Synthesis and structure of tetra- and triarylantimony oximates

Article abstract of DOI:10.1023/A:1020474021779

Reactions of pentaphenyl- and penta-p-tolylantimony with benzophenone oxime or triarylantimony bis(benzophenone oximate) yield tetraarylantimony benzophenone oximates. Triarylantimony bis(benzophenone oximates) were prepared by oxidative addition from triarylstibine and benzophenone oxime in the presence of hydrogen peroxide. X-ray diffraction analysis was performed to show that benzophenone oxime is a dimer and tetraphenylantimony benzophenone oximate has a trigonal bipyramidal antimony atom and an axial oxime oxygen atom.

Full text of DOI:10.1023/A:1020474021779

Russian Journal of General Chemistry, Vol. 72, No. 6, 2002, pp. 893 898. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 6, 2002,
pp. 956 961.
Original Russian Text Copyright
2002 by Sharutin, Sharutina, Molokova, Ettenko, Krivolapov, Gubaidullin, Litvinov.
Synthesis and Structure of Tetra- and Triarylantimony Oximates
V. V. Sharutin, O. K. Sharutina, O. V. Molokova, E. N. Ettenko,
D. B. Krivolapov, A. D. Gubaidullin, and I. A. Litvinov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received August 11, 2000
Abstract Reactions of pentaphenyl- and penta-p-tolylantimony with benzophenone oxime or triarylanti-
mony bis(benzophenone oximate) yield tetraarylantimony benzophenone oximates. Triarylantimony bis(benzo-
phenone oximates) were prepared by oxidative addition from triarylstibine and benzophenone oxime in the
presence of hydrogen peroxide. X-ray diffraction analysis was performed to show that benzophenone oxime is
a dimer and tetraphenylantimony benzophenone oximate has a trigonal bipyramidal antimony atom and an
axial oxime oxygen atom.
It is known that pentaarylantimonies I react with
antimony derivatives of the general formula Ar3SbX2
(Ar = Ph, p-Tol; X = Cl, Br, OC(O)R, OSO2Ar , NO3,
SCN) to give unsymmetrical antimony derivatives
Ar4SbX in high yields [1 4]. Such disproportionation
reactions involving compound I and triarylantimony
dioximates were not previously studied.
The yields of tetraarylantimony oximates in this
case reach 98% (Table 1).
Triarylantimony bis(benzophenone oximates) were
obtained by oxidative addition of benzophenone
oxime to triarylantimony in the presence of hydrogen
peroxide.
We found that tetraarylantimony benzophenone
oximates can be obtained by this disproportionation
reaction from pentaphenyl- and penta-p-tolylantimony
and triarylantimony bis(benzophenone oximates) in
toluene with yields of up to 92%.
Ar3Sb + 2HON=CPh2 + H2O2
Ar3Sb(ON=CPh2)2 + 2H2O.
Note that the first compound prepared by this pro-
cedure was triphenylantimony diacetate [5]. Later the
reaction was used for preparing analogous derivatives
of antimony of the general formula Ar3SbX2, where
X is an electronegative group [1-3, 6], but the prepara-
tion of triarylantimony dioximates has not yet been
reported.
Ar5Sb + Ar3Sb(ON=CPh2)2
2Ar4SbON=CPh2,
Ar = Ph, 4-MeC6H4.
The IR spectra and melting points of the tetraaryl-
antimony benzophenone oximates prepared by this
procedure agree with respective characteristics of the
same compounds obtained from pentaarylantimony
and benzophenone oxime.
According to X-ray diffraction data, the antimony
atom in compound Ia has a usual trigonal bipyramidal
coordination typical for five-coordinate antimony
compounds (Fig. 1). The O2 and C7 atoms are located
in the axial position, the bond angle O2Sb1C7 is
174.9(2) , the angles in the equatorial plane vary from
118.8(2) to 120.2(2) , and their sum is 348.2(3) .
The angles between the equatorial and axial substi-
tuents vary from 81.2(2) to 95.4(2) . The acute
angles are formed with the participation of the oxygen
atom (Table 2). The equatorial Sb C bonds are equal
within the experimental error, and they are slightly
smaller than the axial Sb C7 bond. The Sb O distance
[2.146(4) ] is close to Sb C bond lengths. They are
considerably smaller than in the pentavalent antimony
compound Ph4SbON=C(NO)Me which is structurally
similar to the obtained oximates. The respective
The reactions of pentaphenyl- or penta-p-tolylanti-
mony with oximes give tetraarylantimony oximates.
The products are colorless crystalline compounds
soluble in aromatic hydrocarbons and polar organic
solvents.
Ar5Sb + HON=CRR
Ar4SbON=CRR + ArH,
I
IIa IIj
Ar = Ph; R = R = Ph (a), R = H, R = C6H3(OH)-2-(Br)-5
(b), R = H, R = C6H4(NO2)-3 (c), R,R = cyclohexyl (d);
Ar = C6H4(Me)-4; R = Ph, R = Me (e), R = H, R =
C4H3O (f), R = R = Ph (g), R = H, R = C6H3(OH)-2-(Br)-
5 (h), R = H, R = C6H4(NO2)-3 (i), R,R = cyclohexyl (j).
1070-3632/02/7206-0893$27.00 2002 MAIK Nauka/Interperiodica

