4-(Antipyrin-4-yl­imino­methyl)­benzoic acid

The title compound, C₁₉H₁₇­N₃O₃, 4-(1,2-di­hydro-1,5-di­methyl-3-oxo-2-phenyl-3H-pyrazol-4-yl­imino­methyl)­benzoic acid, has a basal plane containing a benzoic acid moiety and a pyrazole ring. The phenyl ring is twisted out of the plane with a dihedral angle of 70.25 (4)°. Molecules are associated in a one-dimensional zigzag structure through O—H...O hydrogen bonding and weak interactions between the carboxyl­ic acid group and the antipyrine moiety.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.076
• Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

In recent years, there has been considerable interest in the chemistry of antipyrine and its derivatives. These compounds have been widely used in spectrophotometric determination of metal ions. Many of these reagents can color sensitively with transition-metal ions [Please clarify] (Saraswathi et al., 2000), some of which can also coordinate to rare earth ions to form metal complexes with interesting structures (Singh et al., 1999). The antipyrine Schiff base derivatives may possess antibacterial and anti-inflammatory activities (Alaudeen et al., 1995) and can serve as antiparasitic and analgesic agents (Gursoy et al., 2000). Their complexes with platinum(II) and cobalt(II) ions have been shown to act as antitumor substances (Stupariu et al., 1995). We report here the synthesis and structure of the title compound, (I). The X-ray crystallographic study shows that the bond lengths and angles are within normal ranges. The C7—O1 bond distance is slightly longer than that in the 4-aminoantipyrine derivative 4-{[(1E)-(2-hydroxyphenyl)methylidene]amino}-1,5-dimethyl-2-phenyl-2,3- dihydro-1H-pyrazol-3-one, in which the C—O double-bond distance is 1.230 (2) Å (Hokelek et al., 2001). The C—N bond lengths of N1—C7 and N3—C8 are normal for C—N single-bond distances. The distance between N3 and C10 is typical for a C═N double-bond distance. These bonds are comparable with those in N-(1H-benzoimidazol-2-ylmethyl)-N-(2,6-di-chlorophenyl)amine (Eryigit & Kendy, 1998). The N1—N2 single-bond length is comparable with that in 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine (Manikandan et al., 2000). The title compound has a basal plane involving the benzoic acid moiety and the pyrazole ring with a mean deviation of 0.05 Å. The phenyl ring is erect to the plane, with a dihedral angle of 70.25 (4)°. The orientation of the phenyl ring is defined by the torsion angles N2—N1—C1—C2 of -58.5 (3)° and N2—N1—C1—C6 of 123.9 (2)°. The shortest distance between the carboxylic acid moiety and the phenyl ring is 3.283 (2) Å of C1···O3 (x, -y + 3/2, z - 1/2). Compared with 4-{[(1E)-(2-hydroxyphenyl)methylidene]amino}-1,5-dimethyl-2- phenyl-2,3-dihydro-1H-pyrazol-3-one (Hokelek et al., 2001), due to introducing the carboxylic acid group in the title compound, the molecules in the crystal are arranged in a head-to tail fashion, with intermolecular hydrogen bonds (Table 2) and weak interactions between the carboxylic acid moiety and the phenyl ring, to form a one-dimensional zigzag structure.

S2. Experimental

The title compound was synthesized by condensation of p-carboxylic acid benzaldehyde and 4-aminoantipyrine based on the following procedure. A 25 ml e thanol solution of 4-aminoantipyrine (0.20 g, 0.1 mmol) was mixed with 0.15 g (0.1 mmol) p-carboxylic acid benzaldehyde in 15 ml e thanol (95%). The reaction mixture was stirred at room temperature overnight, whereupon a yellow precipitate was formed and collected by filtration and washed with ethanol and ether several times. Single crystals suitable for crystallographic analysis were obtained by slow evaporation of an acetonitrile solution of the compound.

S3. Refinement

All H atoms were placed in geometrically calculated positions (C—H = 0.93 Å and N—H = 0.86 Å), with U_iso = 1.2U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids with the atom-numbering scheme.

