2-(4-Nitrophenoxy)benzoic acid: A three-dimensional hydrogen-bonded framework in a triclinic structure having Z′ = 3

Article abstract of DOI:10.1107/S0108270104007036

The title compound, C₁₃H₉NO₅, crystallizes in space group P1..., with Z′ = 3. The molecules are linked by O-H...O hydrogen bonds [H...O = 1.79-1.81 A, O...O = 2.625 (3)-2.648 (3) A and O-H...O = 172-176°] into two types of R₂²(8) dimer, only one of which is centrosymmetric. An extensive series of soft hydrogen bonds, of C-H...O and C-H...π(arene) types, links the dimers into a three-dimensional framework.

Full text of DOI:10.1107/S0108270104007036

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
2-(4-Nitrophenoxy)benzoic acid: a
three-dimensional hydrogen-bonded
framework in a triclinic structure
having Z0 = 3
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
Received 23 March 2004
Accepted 24 March 2004
Online 30 April 2004
The title compound, C13H9NO5, crystallizes in space group P1,
with Z0 = 3. The molecules are linked by OÐHÁ Á ÁO hydrogen
Ê
Ê
bonds [HÁ Á ÁO = 1.79±1.81 A, OÁ Á ÁO = 2.625 (3)±2.648 (3) A
and OÐHÁ Á ÁO = 172±176ꢀ] into two types of R22(8) dimer, only
one of which is centrosymmetric. An extensive series of soft
hydrogen bonds, of CÐHÁ Á ÁO and CÐHÁ Á Áꢀ(arene) types,
links the dimers into a three-dimensional framework.
Figure 1
The independent molecules of (I), showing the atom-labelling scheme
and the dimers formed by the OÐHÁ Á ÁO hydrogen bonding. (a) The
centrosymmetric dimer formed by the type 2 molecules, where atoms
labelled with the suf®x a are at the symmetry position (1 x, 1 y,
1 z). (b) The dimer formed by the type 1 and type 3 molecules.
Displacement ellipsoids are drawn at the 30% probability level.
Comment
The CÐO distances within the carboxy groups are consis-
tent with the fully ordered locations of the carboxy H atoms as
deduced from difference maps. In each molecule, the central
CÐOÐC angle has a value signi®cantly larger than the
idealized tetrahedral angle. The remaining bond lengths and
angles show no unusual values.
Persulfate oxidation of substituted 2-aryloxybenzoic acids
yields asymmetrically substituted bis(salicylates), whose
formation has been ascribed to the 2-4 coupling of phenoxyl
radicals (Thomson & Wylie, 1966). We report here the mole-
cular and supramolecular structure of one such precursor
compound, namely 2-(4-nitrophenoxy)benzoic acid, (I).
Molecules of types 1 and 3, containing atoms O1 and O3,
respectively (Fig. 1a), are linked into hydrogen-bonded dimers
by two independent OÐHÁ Á ÁO hydrogen bonds, both of which
are short for their type and nearly linear (Table 2). By
contrast, molecules of type 2, containing atom O2 (Fig. 1b),
are linked by pairs of OÐHÁ Á ÁO hydrogen bonds into
centrosymmetric R22(8) (Bernstein et al., 1995) dimers. With
the centrosymmetric dimer centred at (12, 21, 21 ), the centroid of
the non-centrosymmetric dimer is at approximately (0.265,
0.225, 0.416), thus precluding the possibility of any additional
inversion centres.
The two types of dimer are linked by an extensive series of
soft hydrogen bonds (Braga et al., 1995; Desiraju & Steiner,
1999) into a continuous three-dimensional framework of
considerable complexity. However, the descriptive analysis of
the framework formation is eased by the adoption of the
Compound (I) crystallizes in the triclinic space group P1,
with Z0 = 3 (Fig. 1). In each of the three independent mol-
ecules, the two aryl rings are both rotated away from the plane
of the central C/O/C fragment, as shown by the leading torsion
angles (Table 1). Likewise, each of the nitro and carboxy
groups is rotated away from the plane of the adjacent aryl ring.
Comparison of the corresponding values for the three mol-
ecules is suf®cient to rule out the possibility of any additional
symmetry.
Acta Cryst. (2004). C60, o361±o363
DOI: 10.1107/S0108270104007036
# 2004 International Union of Crystallography o361

