STERIC INHIBITION OF RESONANCE

V. NITROMESITYLENE1

ABSTRACT
A detailed X-ray investigation of the crystal structure of nitrornesityleile has shown that
the nitro group is twisted 66" out of the plane of the aromatic ring about the C-N bond. T h e
resulting decrease in resonance interaction conlpared with a completely planar model has been
correlated with the characteristic XO? vibration frequencies.

INTRODUCTION
T h e physical properties of the nitro and acetyl derivatives of mesityleile and durene
indicate that resonance interaction betmeell the nitro and acetyl groups and the aromatic
rings is markedly reduced in conlparisoil with nitrobenzene and acetophenone, suggesting
t h a t the steric effect of the methyl groups prevents the attainment of completely coplanar
configurations (I).
T h e dipole moments, for example, of conjugated aromatic nitro compounds, such a s
nitrobenzene ( I ) , are larger than those of the correspondi~lgaliphatic molecules, the
mome~ltof nitrobenze~lein benzene solution being 3.05 Debye units compared with
about 3.3 D for an aliphatic nitro compound. T h e increased dipole moments are due to
contributions from ionic structures (I1 aild 111) which are a t a maximum when the nitro

group is coplailar with the aromatic ring. T h c i n t r o d ~ ~ c t i oofn mcthyl groups ortho t o the
nitro group, a s in nitromesitylene (IV), reduces the dipole moment t o 3.G5 D , suggesting
that the nitro group is twisted out of the plane of the benzene nucleus, and the contribu-
tions of structures I1 and 111 are reduced.
1.1fa~i11scriptreceived February 37, 1959.
Co~lt~.ibz~t~o?z
frovz the Diazsio?~of Pure Plzysics, ~VatioilalResearclz Coz~t~cil,
Ottawa, Caxada.
Issz~edas 1V.R. C. No. 5282.
?iVational Researclr Cozrncil Postdoctot,ate Fellow.
Can. J. Chem. Val. 37 (1959)
1487
1488 CANADIAN JOURNAL O F CHEMISTRY. VOL. 37, 1969

Raman spectra evidence leads to similar conclusions. The Ramail shift correspo~lding
to the NO2 symmetrical stretching vibration is a t 1367 cm-' in phenylnitromethane,
Ph.CH2.NO2, where the nitro group is not coiljugated with the ring, and a t 1341 cm-I in
nitrobenzene; the frequency in nitromesitylene is 1363 cm-I, much closer to the value in
the non-conjugated molecule, again indicating a significant inhibition of the resonance
between the nitro group and the aromatic a-electrons. The ultraviolet absorption spectrum
of nitromesitylene also suggests a marked reduction i l l the resollance interaction.
Similar deviations from coplanarity and consequent resonance inhibition are to be
expected in 9-nitroanthracene and 9,lO-dinitroanthracene where the nitro group environ-
ments are similar to those in nitromesitylene. Detailed investigations of the crystal
struct~iresof these anthracene derivatives by X-ray diffraction methods have shown that
the nitro groups are twisted marlcedly out of the planes of the aromatic rings, by 64" i11
crystals of 9,lO-dinitroanthracene, and by 85" in crystals of the 9-nitro derivative. The
reductions in resonance interaction resulting from these deviatioils from coplanarity have
been correlated with the infrared spectra and with the bond length variations i11 the
molecules, the energy of resonance interaction between a nitro group and the aromatic
a-electrons in 9,lO-dinitroanthracene in the solid state being about one-fifth of that in a
completely planar model, while for 9-nitroanthracelie this resonance energy is negligible.
Configurations with 64" twist are the most stable for isolated molecules of both substances,
but in crystals of 9-nitroanthracene crystal forces apparently result in minimurn energy
when the twist is 85". I n solution the angles are the same in both molecules, the exact
values possibly depending on solvent-solute interactions.
The .present communication describes the extension of these investigations to nitro-
rnesitylene; the angle between the plane of the nitro group and the aromatic plane
has been determined by an accurate X-ray analysis of the crystals, and the resultant
resonance inhibition has been correlated with the characteristic vibration frequencies of
the nitro group, both in the solid state and in solution.

EXPERIMENTAL
Infrared Spectra
The spectra measured (Fig. I) were those of pure nitromesitylene in carbon tetrachloride
solution and dispersed in a Nujol mull, as observed with a Perkin-Elmer model 21
infrared spectrophotometer with a rock salt prism.