894
SHARUTIN et al.
Table 1. Yields, melting points, and elemental analyses of tetraarylantimony oximates
Found, %
Calculated, %
H
Comp.
no.
Yield, %
mp,
C
Formula
C
H
N
C
N
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
90
96
92
70
98
97
98
87
97
84
168
70.02
56.97
62.31
66.20
70.44
67.03
71.65
60.53
64.02
67.69
4.89
3.95
4.58
5.76
6.57
5.88
5.90
4.89
4.73
6.81
2.37
2.02
4.95
2.79
2.61
2.62
2.38
1.86
4.00
2.11
C37H30NOSb
C31H25BrNO2Sb
C31H25N2O3Sb
C30H30NOSb
C36H36NOSb
C33H32NO2Sb
C41H38NOSb
C35H33BrNO2Sb
C35H33N2O3Sb
C34H38NOSb
70.93
57.67
62.52
66.42
69.68
66.44
72.14
59.91
64.52
68.23
4.79
3.88
4.20
5.53
5.81
5.37
5.57
4.71
5.07
6.35
2.24
2.17
4.71
2.58
2.26
2.35
2.05
2.00
4.30
2.34
150
139
122
Oil
148
166
125
158
IIj
distances in Ph4SbON=C(NO)Me are 2.266 and
2.235 [7].
benzophenone oxime (III). It was shown that two
symmetrically independent molecules of compound
III form a pseudosymmetrical dimer by means of
N HO hydrogen bonds (Fig.3). The O1 N2 and
O2 N1 distances are 2.841 and 2.747 , and the
O1H1N2 and O2H2N1 angles are 140 and 138 , respec-
tively. The planar six-membered ring O1H1N2O2H2N1
is formed by hydrogen bonds. Hydrogen bonds pro-
duce no considerable distortion of bond angles in
molecule III (Table 4) but considerably increase
O N distances [1.427(6) and 1.432(7) ] as com-
pared to organoantimony benzophenone oxime IIa
[1.387(6) ].
The geometry of the Ph2C=NO substituent is usual.
The planar trigonal coordination of C25 and the N2
C25 distance [1.281(7) ] correspond to the proposed
structure.
The crystal packing of molecules IIa is determined
by multiple C H
contacts and dispersion interac-
tions between parallel benzene rings (Fig. 2).
To reveal peculiar features of the crystal structure
of IIa, we performed an X-ray diffraction study of
C21
C22
C20
C10
C11
C24
C28
C23
C12
C9
C19
C8
C7
C14
C27
C15
C29
C30
C26
C33
C16
SB1
C18
C13
N2
C34
C31
C25
O2
C2
C32
C6 C1
C17
C35
C5
C37
C36
C3
Fig. 1. Spatial arrangement of complex IIa in crystal.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002
C4

