4-[1-(4-Chloro­phen­yl)-3-oxobutyl­amino]benzoic acid

Geometric parameters of the title compound, C₁₇H₁₆ClNO₃, are in the usual ranges. The two aromatic rings are almost perpendicular, with a dihedral angle of 89.26 (5)°. The carboxyl group is coplanar with the aromatic ring to which it is attached [dihedral angle = 1.70 (17)°]. The packing involves inversion-symmetric dimers bridged via hydrogen bonding of the carboxyl groups. In addition, there is an N—H...O hydrogen bond between the amino group and the carbonyl O atom.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.105
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

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PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          S

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S1. Comment

The synthesis and structure of Schiff bases have attracted much attention in biology and chemistry (Kahwa et al., 1986). One of the aims of investigating the structural chemistry of Schiff bases is to develop protein and enzyme mimics (Santos et al., 2001). Structural information is useful in investigating the coordination properties of Schiff bases functioning as ligands (Saim et al., 2004). Some Schiff base derivatives were reported to possess antimicrobial, anti-inflammatory and central nervous system activities. Moreover, Schiff bases are also known to have biological activities such as antimicrobial (El-Masry et al., 2000 & Pandey et al., 1999), antifungal (Singh et al., 1988 & Varma et al., 1986), antitumor (Hodnett et al., 1970. Misra et al., 1981 & Desai et al., 2001), and as herbicides.

The crystal structures of some schiff base compounds, viz., 2-bromo-N-[(E)-4-chlorobenzylidene]-5-methoxybenzohydrazide (Butcher et al., 2007), 2-bromo-N'-[(E)-(4-fluorophenyl)methylene]-5-methoxybenzohydrazide monohydrate (Narayana et al., 2007), bis{4-[(2-hydroxybenzylidine)hydrazino]-8-(trifluoromethyl)quinolinium} sulfate tetrahydrate (Yathirajan, et al., 2007) and 2-Bromo-N'-[(1E)-(4-hydroxyphenyl)methylene]-5-methoxybenzohydrazide (Sarojini et al., 2007) have been reported. A new Schiff base, C₁₄H₁₀ClNO₂ was synthesized and during crystallization it reacted with the solvent acetone to form a new compound, (I), C₁₇H₁₆ClNO₃ and its crystal structure is reported.

Geometric parameters of the title compound are in the usual ranges. The two aromatic rings are almost mutally perpendicular [dihedral angle 89.26 (5)°]. The carboxyl moiety is coplanar with the aromatic ring to which it is attached [dihedral angle 1.70 (17)°]. The packing involves inversion-symmetric dimers bridged via hydrogen bonding of the carboxyl groups. In addition, there is an N—H···O hydrogen bond between the amino group and the carbonyl O atom.

Related literature

For related literature, see: Butcher et al. (2007); Desai et al. (2001); El-Masry, Fahmy & Abdelwahed (2000); Hodnett & Dunn (1970); Kahwa et al. (1986); Misra et al. (1981); Narayana et al. (2007); Pandey et al. (1999); Saim et al. (2004); Santos et al. (2001); Sarojini et al. (2007); Singh & Dash (1988); Varma et al. (1986); Yathirajan et al. (2007).

S2. Experimental

The reaction is illustrated in scheme 2. A mixture of 4-aminobenzoic acid (1.37 g, 0.01 mol) and 4-chlorobenzaldehyde (1.4 g, 0.01 mol) in 15 ml of absolute ethanol containing 2 drops of 4 M sulfuric acid was refluxed for about 3 h. On cooling, the solid separated was filtered and recrystallized from acetone (m.p.: 441–443 K). During repeated crystallization, the Schiff base formed reacted with acetone and formed a new compound, (I). Analysis found: C: 64.18, H: 5.03, N: 4.37% for C₁₇H₁₆ClNO₃ requires: C: 64.26, H: 5.08, N: 4.41%.

S3. Refinement

H atoms bonded to C were refined with fixed individual displacement parameters [U(H) = 1.2 U_eq(C) or U(H) = 1.5 U_eq(C_methyl)] using a riding model with C—H ranging from 0.95 Å to 1.00 Å. The methyl group was allowed to rotate but not to tip. The H atoms bonded to N and O were freely refined.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
	Fig. 2. The formation of the title compound.

