3-(Phenyl­carbamoyl)acrylic acid

Abstract

In the title compound, C₁₀H₉NO₃, the dihedral angle between the phenyl ring and the amide group is 10.8 (2)°. The C=O and O—H bonds of the carboxyl group adopt an anti orientation and an intra­molecular O—H⋯O hydrogen bond closes an S(7) ring. In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into C(7) chains propagating in [101]. The packing is consolidated by C—H⋯O inter­actions, generating sheets aligned at an angle of ca 60° with the bc plane.

Related literature  

For background to carb­oxy­lic acids in supra­molecular chemistry, see: Grossel et al. (2006 ▶). For a related structure, see: Jin et al. (2010 ▶).

Experimental  

Crystal data  

• C₁₀H₉NO₃

• M _r = 191.18

• Monoclinic,

• a = 7.2396 (8) Å

• b = 10.5918 (11) Å

• c = 11.7718 (15) Å

• β = 99.122 (1)°

• V = 891.25 (18) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 298 K

• 0.38 × 0.36 × 0.33 mm

Data collection  

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.960, T _max = 0.965

• 5497 measured reflections

• 2190 independent reflections

• 1356 reflections with I > 2σ(I)

• R _int = 0.043

Refinement  

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.157

• S = 1.03

• 2190 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812035581/hb6935Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3	0.82	1.68	2.4947 (19)	175
N1—H1A⋯O2i	0.86	2.04	2.885 (2)	169
C9—H9⋯O3ii	0.93	2.51	3.389 (2)	157
C10—H10⋯O2i	0.93	2.58	3.335 (2)	138

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The carboxylic acid contains the important hydrogen bonding functional group for crystal engineering (Grossel et al., 2006). As an extension of our study concentrating on hydrogen bonded assembly of organic acid and organic base (Jin et al., 2010), herein we report the crystal structure of 3-phenylcarbamoyl-acrylic acid.

The single-crystal of the title compound (Fig.1) with the formula C₁₀H₉NO₃ was obtained by recrystallization of 3-phenylcarbamoyl-acrylic acid and 2-methylquinoline from a methanol solution. However the 2-methylquinoline molecules do not appear in the title compound. X-ray diffraction analysis indicated that the asymmetric unit of the structure contains one molecule. The conformations of the amide oxygen and the carbonyl oxygen of the acid segments are anti to each other and the amide oxygen is anti to the H atom on the olefinic group, while the carbonyl oxygen of the acid is syn to the CH at the olefinic group. Thus there existed intramolecular O—H···O hydrogen bond producing a S₁¹(7) ring.

The dihedral angle between the phenyl ring and the amide group in the molecule is 10.8 (2)°.

Two adjacent 3-phenylcarbamoyl-acrylic acids were joined together via the N—H···O, and CH—O interactions to form a dimer. Both carboxylic acids in the dimer were almost perpendicular with each other. In the dimer there are hydrogen-bonded ring motifs with descriptors of R₂¹(6), and R₂²(8). The two ring motifs were fused together by the N—H···O hydrogen bond. The neighboring carboxylic dimers were linked together through the CH—O associations between the benzene CH and the carbonyl group with C—O distance of 3.389 Å to form one-dimensional chain. The one-dimensional chains were combined together by the interchain CH—O, and N—H···O interactions to form two-dimensional sheet extending at the direction that made a dihedral angle of ca 60° with the bc plane (Fig. 2). Two two-dimensional sheets were further held together by the intersheet C–π interactions with C···C_g distance of 3.369 Å to generate two-dimensional double sheet structure.

Experimental

Crystals of 3-phenylcarbamoyl-acrylic acid were formed by slow evaporation of its methanol solution at room temperature. 3-phenylcarbamoyl-acrylic acid (19.1 mg, 0.10 mmol) was dissolved in 4 ml of methanol, and 2-methylquinoline (14.3 mg, 0.1 mmol) was added to the methanol solution. The solution was then filtered into a test tube and left standing at room temperature. After about one week colorless blocks crystals were obtained.

Refinement

H atoms bonded to O, and N atoms were located in a difference Fourier map and refined isotropically.

