4-(4-Iodo­anilino)-2-methyl­ene-4-oxo­butanoic acid

Abstract

In the title compound, C₁₁H₁₀INO₃, an addition product of itaconic acid anhydride and 4-iodo­aniline, the least-squares planes defined by the atoms of the aromatic moiety and the non-H atoms of the carb­oxy­lic acid group enclose an angle of 74.82 (11)°. In the crystal, classical O—H⋯O hydrogen bonds formed by carb­oxy­lic groups, as well as N—H⋯O hydrogen bonds formed by amide groups, are present along with C—H⋯O contacts. Together, these connect the mol­ecules into dimeric chains along the b-axis direction.

Related literature  

For applications of itaconic acid anhydride, see: Oishi (1980 ▶); Urzua et al. (1998 ▶); Shetgiri & Nayak (2005 ▶); Katla et al. (2011 ▶); Hanoon (2011 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental  

Crystal data  

• C₁₁H₁₀INO₃

• M _r = 331.10

• Monoclinic,

• a = 23.1111 (6) Å

• b = 4.7863 (1) Å

• c = 10.4262 (2) Å

• β = 97.071 (1)°

• V = 1144.54 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 2.79 mm⁻¹

• T = 200 K

• 0.29 × 0.16 × 0.10 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.503, T _max = 0.776

• 12435 measured reflections

• 2839 independent reflections

• 2612 reflections with I > 2σ(I)

• R _int = 0.015

Refinement  

• R[F ² > 2σ(F ²)] = 0.018

• wR(F ²) = 0.047

• S = 1.06

• 2839 reflections

• 150 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.73 e Å⁻³

• Δρ_min = −0.61 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

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⋯O2i	0.84	1.83	2.6597 (19)	170
N1—H71⋯O3ii	0.83 (2)	2.10 (2)	2.8963 (18)	161 (2)
C3—H3B⋯O3ii	0.99	2.51	3.266 (2)	134

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Itaconic acid anhydride is a monomeric building block obtained from renewable sources. Copolymers containing both hydrophilic and hydrophobic segments are drawing considerable attention because of their possible use in biological systems. In this aspect, N-substituted itaconamic acid derivatives have attracted attention due to their amphiphilic properties. Being more reactive than maleic anhydride, itaconic anhydride has already been applied for introducing polar functional groups into polymers (Oishi, 1980; Urzua et al.,1998). In addition, the basic skeleton of itaconic anhydride is useful for the synthesis of cyclic derivatives of imides (Shetgiri & Nayak, 2005), pyridazines (Katla et al., 2011), oxazepines and diazepines (Hanoon, 2011) which show pharmacological activity. In continuation of our studies of pharmacologically active compounds, the crystal structure of the title compound was determined.

The C=C bond is present as its anti-Saytzeff tautomer. The N–C(=O) bond length of 1.351 (2) Å is indicative of amide-type resonance. The least-squares plane defined by the atoms of the aromatic moiety on the one hand and the non-hydrogen atoms of the carboxylic acid group on the other hand enclose an angle of 74.82 (11) ° (Fig. 1).

In the crystal, C–H···O contatcs whose range falls by more than 0.1 Å below the sum of van-der-Waals radii are observed next to classical hydrogen bonds of the N–H···O and C–H···O type. The N–H···O hydrogen bonds are supported by the carbonyl oxygen atom of the amide functionality as acceptor. Simultaneously, one of the hydrogen atoms of the methylene group forms a C–H···O contact to the same oxygen atom which, therefore, acts as twofold acceptor. The carboxylic acid groups engage in the common dimeric hydrogen bonding pattern frequently encountered for many carboxylic acids. In total, the molecules are connected to dimeric chains along the crystallographic b axis. Metrical parameters as well as information about the symmetry of these contacts are summarized in Table 1. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is C¹₁(4)C¹₁(4)R²₂(8) on the unary level. The shortest intercentroid distance between two aromatic systems was found at 4.7863 (11) Å which is about the length of axis b (Fig. 2).

The packing of the title compound in the crystal structure is shown in Figure 3.

Experimental

Itaconic anhydride (0.112 g, 1 mmol) was dissolved in acetone (30 ml) and 4-iodoaniline (0.219 g, 1 mmol) was added in small portions under stirring at room temperature over a timespan of 30 minutes. The mixture turned into a yellow slurry. Stirring was continued for 1.5 h after which the slurry was filtered and the solid obtained was washed with acetone and dried to yield the title compound. Single crystals suitable for the X-ray diffraction study were grown from methanol by slow evaporation at room temperature.

Refinement

Carbon-bound H atoms were placed in calculated positions (C–H 0.95 Å for aromatic and vinylic carbon atoms, C–H 0.99 Å for methylene groups) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U_eq(C). The H atom of the hydroxyl group was allowed to rotate with a fixed angle around the C–O bond to best fit the experimental electron density (HFIX 147 in the SHELX program suite (Sheldrick, 2008)), with U(H) set to 1.5U_eq(O). The nitrogen-bound H atom was located on a difference Fourier map and refined freely.

