2-Nitro­phenyl­acetic acid: hydrogen-bonded sheets of R22(8) and R44(18) rings

Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536806013274

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 5| May 2006| Pages o1915-o1917

https://doi.org/10.1107/S1600536806013274

2-Nitrophenylacetic acid: hydrogen-bonded sheets of R₂²(8) and R₄⁴(18) rings

James L. Wardell,^a John N. Low ^b and Christopher Glidewell ^c ^*

^aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 11 April 2006; accepted 11 April 2006; online 21 April 2006)

Molecules of the title compound, C₈H₇NO₄, are linked into centrosymmetric R₂²(8) dimers by paired O—H⋯O hydrogen bonds, and these dimers are linked by two C—H⋯O hydrogen bonds into sheets of R₂²(8) and R₄⁴(18) rings.

Comment

As part of our investigations of compounds containing nitro and carboxylic acid groups (Glidewell et al., 2003a ,b , 2004 , 2006 ; Wardell et al., 2005 ), we now report the molecular and supramolecular structure of 2-nitrophenylacetic acid, (I) (Fig. 1).

The plane of atoms C1/C11/C12 is almost orthogonal to the plane of the aryl ring (Fig. 1, Table 1), while the C—NO₂ plane makes a dihedral angle of 30.1 (2)° with the ring.

The molecules of (I) are linked into sheets by a combination of N—H⋯O and C—H⋯O hydrogen bonds (Table 2). Paired O—H⋯O hydrogen bonds link the molecules into centrosymmetric R₂²(8) (Bernstein et al., 1995 ) dimers (Fig. 2). Two C—H⋯O hydrogen bonds link the dimers, so forming a (100) sheet built from R₂²(8) and R₄⁴(18) rings. The resulting net is of type (4,4) (Batten & Robson, 1998 ). There are no direction-specific interactions between adjacent sheets. In particular, C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking interactions are both absent.

The structure of the isomeric 4-nitrophenylacetic acid, (II), was reported some years ago [Cambridge Structural Database (Version of November 2005; Allen, 2002 ) refcode SEMTAF; Grabowski et al., 1990 ]. The authors reported the formation of a centrosymmetric hydrogen-bonded dimer, but further aggregation of the dimers was not reported. In the event, the dimers are linked into sheets by a single aromatic π–π stacking interaction (Fig. 4).

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of (I)

, showing the formation of a centrosymmetric R₂²(8) dimer. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 3
A stereoview of part of the crystal structure of (I)

, showing the formation of a (100) sheet of R₂²(8) and R₄⁴(18) rings. For the sake of clarity, H atoms bonded to aromatic C atoms have been omitted.

Figure 4
A stereoview of part of the crystal structure of (II)

, showing the formation of a sheet of π-stacked hydrogen-bonded dimers. The original atomic coordinates (Grabowski et al., 1990

) have been used. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Experimental

A commercial sample of (I) (Acros) was crystallized from ethanol (m.p. 412–413 K).

Crystal data

C₈H₇NO₄
M_r = 181.15
Monoclinic, P 2₁ /c
a = 9.3182 (3) Å
b = 9.4466 (2) Å
c = 9.9733 (3) Å
β = 114.7990 (17)°
V = 796.95 (4) Å³
Z = 4
D_x = 1.510 Mg m⁻³
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 (2) K
Lath, colourless
0.52 × 0.26 × 0.10 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.949, T_max = 0.988
8852 measured reflections
1829 independent reflections
1682 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.7°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.108
S = 1.16
1829 reflections
120 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0444P)² + 0.341P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.103 (10)

Table 1
Selected torsion angles (°)

C2—C1—C11—C12	83.34 (16)
C1—C11—C12—O12	−159.51 (11)
C1—C2—N2—O21	−29.64 (17)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12⋯O11ⁱ	0.84	1.83	2.6622 (14)	173
C11—H11A⋯O21ⁱⁱ	0.99	2.35	3.1758 (16)	140
C11—H11B⋯O22ⁱⁱⁱ	0.99	2.54	3.4398 (19)	151
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z.

All H atoms were located in a difference map and then treated as riding, with C—H distances of 0.95 Å (aromatic) or 0.99 Å (CH₂), and O—H distances of 0.84 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(O).

