2) and 2.861(2)
.
Trialkylantimony dioximates R3Sb(ON=CR R )
(R=Me, Et; R and R are alkyl and aryl groups) have
been prepared either by reactions of trialkylantimony
dibromides with sodium oximates in boiling benzene
[1] or THF [2] or with oximes in the presence of tri-
ethylamine as hydrogen bromide acceptor [3]. Tri-
phenylantimony dioximates have also been prepared
by reactions of triphenylantimony dimethoxide and
oximes [4]. It is known that triorganylantimony di-
halides are prepared by halogenation of triorganyl-
antimony, whereas triorganylantimony dialkoxides,
by alcoholysis of organylantimony dihalides. The
syntheses of triorganylantimony dioximates described
in [1 4] all are multistage.
might serve as a kind of activity test. It was establi-
shed that the reaction results in formation of triphenyl-
antimony bis(5-bromo-2-hydroxybenzaldoximate) (I).
Ar3Sb + H2O2 + 2HON=C(H)C6H3(OH-2)(Br-5)
Ar3Sb[ON=C(H)C6H3(OH-2)(Br-5)]2 + 2H2O. (2)
The reaction was carried out at room temperature.
The yield of compound I was 82%.
We established that reaction (1) not always pro-
vides a high yield of triarylantimony dioximates,
because in some cases one more reaction product of
the general formula (Ar3SbON=CRR )2O is formed.
Hence, the reactions of triphenyl- and tri-p-tolylanti-
mony with hydrogen peroxide and benzophenone
(1:1:2 molar ratio) resulted in isolation, along with
triphenylantimony bis(benzophenone oximate) (72%)
and tri-p-tolylantimony bis(benzophenone oximate)
(21%), of -oxobis[(benzophenone oximato)triphenyl-
antimony] (26%) and -oxobis[(benzophenone oxi-
mato)tri-p-tolylantimony] (30%) [6].
We have been the first to synthesize triarylam-
monium dioximates by an oxidative addition proce-
dure based on the reaction of triarylantimony with
hydrogen peroxide in the presence of an oxime at a
1:1:2 molar reagent ratio [5].
Ar3Sb + H2O2 + 2HON=CRR
Ar3Sb(ON=CRR )2 + 2H2O.
(1)
According to [9 12], hydrogen peroxide oxidizes
triarylantimony to Ar3SbO or Ar3Sb(OH)2, depending
on the size of the organic radical. In the presence of
HX, derivatives of the general formula Ar3SbX2 are
formed [13]. We found that with keto- or aldoximes
as hydrogen-containing reagents, a competing reaction
pathway appears, leading to compounds of the
(Ar3SbX)2O type. This transformation probably
occurs by schemes (3) (5).
Using this procedure we have prepared a series of
triarylantimony dioximates, including new and pre-
viously described compounds [6 8]. Proceeding with
the research into the synthesis of compounds of the
Ar3SbX2 type, we focused on the reaction of triaryl-
antimony, hydrogen peroxide, and 5-bromo-2-hydroxy-
benzaldoxime. The hydrogen atoms in the two hydr-
oxy groups in the latter differ from each other in
mobility, and, therefore, their involvement in reaction
Ar3Sb + H2O2
Ar3Sb(OH)2,
(3)
1070-3632/04/7410-1485 2004 MAIK Nauka/Interperiodica

1486
SHARUTIN et al.
Note that small amounts of tetraarylantimony
Ar3Sb(OH)2 + HON=CRR
Ar3Sb(OH)ON=CRR + 2H2O,
2Ar3Sb(OH)ON=CRR
oximates (up to 10%) were found among the reaction
products. This fact suggests that not all pentaarylanti-
mony reacts according to the above-presented scheme.
(4)
(Ar3SbON=CRR )2O + H2O.
(5)
The reactions of equimolar amounts of pentaarylan-
timony with cyclohexanone oxime or acetophenone
oxime at 90 C gave triarylantimony dioximates in
yields of up to 89%. If the reactions were carried out
at room temperature or under short heating, tetraaryl-
antimony oximates formed in yields of up to 93% [19].