4-[1-(4-Chlorophenyl)-3-oxobutylamino]benzoic acid

Crystal data

C17H16ClNO3	F(000) = 664
Mr = 317.76	Dx = 1.351 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9512 reflections
a = 6.0059 (5) Å	θ = 4.4–26.5°
b = 34.018 (3) Å	µ = 0.26 mm^−1
c = 8.0271 (6) Å	T = 173 K
β = 107.727 (6)°	Block, colourless
V = 1562.1 (2) Å^3	0.22 × 0.18 × 0.17 mm
Z = 4

Data collection

Stoe IPDSII two-circle diffractometer	3176 independent reflections
Radiation source: fine-focus sealed tube	2693 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 26.3°, θmin = 2.4°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −7→7
Tmin = 0.936, Tmax = 0.948	k = −41→42
10524 measured reflections	l = −8→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0636P)^2 + 0.1867P] where P = (Fo^2 + 2Fc^2)/3
3176 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

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
Cl1	0.78406 (8)	0.233987 (12)	0.49552 (6)	0.04873 (16)
O1	1.40294 (18)	0.37231 (3)	1.05669 (14)	0.0351 (3)
O2	−0.00560 (18)	0.49116 (3)	0.19948 (14)	0.0360 (3)
O3	0.28629 (19)	0.47831 (3)	0.08845 (14)	0.0356 (3)
H3	0.186 (5)	0.4902 (8)	−0.014 (4)	0.076 (8)*
N1	0.7119 (2)	0.41099 (3)	0.86357 (16)	0.0266 (3)
H1	0.623 (3)	0.4061 (5)	0.925 (3)	0.037 (5)*
C1	0.9242 (2)	0.38766 (4)	0.89325 (18)	0.0238 (3)
H1A	1.0412	0.4038	0.8574	0.029*
C2	1.0228 (2)	0.37941 (4)	1.08945 (18)	0.0258 (3)
H2A	1.0076	0.4035	1.1545	0.031*
H2B	0.9278	0.3586	1.1211	0.031*
C3	1.2763 (2)	0.36668 (4)	1.14671 (18)	0.0268 (3)
C4	1.3646 (3)	0.34730 (5)	1.3232 (2)	0.0381 (4)
H4A	1.3032	0.3204	1.3159	0.057*
H4B	1.3122	0.3623	1.4085	0.057*
H4C	1.5358	0.3465	1.3602	0.057*
C11	0.8857 (2)	0.34943 (4)	0.78887 (17)	0.0235 (3)
C12	0.7091 (2)	0.32344 (4)	0.79678 (19)	0.0287 (3)
H12	0.6102	0.3301	0.8650	0.034*
C13	0.6762 (3)	0.28804 (4)	0.7062 (2)	0.0320 (3)
H13	0.5563	0.2704	0.7127	0.038*
C14	0.8206 (3)	0.27882 (4)	0.60664 (19)	0.0306 (3)
C15	0.9960 (3)	0.30408 (4)	0.59526 (19)	0.0315 (3)
H15	1.0936	0.2974	0.5260	0.038*
C16	1.0272 (2)	0.33933 (4)	0.68662 (19)	0.0271 (3)
H16	1.1470	0.3569	0.6792	0.032*
