(Cyclohexylideneamino)oxyacetic acid and [chloro(phenyl)methyleneamino] oxyacetic acid: Hydrogenbonded R22(8) dimers and aromatic π-π stacking interactions

Article abstract of DOI:10.1107/S0108270104004299

The hydrogen bonded dimers and aromatic π-π stacking interactions in (cyclohexylideneamino)oxyacetic acid and [chloro(phenyl)methylene-amino] oxyacetic acid were investigated. The molecules of (cyclohexylideneamino) oxyacetic acid was linked into centrosy

Full text of DOI:10.1107/S0108270104004299

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
In both (I) and (II) (Figs. 1 and 2), the CÐO distances in the
carboxy groups (Tables 1 and 3) are consistent with the fully
ordered locations of the carboxy H atoms as deduced from
difference maps. In the side chains of (I) and (II), the corre-
sponding distances show very similar values, apart from the
O3ÐN4 distances, which are signi®cantly different; for
comparison, the mean value for the ÐOÐN bond in oximes
ISSN 0108-2701
(Cyclohexylideneamino)oxyacetic
acid and [chloro(phenyl)methylene-
amino]oxyacetic acid: hydrogen-
bonded R22(8) dimers and aromatic
p±p stacking interactions
Ê
is 1.416 A (Allen et al., 1987). The other distances are typical
for bonds of their types.
The conformations of the side chains both exhibit near-
planar fragments, viz. O1ÐC1ÐC2ÐO3 and C2ÐO3ÐN4Ð
Cn [n = 11 in (I) and n = 5 in (II); see Figs. 1 and 2], but while
the intervening C1ÐC2ÐO3ÐN4 torsion angles have similar
magnitudes in (I) and (II), they have opposite signs, and it is
this difference that determines the different overall confor-
mations of these two molecules. For the cyclohexylidene ring
in (I), the ring-puckering parameters (Cremer & Pople, 1975)
corresponding to the atom sequence C11±C16 [' = 174.0 (2)ꢀ
and ꢁ = 12 (2)ꢀ] indicate a conformation close to the chair
form (Evans & Boeyens, 1989), despite the planarity at atom
C11.
Christopher Glidewell,a* John N. Low,b Janet M. S.
Skakleb and James L. Wardellc
aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland,
bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
c
Â
Â
AB24 3UE, Scotland, and Instituto de Quõmica, Departamento de Quõmica
Ã
Inorganica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro,
RJ, Brazil
Correspondence e-mail: cg@st-andrews.ac.uk
In the structures of both (I) and (II), the molecules are
linked into centrosymmetric R22(8) (Bernstein et al., 1995)
dimers (Figs. 3 and 4) by paired OÐHÁ Á ÁO hydrogen bonds,
which are fairly short and effectively linear (Tables 2 and 4). In
Received 12 February 2004
Accepted 23 February 2004
Online 20 March 2004
Molecules of (cyclohexylideneamino)oxyacetic acid, C8H13-
NO3, (I), are linked into centrosymmetric dimers by pairs of
Ê
OÐHÁ Á ÁO hydrogen bonds [HÁ Á ÁO = 1.84 A, OÁ Á ÁO =
ꢀ
Ê
2.6782 (12) A and OÐHÁ Á ÁO = 178 ]. In [chloro(phenyl)-
methyleneamino]oxyacetic acid, C9H8ClNO3, (II), the mol-
ecules are similarly linked into centrosymmetric dimers by
Ê
pairs of OÐHÁ Á ÁO hydrogen bonds [HÁ Á ÁO = 1.79 A,
ꢀ
Ê
OÁ Á ÁO = 2.6329 (17) A and OÐHÁ Á ÁO = 176 ], and these
dimers are weakly linked into chains by a single type of
aromatic ꢀ±ꢀ stacking interaction.
Comment
Persulfate oxidation of iminooxyacetic acids, R(R0)C
NOCH2COOH, provides a useful route to iminyl radicals
(Forrester et al., 1979). The subsequent reactions of the iminyl
radicals thus generated depend greatly on the substituents,
and important species including nitrogen-containing hetero-
cycles can result. We report here the molecular and supra-
molecular structures of two representative examples of such
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 2
The molecule of (II), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
precursors, viz. (cyclohexylideneamino)oxyacetic acid, (I),
and [chloro(phenyl)methyleneamino]oxyacetic acid, (II).
o270 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104004299
Acta Cryst. (2004). C60, o270±o272