As shown in [14], unsymmetrical compounds
Ar3Sb(OH)X are unstable and transform to products
with an Sb O Sb bridging bond.
The formation of compounds (Ar3SbON=CRR )2O
might by explained in terms of hydrolytic instability
of derivatives Ar3Sb(ON=CRR )2 and their hydrolysis
under the reaction conditions. However, Bajpai and
Srivastava [4] showed that triarylantimony dioximates
are resistant to hydrolysis. We also confirmed it by
special experiments. That means that the formation of
two products in the oxidation of triarylstibine with
hydrogen peroxide in the presence of oximes evi-
dently arises from other reasons.
The reaction of pentaarylantimony with oximes
evidently involves several stages, the first afording
tetraarylantimony oximate. However, in spite of the
fairly high strength of the Sb C bond, elimination of
the second aryl group and formation of triarylanti-
mony doximates occur under sufficiently mild condi-
tions. Evidently, triarylantimony dioximates are more
preferred by energy than tetraarylantimony oximate.
By special experiment it was established that the
reaction of tetraphenylantimony benzophenone
oximate with benzophenone oxime (toluene, 90 C,
5 h) gives rise to triphenylantimony bis(benzophenone
oximate) (76%).
We previously found that at a 1:1:1 reagent molar
ratio, oxidative addition (1) provides a single organo-
antimony product, -oxobis[(oximato)triarylantimony],
in 90% yield [6, 15].
2Ar3Sb + 2H2O2 + 2HON=CRR
Ph4SbON=CPh2 + HON=CPh2
(Ar3SbON=CRR )2 + 3H2O2,
(6)
Ph3Sb(ON=CPh2)2 + PhH.
(8)
Ar = Ph, p-Tol; R R = Ph; R = H, R = C4H3O.
Note that Dodonov et al. [16], using tert-butyl
hydroperoxide as oxidative agent in the synthesis of
triphenyl and trimethylantimony dioximates (R3Sb:
t-BuOOH:HON=CR R 1:1:2, hexane), obtained
87 96% of the target product and observed no forma-
tion of -oxobis[(oximato)triorganylantimony].
To gain insight into structural features of triarylanti-
mony dioximates, we performed an X-ray diffraction
analysis of triphenylantimony bis(5-bromo-2-hydroxy-
benzaldoximate) (I) and tri-p-tolylantimony bis(cyclo-
hexanone oximate) (II) (Figs. 1 and 2). According to
these data, the antimony atoms in compounds I and II
have an almost undistorted trigonal bipyramidal co-
ordination. The axial positions are occupied by the O
atoms of the oximate ligands. The axial OSbO angle
in compound I is 175.49(6) , and in product II it is
174.25(6) (Table 2). The O1,2SbC bond angles in
structures I and II vary within 83.88(8) 93.23(9) and
84.65(7) 93.07(7) , respectively. The deviation of
antimony atoms from the equatorial plane in structure
I is 0.0184 , and in the structure II the antimony
atom locates exactly in the equatorial plane. The sum
of CSbC angles in the equatorial plane practically
does not differ from 360 C. The angles between
equatorial aryl ligands are unequal: 115.4(9),
118.62(9) and 125.87(9) in I and 117.65(7),
120.94(7), and 121.40(7) in II. The Sb C bond
lengths are 2.095(2) 2.103(2) in I and 2.107(2)
It is known that in reactions of pentaarylantimony
with protic acids only one aryl group is easily sub-
stituted to form Ar4SbX (where X is the acid residue)
[14]. Further dearylation requires special conditions,
which is explained by a high strength of the Sb C
bond. For example, dimethoxytriphenylantimony was
prepared by boiling pentaphenylantimony in methanol
for 5 weeks in 80% yield [17]. Reactions of penta-
organylantimony with excess carboxylic acids gives
adducts like R4SbOC(O)R HOC(O)R rather than tri-
organylantimony dicarboxylates [18].