Figures

Fig. 1.

The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids drawn at 50% probability level.

Fig. 2.

Intermolecular contacts, viewed along [0 0 - 1]. Symmetry operators: ix, y - 1, z; iix, y + 1, z; iii -x + 1, -y, -z + 1.

Fig. 3.

Molecular packing of the title compound, viewed along [0 1 0] (anisotropic displacement ellipsoids drawn at 50% probability level). Blue dashed lines indicate hydrogen bonds between the carboxylic acid groups.

Crystal data

C11H10INO3	F(000) = 640
Mr = 331.10	Dx = 1.921 Mg m−3
Monoclinic, P21/c	Melting point = 447–445 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 23.1111 (6) Å	Cell parameters from 9343 reflections
b = 4.7863 (1) Å	θ = 2.7–28.3°
c = 10.4262 (2) Å	µ = 2.79 mm−1
β = 97.071 (1)°	T = 200 K
V = 1144.54 (4) Å3	Rectangular, colourless
Z = 4	0.29 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	2839 independent reflections
Radiation source: fine-focus sealed tube	2612 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −30→30
Tmin = 0.503, Tmax = 0.776	k = −6→6
12435 measured reflections	l = −8→13

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0202P)2 + 0.979P] where P = (Fo2 + 2Fc2)/3
2839 reflections	(Δ/σ)max = 0.002
150 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

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

	x	y	z	Uiso*/Ueq
I1	0.056006 (5)	−0.19408 (3)	0.680940 (13)	0.03784 (5)
O1	0.48205 (6)	−0.1867 (3)	0.34828 (13)	0.0334 (3)
H1	0.5045	−0.1852	0.4180	0.050*
O2	0.43726 (6)	0.1500 (3)	0.44728 (13)	0.0335 (3)
O3	0.30129 (6)	−0.2166 (2)	0.35760 (14)	0.0301 (3)
N1	0.26626 (6)	0.2123 (3)	0.39810 (15)	0.0238 (3)
H71	0.2679 (10)	0.382 (5)	0.380 (2)	0.031 (6)*
C1	0.43994 (7)	−0.0058 (4)	0.35485 (16)	0.0232 (3)
C2	0.39444 (7)	0.0026 (3)	0.24115 (16)	0.0225 (3)
C3	0.34191 (7)	0.1767 (3)	0.25648 (16)	0.0232 (3)
H3A	0.3198	0.2104	0.1703	0.028*
H3B	0.3547	0.3601	0.2937	0.028*
C4	0.30202 (7)	0.0375 (3)	0.34331 (15)	0.0202 (3)
C5	0.40223 (8)	−0.1299 (4)	0.13366 (18)	0.0330 (4)
H5A	0.4371	−0.2318	0.1286	0.040*
H5B	0.3729	−0.1235	0.0614	0.040*
C11	0.21964 (7)	0.1204 (3)	0.46527 (16)	0.0218 (3)
C12	0.22773 (7)	−0.0842 (4)	0.55994 (17)	0.0263 (3)
H12	0.2652	−0.1644	0.5823	0.032*
C13	0.18104 (8)	−0.1721 (4)	0.62227 (18)	0.0284 (4)
H13	0.1864	−0.3137	0.6865	0.034*
C14	0.12659 (7)	−0.0515 (4)	0.58994 (16)	0.0265 (3)
C15	0.11850 (8)	0.1576 (4)	0.49805 (19)	0.0308 (4)
H15	0.0813	0.2421	0.4777	0.037*
C16	0.16521 (8)	0.2432 (4)	0.43571 (18)	0.0290 (4)
H16	0.1599	0.3867	0.3724	0.035*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
I1	0.02465 (7)	0.04793 (9)	0.04370 (9)	−0.00628 (5)	0.01530 (5)	−0.00051 (6)
O1	0.0276 (6)	0.0373 (7)	0.0342 (7)	0.0105 (5)	−0.0003 (5)	−0.0044 (6)
O2	0.0336 (7)	0.0386 (8)	0.0276 (6)	0.0087 (6)	0.0003 (5)	−0.0064 (5)
O3	0.0333 (7)	0.0172 (5)	0.0428 (7)	0.0000 (5)	0.0167 (6)	0.0006 (5)
N1	0.0239 (7)	0.0160 (6)	0.0331 (7)	0.0002 (5)	0.0096 (6)	0.0033 (6)
C1	0.0217 (7)	0.0230 (7)	0.0258 (7)	0.0002 (6)	0.0066 (6)	0.0026 (6)
C2	0.0204 (7)	0.0216 (7)	0.0262 (7)	−0.0017 (6)	0.0060 (6)	0.0036 (6)
C3	0.0205 (7)	0.0223 (8)	0.0274 (8)	0.0007 (6)	0.0050 (6)	0.0052 (6)
C4	0.0179 (7)	0.0194 (7)	0.0230 (7)	−0.0010 (5)	0.0011 (5)	0.0009 (6)
C5	0.0271 (9)	0.0400 (10)	0.0320 (9)	0.0016 (7)	0.0040 (7)	−0.0066 (8)
C11	0.0201 (7)	0.0201 (7)	0.0261 (7)	−0.0020 (6)	0.0064 (6)	−0.0024 (6)
C12	0.0194 (7)	0.0279 (8)	0.0318 (8)	0.0017 (6)	0.0046 (6)	0.0035 (7)
C13	0.0251 (8)	0.0316 (9)	0.0294 (8)	−0.0007 (7)	0.0072 (7)	0.0045 (7)
C14	0.0194 (7)	0.0323 (9)	0.0291 (8)	−0.0046 (6)	0.0083 (6)	−0.0042 (7)
C15	0.0182 (7)	0.0390 (10)	0.0356 (9)	0.0038 (7)	0.0055 (7)	0.0012 (8)
C16	0.0246 (8)	0.0306 (9)	0.0324 (9)	0.0044 (7)	0.0060 (7)	0.0070 (7)