organic compounds
each structure, the reference molecule has been selected so
that the hydrogen-bonded dimer in which this molecule
participates is centred at (12, 21, 12 ). In the structure of (I), there
are no further direction-speci®c interactions between the
molecules, but in (II), the R22(8) dimers are weakly linked into
chains by a single aromatic ꢀ±ꢀ stacking interaction. The aryl
rings in the molecules at (x, y, z) and (2 x, 1 y, 2 z) are
Ê
parallel, with an interplanar spacing of 3.422 (2) A; the ring-
Ê
centroid separation is 3.856 (2) A, corresponding to a centroid
Ê
offset of 1.777 (2) A. The molecules at (x, y, z) and (2 x,
1
y, 2 z) are components of hydrogen-bonded dimers
1
1
1
centred at (12, , ) and (1, , 1), respectively, and propagation
2
2
2
by inversion of the two intermolecular interactions generates a
chain running parallel to the [101] direction (Fig. 5).
In neither (I) nor (II) do atoms O3 and N4 act as acceptors
of CÐHÁ Á ÁX (X = O or N) hydrogen bonds; there are no
intermolecular HÁ Á ÁX contact distances involving O3 or N4
Ê
Ê
that are less than 2.60 A in (I), and none of less than 2.70 A in
(II).
Experimental
Benzhydroxamoyl chloride, Cl(Ph)C NOH, was prepared from
H(Ph)C NOH according to the method of Baruah et al. (1988).
Compounds (I) and (II) were prepared by reaction of chloroacetic
acid with either cyclohexanone oxime [for (I)] or Cl(Ph)C NOH
[for (II)], using the following modi®cation of the procedure of
Forrester et al. (1979). A solution of the oxime (0.10 mol), chloro-
acetic acid (0.20 mol) and sodium hydroxide (0.40 mol) in a mixture
of water (100 ml) and ethanol (50 ml) was heated under re¯ux
overnight. The cooled solution was poured on to ice and acidi®ed
with dilute hydrochloric acid. The precipitate was collected, washed
with water and dissolved in NaHCO3 solution (100 ml of
1 mol dm 3). This solution was extracted with diethyl ether and
acidi®ed with dilute hydrochloric acid. The resulting solid was
collected, washed with water and recrystallized from ethanol, yielding
crystals suitable for single-crystal X-ray diffraction; m.p: (I) 365±
367 K, (II) 381±383 K.
Figure 3
Part of the crystal structure of (I), showing the formation of an R22(8)
dimer centred at (12, , 21 ). For clarity, H atoms bonded to C atoms have
1
2
been omitted. Atoms marked with an asterisk (*) are at the symmetry
position (1 x, 1 y, 1 z).
Compound (I)
Crystal data
C8H13NO3
Mr = 171.19
Triclinic, P1
a = 5.0776 (1) A
Ê
b = 8.6533 (3) A
c = 10.7804 (3) A
ꢂ = 111.2609 (15)ꢀ
ꢃ = 102.437 (2)ꢀ
ꢄ = 93.597 (2)ꢀ
Z = 2
Dx = 1.335 Mg m
Mo Kꢂ radiation
Figure 4
3
Part of the crystal structure of (II), showing the formation of an R22(8)
dimer centred at (12, , 21 ). For clarity, H atoms bonded to C atoms have
1
2
been omitted. Atoms marked with an asterisk (*) are at the symmetry
position (1 x, 1 y, 1 z).
Ê
Cell parameters from 1945
re¯ections
ꢁ = 3.9±27.5ꢀ
ꢅ = 0.10 mm
T = 120 (2) K
Ê
1
Block, colourless
0.40 Â 0.30 Â 0.30 mm
3
Ê
V = 425.88 (2) A
Data collection
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢆ offsets
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.917, Tmax = 0.968
1621 re¯ections with I > 2ꢇ(I)
Rint = 0.042
ꢁmax = 27.5ꢀ
h = 5 ! 6
k = 11 ! 11
l = 13 ! 13
9176 measured re¯ections
1945 independent re¯ections
Re®nement
Re®nement on F2
R[F2 > 2ꢇ(F2)] = 0.038
wR(F2) = 0.098
S = 1.04
1945 re¯ections
w = 1/[ꢇ2(F2o) + (0.0482P)2
+ 0.1199P]
where P = (F2o + 2Fc2)/3
(Á/ꢇ)max < 0.001
Figure 5
3
Ê
A stereoview of part of the crystal structure of (II), showing the
formation of a ꢀ-stacked [101] chain of hydrogen-bonded dimers. For
clarity, H atoms bonded to C atoms have been omitted.
Áꢈmax = 0.25 e A
3
Ê
0.29 e A
110 parameters
H-atom parameters constrained
Áꢈmin
=
ꢁ
Acta Cryst. (2004). C60, o270±o272
Christopher Glidewell et al. C9H8ClNO3 and C8H13NO3 o271

