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In the title compound, C11H9N3, all bond lengths and angles are normal. The crystal packing is stabilized by inter­molecular N—H...N hydrogen-bond inter­actions involving the H atoms of the amino groups and N atoms of the cyano groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047423/ez2100sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047423/ez2100Isup2.hkl
Contains datablock I

CCDC reference: 667355

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.051
  • wR factor = 0.124
  • Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.45 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C3 ... 1.42 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Knoevenagel condensation of carbonyl compounds with compounds containing an active methylene group is one of the most important methods of preparing substituted alkenes. As a part of our study of benzylidenemalonontriles, which are effective anti-fouling agents, fungicides, cytotoxic agents and insecticides (Freeman, 1980; Bigi et al., 2000), we report here the structure of the title compound, (I), synthesized by Knoevenagel condensation of m-aminoacetophenone with malononitrile.

In (I) (Fig. 1), all bond lengths and angles agree well with those reported for related compounds (Wardell et al., 2006). The amino and cyano groups are involved in intermolecular N—H···N hydrogen bonds (Table 1), which link the molecules into 26-membered rings (Fig. 2). The amino N atom acts as a hydrogen-bond donor to the cyano N atom in a neighbouring molecule, thus forming layers along the bc-plane.

Related literature top

For related literature, see: Bigi et al. (2000).

For related literature, see: Freeman (1980); Wardell et al. (2006).

Experimental top

A mixture of m-aminoacetophenone (15 mmol) and malononitrile (15 mmol) in distilled water (15 ml) was heated to 353 K for 2 h. Upon cooling to room temperature, a crude product crystallized. The precipitate was filtered off, washed with ethanol and recrystallized from ethanol to afford the desired product as a colourless solid. Colourless single crystals of (I) were obtained by slow evaporation of an aqueous ethanol (95%) solution at ambient temperatures after 10 d. Elemental analysis, calculated for C11 H9 N3: C 72.11, H 4.95, N 22.94%; found: C 72.04. H 4.91, N 22.98%.

Refinement top

All hydrogen atoms were geometrically fixed at calculated positions and allowed to ride on their parent atoms with C—H = 0.93–0.96 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N).

Structure description top

Knoevenagel condensation of carbonyl compounds with compounds containing an active methylene group is one of the most important methods of preparing substituted alkenes. As a part of our study of benzylidenemalonontriles, which are effective anti-fouling agents, fungicides, cytotoxic agents and insecticides (Freeman, 1980; Bigi et al., 2000), we report here the structure of the title compound, (I), synthesized by Knoevenagel condensation of m-aminoacetophenone with malononitrile.

In (I) (Fig. 1), all bond lengths and angles agree well with those reported for related compounds (Wardell et al., 2006). The amino and cyano groups are involved in intermolecular N—H···N hydrogen bonds (Table 1), which link the molecules into 26-membered rings (Fig. 2). The amino N atom acts as a hydrogen-bond donor to the cyano N atom in a neighbouring molecule, thus forming layers along the bc-plane.

For related literature, see: Bigi et al. (2000).