SYNTHESIS AND STRUCTURE OF TETRA- AND TRIARYLANTIMONY OXIMATES
895
Fig. 2. Crystal packing of molecules IIa.
Table 2. Bond lengths (d, ) and bond angles ( , deg) in
structure IIa
intensities of 5575 reflections, of which 3138 had I >
3 , were measured on an Enraf Nonius CAD-4 auto-
mated four-circle K-diffractometer at 20 C (MoK
radiation, MoK 0.71073 , graphite monochro-
mator, /2 scanning, < 29.96 ). Crystals of com-
pound IIa, C37H30NOSb, are monoclinic; at 20 C, a
Bond
d
Bond
d
Sb1 O2
Sb1 C1
Sb1 C7
Sb1 C13
Sb1 C19
2.146(4)
2.135(6)
2.180(5)
2.120(6)
2.132(6)
O2 N2
1.387(6)
1.281(7)
1.501(8)
1.499(8)
N2 C25
C25 C26
C25 C32
11.565(1), b 16.545(8), c 15.713(4)
,
94.09(2) ,
V 2999(2) 3, Z 4, dcalc 1.39 g/cm3, space group
P21/n. Absorption was not considered ( Mo
1
9.52 cm ). The structure was solved by the direct
method by means of the SIR program [8] and refined
first isotropically and then anisotropically. Hydrogen
atoms were located by difference synthesis and refined
isotropically on the final stage. The final divergence
factors were R 0.038 and RW 0.043, on 2905 unique
reflections with F2 > 3 . All the calculations were
performed using the MolEN program package [9] on a
DEC Alpha Station computer. Analysis of molecular
contacts and molecular drawings were made by means
of the WINPL98 program [10].
Angle
Angle
O2Sb1C1
O2Sb1C7
O2Sb1C13
O2Sb1C19
C1Sb1C7
C1Sb1C13
C1Sb1C19
C7Sb1C13
81.2(2)
174.9(2)
88.8(2)
86.6(2)
94.2(2)
118.8(2)
120.2(2)
95.4(2)
C7Sb1C19
C13Sb1C19
Sb1O2N2
O2N2C25
N2C25C26
N2C25C32
C26C25C32
93.8(2)
119.2(2)
112.2(3)
114.3(5)
114.9(5)
126.3(5)
118.6(5)
Single-crystal X-ray diffraction analysis of
benzophenone oxime (III). The intensities of
1031 reflections, 938 of which had I > 3 , were
measured on an Enraf Nonius CAD-4 automated four-
circle K-diffractometer at 20 C (MoK radiation,
MoK 0.71073 , graphite monochromator). Crys-
tals of compound III, C26H22N2, are monoclinic; at
EXPERIMENTAL
The IR spectra were recorded on a Hitachi-215
spectrometer for suspensions in Vaseline oil.
Single-crystal X-ray diffraction analysis of tetra-
phenylantimony benzophenone oximate (IIa). The
20 C, a 9.466(2), b 8.369(2), c 26.710(5)
,
92.89(3) , V 2113.3(8) , Z 4, dcalc 1.24 g/cm3, space
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

896
SHARUTIN et al.
C18
C19
C20
C17
C16
C15
C6
C5
C4
C22
O1
N2
C7
C14
C21
C23
C2
C1
C26
C3
N1
C8
O2
C24
C25
C13
C12
C9
C10
C11
Fig. 3. Spatial arrangement of compound III in crystal.
group P21/n. The structure was solved by the heavy-
atom method and refined anisotropically (isotropically
for hydrogen atoms) to R 0.0483 and RW 0.1345. All
the calculations were carried out using the SHELXL-
97 program package [11].
Tetraphenylantimony benzophenone oximate
(IIa). a. A mixture of 1.00 g of pentaphenylantimony,
0.39 g of benzophenone oxime, and 10 ml of toluene
was kept for 1 h at 90 C. The solvent was then
removed, and the residue was crystallized from hep-
tane benzene, 3:1. Yield 1.11 g (90%), mp 168 C.
Tetraarylantimony oximates were synthesized by
the following typical procedures.
b. A mixture of 0.40 g of pentaphenylantimony and
Table 3. Bond lengths (d, ) and bond angles ( , deg) in
structure III
0.59
g
of triphenylantimony bis(benzophenone
oximate) was kept for 1 h at 90 C in 10 ml of toluene.
The solvent was then removed, and the residue was
crystallized from heptane benzene, 3:1. Yield 0.96 g
(97%), mp 168 C.
Bond
d
Bond
d
O1 N1
N1 C1
C1 C2
C1 C8
1.432(7)
1.251(8)
1.469(10)
1.479(9)
O2 N2
1.427(6)
1.286(8)
1.471(9)
1.472(9)
N2 C14
C14 C21
C14 C15
Triphenylantimony bis(benzophenone oximate).
To a solution of 1.00 g of triphenylstibine and
0.76 g of benzophenone oxime in 20 ml of ether,
0.32 ml of 31% aqueous hydrogen peroxide was
added. The resulting mixture left to stand for 12 h
at 20 C. Colorless crystals formed and were fil-
tered off and dried. Yield 1.52 g (72%), mp 104 C.
Angle
Angle
C1N1O1
N1C1C2
N1C1C8
C2C1C8
113.5(6)
124.2(6)
116.8(6)
119.0(7)
C14N2O2
N2C14C21
N2C14C15
C21C14C15
114.6(6)
125.1(6)
113.9(7)
121.0(6)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