organic compounds
substructure approach (Gregson et al., 2000). The dimeric
units formed by the OÐHÁ Á ÁO hydrogen bonds are linked by
the three strongest CÐHÁ Á ÁO hydrogen bonds (the ®rst three
such entries in Table 2, all having CÐHÁ Á ÁO angles greater
than 160ꢀ) into two distinct types of chain running parallel to
the [001] direction. These chains are then linked by two
weaker CÐHÁ Á ÁO hydrogen bonds (the fourth and ®fth such
entries in Table 2, with CÐHÁ Á ÁO angles of ꢂ140ꢀ but with
Ê
HÁ Á ÁO distances shorter than 2.50 A). The resulting frame-
work is further reinforced, albeit weakly, by the remaining CÐ
HÁ Á ÁO hydrogen bonds (which have HÁ Á ÁO distances slightly
Ê
longer than 2.50 A) and by a single CÐHÁ Á Áꢀ(arene)
hydrogen bond.
The centrosymmetric dimers formed by the type 2 mol-
ecules are linked by a single CÐHÁ Á ÁO hydrogen bond. Atom
C46 in the molecule at (x, y, z), which forms part of the
centrosymmetric dimer centred at (12, 21, 21 ), acts as a hydrogen-
bond donor to nitro atom O31 in the type 2 molecule at (1 x,
Figure 3
A stereoview of part of the crystal structure of (I), showing the formation
of a complex chain along [001] containing R22(8), R44(20) and R44(40) rings
and built from type 1 and type 3 molecules only. For clarity, H atoms not
involved in the motif shown have been omitted.
1
y, 2 z), which forms part of the corresponding dimer
1
centred at (12, , ). Propagation of this hydrogen bond then
generates a chain of rings running parallel to [001] containing
3
chains of rings into pairs, forming a complex chain enclosing
R44(20) rings centred at (12, 0, n) (n = zero or integer) alter-
nating with R44(40) rings centred at (21, 0, n + 12 ) (n = zero or
integer) (Fig. 3).
2
2
R22(8) rings centred at (21, , n + 12 ) (n = zero or integer) and
R22(20) rings centred at (12, , n) (n = zero or integer) (Fig. 2).
1
2
1
2
There are thus chains of type 2 molecules running along
Molecules of types 1 and 3 are also linked into a [001] chain,
but this is more complex than that formed by the type 2
molecules and its formation involves two CÐHÁ Á ÁO hydrogen
bonds. In the ®rst such interaction, atom C26 in the type 1
molecule at (x, y, z) acts as a hydrogen-bond donor to nitro
atom O51 in the type 3 molecule at (x, y, 1 + z), so linking
the dimers formed by molecules 1 and 3 into a C22(18)[R22(8)]
chain of rings (Fig. 3).
1
(12, , z), and chains containing type 1 and type 3 molecules
2
running along (12, 0, z). Two further CÐHÁ Á ÁO hydrogen bonds
suf®ce to link these two types of chain into a single framework.
Atom C16 in the type 1 molecule at (x, y, z), which lies in the
chain along (12, 0, z), acts as a hydrogen-bond donor to nitro
atom O32 in the type 2 molecule at ( 1 + x, y, 1 + z), which
forms part of the chain along ( 12, 12, z). Finally, atom C52 in the
type 3 molecule at (x, y, z) acts as a donor to nitro atom O31 in
the type 2 molecule at (1 x, 1 y, 2 z), which lies in the
chain along (12, 12, z). Propagation of these two hydrogen bonds
by translation and inversion links all of the [001] chain, and the
three remaining hydrogen bonds simply reinforce the resulting
framework.
In the second of these interactions, atom C13 in the type 1
molecule at (x, y, z) acts as a donor to nitro atom O52 in the
type 3 molecule at (1 x, y, 1 z), thereby generating a
1
centrosymmetric four-molecule aggregate centred at (12, 0, )
2
and containing two R22(8) rings and one R44(40) ring (Fig. 3).
The effect of the R44(40) motif is to link the C22(18)[R22(8)]
The pattern of the CÐHÁ Á ÁO hydrogen bonds is itself
suf®cient to preclude any possible additional symmetry; for
example, the nitro O atoms in the type 1 molecule, O11 and
O12, do not act as hydrogen-bond acceptors, while both of the
O atoms in the type 3 molecule, O51 and O52, are acceptors of
CÐHÁ Á ÁO hydrogen bonds.
In addition to the hydrogen bonds, there is a short dipolar
interaction involving the type 3 molecules only. The C61ÐO3
bonds in the molecules at (x, y, z) and ( x, y, 1 z) are
antiparallel; the corresponding OÁ Á ÁCvii and OÁ Á ÁOvii distances
[symmetry code: (vii) x, y, 1 z] are 2.978 (4) and
vii
Ê
2.758 (3) A, respectively, and the CÐOÁ Á ÁC
angle is
112.7 (2)ꢀ. In this respect, this interaction is reminiscent of the
type II interaction between antiparallel pairs of carbonyl
groups (Allen et al., 1998).
Figure 2
Experimental
A stereoview of part of the crystal structure of (I), showing the formation
of a [001] chain of R22(8) and R22(20) rings formed by type 2 molecules
only. For clarity, H atoms not involved in the motif shown have been
omitted.
A sample of (I) was prepared by the Ullmann reaction of 2-chloro-
benzoic acid with 4-nitrophenol, according to the procedure
published by Thomson & Wylie (1966). Crystals suitable for single-
ꢁ
o362 Christopher Glidewell et al.
C13H9NO5
Acta Cryst. (2004). C60, o361±o363

