2-Cyano-N-(2-hydroxy­phenyl)­acet­amide

The crystal structure of the title compound, C₉H₈O₂N₂, is described. The crystal structure is stabilized by a hydrogen-bonded network along the [101] and [301] directions.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.131
• Data-to-parameter ratio = 10.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



STRVAL_01
         From the CIF: _refine_ls_abs_structure_Flack   -2.900
         From the CIF: _refine_ls_abs_structure_Flack_su    1.600
           Alert C Flack parameter is too small

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     18
                   C7  -C8  -C9  -N2      3.00  0.00   1.555   1.555   1.555   1.555

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               1436
         Count of symmetry unique reflns          733
         Completeness (_total/calc)            195.91%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       703
         Fraction of Friedel pairs measured     0.959
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Coumarins are a family of compounds that have been studied extensively due to its practical applications. Optical brightness, laser dyes, sensitizes in phototerapy, etc., is some of the usefulness of this class of compounds (Machado & Miranda, 2001).

The title compound, (4), was obtained during the synthesis of the 3-substituted 7-hydroxycoumarins, (3), from 2,4-dihydroxybenzaldeyde, (1), and benzoxazol-2-ylacetonitrile, (2), as outlined in the Scheme. Possibly, the final mixture contained some of the unreacted precursor (2), this being hydrolyzed during the second step of the reaction or during work-up (Luan et al., 2002; Elnagdi et al., 1997). An ORTEP-3 (Farrugia, 1997) drawing of (4) is shown in Fig. 1, and selected geometric parameters presented in Table 1. The 2-hydroxyphenyl and 2-cyanoacetamide moieties are planar and the angle between these systems is 7.48 (18)°.

In the crystal structure, the molecule is linked by two kinds of hydrogen bonds, viz. a two-center and a three-center bonding (Table 2). The two-center hydrogen bond O1—H1···N2 links the molecules in an infinite zigzag in the [301] direction (Fig. 2a). The three-center hydrogen bond involves the intramolecular interaction N1—H···O1 and the intermolecular interaction N1—H···O2 that produces an infinite zigzag the [101] direction (Fig. 2 b). The H atom is in the plane formed by atoms N1, O1 and O2 that indicate the presence of the three-center hydrogen bond (Jeffrey & Maluszynska, 1982). The N1···O1 distance of 2.627 (3) Å is clearly indicative of strong intramolecular hydrogen bonding; this distance is significantly shorter than the sum of the van der Waals radii for oxygen and nitrogen (3.07 Å; Bondi, 1964). This intramolecular N1···O1 distance is comparable to those observed for 2-[(2-iodophenyl)iminomethyl]phenol [2.624 (5) Å], N,N'-bis(p-chlorosalicylideneamine)-1,2-diaminobenzene [2.615 (6) Å] and 2,2'-azinodimethyldiphenol [2.611 (6) Å] (Elmali & Elerman, 1997; Xu et al., 1994; Elerman et al., 1994).

S2. Experimental

The method of preparation included heating ortho-aminophenol and ethyl cyanoacetate at 453 K for 6 h. Without isolation of the intermediate, after cooling, 2,4-dihydroxybenzaldehyde, ammonium acetate and ethanol were added and the mixture was heated to reflux for 30 min. After cooling, the solid obtained was filtered and washed with water, ethanol and diethyl ether. Possibly the hydrolysis of the benzoxazol-2-ylacetonitrile, (2), produced the title compound (Luan et al., 2002; Elnagdi et al., 1997).

S3. Refinement

H atoms were located by difference Fourier syntesis, the positional parameters have been refined with U_iso set to 1.5 (for methyl H atoms) or 1.2 (for the remaining H atoms) times the value of U_eq of the atom to which they are attached.

Computing details

Data collection: COLLECT (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (CCDC, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. An ORTEP-3 view (Farrugia, 1997) of (4) showing 30% probability displacement ellipsoids.
	Fig. 2. A Mercury view (CCDC, 2003) of the (a) two-center and (b) three-center hydrogen bonds in the crystal packing.

(4)

Crystal data

C9H8N2O2	F(000) = 368
Mr = 176.17	Dx = 1.413 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 5.6672 (3) Å	Cell parameters from 8167 reflections
b = 18.0609 (11) Å	θ = 1.0–27.5°
c = 8.1949 (5) Å	µ = 0.10 mm^−1
β = 99.135 (3)°	T = 120 K
V = 828.15 (8) Å^3	Prism, yellow
Z = 4	0.12 × 0.06 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer	Rint = 0.096
CCD rotation images, thick slices scans	θmax = 25°, θmin = 2.3°
2565 measured reflections	h = −6→6
1436 independent reflections	k = −20→21
1301 reflections with I > 2σ(I)	l = −9→9

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0677P)^2] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.004
R[F^2 > 2σ(F^2)] = 0.051	Δρmax = 0.23 e Å^−3
wR(F^2) = 0.131	Δρmin = −0.19 e Å^−3
S = 1.06	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1436 reflections	Extinction coefficient: 0.14 (2)
143 parameters	Absolute structure: Flack (1983)
2 restraints	Absolute structure parameter: −2.9 (16)
H atoms treated by a mixture of independent and constrained refinement

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.