Other H atoms were positioned geometrically with C—H = 0.93 Å for aromatic, and constrained to ride on their parent atoms with U_iso(H) = 1.2Ueq(C).

Figures

Fig. 1.

The structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.

Fig. 2.

Two-dimensional sheet structure formed through hydrogen bonds.

Crystal data

C10H9NO3	Z = 4
Mr = 191.18	F(000) = 400
Monoclinic, P21/n	Dx = 1.425 Mg m−3
a = 7.2396 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5918 (11) Å	µ = 0.11 mm−1
c = 11.7718 (15) Å	T = 298 K
β = 99.122 (1)°	BLOCK, colorless
V = 891.25 (18) Å3	0.38 × 0.36 × 0.33 mm

Data collection

Bruker SMART CCD diffractometer	2190 independent reflections
Radiation source: fine-focus sealed tube	1356 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
phi and ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
Tmin = 0.960, Tmax = 0.965	k = −14→8
5497 measured reflections	l = −15→14

Refinement

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)] = 0.049	H-atom parameters constrained
wR(F2) = 0.157	w = 1/[σ2(Fo2) + (0.0804P)2 + 0.0617P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2190 reflections	Δρmax = 0.20 e Å−3
128 parameters	Δρmin = −0.26 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0940 (2)	−0.19833 (13)	0.83751 (12)	0.0561 (5)
H1	1.0527	−0.1373	0.7987	0.084*
N1	0.7880 (2)	0.00622 (13)	0.53533 (12)	0.0340 (4)
H1A	0.7299	−0.0337	0.4767	0.041*
O2	1.0652 (2)	−0.40422 (14)	0.83105 (12)	0.0546 (4)
C4	0.8638 (3)	−0.06557 (17)	0.62392 (15)	0.0348 (4)
O3	0.9581 (2)	−0.02077 (13)	0.71212 (13)	0.0585 (5)
C3	0.8248 (3)	−0.20179 (16)	0.60914 (15)	0.0358 (4)
H3	0.7460	−0.2246	0.5421	0.043*
C5	0.7910 (2)	0.14022 (16)	0.52529 (14)	0.0326 (4)
C10	0.6725 (3)	0.19311 (17)	0.43353 (16)	0.0401 (5)
H10	0.5983	0.1413	0.3811	0.048*
C6	0.9055 (3)	0.21772 (18)	0.60146 (16)	0.0414 (5)
H6	0.9883	0.1831	0.6619	0.050*
C2	0.8880 (3)	−0.29664 (17)	0.67949 (16)	0.0395 (5)
H2	0.8378	−0.3748	0.6554	0.047*
C1	1.0230 (3)	−0.30190 (18)	0.78871 (16)	0.0395 (5)
C9	0.6645 (3)	0.32210 (18)	0.41997 (17)	0.0476 (5)
H9	0.5842	0.3573	0.3586	0.057*
C7	0.8946 (3)	0.34771 (19)	0.58618 (17)	0.0487 (5)
H7	0.9698	0.4001	0.6374	0.058*
C8	0.7752 (3)	0.39960 (19)	0.49705 (18)	0.0496 (6)
H8	0.7683	0.4868	0.4882	0.060*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0747 (11)	0.0394 (9)	0.0446 (9)	0.0003 (7)	−0.0197 (7)	0.0041 (6)
N1	0.0425 (9)	0.0265 (8)	0.0302 (8)	−0.0006 (6)	−0.0026 (6)	−0.0013 (6)
O2	0.0712 (11)	0.0410 (9)	0.0462 (9)	0.0107 (7)	−0.0073 (7)	0.0127 (7)
C4	0.0423 (10)	0.0309 (10)	0.0290 (9)	0.0009 (8)	−0.0007 (7)	−0.0001 (7)
O3	0.0913 (12)	0.0311 (8)	0.0420 (8)	−0.0062 (7)	−0.0235 (7)	0.0000 (6)
C3	0.0426 (10)	0.0298 (10)	0.0324 (9)	−0.0020 (8)	−0.0023 (7)	−0.0014 (7)
C5	0.0402 (10)	0.0272 (9)	0.0298 (9)	0.0003 (7)	0.0043 (7)	0.0001 (7)
C10	0.0482 (11)	0.0320 (10)	0.0367 (10)	−0.0003 (8)	−0.0038 (8)	0.0016 (8)
C6	0.0533 (12)	0.0332 (11)	0.0346 (10)	−0.0037 (8)	−0.0022 (8)	0.0009 (8)
C2	0.0492 (12)	0.0294 (10)	0.0375 (10)	−0.0016 (8)	−0.0006 (8)	−0.0006 (8)
C1	0.0468 (12)	0.0357 (11)	0.0347 (10)	0.0038 (8)	0.0022 (8)	0.0047 (8)
C9	0.0596 (13)	0.0371 (11)	0.0414 (11)	0.0067 (10)	−0.0061 (9)	0.0071 (9)
C7	0.0679 (15)	0.0329 (11)	0.0420 (11)	−0.0073 (10)	−0.0018 (10)	−0.0023 (9)
C8	0.0715 (15)	0.0297 (11)	0.0459 (12)	0.0000 (10)	0.0041 (11)	0.0037 (9)