(I)

Crystal data

C19H17N3O3	Dx = 1.322 Mg m^−3
Mr = 335.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from none reflections
a = 13.0859 (14) Å	θ = −28–−28°
b = 11.4837 (13) Å	µ = 0.09 mm^−1
c = 22.422 (2) Å	T = 293 K
V = 3369.5 (6) Å^3	Prism, yellow
Z = 8	0.30 × 0.20 × 0.15 mm
F(000) = 1408

Data collection

SMART APEX CCD diffractometer	1643 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.086
Graphite monochromator	θmax = 25.1°, θmin = 1.8°
ϕ and w scans with κ offsets	h = −15→8
16332 measured reflections	k = −13→13
2986 independent reflections	l = −26→26

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.015P)^2] where P = (Fo^2 + 2Fc^2)/3
2986 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.15 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
C1	0.33395 (16)	1.06156 (18)	0.23355 (9)	0.0466 (5)
C2	0.25674 (17)	0.99866 (19)	0.20789 (10)	0.0634 (7)
H2	0.2067	0.9643	0.2315	0.076*
C3	0.2538 (2)	0.9867 (2)	0.14697 (12)	0.0811 (8)
H3	0.2014	0.9444	0.1291	0.097*
C4	0.3276 (2)	1.0368 (2)	0.11269 (11)	0.0802 (8)
H4	0.3262	1.0273	0.0715	0.096*
C5	0.40325 (19)	1.1005 (2)	0.13826 (11)	0.0786 (8)
H5	0.4531	1.1349	0.1145	0.094*
C6	0.40653 (16)	1.1143 (2)	0.19937 (10)	0.0633 (7)
H6	0.4576	1.1590	0.2170	0.076*
C7	0.39880 (16)	0.99487 (18)	0.33258 (9)	0.0436 (5)
C8	0.35261 (15)	1.00154 (16)	0.38990 (9)	0.0412 (5)
C9	0.26972 (15)	1.07502 (18)	0.38594 (9)	0.0456 (6)
C10	0.45656 (16)	0.88319 (18)	0.44854 (8)	0.0453 (5)
H10	0.5025	0.8769	0.4171	0.054*
C11	0.47756 (16)	0.82356 (17)	0.50478 (8)	0.0429 (5)
C12	0.56452 (16)	0.75732 (18)	0.51280 (9)	0.0506 (6)
H12	0.6110	0.7500	0.4817	0.061*
C13	0.58365 (15)	0.70187 (17)	0.56612 (9)	0.0502 (6)
H13	0.6423	0.6569	0.5704	0.060*
C14	0.51649 (15)	0.71240 (17)	0.61332 (9)	0.0435 (5)
C15	0.42974 (16)	0.77912 (18)	0.60565 (9)	0.0586 (7)
H15	0.3838	0.7877	0.6370	0.070*
C16	0.41074 (15)	0.83277 (19)	0.55226 (9)	0.0563 (6)
H16	0.3514	0.8765	0.5478	0.068*
C17	0.53889 (18)	0.6524 (2)	0.67018 (9)	0.0502 (6)
C18	0.19721 (16)	1.2054 (2)	0.30667 (10)	0.0761 (8)
H18A	0.1499	1.2302	0.3368	0.114*
H18B	0.1601	1.1765	0.2728	0.114*
H18C	0.2388	1.2702	0.2947	0.114*
C19	0.19754 (15)	1.1105 (2)	0.43377 (9)	0.0672 (7)
H19A	0.1939	1.1940	0.4354	0.101*
H19B	0.2211	1.0811	0.4714	0.101*
H19C	0.1310	1.0795	0.4254	0.101*
