Synthesis and structure of μ-oxobis[(nitrito)triphenylantimony]

Article abstract of DOI:10.1023/B:RUGC.0000025502.67262.76

Triphenylantimony dibromide was reacted with sodium nitrite in aqueous acetone to obtain μ-oxobis[(nitrito)triphenylantimony]. According to single-crystal X-ray diffraction data, the Sb atoms in the molecule have a trigonal bipyramidal coordination. The molecule is centrosymmetric, the two Sb atoms are linked with each other by a bridging oxygen atom [the SbOSb angle is 141.8(2)°, and the Sb...Sb distance is 3.7354(5) A]. The Sb-O_br and Sb-O_term bond lengths are 1.9768(1) and 2.257(3) A, and the Sb...O and Sb...N distances are 3.020(4) and 3.070(6) A, respectively.

Full text of DOI:10.1023/B:RUGC.0000025502.67262.76

Russian Journal of General Chemistry, Vol. 74, No. 2, 2004, pp. 211 213. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 2, 2004,
pp. 238 240.
Original Russian Text Copyright
2004 by Sharutin, Pakusina, Platonova, Nasonova, Sharutina, Bukvetskii.
Synthesis and Structure of -Oxobis[(nitrito)triphenylantimony]
V. V. Sharutin, A. P. Pakusina, T. P. Platonova,
N. V. Nasonova, O. K. Sharutina, and B. V. Bukvetskii
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received February 5, 2002
Abstract Triphenylantimony dibromide was reacted with sodium nitrite in aqueous acetone to obtain
-
oxobis[(nitrito)triphenylantimony]. According to single-crystal X-ray diffraction data, the Sb atoms in the
molecule have a trigonal bipyramidal coordination. The molecule is centrosymmetric, the two Sb atoms are
linked with each other by a bridging oxygen atom [the SbOSb angle is 141.8(2) , and the Sb Sb distance is
3.7354(5) ]. The Sb Obr and Sb Oterm bond lengths are 1.9768(1) and 2.257(3) , and the Sb O and Sb N
distances are 3.020(4) and 3.070(6) , respectively.
It is known that the molecule of -oxobis[(nitrato)-
triphenylantimony] [Ph3(NO3)Sb]2O (I) has a V-like
shape [the SbOSb angle is 137.4(2) ] [1]. At the same
time, the Sb O Sb fragment in anhydride molecules
may be linear, as in -oxobis[(2,5-dimethylbenzene-
sulfonato)tri-p-tolylantimony] [2]. Note that most
structurally characterized Sb(V) compounds of the
general formula (Ar3SbX)2O are have a V-like struc-
ture which, in our opinion, are energetically more
favorable because of the additional interaction
between the antimony atoms. Actually, the Sb Sb
distances in I, (Ph3SbCl)2O [3], and (Ph3SbI)2O [4]
are 3.668, 3.715, and 3.755 , respectively, which is
much shorter than the sum of the van der Waals radii
shortening of these distances in II is accompanied by
lengthening of the Sb Obr [1.9768(1) ] bond com-
pared with I [1.968(3) A]. The distances between the
antimony atoms and their nonbonded nitrogen atoms,
Sb N [3.070(6) ] and Sb O=N [3.020(4) ], are
Table 1. Coordinates of atoms ( 104) and their equivalent
isotropic thermal parameters ( 103) in -oxobis[(nitrito)tri-
phenylantimony] (II)
2
Atom
x
y
z
Ueq,
Sb
1326.6(2) 3482.3(1) 7138.3(1)
50.3(1)
O1
O2
O3
N
0
3837(2)
3082(2)
4114(3)
3498(3)
3520(2)
4059(2)
4059(3)
3537(3)
3010(3)
2996(3)
4301(2)
4192(2)
4711(3)
5321(3)
5436(2)
4924(2)
2474(2)
1800(2)
1171(2)
1199(3)
1862(3)
2499(2)
7500
54.0(8)
73.9(8)
122(1)
108(2)
56.8(9)
68(1)
84(1)
95(2)
93(1)
75(1)
54.2(9)
67(1)
81(1)
79(1)
75(1)
63(1)
53.6(9)
70(1)
78(1)
75(1)
2839(2)
2955(4)
3313(5)
5980(3)
1570(3)
6950(4)
4960(5)
2680(4)
8240(4)
2257(3)
3357(3)
3934(4)
3438(4)
2356(4)
1761(3)
1424(3)
1424(4)
1421(4)
1437(4)
1443(4)
1443(3)
6717(2)
6128(3)
6255(4)
5693(3)
5380(3)
4449(3)
3851(4)
4160(3)
5079(3)
7970(2)
8332(3)
8920(3)
9162(3)
8814(3)
8207(3)
7855(2)
7429(3)
7941(3)
8865(3)
9298(3)
8794(3)
of antimony atoms (4.40
[5]).
We have synthesized -oxobis[(nitrito)triphenyl-
antimony] [Ph3(NO2)Sb]2O (II) and studied its crystal
and molecular structure.
C1
C2
C3
Compound II was prepared from triphenylanti-
mony dibromide and sodium nitrite in aqueous
acetone.
C4
C5
C6
C7
Ph3SbBr2 + 2NaNO2
Ph3Sb(NO2)2
H2O
C8
(Ph3SbNO2)2O
C9
II
C10
C11
C12
C13
C14
C15
C16
C17
C18
We found that the antimony atoms in molecule II
have a trigonal bipyramidal coordination with axial
oxygen atoms (Tables 1, 2; see figure). The molecule
is centrosymmetric (the inversion center is a bridging
oxygen atom) and has a puckered shape [the SbOSb
angle is 141.8(2) ], and the distance between the two
antimony atoms is 3.7354(5) . The Sb Oterm bond
lengths are 2.257(3) ^A, which is slightly shorter than
in molecule I [2.264(3) and 2.295(3) ]. Note that
76(1)
66(1)
1070-3632/04/7402-0211 2004 MAIK Nauka/Interperiodica

