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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008316/ac6036sup1.cif
Contains datablocks global, 4

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008316/ac60364sup2.hkl
Contains datablock 4

CCDC reference: 214641

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


Yellow Alert 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

Comment top

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).

Experimental top

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).

Refinement top

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

Computing details top

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 top
[Figure 1] Fig. 1. An ORTEP-3 view (Farrugia, 1997) of (4) showing 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. A Mercury view (CCDC, 2003) of the (a) two-center and (b) three-center hydrogen bonds in the crystal packing.
(4) top
Crystal data top
C9H8N2O2F(000) = 368
Mr = 176.17Dx = 1.413 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 5.6672 (3) ÅCell parameters from 8167 reflections
b = 18.0609 (11) Åθ = 1.0–27.5°
c = 8.1949 (5) ŵ = 0.10 mm1
β = 99.135 (3)°T = 120 K
V = 828.15 (8) Å3Prism, yellow
Z = 40.12 × 0.06 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
Rint = 0.096
CCD rotation images, thick slices scansθmax = 25°, θmin = 2.3°
2565 measured reflectionsh = 66
1436 independent reflectionsk = 2021
1301 reflections with I > 2σ(I)l = 99
Refinement top
Refinement on F2 w = 1/[σ2(Fo2) + (0.0677P)2]
where P = (Fo2 + 2Fc2)/3
Least-squares matrix: full(Δ/σ)max = 0.004
R[F2 > 2σ(F2)] = 0.051Δρmax = 0.23 e Å3
wR(F2) = 0.131Δρmin = 0.19 e Å3
S = 1.06Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1436 reflectionsExtinction coefficient: 0.14 (2)
143 parametersAbsolute structure: Flack (1983)
2 restraintsAbsolute structure parameter: 2.9 (16)
H atoms treated by a mixture of independent and constrained refinement
Crystal data top
C9H8N2O2V = 828.15 (8) Å3
Mr = 176.17Z = 4
Monoclinic, CcMo Kα radiation
a = 5.6672 (3) ŵ = 0.10 mm1
b = 18.0609 (11) ÅT = 120 K
c = 8.1949 (5) Å0.12 × 0.06 × 0.06 mm
β = 99.135 (3)°
Data collection top
Nonius KappaCCD
diffractometer
1301 reflections with I > 2σ(I)
2565 measured reflectionsRint = 0.096
1436 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131Δρmax = 0.23 e Å3
S = 1.06Δρmin = 0.19 e Å3
1436 reflectionsAbsolute structure: Flack (1983)
143 parametersAbsolute structure parameter: 2.9 (16)
2 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
O11.5419 (3)0.66992 (11)1.0278 (3)0.0452 (6)
O20.7768 (3)0.71253 (10)0.6798 (2)0.0411 (5)
N11.1093 (4)0.70133 (13)0.8761 (3)0.0368 (6)
N20.4490 (5)0.86111 (15)0.7505 (3)0.0491 (7)
C11.2195 (4)0.63753 (16)0.8222 (3)0.0364 (6)
C21.1167 (5)0.59047 (16)0.6956 (3)0.0392 (7)
C31.2436 (6)0.52986 (17)0.6520 (4)0.0440 (7)
C41.4707 (6)0.51492 (17)0.7357 (4)0.0437 (7)
C51.5747 (4)0.56132 (17)0.8617 (3)0.0412 (7)
C61.4499 (4)0.62188 (15)0.9051 (3)0.0370 (6)
C70.9075 (4)0.73486 (14)0.8029 (3)0.0347 (6)
C80.8534 (5)0.80604 (16)0.8918 (4)0.0402 (7)
C90.6276 (5)0.83698 (17)0.8142 (3)0.0409 (7)
H11.678 (7)0.652 (2)1.088 (5)0.061*
H1.189 (6)0.7213 (19)0.965 (5)0.049*
H20.962 (6)0.601 (2)0.634 (5)0.049*
H31.174 (6)0.497 (2)0.563 (5)0.049*
H41.557 (6)0.4738 (19)0.709 (5)0.049*
H51.755 (6)0.553 (2)0.919 (4)0.049*
H810.841 (6)0.7933 (18)1.006 (5)0.049*
H820.975 (6)0.844 (2)0.900 (4)0.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0354 (10)0.0493 (12)0.0468 (11)0.0038 (9)0.0059 (8)0.0061 (9)
O20.0413 (11)0.0397 (10)0.0390 (10)0.0013 (8)0.0041 (8)0.0008 (8)
N10.0324 (12)0.0395 (12)0.0357 (12)0.0032 (9)0.0033 (9)0.0026 (10)
N20.0414 (13)0.0482 (14)0.0527 (14)0.0039 (11)0.0076 (11)0.0031 (11)
C10.0340 (13)0.0366 (14)0.0381 (14)0.0000 (10)0.0046 (10)0.0029 (11)
C20.0350 (14)0.0427 (17)0.0386 (14)0.0025 (11)0.0019 (11)0.0014 (11)
C30.0462 (16)0.0404 (15)0.0442 (15)0.0007 (12)0.0036 (12)0.0034 (12)
C40.0484 (16)0.0397 (15)0.0438 (16)0.0044 (13)0.0095 (12)0.0012 (11)
C50.0357 (14)0.0441 (15)0.0432 (14)0.0052 (12)0.0045 (11)0.0015 (12)
C60.0348 (14)0.0396 (15)0.0356 (14)0.0050 (11)0.0024 (11)0.0009 (11)
C70.0333 (13)0.0360 (14)0.0327 (12)0.0020 (10)0.0011 (10)0.0045 (11)
C80.0377 (14)0.0391 (15)0.0407 (16)0.0036 (12)0.0030 (11)0.0006 (12)
C90.0415 (14)0.0390 (15)0.0399 (14)0.0025 (12)0.0006 (11)0.0021 (11)
Geometric parameters (Å, º) top
O1—C61.367 (3)C2—C31.387 (4)
O2—C71.222 (3)C3—C41.386 (5)
N1—C71.348 (3)C4—C51.387 (4)
N1—C11.414 (4)C5—C61.379 (4)
N2—C91.148 (4)C7—C81.532 (4)
C1—C21.395 (4)C8—C91.448 (4)
C1—C61.402 (4)
C7—N1—C1127.8 (2)O1—C6—C5122.8 (2)
C2—C1—C6119.0 (2)O1—C6—C1116.5 (2)
C2—C1—N1125.1 (2)C5—C6—C1120.8 (2)
C6—C1—N1115.9 (2)O2—C7—N1125.4 (2)
C3—C2—C1120.0 (3)O2—C7—C8121.9 (2)
C4—C3—C2120.3 (3)N1—C7—C8112.7 (2)
C3—C4—C5120.2 (3)C9—C8—C7110.2 (2)
C6—C5—C4119.8 (2)N2—C9—C8179.0 (3)
C7—N1—C1—C211.0 (4)C2—C1—C6—O1179.9 (2)
C7—N1—C1—C6169.1 (2)N1—C1—C6—O10.2 (3)
C6—C1—C2—C30.9 (4)C2—C1—C6—C50.5 (4)
N1—C1—C2—C3179.2 (3)N1—C1—C6—C5179.5 (2)
C1—C2—C3—C41.2 (4)C1—N1—C7—O24.4 (4)
C2—C3—C4—C51.2 (5)C1—N1—C7—C8175.9 (2)
C3—C4—C5—C60.9 (4)O2—C7—C8—C93.3 (4)
C4—C5—C6—O1179.8 (3)N1—C7—C8—C9176.4 (2)
C4—C5—C6—C10.6 (4)C7—C8—C9—N23E1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H···O10.87 (4)2.17 (4)2.629 (4)111 (3)
N1—H···O2i0.87 (4)2.08 (4)2.961 (4)162 (3)
O1—H1···N2ii0.90 (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.

