Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047423/ez2100sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047423/ez2100Isup2.hkl |
CCDC reference: 667355
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.051
- wR factor = 0.124
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
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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
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%.
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).
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).
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).
C11H9N3 | F(000) = 384 |
Mr = 183.21 | Dx = 1.266 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1277 reflections |
a = 7.4654 (8) Å | θ = 2.5–22.2° |
b = 13.7051 (18) Å | µ = 0.08 mm−1 |
c = 9.5361 (17) Å | T = 298 K |
β = 99.961 (2)° | Needle, colourless |
V = 961.0 (2) Å3 | 0.40 × 0.35 × 0.11 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1687 independent reflections |
Radiation source: fine-focus sealed tube | 944 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
φ and ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→7 |
Tmin = 0.969, Tmax = 0.991 | k = −12→16 |
4744 measured reflections | l = −11→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-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 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C11H9N3 | V = 961.0 (2) Å3 |
Mr = 183.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.4654 (8) Å | µ = 0.08 mm−1 |
b = 13.7051 (18) Å | T = 298 K |
c = 9.5361 (17) Å | 0.40 × 0.35 × 0.11 mm |
β = 99.961 (2)° |
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 = 0.991 | Rint = 0.053 |
4744 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.16 e Å−3 |
1687 reflections | Δρmin = −0.17 e Å−3 |
127 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2598 (3) | 0.98666 (15) | 0.4529 (3) | 0.0732 (7) | |
N2 | 0.1402 (3) | 0.89557 (17) | 0.0215 (3) | 0.0784 (7) | |
N3 | 0.2430 (3) | 0.53195 (15) | 0.7174 (2) | 0.0798 (7) | |
H3A | 0.2525 | 0.5189 | 0.8066 | 0.096* | |
H3B | 0.2815 | 0.4908 | 0.6613 | 0.096* | |
C1 | 0.2043 (3) | 0.92393 (18) | 0.3799 (3) | 0.0536 (7) | |
C2 | 0.1377 (3) | 0.84685 (16) | 0.2806 (2) | 0.0461 (6) | |
C3 | 0.1375 (3) | 0.87283 (17) | 0.1360 (3) | 0.0553 (7) | |
C4 | 0.0880 (3) | 0.75772 (16) | 0.3203 (2) | 0.0444 (6) | |
C5 | 0.0877 (3) | 0.73249 (16) | 0.4696 (2) | 0.0435 (6) | |
C6 | 0.1566 (3) | 0.64313 (16) | 0.5219 (3) | 0.0499 (6) | |
H6 | 0.1970 | 0.5988 | 0.4604 | 0.060* | |
C7 | 0.1666 (3) | 0.61835 (18) | 0.6645 (3) | 0.0536 (7) | |
C8 | 0.1040 (3) | 0.68524 (19) | 0.7545 (3) | 0.0577 (7) | |
H8 | 0.1115 | 0.6709 | 0.8507 | 0.069* | |
C9 | 0.0308 (3) | 0.7728 (2) | 0.7010 (3) | 0.0592 (7) | |
H9 | −0.0139 | 0.8161 | 0.7616 | 0.071* | |
C10 | 0.0223 (3) | 0.79763 (17) | 0.5605 (3) | 0.0509 (6) | |
H10 | −0.0265 | 0.8573 | 0.5267 | 0.061* | |
C11 | 0.0328 (3) | 0.68186 (16) | 0.2086 (3) | 0.0583 (7) | |
H11A | 0.0460 | 0.7075 | 0.1172 | 0.088* | |
