4-[(4-Chlorophenyl)carbamoyl]butanoic Acid

: The X-ray crystal structure determination of the glutaric acid-amide derivative, 4-ClC 6 H 4 N (H)C(=O)(CH 2 ) 3 C(=O)OH ( 1 ), is described. The backbone of the molecule adopts an extended, all-trans conﬁguration but the terminal carboxylic acid and phenyl resides are twisted out of the plane through the bridging atoms, as seen in the torsion angles of O(carboxylic acid)–C(m)–C(m)–C(m) [13.9(5) ◦ ] and C(m)–N–C(p)–C(p) [47.1(4) ◦ ]; m = methylene and p = phenyl. The most striking feature of the molecular packing is the formation of supramolecular tapes mediated by carboxylic acid-O–H · · · O(carbonyl) and amide-N–H · · · O(amide) hydrogen bonding. Abstract: The X-ray crystal structure determination of the glutaric acid-amide derivative, 4-ClC 6 H 4 N(H)C(=O)(CH 2 ) 3 C(=O)OH ( 1 ), is described. The backbone of the molecule adopts an extended, all-trans configuration but the terminal carboxylic acid and phenyl resides are twisted out of the plane through the bridging atoms, as seen in the torsion angles of O(carboxylic acid)–C(m)– C(m)–C(m) [13.9(5)°] and C(m)–N–C(p)–C(p) [47.1(4)°]; m = methylene and p = phenyl. The most striking feature of the molecular packing is the formation of supramolecular tapes mediated by carboxylic acid-O–H … O(carbonyl) and amide-N–H … O(amide) hydrogen bonding.


Results and Discussion
Colorless crystals of (1) were prepared in 81% yield from aniline and glutaric anhydride, and was characterized by IR UV spectroscopy; original spectra are found in the Supplem spectrum, characteristic absorptions were apparent, for exam cm −1 , assigned to ν(amide C=O), ν(COasym), and ν(COsym), res
The molecular structure of (1) is shown in Figure 1. The confirmation of the carboxylic acid assignment is readily seen in the values of the C1-O1 and C1-O2 bond lengths of 1.226(4) and 1.301(4) Å, and in the supramolecular association, as detailed below. are ascribed to n-π*(C=O), π-π*(C=O), and π-π*(C=C) transition characterization of (1) was achieved through X-ray crystallogr The molecular structure of (1) is shown in Figure 1. The c ylic acid assignment is readily seen in the values of the C1-O of 1.226 (4)   The most closely related structure in the literature is tha analog [3]. Here, the basic features as noted for (1) are evident about the C3-C4 bond, as seen in the value of the C2-C3-C4-C As anticipated from the chemical composition, there are s ing interactions at play in the molecular packing in the crystal o describing these are given in the caption to Figure 2. The carbox about a center of inversion to form eight-membered { … OCOH}2 ecule aggregates. As shown in Figure 2a, the two-molecule agg a supramolecular tape via amide-N-H … O(amide) hydrogen bo distance criteria in PLATON [10], the tapes, which lie parallel t without directional interactions between them, as shown in F molecular tape was observed in the crystal of the aforemention alog [3].  (1) showing atom labeling and displacement ellipsoids at the 50% probability level.
The most closely related structure in the literature is that of the 3,5-dichlorophenyl analog [3]. Here, the basic features as noted for (1) are evident but there is a notable twist about the C3-C4 bond, as seen in the value of the C2-C3-C4-C5 torsion angle of 78.5(2) • .
As anticipated from the chemical composition, there are significant hydrogen-bonding interactions at play in the molecular packing in the crystal of (1); geometric parameters describing these are given in the caption to Figure 2. The carboxylic acid residues assemble about a center of inversion to form eight-membered {· · · OCOH} 2 synthons within twomolecule aggregates. As shown in Figure 2a, the two-molecule aggregates are assembled into a supramolecular tape via amide-N-H· · · O(amide) hydrogen bonds. In accordance with the distance criteria in PLATON [10], the tapes, which lie parallel to (1 0 1), pack in the crystal without directional interactions between them, as shown in Figure 2b. A similar supramolecular tape was observed in the crystal of the aforementioned 3,5-dichlorophenyl analog [3].
In conclusion, the X-ray crystallographic study established an all-trans configuration in the bridge linking the carboxylic acid and phenyl residues, with each of the latter being twisted out of the plane through the rest of the molecule, in particular the phenyl ring. Supramolecular tapes, two molecules wide, feature in the molecular packing mediated by carboxylic acid-O-H· · · O(carbonyl) hydrogen bonding, to form two-molecule aggregates, and amide-N-H· · · O(amide) hydrogen bonding which links the former into the tape.
describing these are given in the caption to Figure 2. The carboxylic acid residues assemble about a center of inversion to form eight-membered { … OCOH}2 synthons within two-molecule aggregates. As shown in Figure 2a, the two-molecule aggregates are assembled into a supramolecular tape via amide-N-H … O(amide) hydrogen bonds. In accordance with the distance criteria in PLATON [10], the tapes, which lie parallel to (1 0 1), pack in the crystal without directional interactions between them, as shown in Figure 2b. A similar supramolecular tape was observed in the crystal of the aforementioned 3,5-dichlorophenyl analog [3]. In conclusion, the X-ray crystallographic study established an all-trans configuration in the bridge linking the carboxylic acid and phenyl residues, with each of the latter being