Experimental details

Crystal data
Chemical formulaC9H8N2O2
Mr176.17
Crystal system, space groupMonoclinic, Cc
Temperature (K)120
a, b, c (Å)5.6672 (3), 18.0609 (11), 8.1949 (5)
β (°) 99.135 (3)
V3)828.15 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.12 × 0.06 × 0.06
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2565, 1436, 1301
Rint0.096
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.131, 1.06
No. of reflections1436
No. of parameters143
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.19
Absolute structureFlack (1983)
Absolute structure parameter2.9 (16)

Computer programs: COLLECT (Nonius BV, 1997-2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (CCDC, 2003), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
O1—C61.367 (3)N1—C11.414 (4)
O2—C71.222 (3)N2—C91.148 (4)
N1—C71.348 (3)
C7—N1—C1127.8 (2)O1—C6—C1116.5 (2)
C2—C1—N1125.1 (2)O2—C7—N1125.4 (2)
C6—C1—N1115.9 (2)N1—C7—C8112.7 (2)
O1—C6—C5122.8 (2)N2—C9—C8179.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H···O10.87 (4)2.17 (4)2.629 (4)111 (3)
N1—H···O2i0.87 (4)2.08 (4)2.961 (4)162 (3)
O1—H1···N2ii0.90 (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.
 

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