11-1.
NO2 STRETCHINGS
A m o n g the six vibrations involving the NO2 group in nitrocompounds,
the NO2 stretchings are the two most useful group frequencies. The antisymmetric stretching m o d e is quite constant in spectral position, while the
symmetric stretching m o d e is more prone to vibrational couphng [1].
Therefore, caution should be exercised in applying the NO2 symmetric
stretching mode as a characteristic vibration. Nevertheless, with the
combination of their spectral positions and intensities, these two characteristic vibrations usually provide enough information for differentiating the
unconjugated [2-6] and conjugated NO2 groupings [3, 4, 7-9]. In addition,
the atom (C, O, or N) adjacent to the NO2 moiety can be determined by the
vibrational spectra of the c o m p o u n d s [10-12]. The C stretching m o d e
is used as a characteristic frequency of NO2 groupings only for smaU
nitroalkanes. However, the vibration is sensitive to the type of nitroalkane
(i.e., primary, secondary, etc.) and to nitroalkanes' rotational conformations. T h u s , these vibrations can be useful in conformational studies.
11-1.1.
Nitroalkanes (R-NO2)
180
Chapter 11 :
than in the hquid state (1601-1531 cm"^). Usually, the Vas(N02) frequency
decreases by 18-32 cm"^ as the sample phase changes from vapor to hquid
state. O n the other h a n d , the frequency shift of the symmetric NO2
stretching m o d e u p o n a change in the sample state is not as predictable
as that for the corresponding antisymmetric m o d e . The Vs(N02) frequencies
of nitroalkanes can either decrease by as much as 1 0 c m " \ or increase
by as much as 22 c m " S when the measuring state changes from vapor
(1397-1310cm"^) to liquid phase (1381-1310cm"^) [3]. In the IR spectra
of unconjugated nitroalkanes, the intensity of the antisymmetric NO2
stretching band is very strong, while the symmetric stretching b a n d is
somewhat weaker (strong-medium) [4, 13]. The peak intensity ratio of
Vas(N02)/Vs(N02) has been observed to vary from 5.9 to 1.8 in vapor-phase
IR spectra [3]. Although there was no definite number reported for the
intensity ratio in liquid-state IR spectra, the existence of an unconjugated
NO2 group can stiU be recognized by the spectral pattern of these two bands
[4, 13]. The symmetric (2) m o d e is predicted and found to be very
strong and polarized in R a m a n spectra, while the antisymmetric stretching
m o d e exhibits only medium to weak intensity [13]. Therefore, the relative
intensities of the NO2 antisymmetric and symmetric stretchings are reversed
in R a m a n spectra.
Slovetskn et al. Have studied the correlation between the NO2 stretching frequencies and the type of nitroalkanes (i.e., primary, secondary, or
tertiary) by R a m a n spectroscopy [2]. Their results are summarized in Table
11-1 along with correlations from other references. It appears that the
branching on the -carbon a t o m lowers the vibrational frequencies in b o t h
antisymmetric and symmetric NO2 stretching vibrations. Investigations on
the available IR data suggest that these correlations are also appropriate in
interpreting the IR absorption frequencies. The table shows the c o m p o u n d s
used for this examination.
-,^-,
Vas(NO)2
,(2)
1562-1553 cm"^
Ref.
1387-1378 cm"^
4, 14
Me2CH-N02:
1552 cm'^
-1360 cm"^
4, 14, 15
Me3C-N02:
-1540 cm-^
1358 cm-^
to A-C6H13-NO2:
M.
IM.
181
NO2 Stretchings
Table 1 1 - 1 .
