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In the structure of the title compound, C11H9N3O, the mol­ecule is almost planar; the dihedral angle between the o-methoxy­aniline and di­cyano­ethyl­ene fragments is 4.8 (1)°. There is a weak conjugation between these fragments of the mol­ecule. An intramolecular N—H...O hydrogen bond forms a planar five-membered ring. Molecules form stacks with head-to-head orientations in the crystal. Weak intermolecular C—H...N hydrogen bonds link mol­ecules into centrosymmetric dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007293/lh6053sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007293/lh6053Isup2.hkl
Contains datablock I

CCDC reference: 214604

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.069
  • wR factor = 0.183
  • Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(9) - C(10) = 1.42 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(9) - C(11) = 1.43 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

The present work is a part of our project on synthesis and structural investigations of organic potential non-linear optical compounds. We have investigated a large series of polar molecules that have a dicyano group as an acceptor part and various donor groups connected by π-conjugated chains of different lengths (Antipin, Clark et al., 1998; Antipin, Timofeeva et al., 1998; Timofeeva, Nesterov, Antipin et al., 2000; Timofeeva, Nesterov, Dolgushin et al., 2000; Nesterov, Antipin et al., 2000; Nesterov, Deng et al., 2000; Nesterov et al., 2002). Continuing our investigations in this direction, we have synthesized and have investigated the structure of [(2-methoxyanilino)methylene]malononitrile, (I) (see Fig. 1), which contains an N atom between the donor and acceptor parts of the molecule.

The X-ray analysis shows that molecule (I) has an almost planar structure in spite of the presence of an intramolecular steric contact H6A···H8A with distance 2.18 Å, that is comparable with the sum of the van der Waals radii of these atoms (Rowlend & Taylor, 1996). The dihedral angle between the o-methoxyaniline and dicyanoethylene fragments is only 4.8 (1)°. On the other hand, the mutual orientation of atom H1A, that is bonded to N1, and atom O1 of the methoxy group in the molecule results in an intramolecular hydrogen bond (N1—H1A···O1) that links a five-membered ring and helps to flatten the molecule. Such a flat stucture is favorable for conjugation between the donor and acceptor parts of the molecule. According to the values of the bond lengths (Table 1), the trigonal N1 atom has stronger conjugation with double bond C8C9 than with aromatic ring. The single C1—N1 bond is only slightly shorter than a standard value for such bonds (Allen et al., 1987). Thus, the presence of N is less favorable for conjugation between the two parts of the molecule.

Molecules in the cystal form stacks with head-to-head orientations (see Fig. 2). Weak intermolecular hydrogen bonds [C8—H8A···N3i; symmetry code: (i) 2 − x, 1 − y, −z] (see Table 2)] link the molecules into centrosymmetric dimers. According to our previous data, similar hydrogen bonds were found when molecules crystallized in centrosymmetric space groups (Antipin, Timofeeva et al., 1998; Nesterov, Deng et al., 2000). The rest of the geometrical parameters in the investigated molecule have standard values (Allen et al., 1987).

Experimental top

The title compound, (I), was obtained by the reaction of o-methoxyaniline (0.005 mol) with (ethoxymethylene)malononitrile (0.005 mol) in ethanol (20 ml) at room temperature. The precipitate was isolated and recrystallized from ethanol (melting point 491 K, yield 79%). Light-yellow crystals were obtained by isothermic evaporation of an ethanolic solution of (I).

Refinement top

All H atoms were included in calculated positions with C—H distances of 0.93 Å (0.96 Å for methyl) and 0.86 Å for N—H. They were included in the refinement in riding-motion approximation, with Uiso = 1.2Ueq (Uiso = 1.5Ueq for methyl) of the carrier atom.