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

	x	y	z	Uiso*/Ueq
O1	1.5419 (3)	0.66992 (11)	1.0278 (3)	0.0452 (6)
O2	0.7768 (3)	0.71253 (10)	0.6798 (2)	0.0411 (5)
N1	1.1093 (4)	0.70133 (13)	0.8761 (3)	0.0368 (6)
N2	0.4490 (5)	0.86111 (15)	0.7505 (3)	0.0491 (7)
C1	1.2195 (4)	0.63753 (16)	0.8222 (3)	0.0364 (6)
C2	1.1167 (5)	0.59047 (16)	0.6956 (3)	0.0392 (7)
C3	1.2436 (6)	0.52986 (17)	0.6520 (4)	0.0440 (7)
C4	1.4707 (6)	0.51492 (17)	0.7357 (4)	0.0437 (7)
C5	1.5747 (4)	0.56132 (17)	0.8617 (3)	0.0412 (7)
C6	1.4499 (4)	0.62188 (15)	0.9051 (3)	0.0370 (6)
C7	0.9075 (4)	0.73486 (14)	0.8029 (3)	0.0347 (6)
C8	0.8534 (5)	0.80604 (16)	0.8918 (4)	0.0402 (7)
C9	0.6276 (5)	0.83698 (17)	0.8142 (3)	0.0409 (7)
H1	1.678 (7)	0.652 (2)	1.088 (5)	0.061*
H	1.189 (6)	0.7213 (19)	0.965 (5)	0.049*
H2	0.962 (6)	0.601 (2)	0.634 (5)	0.049*
H3	1.174 (6)	0.497 (2)	0.563 (5)	0.049*
H4	1.557 (6)	0.4738 (19)	0.709 (5)	0.049*
H5	1.755 (6)	0.553 (2)	0.919 (4)	0.049*
H81	0.841 (6)	0.7933 (18)	1.006 (5)	0.049*
H82	0.975 (6)	0.844 (2)	0.900 (4)	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0354 (10)	0.0493 (12)	0.0468 (11)	0.0038 (9)	−0.0059 (8)	−0.0061 (9)
O2	0.0413 (11)	0.0397 (10)	0.0390 (10)	−0.0013 (8)	−0.0041 (8)	0.0008 (8)
N1	0.0324 (12)	0.0395 (12)	0.0357 (12)	0.0032 (9)	−0.0033 (9)	−0.0026 (10)
N2	0.0414 (13)	0.0482 (14)	0.0527 (14)	0.0039 (11)	−0.0076 (11)	−0.0031 (11)
C1	0.0340 (13)	0.0366 (14)	0.0381 (14)	0.0000 (10)	0.0046 (10)	0.0029 (11)
C2	0.0350 (14)	0.0427 (17)	0.0386 (14)	−0.0025 (11)	0.0019 (11)	−0.0014 (11)
C3	0.0462 (16)	0.0404 (15)	0.0442 (15)	−0.0007 (12)	0.0036 (12)	−0.0034 (12)
C4	0.0484 (16)	0.0397 (15)	0.0438 (16)	0.0044 (13)	0.0095 (12)	0.0012 (11)
C5	0.0357 (14)	0.0441 (15)	0.0432 (14)	0.0052 (12)	0.0045 (11)	0.0015 (12)
C6	0.0348 (14)	0.0396 (15)	0.0356 (14)	−0.0050 (11)	0.0024 (11)	0.0009 (11)
C7	0.0333 (13)	0.0360 (14)	0.0327 (12)	−0.0020 (10)	−0.0011 (10)	0.0045 (11)
C8	0.0377 (14)	0.0391 (15)	0.0407 (16)	0.0036 (12)	−0.0030 (11)	0.0006 (12)
C9	0.0415 (14)	0.0390 (15)	0.0399 (14)	−0.0025 (12)	−0.0006 (11)	−0.0021 (11)

Geometric parameters (Å, º)

O1—C6	1.367 (3)	C2—C3	1.387 (4)
O2—C7	1.222 (3)	C3—C4	1.386 (5)
N1—C7	1.348 (3)	C4—C5	1.387 (4)
N1—C1	1.414 (4)	C5—C6	1.379 (4)
N2—C9	1.148 (4)	C7—C8	1.532 (4)
C1—C2	1.395 (4)	C8—C9	1.448 (4)
C1—C6	1.402 (4)
C7—N1—C1	127.8 (2)	O1—C6—C5	122.8 (2)
C2—C1—C6	119.0 (2)	O1—C6—C1	116.5 (2)
C2—C1—N1	125.1 (2)	C5—C6—C1	120.8 (2)
C6—C1—N1	115.9 (2)	O2—C7—N1	125.4 (2)
C3—C2—C1	120.0 (3)	O2—C7—C8	121.9 (2)
C4—C3—C2	120.3 (3)	N1—C7—C8	112.7 (2)
C3—C4—C5	120.2 (3)	C9—C8—C7	110.2 (2)
C6—C5—C4	119.8 (2)	N2—C9—C8	179.0 (3)
C7—N1—C1—C2	−11.0 (4)	C2—C1—C6—O1	179.9 (2)
C7—N1—C1—C6	169.1 (2)	N1—C1—C6—O1	−0.2 (3)
C6—C1—C2—C3	−0.9 (4)	C2—C1—C6—C5	0.5 (4)
N1—C1—C2—C3	179.2 (3)	N1—C1—C6—C5	−179.5 (2)
C1—C2—C3—C4	1.2 (4)	C1—N1—C7—O2	4.4 (4)
C2—C3—C4—C5	−1.2 (5)	C1—N1—C7—C8	−175.9 (2)
C3—C4—C5—C6	0.9 (4)	O2—C7—C8—C9	3.3 (4)
C4—C5—C6—O1	−179.8 (3)	N1—C7—C8—C9	−176.4 (2)
C4—C5—C6—C1	−0.6 (4)	C7—C8—C9—N2	−3E1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H···O1	0.87 (4)	2.17 (4)	2.629 (4)	111 (3)
N1—H···O2^i	0.87 (4)	2.08 (4)	2.961 (4)	162 (3)
O1—H1···N2^ii	0.90 (4)	1.88 (4)	2.762 (4)	164 (4)

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x+3/2, −y+3/2, z+1/2.