organic compounds
Table 1
Selected geometric parameters (A, ) for (I).
Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
ꢀ
Ê
Ê
C1ÐO1
C1ÐO2
1.3186 (14)
1.2134 (14)
O3ÐN4
N4ÐC11
1.4331 (12)
1.2775 (15)
C5ÐCl1
C1ÐO1
C1ÐO2
1.738 (2)
1.311 (2)
1.226 (2)
O3ÐN4
N4ÐC5
1.405 (2)
1.273 (2)
O1ÐC1ÐO2
O1ÐC1ÐC2
O2ÐC1ÐC2
124.23 (11)
111.52 (10)
124.24 (10)
C2ÐO3ÐN4
O3ÐN4ÐC11
107.87 (8)
111.71 (9)
O1ÐC1ÐO2
O1ÐC1ÐC2
O2ÐC1ÐC2
124.64 (16)
112.36 (14)
123.00 (16)
C2ÐO3ÐN4
O3ÐN4ÐC5
107.45 (13)
113.12 (14)
O1ÐC1ÐC2ÐO3
O2ÐC1ÐC2ÐO3
C1ÐC2ÐO3ÐN4
177.14 (9)
1.83 (17)
83.62 (11)
C2ÐO3ÐN4ÐC11
O3ÐN4ÐC11ÐC12
O3ÐN4ÐC11ÐC16
175.25 (9)
179.11 (9)
1.24 (16)
O1ÐC1ÐC2ÐO3
C1ÐC2ÐO3ÐN4
171.61 (14)
75.87 (17)
C2ÐO3ÐN4ÐC5
173.61 (14)
Table 4
Hydrogen-bonding geometry (A, ) for (II).
Table 2
Hydrogen-bonding geometry (A, ) for (I).
ꢀ
ꢀ
Ê
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH1Á Á ÁO2i
0.84
1.79
2.6329 (17)
176
O1ÐH1Á Á ÁO2i
0.84
1.84
2.6782 (12)
178
Symmetry code: (i) 1 x; 1 y; 1 z.
Symmetry code: (i) 1 x; 1 y; 1 z.
solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Shel-
drick, 1997); program(s) used to re®ne structure: OSCAIL and
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,
2003); software used to prepare material for publication: SHELXL97
and PRPKAPPA (Ferguson, 1999).
Compound (II)
Crystal data
C9H8ClNO3
Mr = 213.61
Triclinic, P1
a = 6.7961 (1) A
Ê
b = 7.3857 (2) A
Z = 2
Dx = 1.498 Mg m
Mo Kꢂ radiation
3
X-ray data were collected at the EPSRC X-ray Crystal-
lographic Service, University of Southampton, England; the
authors thank the staff for all their help and advice. JNL
thanks NCR Self-Service, Dundee, for grants that have
provided computing facilities for this work. JLW thanks CNPq
and FAPERJ for ®nancial support.
Ê
Cell parameters from 2133
re¯ections
c = 10.8173 (3) A
ꢁ = 3.2±27.4ꢀ
ꢅ = 0.38 mm
T = 120 (2) K
Ê
1
ꢂ = 98.4852 (9)ꢀ
ꢃ = 93.4156 (10)ꢀ
ꢄ = 117.0191 (12)ꢀ
Plate, colourless
0.28 Â 0.20 Â 0.05 mm
3
Ê
V = 473.44 (2) A
Data collection
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG1209). Services for accessing these data are
described at the back of the journal.
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢆ offsets
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.922, Tmax = 0.981
1980 re¯ections with I > 2ꢇ(I)
Rint = 0.031
ꢁ
h = 8 ! 8
k = 9 ! 9
l = 13 ! 13
max = 27.4ꢀ
References
3988 measured re¯ections
2133 independent re¯ections
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Re®nement on F2
R[F2 > 2ꢇ(F2)] = 0.040
wR(F2) = 0.141
S = 1.20
2132 re¯ections
w = 1/[ꢇ2(F2o) + (0.0766P)2
+ 0.1738P]
where P = (F2o + 2Fc2)/3
(Á/ꢇ)max < 0.001
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3
Ê
Áꢈmax = 0.34 e A
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3
Ê
0.48 e A
128 parameters
H-atom parameters constrained
Áꢈmin
=
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each and con®rmed in both cases by the subsequent analyses. All H
atoms were located from difference maps and then treated as riding
Ê
atoms, with CÐH distances of 0.95 (aromatic) or 0.99 A (CH2), and
Ê
OÐH distances of 0.84 A.
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(Nonius, 1997); cell re®nement: DENZO±SMN (Otwinowski &
Minor, 1997); data reduction: DENZO±SMN; program(s) used to
ꢁ
o272 Christopher Glidewell et al.
C9H8ClNO3 and C8H13NO3
Acta Cryst. (2004). C60, o270±o272