Computing details top

Data collection: P3/PC (Siemens, 1989); cell refinement: P3/PC; data reduction: SHELXTL (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of the title molecule, (I), with the atom-numbering scheme. The non-H atoms are shown with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary radius for clarity.
[Figure 2] Fig. 2. Projection of a crystal packing of compound (I) along the a axis. Dashed lines show weak C—H···N hydrogen bonds.
[(2-methoxyanilino)methylene]malononitrile top
Crystal data top
C11H9N3OZ = 2
Mr = 199.21F(000) = 208
Triclinic, P1Dx = 1.263 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.5893 (18) ÅCell parameters from 24 reflections
b = 8.105 (4) Åθ = 11–12°
c = 14.641 (7) ŵ = 0.09 mm1
α = 97.77 (4)°T = 297 K
β = 91.18 (4)°Prism, light yellow
γ = 103.48 (3)°0.45 × 0.35 × 0.20 mm
V = 523.9 (4) Å3
Data collection top
Siemens P3/PC
diffractometer
Rint = 0.066
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 2.6°
Graphite monochromatorh = 05
θ/2θ scansk = 99
2065 measured reflectionsl = 1717
1820 independent reflections3 standard reflections every 97 reflections
1389 reflections with I > 2σ(I) intensity decay: 3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.1222P)2 + 0.0112P]
where P = (Fo2 + 2Fc2)/3
1820 reflections(Δ/σ)max < 0.001
137 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C11H9N3Oγ = 103.48 (3)°
Mr = 199.21V = 523.9 (4) Å3
Triclinic, P1Z = 2
a = 4.5893 (18) ÅMo Kα radiation
b = 8.105 (4) ŵ = 0.09 mm1
c = 14.641 (7) ÅT = 297 K
α = 97.77 (4)°0.45 × 0.35 × 0.20 mm
β = 91.18 (4)°
Data collection top
Siemens P3/PC
diffractometer
Rint = 0.066
2065 measured reflections3 standard reflections every 97 reflections
1820 independent reflections intensity decay: 3%
1389 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.183H-atom parameters constrained
S = 1.10Δρmax = 0.31 e Å3
1820 reflectionsΔρmin = 0.21 e Å3
137 parameters
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.

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. All H atoms were placed in geometrically calculated positions and refined using a riding model with N—H distances of 0.86 Å and C—H distances of 0.93 Å for aromatic and 0.96 Å for CH3 group.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.3516 (3)0.3081 (2)0.38559 (9)0.0753 (5)
N10.5799 (3)0.4080 (2)0.23679 (10)0.0519 (5)
H1A0.64100.45210.29260.062*
N21.2028 (5)0.7307 (3)0.35006 (13)0.0886 (7)
N31.3019 (5)0.6977 (3)0.04880 (12)0.0848 (7)
C10.3164 (4)0.2744 (2)0.22534 (12)0.0484 (5)
C20.1946 (4)0.2219 (2)0.30600 (13)0.0548 (5)
C30.0664 (5)0.0931 (3)0.30082 (16)0.0657 (6)
H3A0.15080.05870.35440.079*
C40.2000 (5)0.0164 (3)0.21553 (17)0.0684 (6)
H4A0.37400.07080.21190.082*
C50.0797 (5)0.0670 (3)0.13595 (16)0.0667 (6)
H5A0.17300.01460.07890.080*
C60.1794 (4)0.1955 (3)0.14032 (14)0.0577 (5)
H6A0.26190.22890.08630.069*
C70.2390 (8)0.2628 (5)0.47076 (18)0.1283 (14)
H7A0.35830.33870.52090.192*
H7B0.24800.14700.47510.192*
H7C0.03460.27220.47380.192*
C80.7427 (4)0.4724 (2)0.17084 (12)0.0494 (5)
H8A0.67900.42650.11000.059*
C90.9970 (4)0.6012 (2)0.18540 (12)0.0500 (5)
C101.1147 (4)0.6760 (3)0.27602 (14)0.0578 (5)
C111.1642 (5)0.6560 (2)0.10934 (13)0.0589 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0864 (11)0.0896 (11)0.0406 (8)0.0009 (8)0.0015 (7)0.0125 (7)
N10.0624 (9)0.0521 (9)0.0377 (8)0.0082 (7)0.0001 (7)0.0046 (6)
N20.1094 (17)0.0971 (16)0.0454 (11)0.0032 (12)0.0094 (10)0.0010 (10)
N30.0986 (15)0.0906 (14)0.0451 (10)0.0140 (11)0.0086 (10)0.0029 (9)
C10.0533 (10)0.0452 (10)0.0485 (10)0.0157 (8)0.0015 (8)0.0060 (8)
C20.0630 (11)0.0570 (11)0.0460 (11)0.0159 (9)0.0031 (8)0.0099 (8)
C30.0700 (13)0.0601 (12)0.0681 (14)0.0120 (10)0.0113 (10)0.0186 (10)
C40.0627 (12)0.0514 (11)0.0855 (16)0.0050 (9)0.0039 (11)0.0057 (11)
C50.0706 (14)0.0589 (12)0.0632 (13)0.0097 (10)0.0029 (10)0.0064 (10)
C60.0661 (12)0.0570 (11)0.0461 (10)0.0107 (9)0.0029 (9)0.0005 (8)
C70.140 (3)0.176 (4)0.0455 (14)0.019 (2)0.0057 (15)0.0344 (18)
C80.0618 (11)0.0500 (10)0.0371 (9)0.0152 (8)0.0003 (7)0.0063 (7)
C90.0598 (11)0.0487 (10)0.0396 (10)0.0100 (8)0.0002 (8)0.0047 (7)
C100.0702 (13)0.0556 (11)0.0447 (11)0.0069 (9)0.0035 (9)0.0109 (8)
C110.0718 (13)0.0548 (11)0.0428 (10)0.0027 (9)0.0024 (9)0.0035 (8)
Geometric parameters (Å, º) top
O1—C21.369 (3)C4—C51.371 (3)
O1—C71.421 (3)C4—H4A0.9300
N1—C81.322 (2)C5—C61.380 (3)
N1—C11.412 (3)C5—H5A0.9300
N1—H1A0.8600C6—H6A0.9300
N2—C101.142 (3)C7—H7A0.9600
N3—C111.142 (3)C7—H7B0.9600
C1—C61.385 (3)C7—H7C0.9600
C1—C21.393 (3)C8—C91.363 (3)
C2—C31.387 (3)C8—H8A0.9300
C3—C41.379 (3)C9—C101.421 (3)
C3—H3A0.9300C9—C111.427 (3)
C2—O1—C7117.7 (2)C6—C5—H5A119.9
C8—N1—C1126.95 (16)C5—C6—C1119.9 (2)
C8—N1—H1A116.5C5—C6—H6A120.1
C1—N1—H1A116.5C1—C6—H6A120.1
C6—C1—C2119.84 (19)O1—C7—H7A109.5
C6—C1—N1123.96 (18)O1—C7—H7B109.5
C2—C1—N1116.20 (17)H7A—C7—H7B109.5
O1—C2—C3125.71 (18)O1—C7—H7C109.5
O1—C2—C1114.47 (18)H7A—C7—H7C109.5
C3—C2—C1119.82 (19)H7B—C7—H7C109.5
C4—C3—C2119.5 (2)N1—C8—C9124.80 (17)
C4—C3—H3A120.3N1—C8—H8A117.6
C2—C3—H3A120.3C9—C8—H8A117.6
C5—C4—C3120.91 (19)C8—C9—C10121.42 (18)
C5—C4—H4A119.5C8—C9—C11120.32 (17)
C3—C4—H4A119.5C10—C9—C11118.11 (17)
C4—C5—C6120.1 (2)N2—C10—C9177.4 (2)
C4—C5—H5A119.9N3—C11—C9178.5 (2)
C8—N1—C1—C63.3 (3)C1—C2—C3—C41.1 (3)
C8—N1—C1—C2176.26 (17)C2—C3—C4—C50.6 (3)
C7—O1—C2—C30.1 (4)C3—C4—C5—C60.4 (3)
C7—O1—C2—C1179.3 (2)C4—C5—C6—C10.6 (3)
C6—C1—C2—O1179.29 (16)C2—C1—C6—C51.1 (3)
N1—C1—C2—O10.3 (2)N1—C1—C6—C5179.36 (18)
C6—C1—C2—C31.3 (3)C1—N1—C8—C9179.68 (17)
N1—C1—C2—C3179.10 (17)N1—C8—C9—C101.6 (3)
O1—C2—C3—C4179.57 (18)N1—C8—C9—C11177.03 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.862.182.584 (3)108
C8—H8A···N3i0.932.423.305 (3)160
Symmetry code: (i) x+2, y+1, z.