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806013274/lh2048sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806013274/lh2048Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

2-Nitrophenylacetic acid top

Crystal data top

C₈H₇NO₄	F(000) = 376
M_r = 181.15	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1848 reflections
a = 9.3182 (3) Å	θ = 2.9–27.5°
b = 9.4466 (2) Å	µ = 0.12 mm⁻¹
c = 9.9733 (3) Å	T = 120 K
β = 114.7990 (17)°	Lath, colourless
V = 796.95 (4) Å³	0.52 × 0.26 × 0.10 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	1829 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1682 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.7°, θ_min = 3.2°
φ and ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→12
T_min = 0.949, T_max = 0.988	l = −11→12
8852 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0444P)² + 0.341P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
1829 reflections	Δρ_max = 0.34 e Å⁻³
120 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.103 (10)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.23687 (14)	0.30836 (13)	0.07521 (14)	0.0171 (3)
C11	0.40523 (15)	0.29551 (14)	0.18979 (14)	0.0196 (3)
C12	0.44276 (14)	0.38895 (14)	0.32300 (14)	0.0191 (3)
O11	0.34184 (11)	0.43438 (11)	0.35993 (11)	0.0260 (3)
O12	0.59458 (11)	0.41254 (11)	0.39762 (11)	0.0254 (3)
C2	0.18252 (14)	0.41302 (13)	−0.03303 (14)	0.0161 (3)
N2	0.28971 (12)	0.52395 (11)	−0.03878 (12)	0.0181 (3)
O21	0.39974 (11)	0.56059 (10)	0.07718 (11)	0.0238 (3)
O22	0.26447 (12)	0.57548 (11)	−0.15940 (11)	0.0287 (3)
C3	0.02718 (15)	0.42023 (14)	−0.13979 (14)	0.0191 (3)
C4	−0.07970 (15)	0.31978 (15)	−0.13815 (15)	0.0233 (3)
C5	−0.03015 (16)	0.21349 (15)	−0.03267 (16)	0.0252 (3)
C6	0.12610 (16)	0.20739 (14)	0.07154 (15)	0.0221 (3)
H11A	0.4257	0.1958	0.2228	0.024*
H11B	0.4775	0.3199	0.1435	0.024*
H12	0.6100	0.4558	0.4761	0.038*
H3	−0.0046	0.4929	−0.2123	0.023*
H4	−0.1866	0.3235	−0.2090	0.028*
H5	−0.1035	0.1442	−0.0315	0.030*
H6	0.1581	0.1327	0.1418	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0180 (6)	0.0173 (6)	0.0159 (6)	0.0001 (4)	0.0071 (5)	−0.0028 (5)
C11	0.0185 (6)	0.0190 (6)	0.0184 (6)	0.0023 (4)	0.0048 (5)	0.0015 (5)
C12	0.0175 (6)	0.0211 (6)	0.0163 (6)	0.0006 (5)	0.0047 (5)	0.0043 (5)
O11	0.0179 (5)	0.0390 (6)	0.0195 (5)	−0.0005 (4)	0.0064 (4)	−0.0050 (4)
O12	0.0159 (5)	0.0363 (6)	0.0202 (5)	−0.0015 (4)	0.0038 (4)	−0.0065 (4)
C2	0.0156 (6)	0.0167 (6)	0.0168 (6)	−0.0007 (4)	0.0076 (5)	−0.0030 (5)
N2	0.0160 (5)	0.0173 (5)	0.0202 (5)	0.0021 (4)	0.0069 (4)	0.0010 (4)
O21	0.0209 (5)	0.0234 (5)	0.0228 (5)	−0.0064 (4)	0.0049 (4)	−0.0045 (4)
O22	0.0255 (5)	0.0333 (6)	0.0250 (5)	0.0000 (4)	0.0082 (4)	0.0130 (4)
C3	0.0177 (6)	0.0211 (6)	0.0166 (6)	0.0024 (4)	0.0054 (5)	−0.0031 (5)
C4	0.0153 (6)	0.0282 (7)	0.0234 (7)	−0.0015 (5)	0.0052 (5)	−0.0098 (5)
C5	0.0225 (7)	0.0258 (7)	0.0295 (7)	−0.0083 (5)	0.0132 (6)	−0.0075 (6)
C6	0.0252 (7)	0.0204 (6)	0.0219 (7)	−0.0031 (5)	0.0109 (5)	−0.0002 (5)