SYNTHESIS AND STRUCTURE OF TETRA- AND TRIARYLANTIMONY OXIMATES
897
Table 4. Atomic coordinates in structure IIa, equivalent isotropic thermal parameters of non-hydrogen atoms
3
B = 4/33
(aiaj)B(i, j) ( 2), and isotropic thermal parameters of hydrogen atoms
i=1 j=1
Atom
x
y
z
B
Atom
x
y
z
B
Sb1
O2
N2
C1
C2
C3
C4
C5
C6
0.90643(4)
1.0640(3)
1.1400(4)
0.8628(5)
0.9479(6)
0.9173(7)
0.8037(7)
0.7175(6)
0.7484(6)
0.7443(5)
0.6506(5)
0.5477(5)
0.5324(6)
0.6222(6)
0.7241(6)
0.8819(5)
0.8632(7)
0.8432(7)
0.8412(6)
0.8582(6)
0.8809(6)
1.0113(5)
0.9797(6)
1.0521(6)
1.1475(7)
1.1073(6)
1.1760(6)
1.2472(5)
1.3303(5)
1.3005(6)
1.3769(7)
1.4808(7)
1.5105(7)
1.4360(6)
1.2942(5)
0.22897(2) 0.28967(3) 2.959(7)
C33
C34
C35
C36
C37
H2
H3
H4
H5
H6
1.3745(6)
1.4153(6)
1.3762(7)
1.2990(6)
1.2573(6)
0.531(4)
0.989(6)
0.785(7)
0.143(4)
0.189(5)
0.667(5)
0.495(4)
0.458(5)
0.108(4)
0.278(3)
0.843(6)
0.827(5)
0.826(6)
0.866(4)
0.900(4)
0.921(5)
1.031(5)
1.185(8)
0.626(4)
1.241(4)
1.228(5)
1.354(5)
1.535(5)
1.576(5)
1.462(4)
1.409(4)
0.959(4)
0.087(4)
1.270(5)
0.710(4)
0.3089(4) 0.3034(4)
0.3859(4) 0.2919(5)
0.4502(4) 0.3386(6)
0.4348(4) 0.3972(5)
0.3584(4) 0.4104(4)
4.7(2)
5.7(2)
5.7(2)
5.3(2)
4.1(2)
4(1)
0.2548(2) 0.3652(3)
0.1898(3) 0.3687(3)
0.3460(3) 0.3348(4)
0.4021(4) 0.3600(5)
0.4773(4) 0.3899(6)
0.4970(4) 0.3956(5)
0.4419(4) 0.3701(4)
0.3665(4) 0.3394(4)
0.2143(3) 0.2116(4)
0.1704(4) 0.2405(4)
0.1656(4) 0.1915(5)
0.2055(4) 0.1152(5)
0.2510(4) 0.0865(5)
0.2550(4) 0.1353(4)
0.1272(3) 0.3684(4)
0.0515(4) 0.3309(5)
3.46(9)
3.3(1)
3.3(1)
5.1(2)
6.1(2)
5.2(2)
4.6(2)
4.1(2)
3.0(1)
3.9(2)
4.6(2)
4.8(2)
4.7(2)
4.0(2)
3.1(1)
4.9(2)
6.5(2)
6.0(2)
5.2(2)
4.6(2)
3.0(1)
4.5(2)
5.6(2)
6.3(2)
4.4(2)
6.1(2)
3.1(1)
3.9(2)
4.9(2)
7.0(2)
7.5(2)
6.6(2)
5.2(2)
3.2(1)
0.110(3)
0.512(5)
0.544(5)
0.045(3)
0.170(3)
0.148(3)
0.137(3)
0.207(3)
0.222(3)
0.215(2)
0.041(4)
0.059(3)
0.052(4)
0.074(3)
0.177(3)
0.136(4)
0.119(3)
0.182(6)
0.199(3)
0.291(3)
0.066(3)
0.033(3)
0.030(3)
0.085(3)
0.189(3)
0.270(3)
0.106(3)
0.000(3)
0.473(4)
0.152(3)
0.853(3)
0.398(5)
0.418(5)
0.882(3)
0.826(3)
0.301(3)
0.209(3)
0.081(3)
0.531(3)
0.623(2)
0.276(4)
0.351(4)
0.504(4)
0.565(3)
0.475(3)
0.121(4)
0.010(4)
0.004(6)
0.720(3)
0.107(3)
0.293(3)
0.293(3)
0.366(4)
0.450(3)
0.451(3)
0.275(3)
0.758(3)
0.178(3)
0.426(4)
0.958(3)
10(2)
13(3)
4(1)
5(1)
5(1)
4(1)
5(1)
4(1)
C7
C8
C9
H8
H9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
H10
H11
H12
H14
H15
H16
H17
H18
H20
H21
H22
H23
H24
H27
H28
H29
H30
H31
H33
H34
H35
H36
H37
0.8(8)
10(2)
5(1)
8(2)
5(1)
4(1)
8(2)
7(2)
14(3)
2(1)
3(1)
5(2)
6(2)
6(2)
5(1)
5(1)
4(1)
3(1)
5(1)
7(2)
4(1)
0.0141(4)
0.0062(4)
0.3827(5)
0.4677(5)
0.0681(5) 0.5057(5)
0.1339(4) 0.4541(4)
0.2172(3) 0.1842(4)
0.1624(4) 0.1191(4)
0.1548(4) 0.0532(5)
0.2030(5) 0.0474(5)
0.2647(4) 0.1780(4)
0.2572(5) 0.1098(5)
0.2097(3) 0.3702(4)
0.1399(4) 0.3715(4)
0.0704(4) 0.3265(5)
0.0061(5) 0.3276(6)
0.0112(5) 0.3729(6)
0.0786(5) 0.4187(5)
0.1443(4) 0.4185(5)
0.2938(3) 0.3638(4)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