We found that triarylantimony dioximates can be
prepared by the reaction of pentaarylantimony and
oximes in a 1:2 molar ratio (toluene, 90 100 C,
1 5 h).
2.117(2)
in II. The Sb O1,2 bonds [2.069(2) and
Ar3Sb + 2HON=CRR
Ar3Sb(ON=CRR )2 + 2ArH, (7)
Ar = p-Tol; R, R = cyclo-C60H10 (II); Ar = Ph, R, R =
cyclo-C6H10 (III); Ar = Ph; R = R = Ph (IV); Ar = p-Tol;
R = Me, R = Ph (V).
2.083(2) in I and 2.049(2) and 2.057(2) in II] are
shorter than equatorial Sb C bonds. These results
contradict one of the rules of the valence shell elec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 10 2004

SYNTHESIS AND STRUCTURE OF TRIARYLANTIMONY DIOXIMATES
1487
4
Table 1. Atomic coordinates ( 10 ) and equivalent isotropic thermal parameters ( 103) in I and II
Compound I
Compound II
atom
x
y
z
Ueq,
atom
x
y
z
Ueq,
Sb
2979.0(1)
655.5(3)
5982.4(3)
2995(1)
2935(1)
2824(2)
6130(2)
2787(2)
3987(2)
1309(2)
613(2)
4824.4(1)
8431.2(3)
2021.3(4)
5003(1)
4515(1)
8316(2)
4139(2)
6109(2)
4243(2)
5200(2)
4954(2)
5152(2)
5586(2)
5854(2)
5665(2)
3135(2)
2400(2)
1283(2)
895(2)
1604(2)
2748(2)
6132(2)
6217(2)
7135(3)
7988(3)
7908(3)
6978(2)
7310(2)
8307(2)
9328(2)
9355(3)
8400(2)
7376(2)
6212(2)
3479(2)
3651(2)
3314(2)
2823(3)
2675(2)
2990(2)
3798(2)
768(2)
8550.31(8)
11813.1(2)
5324.5(2)
9547(1)
7566(1)
9603(1)
7966(1)
9692(1)
7550(1)
8187(1)
8567(2)
8299(2)
7673(2)
7304(2)
7550(1)
8821(1)
8745(1)
8917(2)
9169(1)
9243(2)
9067(1)
8639(1)
9172(1)
9240(2)
8790(2)
8250(2)
8173(2)
10435(1)
10123(1)
10329(2)
10826(2)
11137(1)
10951(1)
10223(1)
6889(1)
7374(1)
7237(2)
6632(2)
6159(1)
6278(1)
6996(1)
953.1(1)
799.6(1)
43.79(4)
91.1(1)
115.1(2)
55.0(5)
53.7(5)
71.4(6)
74.4(6)
51.5(6)
50.8(6)
49.6(7)
67(1)
83(1)
82(1)
75(1)
61.5(8)
44.7(6)
61.0(8)
73(1)
73(1)
75(1)
63.1(8)
44.1(6)
63.0(8)
74(1)
77(1)
100(1)
77(1)
52.0(7)
58.8(8)
82(1)
Sb
7244.7(1) 7148.9(1)
6530.5(1) 52.21(4)
Br1
Br2
O1
O1
6750(1)
7872(1)
6717(2)
6877(2)
6787(2)
6761(3)
7977(3)
8083(3)
8162(3)
6957(3)
7336(3)
8798(3)
8980(4)
8061(4)
6576(4)
6368(3)
5582(2)
5588(2)
4484(2)
3338(2)
3335(2)
4440(2)
2130(3)
9185(2)
9769(2)
11037(2)
11754(2)
11161(2)