The Group Frequencies (cm"') of NOj Containing Compounds
Vibrational Mode
Compound
Vapor
IR
Liquid/SoHd
IR
1621-1555
vs
1601-1531
vs
m-w
-CH2-NO2
1560-1548
vs
m-w
-CHR-NO2
1553-1547
vs
m-w
-CR2-NO2
1554-1534
vs
m-w
-C(N02)2
1587-1563
vs
m-w
-C(N02)3
1603-1597
vs
1555-1487
vs
1640-1620
vs
1630-1550
vs
-2
O-NO2
1580-1530
vs
N-NO2
NO2 symmetric stretch
1310-1381
vs
-CH2-NO2
1388-1376
vs
-CHR-NO2
1374-1366
vs
-CR2-NO2
1354-1344
vs
-C(N02)2
1337-1327
1357-1318
vs
vs
1285-1270
vs
1300-1250
vs
gauche:
894-873
m-w
trans:
914-898
gauche:
863-847
trans:
908-868
R-NO2
1397-1310
1307-1297
-C(N02)3
-02
0-N02
1371-1325
N-N02
C - N stretch
R-N02
R-CH2-N02
R-CHR-N02
NO2 scissors
NO2 rock
m-s
m-w
s
m
R-N02
R-CH2-N02
618-609
R-CHR-N02
627-619^^
857-830
m-w
R-CH2-NO2
643-614
w, sh
R-CHR-NO2
670-650
w-vw
Ar-N02
NO2 wag
m-s
m-w
R-NO2
R-NO2
R-CH2-NO2
494-472
m-w
R-CHR-NO2
557-522
182
11 - 1 . 2 .
Substituted Nitroalkanes
11-1.3.
M.
NO2 Stretchings
183
Table
11-2.
,3(2)
-substituent:
-H
0
-5
-5
-CH3
-C2H5
-C6H3
- c = o
-F
-Cl
-Br
-NO2
yff-substituent:
-H
-OH
-Cl
-Br
-NO2
,(2)
+ 10
+ 17
+ 17
+ 17
+ 29
0
-8
-8
-8
-8
-23
-23
-23
-29
0
-4
+2
+2
+2
0
-6
-4
-4
-15
Example: CH3CCI2--2
Vas(N02)
1558
+ 1 x(-5)
+ 2 x (17)
calc. 1587 cm" ^
obs. 1581 cm"^
Vs(N02)
1375
+ 1 X ( - 8 ) ...
+ 2 x ( - 2 3 ) ...
1 (-CH3)
2 (-Cl)
frquencies for y-nitrostyrenes are essentially in the same regions as those for
monoalkyl nitroethylenes. T h e NO2 stretchings of m-bis(2-nitropropenyl)benzene,
Me
occur at approximately 1505 cm"^ and 1330 cm"^ [13b]. These frequencies
are similar to those found for di- and trialkyl nitroethylenes. In the IR
spectra of these ring-substituted y^-styrenes, the symmetric NO2 stretching
184
Chapter 11 :
11-1.4.
Aromatic Nitrocompounds
11-2.
C - N Stretching
185
11-2.
C - N STRETCHING
11-2.1.
Nitroalkanes
11-2.2.
Aromatic Nitrocompounds
186
Chapter 11 :
11-3.
NO2 DEFORMATIONS
The NO2 deformation vibrations, which include NO2 scissoring (in-plane),
NO2 wagging (out-of-plane), and NO2 rocking (in-plane), usually occur at
frequencies lower than 900 c m " ^ For the majority of c o m p o u n d s , the
scissoring mode possesses the higher vibrational frequency of the three
deformations, and it is by far the most characteristic deformation m o d e .
The NO2 rocking m o d e , on the other hand, has the lowest frequency for
these three deformations.
According to the vibrational assignments of nitroalkanes [ 1 4 , 6 , 3 6 ] ,
nitroethylene [16] and nitrobenzene [16, 21], the NO2 deformation frequencies of unconjugated nitroalkanes are situated at lower frequencies than the
corresponding vibrations of conjugated deformations. In the example of
nitromethane, the NO2 scissors, wagging, and rocking modes are observed
at 656 cm"^ (liq.; IR : s; R : s, p), 608 cm"^ (liq; IR : m; R : w), and 482 cm"^
(liq.; I R : m ; R : m ) , respectively [14]. Other A2-nitroalkanes exhibit NO2
scissoring bands in the region of 658-610cm"^ [14]. The wagging mode
occurs in a wider range of vibrational frequencies, 560-477 cm"^ [14].