Geometric parameters (Å, º)

O1—C1	1.305 (2)	C10—C9	1.376 (2)
O1—H1	0.8200	C10—H10	0.9300
N1—C4	1.336 (2)	C6—C7	1.389 (3)
N1—C5	1.425 (2)	C6—H6	0.9300
N1—H1A	0.8600	C2—C1	1.488 (3)
O2—C1	1.212 (2)	C2—H2	0.9300
C4—O3	1.243 (2)	C9—C8	1.382 (3)
C4—C3	1.475 (2)	C9—H9	0.9300
C3—C2	1.336 (3)	C7—C8	1.365 (3)
C3—H3	0.9300	C7—H7	0.9300
C5—C10	1.387 (3)	C8—H8	0.9300
C5—C6	1.389 (3)
C1—O1—H1	109.5	C5—C6—H6	120.4
C4—N1—C5	128.47 (15)	C7—C6—H6	120.4
C4—N1—H1A	115.8	C3—C2—C1	132.65 (18)
C5—N1—H1A	115.8	C3—C2—H2	113.7
O3—C4—N1	122.54 (17)	C1—C2—H2	113.7
O3—C4—C3	122.77 (17)	O2—C1—O1	120.98 (18)
N1—C4—C3	114.68 (15)	O2—C1—C2	118.50 (18)
C2—C3—C4	128.48 (17)	O1—C1—C2	120.51 (16)
C2—C3—H3	115.8	C10—C9—C8	120.30 (19)
C4—C3—H3	115.8	C10—C9—H9	119.9
C10—C5—C6	119.76 (17)	C8—C9—H9	119.9
C10—C5—N1	116.85 (16)	C8—C7—C6	120.97 (19)
C6—C5—N1	123.40 (16)	C8—C7—H7	119.5
C9—C10—C5	120.07 (18)	C6—C7—H7	119.5
C9—C10—H10	120.0	C7—C8—C9	119.76 (19)
C5—C10—H10	120.0	C7—C8—H8	120.1
C5—C6—C7	119.11 (18)	C9—C8—H8	120.1
C5—N1—C4—O3	−3.0 (3)	N1—C5—C6—C7	−178.30 (17)
C5—N1—C4—C3	176.37 (16)	C4—C3—C2—C1	−4.5 (4)
O3—C4—C3—C2	−4.1 (3)	C3—C2—C1—O2	−174.8 (2)
N1—C4—C3—C2	176.5 (2)	C3—C2—C1—O1	5.2 (3)
C4—N1—C5—C10	−168.15 (18)	C5—C10—C9—C8	0.4 (3)
C4—N1—C5—C6	12.2 (3)	C5—C6—C7—C8	−0.8 (3)
C6—C5—C10—C9	−1.9 (3)	C6—C7—C8—C9	−0.7 (3)
N1—C5—C10—C9	178.43 (17)	C10—C9—C8—C7	0.8 (3)
C10—C5—C6—C7	2.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.82	1.68	2.4947 (19)	175
N1—H1A···O2i	0.86	2.04	2.885 (2)	169
C9—H9···O3ii	0.93	2.51	3.389 (2)	157
C10—H10···O2i	0.93	2.58	3.335 (2)	138

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