9909(2)
13161(3)
7035(2)
5999(2)
5910(2)
6865(3)
7891(3)
7967(2)
6782(4)
6068(1)
8105(1)
6600(2)
8193(2)
5918(2)
6380(2)
5928(2)
4689(2)
4285(2)
4691(2)
8450(3)
8616(3)
9391(5)
9432(4)
9467(3)
8550(3)
8229(2)
9330(2)
10032(2)
9653(2)
8556(2)
7856(2)
10411(2)
7413(2)
6669(2)
6838(2)
7755(2)
8492(2)
8313(2)
7946(3)
5771(2)
5045(2)
4146(2)
3923(2)
4656(2)
5570(2)
2888(3)
5771(1)
7324(1)
4709(1)
8354(2)
4093(2)
2965(2)
59.4(4)
72.4(5)
62.9(5)
77.4(6)
63.0(6)
87.9(9)
O2
N1
O2
N2
O3
C11
C12
C13
C14
C15
C16
C21
C22
C23
C24
C25
C26
C31
C32
C33
C34
C35
C36
C37
C41
C42
C43
C44
C45
C46
C47
C51
C52
C53
C54
C55
C56
C57
O4
N1
2085(2) 101.6(10)
N2
2345(2)
3475(2)
4383(2)
83.5(8)
85.0(8)
76.8(7)
C11
C12
C13
C14
C15
C16
C21
C22
C23
C24
C25
C26
C31
C32
C33
C34
C35
C36
C41
C42
C43
C44
C45
C46
C47
C51
C52
C53
C54
C55
C56
C57
H1
507(2)
906(2)
228(2)
883(2)
9024(2) 101.1(9)
8800(3) 156(1)
9278(4) 264(2)
10458(3) 180(2)
10508(3) 166(2)
10150(2) 118(1)
3355(2)
2506(2)
2692(2)
3724(3)
4575(2)
4395(2)
4111(2)
5027(2)
5706(2)
5457(2)
4552(3)
3881(3)
2212(2)
2365(2)
2050(3)
1547(3)
1386(2)
1722(2)
2486(2)
5052(2)
6052(2)
7014(2)
6988(2)
5997(2)
5042(2)
4013(2)
299(2)
6481(2)
6537(2)
6520(2)
6492(2)
6441(2)
6424(2)
6494(2)
5275(2)
4585(2)
3777(2)
3635(2)
4334(2)
5148(2)
50.2(5)
59.6(6)
65.7(7)
60.0(7)
67.7(7)
62.0(6)
86.2(9)
47.8(5)
61.9(6)
78.2(8)
72.1(7)
70.1(7)
60.8(6)
83(1)
2743(3) 121(1)
65.2(8)
59.5(8)
54.0(7)
48.5(7)
55.4(8)
70(1)
7856(2)
8215(2)
9046(2)
9553(2)
9202(2)
8378(2)
56.4(6)
66.6(7)
75.0(8)
74.8(8)
83.0(9)
73.8(8)
71(1)
10457(2) 118(1)
66.2(8)
57.2(8)
48.9(7)
85(1)
H2
535(2)
437(2)
85(1)
tron pair repulsion theory which states that in mole-
cules with a trigonal bipyramidal configuration axial
ligands are more remote from the central atom than
equatorial [20]. In other structurally characterized tri-
arylantimony dioximates, the Sb C and Sb O bond
lengths span the ranges 2.097 2.120 and 2.044 2.080
[7, 8, 16], i.e. here, too, violation of the above-
mentioned rule takes place. Note that the Sb O bond
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 10 2004

1488
SHARUTIN et al.