General Information
All standard chemicals and solvents were sourced from Macklin (Pudong, Shanghai, China) and Sigma (Saint Louis, MO, USA) and used without further purification. The melting point was determined on a BioCote melting point apparatus (Staffordshire, UK). Elemental analyses were performed on a PerkinElmer CHNS 2400 instrument (Waltham, MA, USA). The FTIR spectrum was measured on a Thermo Nicolet-6700 spectrophotometer (Vienna, Austria) from 4000-450 cm −1 . The 1 H and 13 C{ 1 H} NMR spectra were recorded in DMSO-d 6 solution on a Bruker Avance 500 MHz NMR (Billerica, MA, USA) spectrometer with chemical shifts relative to tetramethylsilane. The optical absorption spectrum was obtained from an acetonitrile solution (4.14 × 10 −5 M) in the range 185-340 nm on a Shimadzu UV-3600 plus UV/VIS/NIR (Shimadzu Corporation, Kyoto Prefecture, Japan) spectrophotometer.

Crystallography
Intensity data for colorless crystal of (1) (0.04 × 0.11 × 0.17 mm) were measured at T = 294(2) K on a XtaLAB Synergy Dual AtlasS2 (Rigaku Polska SP. Z O O, Wrocław, Poland) diffractometer fitted with Cu Kα radiation (λ = 1.54184 Å) using ω-scans in the θ max range 3.7 • -67.1 • . Data reduction, including absorption correction, was accomplished with CrysAlis Pro [11]. Of the 13,024 reflections measured, 2014 were unique (R int = 0.054), and of these, 1692 data satisfied the I ≥ 2σ(I) criterion of observability. The structure was solved by direct methods [12] and refined (anisotropic displacement parameters and C-bound H atoms in the riding model approximation) on F 2 [13]. The O-H and N-H atoms were located from a difference map and refined with O-H and N-H distance restraints of 0.82 ± 0.01 and 0.86 ± 0.01 Å, respectively. A weighting scheme of the form w = 1/[σ 2 (F o 2 ) + (0.087P) 2 + 1.129P] was introduced, where P = (F o 2 + 2F c 2 )/3). Based on the refinement of 151 parameters, the final values of R[I ≥ 2σ(I)] and wR (all data) were 0.067 and 0.195, respectively. The molecular structure diagram was generated with ORTEP for Windows [14] and the packing diagram using DIAMOND [15].
Crystal data for C 11 (1). Crystallographic data for (1) in crystallographic information file (CIF) format. CCDC 2077071 also contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac. uk/conts/retrieving.html.