212
SHARUTIN et al.
Table 2. Selected interatomic distances and valence angles in -oxobis[(nitrito)triphenylantimony] (II)
Bond
d,
Angle
, deg
Bond
d,
Angle
, deg
Sb Sb
Sb O1
Sb C31
Sb C21
Sb C11
Sb O2
Sb O3
Sb N
3.7354(5)
1.9768(1)
2.110(4)
2.118(4)
2.128(4)
2.257(3)
3.020(4)
3.070(6)
1.254(6)
1.210(6)
1.379(5)
1.388(6)
1.391(6)
1.357(7)
SbO1Sb
O1SbC13
O1SbC7
C13SbC7
O1SbC1
C13SbC1
C7SbC1
O1SbO2
C13SbO2
C7SbO2
C1SbO2
O1SbO3
C13SbO3
C7SbO3
141.8(2)
96.4(1)
90.6(1)
111.1(1)
92.9(1)
119.6(1)
128.4(1)
179.6(1)
84.0(1)
89.4(1)
86.8(1)
135.9(1)
127.4(1)
70.3(1)
C4 C5
1.369(7)
1.382(6)
1.380(5)
1.391(5)
1.380(6)
1.363(7)
1.369(6)
1.393(6)
1.378(5)
1.380(6)
1.373(6)
1.357(6)
1.367(6)
1.379(6)
C1SbO3
O2SbO3
NO2Sb
71.8(1)
43.8(1)
119.1(3)
80.9(3)
C5 C6
C7 C12
C7 C8
NO3Sb
C8 C9
O3NO2
C2C1C6
C1C2C3
C4C3C2
C3C4C5
C4C5C6
C5C6C1
C12C7C8
C9C8C7
C10C9C8
116.0(5)
120.0(4)
119.0(4)
121.3(5)
119.6(5)
120.7(5)
119.4(4)
119.5(4)
119.4(4)
120.8(4)
C9 C10
C10 C11
C11 C12
C13 C18
C13 C14
C14 C15
C15 C16
C16 C17
C17 C18
O2
O3
N
N
C1 C2
C1 C6
C2 C3
C3 C4
The unit cell parameters and the intensities of
2108 unique reflections with I > 2 (I) were measured
on a SMART-1000CCD automated diffractometer
Monoclinic crystals; at 23 C, a 12.650(1), b 18.239(2),
c 14.722(1)
;
102.576(2) , V 3315.0(5) 3, Z 4,
dcalc 1.631 g/cm3, space group C2/c. The structure
( MoK radiation,
0.71073 , 2 / scanning).
was solved by the direct method and refined by least-
O3
N
C9
O2
C5
C6
C8
C10
C1
C4
C7
C3
C11
C12
Sb
C2
C14
C15
C13
C18
C17
O1
C17
Molecular structure of -oxobis[(nitrito)triphenylantimony] (II).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004

SYNTHESIS AND STRUCTURE OF -OXOBIS[(NITRITO)TRIPHENYLANTIMONY]
213
squares anisotropically for non-hydrogen atoms to R
0.0258 and RW 0.0651. The positions of hydrogen
atoms were calculated geometrically and refined by
the rider model. The coordinates of non-hydrogen
atoms are listed in Table 1, and interatomic distances
and valence angles, in Table 2. A perspective view of
the molecule is given in the figure. Data collection
and processing, as well as refinement of unit cell
parameters were performed using SMART and
SAINT-Plus programs [7]. Structure calculation and
refinement were performed using SHELXTL/PC
programs [8].
REFERENCES
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Akad. Nauk, Ser. Khim., 1999, no. 1, p . 174.
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Ivashchik, I.A., Krivolapov, D.B., Gubaidullin, A.T.,
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no. 1, p. C14.
-Oxobis[(nitrito)triphenylantimony] (II).
A
solution of 1.00 g of triphenylantimony dibromide in
10 ml of acetone was added to a solution of 0.27 g of
sodium nitrite in 80 ml of water. The precipitate that
formed was filtered off, washed with water, dried, and
recrystallized from toluene heptane, 1:1. Yield 0.79 g
(99%), mp 142 C.
5. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36, no. 12,
p. 3015.
6. Mahon, M.F., Molloy, K.C., Omotowa, B.A., and
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7. SMART and SAINT-Plus, Ver. 5.0, Data Collection and
Processing Software for the SMART System, Madison:
Bruker, 1998.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 99-07-
90133).
8. SHELXTL/PC, Ver. 5.0, An Integrated System for
Solving, Refining and Displaying Crystal Structures
From Diffraction Data, Madison: Bruker, 1998.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004