Table 2. Principal bond lengths (d) and bond angles ( ) in I and II
Compound I
Compound II
bond
d,
angle
, deg
bond
d,
angle
, deg
Sb N1
Sb N2
Sb O2
Sb O1
Sb C31
Sb C11
Sb C21
Br1 C45
Br2 C55
O1 N1
O N2
2.896(2)
2.832(2)
2.069(2)
2.083(2)
2.095(2)
2.096(2)
2.103(2)
1.901(3)
1.899(3)
1.391(2)
1.392(2)
1.374(3)
1.339(3)
1.277(3)
1.280(3)
O2SbO1
175.49(6)
92.33(8)
91.61(8)
86.80(8)
93.23(9)
118.62(9)
92.04(8)
83.88(8)
125.87(9)
115.49(9)
111.4(1)
108.2(1)
113.8(2)
113.2(2)
Sb O2
2.049(2)
2.057(2)
2.107(2)
2.116(2)
2.117(2)
2.861(2)
2.890(2)
1.418(2)
1.396(2)
1.276(3)
1.264(4)
1.476(3)
1.493(3)
1.532(4)
1.500(4)
1.490(4)
1.522(3)
1.483(4)
1.500(4)
O2SbO1
174.25(6)
92.56(7)
93.07(7)
91.43(7)
84.65(7)
120.94(7)
85.15(7)
92.92(7)
121.40(7)
117.65(7)
27.14(5)
154.02(5)
79.49(7)
78.22(7)
112.27(7)
111.2(1)
110.8(1)
112.8(2)
113.4(2)
O2SbC31
O1SbC31
O2SbC11
O1SbC11
C31SbC11
O2SbC21
O1SbC21
C31SbC21
C11SbC21
N1O1Sb
Sb O1
O2SbC31
O1SbC31
O2SbC51
O1SbC51
C31SbC51
O2SbC41
O1SbC41
C31SbC41
C51SbC41
O2SbN2
Sb C31
Sb C51
Sb C41
Sb N2
Sb N1
O1 N1
O2 N2
N1 C11
N2 C21
C11 C12
C11 C16
C12 C13
C13 C14
C14 C15
C15 C16
C21 C26
C21 C22
O3 C42
O4 C52
N1 C47
N2 C57
N2O2Sb
O1SbN2
C47N1O1
C57N2O2
C31SbN2
C51SbN2
C41SbN2
N1O1Sb
N2O2Sb
C11N1O1
C21N2O2
length in triarylantimony dioximates is close to the
sum of the covalent radii of antimony and oxygen
mony dimethoxide (2.033 ) [32]. In the latter com-
pound, axial Sb O bonds are shorter than equatorial
Sb C bonds.
(2.07
[21]), being considerably smaller than in tri-
arylantimony dicarboxylates (2.109 2.155 ) [22 28]
and triarylantimony bis(arenesulfonates) (2.105
2.133 ) [29 31] but greater than in triphenylanti-
The O1,2 N1,2 in compounds I and II are 1.391(2),
1.392(2) and 1.277(3), 1.280(3) , respectively, and
C34
C33
C35
O3
C32
C43
C42
C36
O4 C53
H1
C44
C31
H2
C41
C54
Br2
C51
N1
O1
N2
C45
C57
C55
C46
C47
C16
C56
Br1
O2
C21
C26
Sb
C11
C12
C15
C25
C24
C14
C13
C22
C23
Fig. 1. Molecular structure of triphenylantimony bis(5-bromo-2-hydroxybenzaldoximate) (I).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 10 2004

SYNTHESIS AND STRUCTURE OF TRIARYLANTIMONY DIOXIMATES
1489
C24
C25
C26
C23
C21
C22
C57
C54
C55
C56
N2
C51
C53
O2
C52
C32
Sb
C33
C46
C34
C31
O1
C41
C37
C45
C44
C36
C35
C42
N1
C43
C47
C16
C15
C11
C12
C14
C13
Fig. 2. Molecular structure of tri-p-tolylantimony bis(cyclohexanone oximate) (II).
the respective N1,2 C distances are 1.418(2), 1.396(2),
and 1.276(3), 1.264(4) ; these values practically
coincide with analogous interatomic distances in other
triarylantimony dioximates [7, 8, 16]. The SbO1,2N1,2
angles are 111.4(1) and 108.2(1) in structure I and
111.2(1) and 110.8(1) in structure II.
involvement of the first ones in hydrogen-bond
formation.
Note that the geometric parameters of tri-p-tolyl-
antimony bis(cyclohexanone oximate) (II) and tri-
phenylantimony bis(cyclohexanone oximate) [8], as
well as of tri-p-tolylantimony bis(acetophenone
oximate) [8] and its phenyl analog [7] practically do
not differ from each other, implying a weak effect the
electron-donor methyl groups in the aryl ligands on
the antimony atom exert on the geometry of these
molecules.