C21	0.5924 (2)	0.42668 (4)	0.70343 (17)	0.0227 (3)
C22	0.3689 (2)	0.44280 (4)	0.68004 (18)	0.0255 (3)
H22	0.3042	0.4425	0.7743	0.031*
C23	0.2432 (2)	0.45899 (4)	0.52246 (18)	0.0255 (3)
H23	0.0917	0.4693	0.5089	0.031*
C24	0.3347 (2)	0.46046 (4)	0.38183 (18)	0.0235 (3)
C25	0.5592 (2)	0.44553 (4)	0.40492 (18)	0.0248 (3)
H25	0.6255	0.4470	0.3117	0.030*
C26	0.6860 (2)	0.42854 (4)	0.56237 (18)	0.0252 (3)
H26	0.8370	0.4181	0.5753	0.030*
C27	0.1934 (2)	0.47808 (4)	0.21563 (18)	0.0254 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0599 (3)	0.0391 (2)	0.0479 (3)	−0.00685 (18)	0.0175 (2)	−0.01857 (18)
O1	0.0310 (5)	0.0445 (6)	0.0323 (6)	−0.0007 (4)	0.0131 (5)	0.0059 (5)
O2	0.0306 (5)	0.0475 (6)	0.0285 (6)	0.0121 (5)	0.0069 (4)	0.0052 (5)
O3	0.0385 (6)	0.0453 (6)	0.0243 (5)	0.0132 (5)	0.0113 (4)	0.0077 (5)
N1	0.0295 (6)	0.0288 (6)	0.0242 (6)	0.0054 (5)	0.0122 (5)	0.0051 (5)
C1	0.0251 (6)	0.0245 (6)	0.0225 (7)	0.0003 (5)	0.0085 (5)	0.0032 (5)
C2	0.0286 (7)	0.0273 (6)	0.0215 (7)	−0.0022 (5)	0.0078 (5)	0.0007 (5)
C3	0.0298 (7)	0.0257 (6)	0.0235 (7)	−0.0040 (5)	0.0060 (6)	0.0002 (5)
C4	0.0369 (8)	0.0458 (9)	0.0286 (8)	0.0006 (7)	0.0055 (6)	0.0104 (7)
C11	0.0246 (6)	0.0246 (6)	0.0195 (6)	0.0035 (5)	0.0042 (5)	0.0036 (5)
C12	0.0254 (6)	0.0323 (7)	0.0297 (7)	0.0001 (5)	0.0105 (5)	−0.0001 (6)
C13	0.0283 (7)	0.0320 (7)	0.0349 (8)	−0.0040 (5)	0.0082 (6)	−0.0005 (6)
C14	0.0336 (7)	0.0295 (7)	0.0255 (7)	0.0021 (6)	0.0043 (6)	−0.0034 (6)
C15	0.0344 (7)	0.0363 (7)	0.0258 (7)	0.0047 (6)	0.0120 (6)	−0.0001 (6)
C16	0.0276 (6)	0.0298 (7)	0.0249 (7)	0.0009 (5)	0.0097 (5)	0.0039 (5)
C21	0.0265 (6)	0.0187 (6)	0.0229 (7)	−0.0019 (5)	0.0077 (5)	0.0011 (5)
C22	0.0289 (7)	0.0241 (6)	0.0266 (7)	0.0003 (5)	0.0129 (5)	0.0023 (5)
C23	0.0245 (6)	0.0231 (6)	0.0298 (7)	0.0014 (5)	0.0094 (5)	0.0011 (5)
C24	0.0254 (6)	0.0204 (6)	0.0240 (7)	−0.0015 (5)	0.0064 (5)	0.0002 (5)
C25	0.0270 (6)	0.0260 (6)	0.0234 (7)	0.0002 (5)	0.0104 (5)	0.0018 (5)
C26	0.0232 (6)	0.0264 (6)	0.0269 (7)	0.0025 (5)	0.0089 (5)	0.0029 (5)
C27	0.0270 (6)	0.0236 (6)	0.0244 (7)	0.0010 (5)	0.0061 (5)	−0.0004 (5)