Thus, these frequencies are less useful as characteristic frequencies. The
NO2 deformation frequencies of nitrocyclopropane are assigned by
Holtzclaw et al. [36] as fohows: scissoring (hq.; R : 771 c m " \ w), wagging
(liq.; R : 646 c m " \ vw), and rocking (liq.; R : 491 c m " \ m).
The NO2 deformation occur at higher frequencies when conjugated to
C = C or phenyl groups. For instance, the NO2 scissoring of nitroethylene is
located at 8 9 0 c m " \ the NO2 wagging at 7 1 4 c m " \ and the rocking at
652 c m " ^ The NO2 deformation frequencies of nitrobenzene are located in
regions very close to those of nitroethylene, as its NO2 scissoring is reported
to be at 853 c m " ^ the wagging mode at 704 c m " \ and the rocking vibration
at 532 cm~^ [16]. The scissoring mode of other aromatic nitrocompounds is
located in the region of 890-800 cm"^ (R : s-m; IR : s-w) [21-23]. In the case
of l,3,5-triamino-2,4,6-trinitrobenzene, the NO2 scissoring frequency
(IR : 782 cm"^) is lower than the characteristic region [28].
11-5.
Nitroamines ( > - 2 )
187
11-4.
COVALENT NITRATES ( - O - N O 2 )
Only a limited a m o u n t of work has been reported on covalent nitrates. The
antisymmetric and symmetric NO2 stretching b a n d s of covalent nitrates are
located at 1640-1620 cm"^ a n d 1285-1270 cm~\ respectively [11]. It should
be noted that the antisymmetric NO2 stretching may be confused with some
substituted C = C moiety or aromatic ring stretchings. The symmetric NO2
stretching b a n d of primary nitrates usually appears as a single b a n d , while
the secondary nitrates, including monocyclic nitrates, exhibit a doublet
structure in this spectral region. One exception for this correlation is
secondary bicychc nitrates, which display only a single
band in their
vibrational spectra. It is to be expected that this symmetric stretching m o d e
is strong and polarized in the R a m a n spectra.
The O stretching frequency of covalent nitrates is observed at
870-855 cm"^ [11]. The NO2 in-plane bending is found at 710-695 c m " \
and the out-of-plane bending at 760-755 cm"^ [11].
11-5.
NITROAMINES O N - N O 2 )
The NO2 symmetric stretching of the )>NNO2 moiety occurs in a region
very similar to that for the ONO2 g r o u p . Infrared studies indicate
that the characteristic Vs(N02) of nitroamines is located at 1300-1250 cm~^
with very strong IR absorption [10, 37, 38]. The R a m a n intensity of this
vibrational m o d e is expected to be strong and polarized. The antisymmetric
NO2 stretching is m o r e sensitive t o the environmental structure of the
NNO2 moiety. F o r example, the alkyl-substituted nitroguanidines
absorb infrared in the 1634-1605 cm"^ region due to Vas(N02), while the
arylguanidines absorb at lower frequencies (1587-1575 cm~^) [37,38].
Recently, Cherskaya et al, investigated the vibrational spectra of ,'dinitroalkylenediamines, N 0 2 - N H - ( C H 2 ) - N H - N 0 2 (n = 1-3) [39].
T h e Vas(N02) vibration is assigned t o b a n d s between 1596 c m " ^ and
1547 cm"^ ( I R : v s , R : n o t observed), while the Vs(N02) is found in the
region of 1365-1290 cm"^ (IR : s-m, R : s-w). It is noteworthy that in-phase
and out-of-phase Vas(N02), as weh as Vs(N02), are possible for these
c o m p o u n d s because of the presence of two nitro groups, but in this case,
they are very weakly coupled and smah frequency shifts are expected. Such
mechanical interactions of the two NO2 groups should be taken into
Chapter 11 :
188
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189