898
SHARUTIN et al.
Table 5. Atomic coordinates ( 104) and equivalent
thermal parameters B (
Fundation for Basic Research (project no. 96-03-
40006).
103) in structure III
Atom
x
y
z
B
ACKNOWLEDGMENTS
O1
3122(6)
4610(6)
5225(8)
4501(8)
4905(9)
4241(12)
3186(12)
2786(10)
3445(9)
6775(8)
7472(8)
8871(10)
9666(9)
9018(10)
7581(9)
4705(5)
3203(5)
2590(7)
1054(8)
480(8)
943(10)
1849(9)
1283(9)
137(8)
3304(8)
2792(8)
3372(9)
4481(9)
5013(7)
4444(7)
2067(7)
2320(7)
2734(9)
3057(10)
2272(10)
2608(13)
3704(16)
4491(12)
4144(11)
2955(9)
4075(10)
4307(10)
3401(12)
2276(11)
2055(10)
1853(7)
1710(7)
1622(7)
1350(8)
263(10)
44(10)
891(12)
1932(11)
2188(9)
1791(8)
928(9)
1066(9)
2062(11)
2941(10)
2813(9)
4999(2)
4963(2)
5368(3)
5831(3)
6283(3)
6716(3)
6706(5)
6280(5)
5850(3)
5366(3)
5672(3)
5667(3)
5354(4)
5048(3)
5058(3)
3947(2)
3943(2)
3503(3)
3505(2)
3835(3)
3833(3)
3508(4)
3182(3)
3171(3)
3029(2)
2615(3)
2159(3)
2099(3)
2498(4)
2967(3)
92(2)
65(2)
55(2)
59(2)
75(2)
95(3)
102(4)
97(3)
74(2)
54(2)
64(2)
75(2)
79(3)
80(3)
71(2)
90(2)
61(2)
50(2)
50(2)
65(2)
75(2)
83(3)
74(2)
65(2)
50(2)
63(2)
67(2)
70(2)
70(2)
58(2)
The authors express their gratitude to V.K. Bel’skii
for X-ray diffraction analysis of benzophenone oxime.
N1
C1
C2
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