Experimental details

Crystal data
Chemical formulaC11H9N3O
Mr199.21
Crystal system, space groupTriclinic, P1
Temperature (K)297
a, b, c (Å)4.5893 (18), 8.105 (4), 14.641 (7)
α, β, γ (°)97.77 (4), 91.18 (4), 103.48 (3)
V3)523.9 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.45 × 0.35 × 0.20
Data collection
DiffractometerSiemens P3/PC
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2065, 1820, 1389
Rint0.066
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.183, 1.10
No. of reflections1820
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.21

Computer programs: P3/PC (Siemens, 1989), P3/PC, SHELXTL (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL, SHELXL97.

Selected geometric parameters (Å, º) top
N1—C81.322 (2)C8—C91.363 (3)
N1—C11.412 (3)C9—C101.421 (3)
N2—C101.142 (3)C9—C111.427 (3)
N3—C111.142 (3)
C8—N1—C1126.95 (16)N2—C10—C9177.4 (2)
O1—C2—C3125.71 (18)N3—C11—C9178.5 (2)
N1—C8—C9124.80 (17)
C8—N1—C1—C2176.26 (17)C1—N1—C8—C9179.68 (17)
C7—O1—C2—C30.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.862.182.584 (3)108
C8—H8A···N3i0.932.423.305 (3)160
Symmetry code: (i) x+2, y+1, z.
 

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