Synthesis and structure of tetraphenylantimony nicotinate

Article abstract of DOI:10.1023/B:RUGC.0000025501.29625.ff

Tetraphenylantimony nicotinate was prepared in 91% yield by reaction of pentaphenylantimony with triphenylantimony bis(nicotinate) in toluene. Triphenylantimony bis(nicotinate), in turn, was prepared in 87% yield by oxidative addition of pyridine-3-carboxylic acid to triphenylstibine in ether in the presence of hydrogen peroxide. The structure of tetraphenylantimony nicotinate was determined by single-crystal X-ray diffraction. The Sb atom has a distorted trigonal bipyramidal coordination surrounding with the carboxy group in the axial position. The Sb-C distances are 2.118(1), 2.121(1), 2.130(1), and 2.170(1) A, and the Sb-O distance is 2.268(1) A. There is an intramolecular contact between the Sb atom and the carbonyl O atom [3.363(1) A].

Full text of DOI:10.1023/B:RUGC.0000025501.29625.ff

Russian Journal of General Chemistry, Vol. 74, No. 2, 2004, pp. 207 210. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 2, 2004,
pp. 234 237.
Original Russian Text Copyright
2004 by Sharutin, Pakusina, Platonova, Sharutina, Gerasimenko, Popov, Pushilin.
Synthesis and Structure of Tetraphenylantimony Nicotinate
V. V. Sharutin, A. P. Pakusina, T. P. Platonova,
O. K. Sharutina, A. V. Gerasimenko, D. Yu. Popov, and M. A. Pushilin
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received January 14, 2002
Abstract Tetraphenylantimony nicotinate was prepared in 91% yield by reaction of pentaphenylantimony
with triphenylantimony bis(nicotinate) in toluene. Triphenylantimony bis(nicotinate), in turn, was prepared
in 87% yield by oxidative addition of pyridine-3-carboxylic acid to triphenylstibine in ether in the presence of
hydrogen peroxide. The structure of tetraphenylantimony nicotinate was determined by single-crystal X-ray
diffraction. The Sb atom has a distorted trigonal bipyramidal coordination surrounding with the carboxy group
in the axial position. The Sb C distances are 2.118(1), 2.121(1), 2.130(1), and 2.170(1) , and the Sb O
distance is 2.268(1) . There is an intramolecular contact between the Sb atom and the carbonyl O atom
[3.363(1) ].
It is known that the antimony atoms in compounds
Ar4SbX have a trigonal bipyramidal configuration; the
electronegative ligand X, as a rule, occupies one of
the axial positions [1]. If ligand X contains free donor
atoms potentially capable of coordination, the coordi-
nation number of antimony can increase to six, as,
e.g., in tetraphenylantinomy carboxylates [2, 3]. Pro-
ceeding with structural studies of tetraphenylantimony
carboxylates [4 8], we have examined in this work
the molecular and crystal structure of tetraphenyl-
antimony nicotinate (I), which was prepared in 91%
yield by reproportionation of pentaphenyl antimony
with triphenylantimony bis(nicotinate) (II):
longer [2.268(1) ] than in tetraphenylantimony ben-
zoate III [2.245(1) ] [8] differing from I only in the
nature of the aromatic ring in the carboxylate ligand.
Note that an increase in the Sb O distance in I com-
pared to III is accompanied by a decrease in the C1
O1 bond length (1.279 , against 1.286
in III).
The C1 C51 distance between the carbon atoms of the
carbonyl group and aromatic ring in the carboxylate
ligand, 1.508(2) , is virtually the same as in III
[1.507(2) ], which suggests that in these molecules
the p electrons of the carbonyl carbon atom are in-
volved in conjugation with the system of the aro-
matic ring to a similar extent.
Ph5Pb + Ph3Sb[OC(O)C5H4N]2
2Ph4SbOC(O)C5H4N.
I
In I, there is an intramolecular contact between the
antimony and carbonyl oxygen atoms. The Sb O(=C)
distance is 3.363(1) , which is smaller than the sum
Triphenylantimony bis(nicotinate), in turn, was
prepared in 87% yield by oxidative addition of pyri-
dine-3-carboxylic acid to triphenylstibine in ether in
the presence of hydrogen peroxide:
of the van der Waals radii of Sb and O (3.70
[9])
but larger than the similar distance in III (3.309 );
thus, in I both the Sb O and Sb O(=C) distances
are longer than in III. The occurrence of the intramo-
lecular contact Sb O(=C) in I is confirmed by in-
creased equatorial angle CSbC (from the side of the
contact), 128.81(5) , and decreased other equatorial
angles, 115.68(5) and 111.36(5) (the ideal value is
120 ).
Ph3Sb + 2HOC(O)C5H4N + H2O2
Ph3Sb[OC(O)C5H4N]2 + 2H2O.
II
The single-crystal X-ray diffraction study (see fig-
ure; Tables 1, 2) shows that the antimony atom in I
has a trigonal bipyramidal coordination with the car-
boxylate oxygen atom occupying the axial position.
The sum of the CSbC angles in the equatorial plane
is 355.85(5) ; the axial angle CSbO is 176.78(4) .
The Sb O bond in the molecule of I is somewhat
EXPERIMENTAL
Single-crystal X-ray diffraction study of tetra-
phenylantimony nicotinate C30H24NO2Sb (I). The
1070-3632/04/7402-0207 2004 MAIK Nauka/Interperiodica