Compound I contains O3H1 N1 and O4H2 N2
hydrogen bonds: The O3,4 H1,2 and H1,2 N1,2 dis-
tances are 0.81(3), 1.05(3), 1.93(3), and 1.73(3)
,
respectively. The O3.4H1,2N1,2 angles are 140 and
144 . The rings formed hydrogen bonds are not fully
planar. The dihedral angle between the N1C47C41 and
C42O3H1 planes is 8.0 , and the angle between the
N2C57C51 and C52O4H2 planes is 2.3 . The lower
mobility of the hydroxyl hydrogen atoms in 5-bromo-
2-hydroxybenzaldoxime compared to the hydrogen
atoms of the oxime groups is probably explained by
The distances between the Sb atom and the oxi-
mate nitrogen atoms Sb N [2.832(2) and 2.895(2)
in I and 2.861(2) and 2.890(2)
in II] are shorter
than the sum of the van der Waals radii of Sb and N
(3.8 ). The presence of an intramolecular Sb N
contact in compounds I and II does not significantly
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 10 2004

1490
SHARUTIN et al.
affect the equatorial angles which only slightly differ
from the theoretical value of 120 , unlike what is ob-
served in triarylantimony dicarboxylates, where intra-
molecular Sb O=C contacts much increase one of
the equatorial angles (143.8 151.7 ) [22 28]. Bi-
dentate ligation of the oximate ligand was observed
in all previously structurally characterized tri- and
tetraarylantimony oximates [5, 7, 8, 15, 19].
out using the SMART and SAINT Plus programs [33].
All calculations on structure determination and refi-
nement were carried out using the SHELXTL/PC
program [34]. The coordinates of non-hydrogen atoms
are listed in Table 1, and the interatomic distances and
bond angles, in Table 2.
Triphenylantimony bis(5-bromo-2-hydroxyben-
zaldoximate (I). To a solution of 0.50 g of triphenyl-
antimony and 0.61 g of 5-bromo-2-hydroxybenzald-
oxime in 20 ml of diethyl ether, 0.16 ml of 30%
aqueous hydrogen peroxide was added. The resulting
mixture was kept for 12 h at 20 C. Colorless crystals
formed and were filtered off and dried to give 0.91 g
(82%) of compound I, mp 203 C (decomp.).
Additional coordination of a ligand with the anti-
mony atom is determined by the presence of atoms
with lone electron pairs and by geometric factors,
specifically by the distances of the central atom to the
ligand and electron-pair donor. The Sb O bond length
in triarylantimony dioximates [7, 8] is close to the
sum of the covalent radii of Sb and O, which ensures
interaction between Sb and the oximate nitrogen. The
fact that the Sb N distances in triarylantimony di-
oximates are much shorter than those expected by the
van der Waals radii points to strong intramolecular
donor acceptor interactions in these compounds,
which may be one of the reasons for their stability.
Tri-p-tolylantimony bis(cyclohexanone oximate)
(II). A mixture of 0.50 g of penta-p-tolylantimony and
0.19 g of cyclohexanone oxime in 10 ml of toluene
was heated for 1 h at 90 C. After cooling, the solvent
was removed, and the residue was crystallized from
toluene petroleum ether, 1:3 v/v. Yield 0.46 g (86%),
mp 160 C (145 C [4]).
EXPERIMENTAL
Similarly we obtained triphenylantimony bis-
(cyclohexanone oximate) (III), 67%, mp 124 C
(116 C [4]); triphenylantimony bis(benzophenone
oximate) (IV), 82%, mp 118 C (117 C [5]); and tri-p-
tolylantimony bis(acetophenone oximate) (V), 91%,
mp 125 C (126 C [8]).
X-ray diffraction analysis of crystals of tri-
phenylantimony bis(5-bromo-2-hydroxybenzald-
oximate) C32H25Br2N2O4Sb (I) was carried out on a
Bruker SMART-1000CCD diffractometer ( MoK
0.71073 , graphite monochromator). Monoclinic
crystals; at 24 C, a 12.774(2), b 11.837(3)
;
ACKNOWLEDGMENTS
3
106.683(3) , V 3030.2(7) 3, Z 4, dcalc 1.717 g cm ,
space group P21/n. Intensities of 20219 reflections
were measured, 4277 of which had I > 2 (I). Final
divergence factors: R 0.036 and RW 0.0787 [on
4277 reflections with F2 > 2 (F2)].