For related literature, see: Freeman (1980); Wardell et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000) and DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title complex showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the 26-membered rings formed by N—H···N intermolecular hydrogen-bonds. Hydrogen bonds are shown as dashed lines.
2-[1-(3-Aminophenyl)ethylidene]propanedinitrile top
Crystal data top
C11H9N3F(000) = 384
Mr = 183.21Dx = 1.266 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1277 reflections
a = 7.4654 (8) Åθ = 2.5–22.2°
b = 13.7051 (18) ŵ = 0.08 mm1
c = 9.5361 (17) ÅT = 298 K
β = 99.961 (2)°Needle, colourless
V = 961.0 (2) Å30.40 × 0.35 × 0.11 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1687 independent reflections
Radiation source: fine-focus sealed tube944 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
φ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 87
Tmin = 0.969, Tmax = 0.991k = 1216
4744 measured reflectionsl = 1111
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0469P)2]
where P = (Fo2 + 2Fc2)/3
1687 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C11H9N3V = 961.0 (2) Å3
Mr = 183.21Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.4654 (8) ŵ = 0.08 mm1
b = 13.7051 (18) ÅT = 298 K
c = 9.5361 (17) Å0.40 × 0.35 × 0.11 mm
β = 99.961 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1687 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
944 reflections with I > 2σ(I)
Tmin = 0.969, Tmax = 0.991Rint = 0.053
4744 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.124H-atom parameters constrained
S = 1.00Δρmax = 0.16 e Å3
1687 reflectionsΔρmin = 0.17 e Å3
127 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2598 (3)0.98666 (15)0.4529 (3)0.0732 (7)
N20.1402 (3)0.89557 (17)0.0215 (3)0.0784 (7)
N30.2430 (3)0.53195 (15)0.7174 (2)0.0798 (7)
H3A0.25250.51890.80660.096*
H3B0.28150.49080.66130.096*
C10.2043 (3)0.92393 (18)0.3799 (3)0.0536 (7)
C20.1377 (3)0.84685 (16)0.2806 (2)0.0461 (6)
C30.1375 (3)0.87283 (17)0.1360 (3)0.0553 (7)
C40.0880 (3)0.75772 (16)0.3203 (2)0.0444 (6)
C50.0877 (3)0.73249 (16)0.4696 (2)0.0435 (6)
C60.1566 (3)0.64313 (16)0.5219 (3)0.0499 (6)
H60.19700.59880.46040.060*
C70.1666 (3)0.61835 (18)0.6645 (3)0.0536 (7)
C80.1040 (3)0.68524 (19)0.7545 (3)0.0577 (7)
H80.11150.67090.85070.069*
C90.0308 (3)0.7728 (2)0.7010 (3)0.0592 (7)
H90.01390.81610.76160.071*
C100.0223 (3)0.79763 (17)0.5605 (3)0.0509 (6)
H100.02650.85730.52670.061*
C110.0328 (3)0.68186 (16)0.2086 (3)0.0583 (7)
H11A0.04600.70750.11720.088*
H11B0.09180.66400.20730.088*
H11C0.10880.62540.22940.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0955 (18)0.0534 (14)0.0705 (17)0.0135 (13)0.0140 (14)0.0121 (13)
N20.1029 (19)0.0718 (16)0.0607 (16)0.0024 (14)0.0152 (14)0.0081 (14)
N30.119 (2)0.0599 (14)0.0606 (15)0.0067 (14)0.0162 (14)0.0154 (13)
C10.0626 (18)0.0447 (15)0.0532 (16)0.0020 (13)0.0090 (13)0.0022 (14)
C20.0488 (15)0.0424 (14)0.0467 (15)0.0022 (11)0.0072 (12)0.0003 (12)
C30.0638 (17)0.0450 (15)0.0570 (17)0.0001 (12)0.0107 (14)0.0013 (14)
C40.0399 (13)0.0436 (13)0.0496 (15)0.0053 (11)0.0073 (11)0.0013 (12)
C50.0424 (14)0.0403 (13)0.0476 (15)0.0037 (11)0.0074 (11)0.0027 (12)
C60.0580 (16)0.0438 (14)0.0487 (15)0.0029 (12)0.0115 (12)0.0002 (13)
C70.0541 (16)0.0506 (15)0.0548 (17)0.0081 (13)0.0062 (13)0.0078 (15)
C80.0611 (17)0.0674 (18)0.0452 (15)0.0068 (15)0.0113 (13)0.0015 (15)
C90.0524 (16)0.0719 (19)0.0561 (18)0.0034 (14)0.0175 (13)0.0129 (15)
C100.0471 (15)0.0494 (14)0.0572 (16)0.0003 (12)0.0119 (12)0.0032 (13)
C110.0678 (17)0.0506 (15)0.0560 (17)0.0070 (13)0.0089 (13)0.0077 (13)
Geometric parameters (Å, º) top
N1—C11.138 (3)C6—C71.391 (3)
N2—C31.139 (3)C6—H60.9300
N3—C71.372 (3)C7—C81.390 (3)
N3—H3A0.8600C8—C91.379 (3)
N3—H3B0.8600C8—H80.9300
C1—C21.448 (3)C9—C101.373 (3)
C2—C41.350 (3)C9—H90.9300
C2—C31.424 (3)C10—H100.9300
C4—C51.466 (3)C11—H11A0.9600
C4—C111.494 (3)C11—H11B0.9600
C5—C61.387 (3)C11—H11C0.9600
C5—C101.391 (3)
C7—N3—H3A120.0N3—C7—C6121.2 (2)
C7—N3—H3B120.0C8—C7—C6118.4 (2)
H3A—N3—H3B120.0C9—C8—C7119.9 (2)
N1—C1—C2176.8 (3)C9—C8—H8120.0
C4—C2—C3122.9 (2)C7—C8—H8120.0
C4—C2—C1123.8 (2)C10—C9—C8121.7 (2)
C3—C2—C1113.2 (2)C10—C9—H9119.2
N2—C3—C2178.2 (3)C8—C9—H9119.2
C2—C4—C5122.2 (2)C9—C10—C5119.2 (2)
C2—C4—C11119.0 (2)C9—C10—H10120.4
C5—C4—C11118.8 (2)C5—C10—H10120.4
C6—C5—C10119.4 (2)C4—C11—H11A109.5
C6—C5—C4119.7 (2)C4—C11—H11B109.5
C10—C5—C4120.9 (2)H11A—C11—H11B109.5
C5—C6—C7121.4 (2)C4—C11—H11C109.5
C5—C6—H6119.3H11A—C11—H11C109.5
C7—C6—H6119.3H11B—C11—H11C109.5
N3—C7—C8120.3 (2)
C3—C2—C4—C5179.5 (2)C4—C5—C6—C7177.0 (2)
C1—C2—C4—C53.5 (3)C5—C6—C7—N3176.7 (2)
C3—C2—C4—C111.0 (3)C5—C6—C7—C80.6 (3)
C1—C2—C4—C11176.0 (2)N3—C7—C8—C9178.6 (2)
C2—C4—C5—C6136.5 (2)C6—C7—C8—C91.3 (4)
C11—C4—C5—C643.0 (3)C7—C8—C9—C101.9 (4)
C2—C4—C5—C1042.3 (3)C8—C9—C10—C50.6 (4)
C11—C4—C5—C10138.2 (2)C6—C5—C10—C91.3 (3)
C10—C5—C6—C71.9 (3)C4—C5—C10—C9177.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N1i0.862.353.209 (3)173
N3—H3B···N2ii0.862.333.182 (3)170
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC11H9N3
Mr183.21
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)7.4654 (8), 13.7051 (18), 9.5361 (17)
β (°) 99.961 (2)
V3)961.0 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.40 × 0.35 × 0.11
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.969, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
4744, 1687, 944
Rint0.053
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.124, 1.00
No. of reflections1687
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000) and DIAMOND (Brandenburg, 2004), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N1i0.862.353.209 (3)173.1
N3—H3B···N2ii0.862.333.182 (3)170.3
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
 

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