208
SHARUTIN et al.
C24
C25
C25
C22
C26
C21
Sb
N
C43
C52
C42
O2
C51
C1
C53
C54
O1
C12
C44
C45
C55
C11
C41
C32
C13
C16
C46
C15
C14
C31
C36
C33
C34
C35
General view of the tetraphenylantimony nicotinate (I) molecule.
unit cell parameters and intensities of 5403 unique re-
flections with I 2 (I) were measured on a SMART
CCD-1000 automatic diffractometer (MoK radiation,
0.71073 , 2 / scanning). Monoclinic system; at
Tetraphenylantimony nicotinate I. A mixture of
1.00 g of pentaphenylantimony, 1.18 g of triphenyl-
antimony bis(nicotinate), and 50 ml of benzene was
heated in an evacuated glass ampule for 2 h at 90
100 C. Then the reaction mixture was cooled, the
solvent was removed, and the residue was recrystal-
lized from a 1 : 3 benzene heptane mixture. Yield of I
1.98 g (91%), mp 179 C.
20 C, a 11.341(1), b 14.622(2), c 17.195(2)
;
3
104.990(2) , V 2511.6(5) 3, Z 4, dcalc 1.461 g cm ,
space group P21/n. The structure was solved by the
direct method and refined by the least-squares method
in the anisotropic approximation for non-hydrogen
atoms to R 0.0243, RW 0.0543. The positions of
hydrogen atoms were calculated geometrically and
included in the refinement in the rider model. The per-
spective view of the molecule is shown in the figure.
The coordinates of non-hydrogen atoms are given in
Table 1, and the principal interatomic distances and
bond angles in I are listed in Table 2. The data collec-
tion and edition, and also the refinement of unit cell
paameters were performed with SMART and SAINT
Plus programs [10]. All the calculations for the struc-
ture determination and refinement were performed
using SHELXTL/PC programs [11].
Triphenylantimony bis(nicotinate) II. A 30%
H2O2 solution (0.32 g) was added to a mixture of
1.00 g of triphenylstibine and 0.70 g of 3-nicotinic
acid in 20 ml of ether. The mixture was allowed to
stand for 12 h, after which the crystalline precipitate
was filtered off and dried. Yield of II 1.47 g (87%),
mp 187 C.
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project no. 99-07-
90133).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004