The authors express their gratitude to the Russian
Foundation for Basic Research for financial support
(project no. 99-07-90133).
REFERENCES
X-ray diffraction analysis of crystals of tri-p-
tolylantimony bis(cyclohexanone oximate) C33H41
N2O2Sb (II) was carried out on a Bruker SMART-
1000CCD diffractometer ( MoK 0.71073 , gra-
phite monochromator). Triclinic crystals; at 20 C, a
1. Jain, V.K., Bohra, R., and Mehrotra, R.C., Inorg.
Chim. Acta, 1981, vol. 51, no. 2, pp. 191 194.
2. Hodali, H.A. and Hussein, A.Q., Synth. React. Inorg.
Met.-Org. Chem., 1990, vol. 20, no. 10, pp. 1413
1423.
3. Bajpai, K., Srivastava, M., and Srivastava, R.C.,
Indian J. Chem., 1981, vol. 20A, no. 7, pp. 736 737.
4. Bajpai, K. and Srivastava, R.C., Synth. Inorg. Met.-
Org. Chem., 1981, vol. 11, no. 1, pp. 7 13.
5. Sharutin, V.V., Sharutina, O.K., Molokova, O.V.,
Ettenko, E.N., Krivolapov, D.B., Gubaidullin, A.T.,
and Litvinov, A.I., Zh. Obshch. Khim., 2001, vol. 71,
no. 8, pp. 1317 1321.
10.632(1), b 12.415(2), c 13.166(2)
;
77.023(2),
68.288, 83.509(2) , V 1572.4(3) 3, Z 2, dcalc
3
1.308 g cm , space group P-1. Intensities of
20143 reflections were measured, 4959 of which had
I > 2 (I). Final divergence factors: R 0.0368 and RW
0.0792 [on 4959 reflections with F2 > 2 (F2)].
Absorption was included by equivalent reflections.
The structures were solved by the direct method and
refined by the least-squares method anisotropically for
non-hydrogen atoms. Hydrogen atoms were located
geometrically and included in the refinement by
means of the rider model. Data collection and edition
and refinement of unit cell parameters were carried
6. Molokova, O.V., Can. Sci. (Chem.) Dissertation,
Vladivostok, 2001.
7. Sharutin, V.V., Sharutina, O.K., Molokova, O.V.,
Pakusina, A.P., Gerasimenko, A.V., and Gerasi-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 10 2004

SYNTHESIS AND STRUCTURE OF TRIARYLANTIMONY DIOXIMATES
1491
menko, E.A., Koord. Khim., 2002, vol. 28, no. 7,
pp. 497 500.
20. Gillespie, R.J. and Hargittai, I., The VSEPR Model of
Molecular Geometry, Boston: Allyn and Bacon, 1991.
8. Sharutin, V.V., Sharutina, O.K., Molokova, O.V.,
Pakusina, A.P., Gerasimenko, A.V., Sergienko, A.S.,
Bukvetskii, B.V., and Popov, D.Yu., Koord. Khim.,
2002, vol. 28, no. 8, pp. 581 590.
21. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36,
no. 12, pp. 3015 3037.
22. Sowbery, D.B., J. Chem. Res., 1979, no. 3, pp. 80
81.
9. Ruther, R., Huber, F., and Preut, H., Z. Anorg. Allg.
Chem., 1986, vol. 539, pp. 110 126.
23. Lebedev, V.A., Bochkova, R.I., Kuzubova, L.F.,
Kuz’min, E.A., and Sharutin, V.V., Dokl. Akad. Nauk
SSSR, 1982, vol. 265, no. 2, pp. 332 335.
10. Westhoff, T., Huber, F., and Preut, H., J. Organomet.
Chem., 1988, vol. 348, no. 2, pp. 185 191.