X-Ray A~zalysis
Crystals of nitromesitylene are orthorhombic with four molecules in a ini it cell of
dimensions a = 15.14, b = 8.41, c = 7.26 A, space group P n ~ 2 The ~ . structure was
determined from projectioils along the three principal crystallographic axes. All the
carbon atoms and the ilitrogen atom lie on one plane, but the oxygen atoms lie one above
and one below this plane a t distances of 0.95 A, so t h a t the nitro group is twisted very
markedly out of the plane of the aromatic ring about the C-N bond, the angle between
the planes of the benzene ring and the nitro group being 66.4". Figure 2 shows a projection
of the structure along the b-axis; the benzene ring is perpendicular to the plane of projec-
tion so that the individual atoms are not resolved, but the large deviation of the oxygen
atoms from coplanarity is well illustrated. Full details of the crystal structure analysis
are published elsewhere (2).
 TROTTER: INHIBITION OF v
RESONANCE. 1489

Q
J

2 1.5 - NITROMESITYLENE
D 1.0
in CCL, A

FREQUENCY (cm-'1

FIG.I. Infrared spectra.

FIG.2. Projection of t h e structure of nitromesitylene along the b-axis.

DISCUSSION
T h e spectra of nitromesitylene in the range 3500 cm-I t o 600 cm-I in carbon
tetrachloride solution and dispersed in a Nujol mull are shown in Fig. 1, and the peak
positions and intensities of the absorption bands are listed in Table I , some peaks of
course being masked by the carbon tetrachloride or Nujol bands. The strong absorption
a t 1364 cm-I in solution and 1362 cm-I in the solid state can be assigned to the NOz
symmetrical stretching vibration. T h e NOz antisymmetrical stretching vibration cannot
be assigned quite so unambiguously, as with the nitroanthracenes, b u t is probably a t
1531 cm-l. T h e absorption maximum a t 828 crn-' correspollds to the C-N stretching
vibration.
T h e characteristic NO? frequencies in nitromesitylene are compared in Table I1 with
the corresponding frequencies in conj ugated (3) and non-conjugated (4) nitro c o m ~ o u n d s
and with those in 9-nitroanthracene and 9,lO-dinitroanthracene. The twists of the nitro
 CANADIAN JOURNAL O F CFIEMISTRY. VOL. 37, 1959

TABLE I
Frequencies and intensities of absorption bands

Solution (CCI,) Solid (Nujol mull)

Frequency, cm-I Intensity Frequency, cm-I Intensity Vibration
Aromatic C-H stretching
CH3 antisy~nrnetricalstretching
CH3 stretching
CH3 symn~etricalstretching
C=C (aromatic) stretching
1531 (sh) NO2 antisymmetrical stretching
1525 C=C (aromatic) stretching
CI-I3 bending
1450 rn CH3 symmetrical bending
1420 (sh) \br 1419 (sh) CH3 bending
1380 (sh) m 1373 (sh) CH3 antisymmetrical bending
1364 s 1362 NO? sylll~lietricalstretcliing
1303 w 1300
1288 w 1288 (sh)
1178 w 1177
1090 3' 1085 Characteristic aromatic bands
1031 137 10'33
849 z\romatic C-H out-of-planevibration
828 C-S stretching

TABLE I1
CharacteristicInitro-zroup frequencies (cni-1) and deviations from coplanarity in nitromesitylene
and related ~nolecules

S O , stretching
C-N S O , twist,
Molecule Symmetrical Antisym~netrical stretching 6 in degrees

Non-conjugatecl 1377 1586 800-,900 90.0

9-Nitroanthracene 1374 1540 836 84.7
Nitromesitylene 1362 1531 828 66.4
9,lO-Dinitro:u~thcene 1367 1642 831 63.7
Conjugated 1349 1518 849 0

groups out of tlne aronnatic planes are included in the last column of the table. The NO?
symmetrical stretching vibration in nitromesityle~nea t 1364 cm-l in solution and a t
1362 cm-l in the solid state indicates, as in 9,lO-dinitroanthracene, that resonance
interaction between the nitro group and the aromatic T-electrons is inarlcedly reduced in
comparison with a completely conjugated nitro compo~uncl,but is not negligible. This
conclusion is in agreement with the effect which would be preclicted from the measured
twist of the nitro group out of the aromatic plane, the predicted resonance energy being
about one-fifth (cos2 66.4" = O.1G) of t h a t for a planar model.
As with the nitroanthracenes the frequencies in soli~tioiicannot be directly correlated
with the values in tlne crystals and with the t~vistsof the nitro groups out of the aromatic
planes, since the possible effects of solvent-solute interactions cannot be estimatec1;:it can
only be deduced that the angle in solution is between 66" and 90".

REFERENCES
1. M:HEL.~ND,G. W. ICes01ia11rein organic chemistry. John Wiley Sr Sons, Inc., New Yorlr. 1956.
2. Taoi~aa,J . ;\eta Cr).st. ( I n press).
3. RANDLB,I?. R. and \VHIFI;BN, D. H. J. Chern. Soc. 4153 (1952).
4. SMITH,D. C., P.m, C., and NIELSEN, J . 1%. J . Chcm. Phys. 18, 506 (1050).