SYNTHESIS AND STRUCTURE OF TETRAPHENYLANTIMONY NICOTINATE
209
Table 1. Coordinates ( 104) and equivalent isotropic
temperature factors ( 103) of atoms in the structure of
tetraphenylantimony nicotinate I
Table 2. Bond lengths (d) and bond angles ( ) in the
molecule of tetraphenylantimony nicotinate I
Bond
d,
Angle
, deg
Atom
x
y
z
Ueq,
Sb C31
Sb C21
Sb C11
Sb C41
Sb O1
2.118(1)
2.121(1)
2.130(1)
2.170(1)
2.268(1)
1.279(2)
1.228(2)
1.382(2)
1.391(2)
1.376(2)
1.370(2)
1.371(2)
1.384(2)
1.381(2)
1.382(2)
1.379(2)
1.377(3)
1.372(2)
1.377(2)
1.384(2)
1.392(2)
1.380(2)
1.371(2)
1.380(2)
1.379(2)
1.371(2)
1.374(2)
1.391(2)
1.358(3)
1.365(2)
1.380(2)
1.375(2)
1.388(2)
1.508(2)
1.337(2)
1.333(3)
1.360(3)
1.391(2)
C31SbC21
C31SbC11
C21SbC11
C31SbC41
C21SbC41
C11SbC41
C31SbO1
128.81(5)
111.36(5)
115.68(5)
97.05(5)
95.02(5)
98.48(5)
84.87(5)
81.77(5)
83.17(5)
176.78(4)
123.0(1)
120.8(1)
121.1(1)
121.3(1)
120.0(1)
119.7(1)
120.2(1)
120.7(1)
119.0(1)
122.0(1)
118.6(1)
120.2(2)
120.2(2)
119.7(2)
120.6(2)
120.2(1)
118.0(1)
120.7(1)
121.3(1)
124.6(2)
115.8(2)
124.6(2)
118.8(2)
118.1(2)
125.9(1)
120.2(1)
113.8(1)
Sb
4618.7(1) 9795.3(1) 1999.9(1) 37.3(3)
O1
2847(1)
2371(1)
768(2)
9100(1)
10225(1)
7851(1)
8501(1)
7736(1)
6908(1)
6827(1)
7575(1)
8412(1)
9792(1)
10583(1)
10545(1)
9723(1)
2299(1) 48.2(3)
3059(1) 58.1(3)
2121(1) 70.1(5)
1483(1) 38.7(3)
1569(1) 50.5(4)
1251(1) 59.2(5)
839(1) 62.8(5)
753(1) 63.1(5)
1073(1) 49.6(4)
3261(1) 40.6(3)
3674(1) 54.0(4)
4493(1) 63.8(5)
4897(1) 62.1(5)
O2
N
C11
C12
C13
C14
C15
C16
C31
C32
C33
C34
4849(1)
4099(2)
4333(2)
5298(2)
6049(2)
5829(2)
5465(1)
5953(2)
6515(2)
6637(2)
O1 C1
O2 C1
C11 C16
C11 C12
C12 C13
C13 C14
C14 C15
C15 C16
C31 C36
C31 C32
C32 C33
C33 C34
C34 C35
C35 C36
C41 C42
C41 C46
C42 C43
C43 C44
C44 C45
C45 C46
C21 C22
C21 C26
C26 C25
C25 C24
C24 C23
C23 C22
C51 C52
C51 C55
C51 C1
C21SbO1
C11SbO1
C41SbO1
C1O1Sb
C42C41Sb
C46C41Sb
C43C42C41
C44C43C42
C43C44C45
C46C45C44
C45C46C41
C22C21C26
C22C21Sb
C26C21Sb
C21C26C25
C24C25C26
C25C24C23
C24C23C22
C21C22C23
C52C51C55
C52C51C1
C55C51C1
NC52C51
C35
C36
C41
C42
C43
C44
C45
C46
C21
C26
C25
C24
C23
C22
C51
C52
C53
C54
C55
C1
6193(2)
5595(2)
6237(1)
5997(2)
7027(2)
8320(2)
8584(2)
7553(2)
3082(1)
2319(2)
1392(2)
1230(2)
1975(2)
2904(2)
906(1)
8936(1)
8967(1)
4478(1) 62.1(5)
3664(1) 51.0(4)
1675(1) 39.8(3)
982(1) 46.1(4)
753(1) 53.4(4)
1209(1) 56.4(4)
1902(1) 58.2(5)
2136(1) 53.1(4)
1308(1) 39.6(3)
584(1) 63.6(5)
78(1) 75.7(6)
299(1) 65.0(5)
1023(1) 68.2(5)
1527(1) 58.5(5)
2747(1) 42.7(3)
2145(1) 54.9(4)
2743(1) 70.5(6)
3375(1) 68.6(5)
3383(1) 56.2(4)
2713(1) 39.7(3)
10517(1)
11041(1)
11473(1)
11377(1)
10857(1)
10435(1)
10643(1)
10320(1)
10889(2)
11764(1)
12082(1)
11526(1)
8949(1)
C53NC52
NC53C54
C53C54C55
C51C55C54
O2C1O1
332(2)
1300(2)
808(2)
321(2)
2134(1)
8343(1)
7958(1)
8528(1)
9048(1)
C52
N
N C53
O2C1C51
C53 C54
C54 C55
O1C1C51
9486(1)
REFERENCES
Fukin, G.K., Zakharov, L.N., Yanovskii, A.I., and
Struchkov, Yu.T., Izv. Ross. Akad. Nauk, Ser. Khim.,
1996, no. 1, p. 194.
1. Sharutina, O.K., Doctoral (Chem.) Dissertation,
Irkutsk, 2001.
5. Sharutin, V.V., Sharutina, O.K., Mel’nikova, I.G.,
Fukin, G.K., Zakharov, L.N., Yanovskii, A.I., and
Struchkov, Yu.T., Izv. Ross. Akad. Nauk, Ser. Khim.,
1996, no. 8, p. 2082.
6. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
Belsky, V.K., J. Organomet. Chem., 1997, vols. 536
537, no. 1, p. 87.
2. Bone, S.P. and Sowerby, D.B., J. Chem. Res., Synop.,
1979, no. 3, p. 82.
3. Bone, S.P. and Sowerby, D.B., Phosphorus Sulfur,
1989, vol. 45, no. 1, p. 23.
4. Sharutina, O.K., Sharutin, V.V., Senchurin, V.S.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004

210
SHARUTIN et al.
7. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
no. 12, p. 3015.
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67,
no. 9, p. 1536.
10. SMART and SAINT-Plus. Ver. 5.0. Data Collection
and Processing Software for the SMART System,
Madison: Bruker AXS, 1998.
8. Sharutin, V.V., Fukin, G.K., Zakharov, L.N., Sharu-
tina, O.K., Platonova, A.P., and Pakusina, A.P., Zh.
Obshch. Khim., 2000, vol. 70, no. 12, p. 1997.
11. SHELXTL/PC. Ver. 5.0. An Integrated System for
Solving, Refining, and Displaying Crystal Structures
from Diffraction Data, Madison: Bruker AXS, 1998.
9. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004