organic compounds
crystal X-ray diffraction were grown by slow evaporation of a solu-
tion in ethanol (m.p. 435±437 K).
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
Cg1 is the centroid of the C61±C66 ring in the type 3 molecule; soft hydrogen
bonds are listed in the order in which they are discussed in the Comment
section.
Crystal data
C13H9NO5
Mr = 259.21
Triclinic, P1
a = 7.8495 (6) A
b = 14.0847 (15) A
Z = 6
Dx = 1.518 Mg m
Mo Kꢁ radiation
3
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Ê
Cell parameters from 7578
re¯ections
Ê
Ê
O22ÐH22Á Á ÁO61
O42ÐH42Á Á ÁO41i
O62ÐH62Á Á ÁO21
C46ÐH46Á Á ÁO31ii
C26ÐH26Á Á ÁO51iii
C13ÐH13Á Á ÁO52iv
C16ÐH16Á Á ÁO32v
C52ÐH52Á Á ÁO31ii
C32ÐH32Á Á ÁO51ii
C44ÐH44Á Á ÁO22vi
C55ÐH55Á Á ÁCg1vii
0.84
0.84
0.84
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
1.79
1.81
1.80
2.49
2.36
2.50
2.48
2.35
2.54
2.53
2.87
2.625 (3)
2.648 (3)
2.637 (3)
3.413 (5)
3.268 (5)
3.422 (5)
3.241 (5)
3.153 (5)
3.388 (5)
3.370 (5)
3.745 (4)
175
172
176
163
161
163
138
142
149
147
154
c = 17.2325 (18) A
ꢄ = 2.9±27.5ꢀ
ꢅ = 0.12 mm
T = 120 (2) K
1
ꢁ = 113.187 (4)ꢀ
ꢂ = 98.515 (6)ꢀ
ꢃ = 96.400 (7)ꢀ
Lath, colourless
0.15 Â 0.06 Â 0.02 mm
3
Ê
V = 1701.5 (3) A
Data collection
Nonius KappaCCD diffractometer
' scans, and ! scans with ꢆ offsets
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.966, Tmax = 0.998
2621 re¯ections with I > 2ꢇ(I)
Rint = 0.122
ꢄ
max = 27.5ꢀ
Symmetry codes: (i) 1 x; 1 y; 1 z; (ii) 1 x; 1 y; 2 z; (iii) x; y; z 1; (iv)
x; y; 1 z; (v) x 1; y; z 1; (vi) x; 1 y; 1 z; (vii) x; y; 1 z.
h = 9 ! 10
k = 18 ! 18
l = 22 ! 22
1
14 193 measured re¯ections
7578 independent re¯ections
program(s) used to re®ne structure: OSCAIL and SHELXL97
(Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); soft-
ware used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
Re®nement
Re®nement on F2
R[F2 > 2ꢇ(F2)] = 0.060
wR(F2) = 0.149
S = 0.87
7578 re¯ections
517 parameters
H-atom parameters constrained
w = 1/[ꢇ2(F2o) + (0.0444P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢇ)max = 0.001
3
Ê
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.
Áꢈmax = 0.27 e A
3
Ê
0.33 e A
Áꢈmin
=
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
C27ÐO21
C47ÐO41
C67ÐO61
1.226 (4)
1.245 (4)
1.234 (4)
C27ÐO22
C47ÐO42
C67ÐO62
1.314 (4)
1.297 (4)
1.297 (4)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1719). Services for accessing these data are
described at the back of the journal.
C14ÐO1ÐC21
C34ÐO2ÐC41
120.1 (3)
119.2 (3)
C54ÐO3ÐC61
118.4 (3)
C13ÐC14ÐO1ÐC21
C33ÐC34ÐO2ÐC41
C53ÐC54ÐO3ÐC61
C14ÐO1ÐC21ÐC22
C34ÐO2ÐC41ÐC42
C54ÐO3ÐC61ÐC62
43.0 (5)
20.9 (5)
9.5 (5)
153.2 (3)
129.4 (3)
115.8 (4)
C12ÐC11ÐN11ÐO11
C32ÐC31ÐN31ÐO31
C52ÐC51ÐN51ÐO51
C21ÐC22ÐC27ÐO21
C41ÐC42ÐC47ÐO41
C61ÐC62ÐC67ÐO61
8.5 (5)
11.9 (5)
19.2 (5)
150.2 (4)
169.0 (3)
170.8 (3)
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located from difference maps and then treated as riding atoms, with
Ê
Ê
CÐH distances of 0.95 A and OÐH distances of 0.84 A, and with
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ꢁ
Acta Cryst. (2004). C60, o361±o363
Christopher Glidewell et al. C13H9NO5 o363