Geometric parameters (Å, º)

I1—C14	2.0994 (16)	C3—H3B	0.9900
O1—C1	1.311 (2)	C5—H5A	0.9500
O1—H1	0.8400	C5—H5B	0.9500
O2—C1	1.226 (2)	C11—C12	1.387 (2)
O3—C4	1.2258 (19)	C11—C16	1.388 (2)
N1—C4	1.351 (2)	C12—C13	1.392 (2)
N1—C11	1.425 (2)	C12—H12	0.9500
N1—H71	0.83 (2)	C13—C14	1.388 (2)
C1—C2	1.485 (2)	C13—H13	0.9500
C2—C5	1.319 (2)	C14—C15	1.382 (3)
C2—C3	1.497 (2)	C15—C16	1.389 (3)
C3—C4	1.523 (2)	C15—H15	0.9500
C3—H3A	0.9900	C16—H16	0.9500
C1—O1—H1	109.5	C2—C5—H5B	120.0
C4—N1—C11	123.75 (14)	H5A—C5—H5B	120.0
C4—N1—H71	117.5 (16)	C12—C11—C16	119.74 (15)
C11—N1—H71	117.8 (16)	C12—C11—N1	121.60 (15)
O2—C1—O1	123.55 (16)	C16—C11—N1	118.65 (15)
O2—C1—C2	120.76 (15)	C11—C12—C13	120.12 (16)
O1—C1—C2	115.69 (15)	C11—C12—H12	119.9
C5—C2—C1	120.52 (16)	C13—C12—H12	119.9
C5—C2—C3	123.74 (16)	C14—C13—C12	119.52 (16)
C1—C2—C3	115.70 (14)	C14—C13—H13	120.2
C2—C3—C4	112.22 (13)	C12—C13—H13	120.2
C2—C3—H3A	109.2	C15—C14—C13	120.72 (16)
C4—C3—H3A	109.2	C15—C14—I1	120.15 (13)
C2—C3—H3B	109.2	C13—C14—I1	119.13 (13)
C4—C3—H3B	109.2	C14—C15—C16	119.43 (16)
H3A—C3—H3B	107.9	C14—C15—H15	120.3
O3—C4—N1	123.00 (15)	C16—C15—H15	120.3
O3—C4—C3	121.66 (15)	C11—C16—C15	120.43 (17)
N1—C4—C3	115.28 (14)	C11—C16—H16	119.8
C2—C5—H5A	120.0	C15—C16—H16	119.8
O2—C1—C2—C5	168.65 (18)	C4—N1—C11—C16	−131.82 (18)
O1—C1—C2—C5	−11.0 (2)	C16—C11—C12—C13	2.0 (3)
O2—C1—C2—C3	−9.2 (2)	N1—C11—C12—C13	−179.01 (16)
O1—C1—C2—C3	171.13 (14)	C11—C12—C13—C14	−0.7 (3)
C5—C2—C3—C4	108.2 (2)	C12—C13—C14—C15	−1.0 (3)
C1—C2—C3—C4	−74.03 (18)	C12—C13—C14—I1	178.29 (14)
C11—N1—C4—O3	−7.6 (3)	C13—C14—C15—C16	1.4 (3)
C11—N1—C4—C3	169.68 (15)	I1—C14—C15—C16	−177.91 (14)
C2—C3—C4—O3	−25.0 (2)	C12—C11—C16—C15	−1.6 (3)
C2—C3—C4—N1	157.71 (14)	N1—C11—C16—C15	179.35 (17)
C4—N1—C11—C12	49.1 (2)	C14—C15—C16—C11	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.84	1.83	2.6597 (19)	170
N1—H71···O3ii	0.83 (2)	2.10 (2)	2.8963 (18)	161 (2)
C3—H3B···O3ii	0.99	2.51	3.266 (2)	134

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