24. Sharutina, O.K., Sharutin, V.V., Senchurin, V.S.,
Fukin, G.K., Zakharov, L.N., Yanovskii, I.A., and
Struchkov, Yu.T., Izv. Ross. Akad. Nauk, Ser. Khim.,
1996, no. 1, pp. 194 198.
11. Huber, F., Westhoff, T., and Preut, H., J. Organomet.
Chem., 1987, vol. 323, no. 1, pp. 173 180.
12. Westhoff, T., Huber, F., Ruther, R., and Preut, H.,
J. Organomet. Chem., 1988, vol. 352, no. 1,
pp. 107 113.
25. Ferguson, G. and Kaitner, B., J. Organomet. Chem.,
1991, vol. 419, no. 2, pp. 283 291.
13. Gushchin, A.V., Doctoral (Chem.) Dissertation,
26. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., Pla-
tonova, T.P., Fukin, G.K., and Zakharov, L.N., Koord.
Khim., 2001, vol. 27, no. 5, pp. 396 398.
Nizhny Novgorod, 1988.
14. Kocheshkov, K.A., Skoldinov, A.P., and Zemlyan-
skii, N.N., Metody elementoorganicheskoi khimii.
Sur’ma, vismut (Methods of Organoelement Chem=-
istry. Antimony, Bismuth), Moscow: Nauka, 1976.
27. Domagala, M., Huber, F., and Preut, H., Z. Anorg.
Allg. Chem., 1989, vol. 574, pp. 130 142.
28. Domagala, M., Huber, F., and Preut, H., Z. Anorg.
Allg. Chem., 1990, vol. 582, pp. 37 50.
15. Sharutin, V.V., Sharutina, O.K., Molokova, O.V.,
Pakusina, A.P., Bondar’, E.N., Krivolapov, D.B.,
Gubaidullin, A.T., and Litvinov, I.A., Zh. Obshch.
Khim., 2001, vol. 71, no. 9, pp. 1507 1510.
29. Ruther, R., Huber, F., and Preut, H., Z. Anorg. Allg.
Chem., 1986, vol. 539, pp. 110 126.
30. Sharutin, V.V., Sharutina, O.K., Panova, L.P., and
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67,
no. 9, pp. 1531 1535.
16. Dodonov, V.A., Gushchin, A.V., Gor’kaev, D.A.,
Fukin, G.K., Starostina, T.I., Zakharov, L.N.,
Kurskii, Yu.A., and Shavyrin, A.S., Izv. Ross. Akad.
Nauk, Ser. Khim., 2002, no. 6, pp. 965 971.
31. Sharutin, V.V., Sharutina, O.K., Platonova, T.P., Pa-
kusina, A.P., Krivolapov, D.B., Gubaidullin, A.T.,
and Litvinov, I.A., Zh. Obshch. Khim., 2000, vol. 70,
no. 10, pp. 1668 1671.
17. McEwen, W.E., Briles, G.H., and Giddings, B.E.,
J. Am. Chem. Soc., 1969, vol. 91, no. 25, pp. 7079
7084.
32. Shen, K., McEwen, W.E., La Pleca, S.J., Hamil-
ton, W.C., and Wolf, A.P., J. Am. Chem. Soc., 1968,
vol. 90, no. 7, pp. 1718 1723.
18. Shmidbaur, H. and Mitschke, K.-H., Angew. Chem.,
1971, vol. 83, no. 4, pp. 149 150.
19. Sharutin, V.V., Sharutina, O.K., Molokova, O.V.,
Rokhmanenko, S.I., Troinina, T.G., Krivolapov, D.B.,
Gubaidullin, A.T., and Litvinov, I.A., Zh. Obshch.
Khim., 2000, vol. 70, no. 12, pp. 1990 1996.
33. SMART and SAINT. Area Detector Control and Integ-
ration Software, Madison: Bruker AXS, 1998.
34. SHELXTL, Version 5.10, Madison: Bruker AXC, 1998.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 10 2004