N1	0.34201 (13)	1.06922 (15)	0.29687 (7)	0.0487 (5)
N2	0.26160 (12)	1.11428 (15)	0.33023 (8)	0.0493 (5)
N3	0.37562 (12)	0.94371 (14)	0.44242 (7)	0.0461 (5)
O1	0.47157 (11)	0.93502 (12)	0.31377 (5)	0.0534 (4)
O2	0.61096 (12)	0.58904 (15)	0.67767 (6)	0.0788 (6)
O3	0.47082 (10)	0.67435 (12)	0.71210 (6)	0.0590 (4)
H33	0.4770	0.6319	0.7413	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0481 (15)	0.0546 (14)	0.0372 (13)	−0.0006 (12)	−0.0047 (12)	0.0114 (12)
C2	0.0618 (17)	0.0786 (19)	0.0497 (16)	−0.0124 (14)	−0.0068 (13)	0.0135 (14)
C3	0.081 (2)	0.100 (2)	0.0624 (19)	−0.0123 (17)	−0.0240 (16)	−0.0001 (17)
C4	0.080 (2)	0.120 (3)	0.0411 (16)	0.0199 (19)	−0.0082 (16)	0.0042 (17)
C5	0.0651 (19)	0.119 (3)	0.0516 (18)	0.0014 (16)	0.0061 (14)	0.0278 (17)
C6	0.0582 (17)	0.0842 (19)	0.0474 (16)	−0.0071 (14)	−0.0036 (12)	0.0137 (14)
C7	0.0489 (15)	0.0460 (14)	0.0360 (13)	−0.0004 (11)	−0.0050 (11)	−0.0001 (12)
C8	0.0498 (15)	0.0417 (13)	0.0322 (12)	0.0035 (11)	−0.0029 (10)	0.0029 (11)
C9	0.0475 (15)	0.0498 (14)	0.0395 (14)	0.0002 (11)	0.0017 (11)	0.0026 (12)
C10	0.0574 (15)	0.0479 (14)	0.0305 (12)	−0.0029 (12)	0.0000 (11)	−0.0006 (11)
C11	0.0532 (15)	0.0423 (14)	0.0331 (13)	0.0015 (11)	−0.0043 (11)	−0.0036 (11)
C12	0.0588 (16)	0.0564 (15)	0.0367 (13)	0.0088 (12)	0.0070 (11)	0.0017 (12)
C13	0.0500 (15)	0.0577 (16)	0.0428 (14)	0.0093 (11)	0.0009 (11)	0.0022 (12)
C14	0.0500 (14)	0.0439 (13)	0.0375 (13)	0.0033 (11)	0.0048 (11)	0.0026 (11)
C15	0.0500 (17)	0.0536 (17)	0.0360 (14)	0.0148 (14)	0.0099 (11)	0.0116 (13)
C16	0.0559 (15)	0.0704 (17)	0.0428 (14)	0.0201 (12)	0.0041 (12)	0.0101 (13)
C17	0.0557 (16)	0.0558 (16)	0.0392 (14)	−0.0002 (13)	0.0001 (13)	0.0018 (12)
C18	0.0666 (17)	0.0797 (19)	0.0818 (18)	0.0251 (14)	0.0012 (14)	0.0262 (15)
C19	0.0668 (16)	0.0752 (18)	0.0598 (16)	0.0135 (13)	0.0117 (13)	0.0018 (14)
N1	0.0492 (12)	0.0650 (13)	0.0319 (11)	0.0075 (10)	−0.0007 (9)	0.0062 (10)
N2	0.0483 (12)	0.0535 (12)	0.0461 (12)	0.0097 (9)	−0.0007 (9)	0.0071 (10)
N3	0.0569 (12)	0.0446 (12)	0.0368 (11)	0.0031 (10)	−0.0028 (9)	0.0007 (9)
O1	0.0550 (10)	0.0682 (10)	0.0369 (8)	0.0156 (8)	−0.0019 (7)	−0.0071 (8)
O2	0.0723 (12)	0.1058 (14)	0.0583 (11)	0.0342 (11)	0.0032 (9)	0.0273 (10)
O3	0.0729 (11)	0.0659 (11)	0.0382 (9)	0.0089 (8)	0.0039 (8)	0.0123 (8)