Geometric parameters (Å, º) top

C1—C2	1.3931 (18)	C2—N2	1.4653 (16)
C1—C6	1.3947 (18)	N2—O22	1.2256 (15)
C1—C11	1.5092 (17)	N2—O21	1.2303 (14)
C11—C12	1.5089 (18)	C3—C4	1.3807 (19)
C11—H11A	0.99	C3—H3	0.95
C11—H11B	0.99	C4—C5	1.386 (2)
C12—O11	1.2226 (17)	C4—H4	0.95
C12—O12	1.3121 (15)	C5—C6	1.3907 (19)
O12—H12	0.84	C5—H5	0.95
C2—C3	1.3930 (17)	C6—H6	0.95

C2—C1—C6	116.14 (11)	O22—N2—O21	123.51 (11)
C2—C1—C11	124.64 (11)	O22—N2—C2	117.97 (10)
C6—C1—C11	119.19 (11)	O21—N2—C2	118.51 (10)
C12—C11—C1	113.77 (10)	C4—C3—C2	118.74 (12)
C12—C11—H11A	108.8	C4—C3—H3	120.6
C1—C11—H11A	108.8	C2—C3—H3	120.6
C12—C11—H11B	108.8	C3—C4—C5	119.64 (12)
C1—C11—H11B	108.8	C3—C4—H4	120.2
H11A—C11—H11B	107.7	C5—C4—H4	120.2
O11—C12—O12	123.51 (12)	C4—C5—C6	120.56 (12)
O11—C12—C11	123.17 (11)	C4—C5—H5	119.7
O12—C12—C11	113.29 (11)	C6—C5—H5	119.7
C12—O12—H12	109.5	C5—C6—C1	121.51 (13)
C3—C2—C1	123.40 (12)	C5—C6—H6	119.2
C3—C2—N2	116.23 (11)	C1—C6—H6	119.2
C1—C2—N2	120.37 (10)

C2—C1—C11—C12	83.34 (16)	C3—C2—N2—O21	150.02 (12)
C6—C1—C11—C12	−98.81 (14)	C1—C2—N2—O21	−29.64 (17)
C1—C11—C12—O11	22.60 (18)	C1—C2—C3—C4	0.71 (19)
C1—C11—C12—O12	−159.51 (11)	N2—C2—C3—C4	−178.94 (11)
C6—C1—C2—C3	0.43 (19)	C2—C3—C4—C5	−0.97 (19)
C11—C1—C2—C3	178.34 (12)	C3—C4—C5—C6	0.1 (2)
C6—C1—C2—N2	−179.94 (11)	C4—C5—C6—C1	1.1 (2)
C11—C1—C2—N2	−2.03 (19)	C2—C1—C6—C5	−1.32 (19)
C3—C2—N2—O22	−29.86 (16)	C11—C1—C6—C5	−179.35 (12)
C1—C2—N2—O22	150.48 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O11ⁱ	0.84	1.83	2.6622 (14)	173
C11—H11A···O21ⁱⁱ	0.99	2.35	3.1758 (16)	140
C11—H11B···O22ⁱⁱⁱ	0.99	2.54	3.4398 (19)	151

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z.

Acknowledgements

The X-ray data were collected at the EPSRC X-Ray Crystallographic Service, University of Southampton, UK; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494. Web of Science CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2003a). Acta Cryst. C59, o124–o126. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2003b). Acta Cryst. C59, o144–o146. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst. C60, o120–o124. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2006). Acta Cryst. C62, o5–o7. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Grabowski, S. J., Krygowski, T. M., Häfelinger, G. & Ritter, G. (1990). Acta Cryst. C46, 428–430. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. E61, o3849–o3851. Web of Science CSD CrossRef IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 5| May 2006| Pages o1915-o1917

https://doi.org/10.1107/S1600536806013274

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)