Geometric parameters (Å, º)

Cl1—C14	1.7465 (15)	C12—C13	1.389 (2)
O1—C3	1.2132 (18)	C12—H12	0.9500
O2—C27	1.2443 (17)	C13—C14	1.383 (2)
O3—C27	1.3041 (17)	C13—H13	0.9500
O3—H3	0.95 (3)	C14—C15	1.384 (2)
N1—C21	1.3750 (18)	C15—C16	1.388 (2)
N1—C1	1.4586 (17)	C15—H15	0.9500
N1—H1	0.85 (2)	C16—H16	0.9500
C1—C11	1.5261 (18)	C21—C22	1.4083 (18)
C1—C2	1.5304 (19)	C21—C26	1.4108 (18)
C1—H1A	1.0000	C22—C23	1.376 (2)
C2—C3	1.5133 (19)	C22—H22	0.9500
C2—H2A	0.9900	C23—C24	1.3991 (19)
C2—H2B	0.9900	C23—H23	0.9500
C3—C4	1.505 (2)	C24—C25	1.3990 (18)
C4—H4A	0.9800	C24—C27	1.4731 (19)
C4—H4B	0.9800	C25—C26	1.3876 (19)
C4—H4C	0.9800	C25—H25	0.9500
C11—C16	1.3922 (19)	C26—H26	0.9500
C11—C12	1.3971 (19)
C27—O3—H3	111.9 (15)	C14—C13—H13	120.5
C21—N1—C1	123.05 (12)	C12—C13—H13	120.5
C21—N1—H1	112.3 (13)	C13—C14—C15	121.42 (13)
C1—N1—H1	118.1 (12)	C13—C14—Cl1	119.34 (11)
N1—C1—C11	113.28 (11)	C15—C14—Cl1	119.23 (11)
N1—C1—C2	108.25 (11)	C14—C15—C16	118.97 (13)
C11—C1—C2	110.80 (10)	C14—C15—H15	120.5
N1—C1—H1A	108.1	C16—C15—H15	120.5
C11—C1—H1A	108.1	C15—C16—C11	121.09 (13)
C2—C1—H1A	108.1	C15—C16—H16	119.5
C3—C2—C1	113.80 (11)	C11—C16—H16	119.5
C3—C2—H2A	108.8	N1—C21—C22	118.73 (12)
C1—C2—H2A	108.8	N1—C21—C26	123.07 (12)
C3—C2—H2B	108.8	C22—C21—C26	118.17 (12)
C1—C2—H2B	108.8	C23—C22—C21	120.84 (12)
H2A—C2—H2B	107.7	C23—C22—H22	119.6
O1—C3—C4	121.66 (13)	C21—C22—H22	119.6
O1—C3—C2	121.94 (13)	C22—C23—C24	121.04 (12)
C4—C3—C2	116.40 (12)	C22—C23—H23	119.5
C3—C4—H4A	109.5	C24—C23—H23	119.5
C3—C4—H4B	109.5	C23—C24—C25	118.66 (12)
H4A—C4—H4B	109.5	C23—C24—C27	119.05 (12)
C3—C4—H4C	109.5	C25—C24—C27	122.28 (12)
H4A—C4—H4C	109.5	C26—C25—C24	120.77 (12)
H4B—C4—H4C	109.5	C26—C25—H25	119.6
C16—C11—C12	118.59 (13)	C24—C25—H25	119.6
C16—C11—C1	121.09 (12)	C25—C26—C21	120.48 (12)
C12—C11—C1	120.31 (12)	C25—C26—H26	119.8
C13—C12—C11	120.93 (13)	C21—C26—H26	119.8
C13—C12—H12	119.5	O2—C27—O3	122.86 (13)
C11—C12—H12	119.5	O2—C27—C24	120.68 (13)
C14—C13—C12	119.00 (13)	O3—C27—C24	116.45 (12)
C21—N1—C1—C11	−63.24 (16)	C12—C11—C16—C15	−0.6 (2)
C21—N1—C1—C2	173.47 (12)	C1—C11—C16—C15	178.31 (12)
N1—C1—C2—C3	−162.23 (11)	C1—N1—C21—C22	169.04 (12)
C11—C1—C2—C3	72.99 (14)	C1—N1—C21—C26	−13.0 (2)
C1—C2—C3—O1	17.90 (19)	N1—C21—C22—C23	179.71 (12)
C1—C2—C3—C4	−163.22 (12)	C26—C21—C22—C23	1.64 (19)
N1—C1—C11—C16	128.90 (13)	C21—C22—C23—C24	−1.0 (2)
C2—C1—C11—C16	−109.22 (14)	C22—C23—C24—C25	−0.78 (19)
N1—C1—C11—C12	−52.24 (16)	C22—C23—C24—C27	179.97 (12)
C2—C1—C11—C12	69.65 (15)	C23—C24—C25—C26	1.86 (19)
C16—C11—C12—C13	0.7 (2)	C27—C24—C25—C26	−178.92 (12)
C1—C11—C12—C13	−178.23 (13)	C24—C25—C26—C21	−1.2 (2)
C11—C12—C13—C14	−0.3 (2)	N1—C21—C26—C25	−178.54 (12)
C12—C13—C14—C15	−0.1 (2)	C22—C21—C26—C25	−0.56 (19)
C12—C13—C14—Cl1	178.84 (11)	C23—C24—C27—O2	−0.66 (19)
C13—C14—C15—C16	0.2 (2)	C25—C24—C27—O2	−179.87 (13)
Cl1—C14—C15—C16	−178.76 (11)	C23—C24—C27—O3	−179.32 (12)
C14—C15—C16—C11	0.1 (2)	C25—C24—C27—O3	1.47 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^i	0.95 (3)	1.68 (3)	2.6248 (15)	177 (2)
N1—H1···O1^ii	0.85 (2)	2.24 (2)	3.0543 (16)	160.5 (17)

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