Geometric parameters (Å, º)

C1—C6	1.362 (3)	C11—C12	1.381 (2)
C1—C2	1.369 (3)	C11—C16	1.382 (2)
C1—N1	1.426 (2)	C12—C13	1.377 (2)
C2—C3	1.373 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.381 (2)
C3—C4	1.362 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.380 (2)
C4—C5	1.358 (3)	C14—C17	1.479 (3)
C4—H4	0.9300	C15—C16	1.369 (2)
C5—C6	1.380 (3)	C15—H15	0.9300
C5—H5	0.9300	C16—H16	0.9300
C6—H6	0.9300	C17—O2	1.203 (2)
C7—O1	1.248 (2)	C17—O3	1.319 (2)
C7—N1	1.387 (2)	C18—N2	1.444 (2)
C7—C8	1.422 (2)	C18—H18A	0.9600
C8—C9	1.377 (2)	C18—H18B	0.9600
C8—N3	1.385 (2)	C18—H18C	0.9600
C9—N2	1.332 (2)	C19—H19A	0.9600
C9—C19	1.486 (2)	C19—H19B	0.9600
C10—N3	1.274 (2)	C19—H19C	0.9600
C10—C11	1.461 (2)	N1—N2	1.391 (2)
C10—H10	0.9300	O3—H33	0.8202
C6—C1—C2	120.8 (2)	C12—C13—C14	120.6 (2)
C6—C1—N1	118.7 (2)	C12—C13—H13	119.7
C2—C1—N1	120.4 (2)	C14—C13—H13	119.7
C1—C2—C3	119.4 (2)	C15—C14—C13	118.46 (19)
C1—C2—H2	120.3	C15—C14—C17	121.9 (2)
C3—C2—H2	120.3	C13—C14—C17	119.6 (2)
C4—C3—C2	120.0 (2)	C16—C15—C14	120.53 (19)
C4—C3—H3	120.0	C16—C15—H15	119.7
C2—C3—H3	120.0	C14—C15—H15	119.7
C5—C4—C3	120.4 (2)	C15—C16—C11	121.62 (19)
C5—C4—H4	119.8	C15—C16—H16	119.2
C3—C4—H4	119.8	C11—C16—H16	119.2
C4—C5—C6	120.3 (2)	O2—C17—O3	123.1 (2)
C4—C5—H5	119.9	O2—C17—C14	123.9 (2)
C6—C5—H5	119.9	O3—C17—C14	113.0 (2)
C1—C6—C5	119.1 (2)	N2—C18—H18A	109.5
C1—C6—H6	120.5	N2—C18—H18B	109.5
C5—C6—H6	120.5	H18A—C18—H18B	109.5
O1—C7—N1	123.57 (18)	N2—C18—H18C	109.5
O1—C7—C8	131.25 (19)	H18A—C18—H18C	109.5
N1—C7—C8	105.13 (18)	H18B—C18—H18C	109.5
C9—C8—N3	121.32 (19)	C9—C19—H19A	109.5
C9—C8—C7	108.03 (18)	C9—C19—H19B	109.5
N3—C8—C7	130.55 (19)	H19A—C19—H19B	109.5
N2—C9—C8	109.31 (18)	C9—C19—H19C	109.5
N2—C9—C19	122.21 (19)	H19A—C19—H19C	109.5
C8—C9—C19	128.5 (2)	H19B—C19—H19C	109.5
N3—C10—C11	120.33 (19)	C7—N1—N2	108.90 (16)
N3—C10—H10	119.8	C7—N1—C1	125.21 (18)
C11—C10—H10	119.8	N2—N1—C1	120.15 (16)
C12—C11—C16	117.61 (19)	C9—N2—N1	108.54 (16)
C12—C11—C10	121.72 (19)	C9—N2—C18	129.42 (19)
C16—C11—C10	120.67 (19)	N1—N2—C18	120.96 (17)
C13—C12—C11	121.17 (19)	C10—N3—C8	122.26 (18)
C13—C12—H12	119.4	C17—O3—H33	112.8
C11—C12—H12	119.4
C6—C1—C2—C3	1.3 (4)	C12—C11—C16—C15	0.4 (3)
N1—C1—C2—C3	−176.2 (2)	C10—C11—C16—C15	−178.96 (19)
C1—C2—C3—C4	0.3 (4)	C15—C14—C17—O2	176.3 (2)
C2—C3—C4—C5	−1.2 (4)	C13—C14—C17—O2	−3.6 (3)
C3—C4—C5—C6	0.5 (4)	C15—C14—C17—O3	−3.1 (3)
C2—C1—C6—C5	−2.0 (3)	C13—C14—C17—O3	177.07 (18)
N1—C1—C6—C5	175.5 (2)	O1—C7—N1—N2	174.70 (18)
C4—C5—C6—C1	1.1 (4)	C8—C7—N1—N2	−3.0 (2)
O1—C7—C8—C9	−175.5 (2)	O1—C7—N1—C1	21.7 (3)
N1—C7—C8—C9	1.9 (2)	C8—C7—N1—C1	−156.04 (19)
O1—C7—C8—N3	0.7 (4)	C6—C1—N1—C7	−85.8 (3)
N1—C7—C8—N3	178.12 (18)	C2—C1—N1—C7	91.8 (3)
N3—C8—C9—N2	−176.71 (17)	C6—C1—N1—N2	123.9 (2)
C7—C8—C9—N2	−0.1 (2)	C2—C1—N1—N2	−58.5 (3)
N3—C8—C9—C19	3.9 (3)	C8—C9—N2—N1	−1.8 (2)
C7—C8—C9—C19	−179.5 (2)	C19—C9—N2—N1	177.67 (18)
N3—C10—C11—C12	180.0 (8)	C8—C9—N2—C18	−169.8 (2)
N3—C10—C11—C16	−0.7 (3)	C19—C9—N2—C18	9.7 (3)
C16—C11—C12—C13	0.4 (3)	C7—N1—N2—C9	3.1 (2)
C10—C11—C12—C13	179.76 (18)	C1—N1—N2—C9	157.70 (18)
C11—C12—C13—C14	−0.8 (3)	C7—N1—N2—C18	172.25 (17)
C12—C13—C14—C15	0.4 (3)	C1—N1—N2—C18	−33.1 (3)
C12—C13—C14—C17	−179.78 (18)	C11—C10—N3—C8	−179.91 (17)
C13—C14—C15—C16	0.4 (3)	C9—C8—N3—C10	−173.96 (19)
C17—C14—C15—C16	−179.42 (19)	C7—C8—N3—C10	10.3 (3)
C14—C15—C16—C11	−0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H33···O1^i	0.82	1.80	2.603 (2)	166

Symmetry code: (i) x, −y+3/2, z+1/2.