H11B | −0.0918 | 0.6640 | 0.2073 | 0.088* | |
H11C | 0.1088 | 0.6254 | 0.2294 | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0955 (18) | 0.0534 (14) | 0.0705 (17) | −0.0135 (13) | 0.0140 (14) | −0.0121 (13) |
N2 | 0.1029 (19) | 0.0718 (16) | 0.0607 (16) | 0.0024 (14) | 0.0152 (14) | 0.0081 (14) |
N3 | 0.119 (2) | 0.0599 (14) | 0.0606 (15) | 0.0067 (14) | 0.0162 (14) | 0.0154 (13) |
C1 | 0.0626 (18) | 0.0447 (15) | 0.0532 (16) | 0.0020 (13) | 0.0090 (13) | 0.0022 (14) |
C2 | 0.0488 (15) | 0.0424 (14) | 0.0467 (15) | 0.0022 (11) | 0.0072 (12) | 0.0003 (12) |
C3 | 0.0638 (17) | 0.0450 (15) | 0.0570 (17) | −0.0001 (12) | 0.0107 (14) | 0.0013 (14) |
C4 | 0.0399 (13) | 0.0436 (13) | 0.0496 (15) | 0.0053 (11) | 0.0073 (11) | −0.0013 (12) |
C5 | 0.0424 (14) | 0.0403 (13) | 0.0476 (15) | −0.0037 (11) | 0.0074 (11) | −0.0027 (12) |
C6 | 0.0580 (16) | 0.0438 (14) | 0.0487 (15) | −0.0029 (12) | 0.0115 (12) | −0.0002 (13) |
C7 | 0.0541 (16) | 0.0506 (15) | 0.0548 (17) | −0.0081 (13) | 0.0062 (13) | 0.0078 (15) |
C8 | 0.0611 (17) | 0.0674 (18) | 0.0452 (15) | −0.0068 (15) | 0.0113 (13) | 0.0015 (15) |
C9 | 0.0524 (16) | 0.0719 (19) | 0.0561 (18) | −0.0034 (14) | 0.0175 (13) | −0.0129 (15) |
C10 | 0.0471 (15) | 0.0494 (14) | 0.0572 (16) | −0.0003 (12) | 0.0119 (12) | −0.0032 (13) |
C11 | 0.0678 (17) | 0.0506 (15) | 0.0560 (17) | −0.0070 (13) | 0.0089 (13) | −0.0077 (13) |
N1—C1 | 1.138 (3) | C6—C7 | 1.391 (3) |
N2—C3 | 1.139 (3) | C6—H6 | 0.9300 |
N3—C7 | 1.372 (3) | C7—C8 | 1.390 (3) |
N3—H3A | 0.8600 | C8—C9 | 1.379 (3) |
N3—H3B | 0.8600 | C8—H8 | 0.9300 |
C1—C2 | 1.448 (3) | C9—C10 | 1.373 (3) |
C2—C4 | 1.350 (3) | C9—H9 | 0.9300 |
C2—C3 | 1.424 (3) | C10—H10 | 0.9300 |
C4—C5 | 1.466 (3) | C11—H11A | 0.9600 |
C4—C11 | 1.494 (3) | C11—H11B | 0.9600 |
C5—C6 | 1.387 (3) | C11—H11C | 0.9600 |
C5—C10 | 1.391 (3) | ||
C7—N3—H3A | 120.0 | N3—C7—C6 | 121.2 (2) |
C7—N3—H3B | 120.0 | C8—C7—C6 | 118.4 (2) |
H3A—N3—H3B | 120.0 | C9—C8—C7 | 119.9 (2) |
N1—C1—C2 | 176.8 (3) | C9—C8—H8 | 120.0 |
C4—C2—C3 | 122.9 (2) | C7—C8—H8 | 120.0 |
C4—C2—C1 | 123.8 (2) | C10—C9—C8 | 121.7 (2) |
C3—C2—C1 | 113.2 (2) | C10—C9—H9 | 119.2 |
N2—C3—C2 | 178.2 (3) | C8—C9—H9 | 119.2 |
C2—C4—C5 | 122.2 (2) | C9—C10—C5 | 119.2 (2) |
C2—C4—C11 | 119.0 (2) | C9—C10—H10 | 120.4 |
C5—C4—C11 | 118.8 (2) | C5—C10—H10 | 120.4 |
C6—C5—C10 | 119.4 (2) | C4—C11—H11A | 109.5 |
C6—C5—C4 | 119.7 (2) | C4—C11—H11B | 109.5 |
C10—C5—C4 | 120.9 (2) | H11A—C11—H11B | 109.5 |
C5—C6—C7 | 121.4 (2) | C4—C11—H11C | 109.5 |
C5—C6—H6 | 119.3 | H11A—C11—H11C | 109.5 |
C7—C6—H6 | 119.3 | H11B—C11—H11C | 109.5 |
N3—C7—C8 | 120.3 (2) | ||
C3—C2—C4—C5 | −179.5 (2) | C4—C5—C6—C7 | 177.0 (2) |
C1—C2—C4—C5 | 3.5 (3) | C5—C6—C7—N3 | −176.7 (2) |
C3—C2—C4—C11 | 1.0 (3) | C5—C6—C7—C8 | 0.6 (3) |
C1—C2—C4—C11 | −176.0 (2) | N3—C7—C8—C9 | 178.6 (2) |
C2—C4—C5—C6 | −136.5 (2) | C6—C7—C8—C9 | 1.3 (4) |
C11—C4—C5—C6 | 43.0 (3) | C7—C8—C9—C10 | −1.9 (4) |
C2—C4—C5—C10 | 42.3 (3) | C8—C9—C10—C5 | 0.6 (4) |
C11—C4—C5—C10 | −138.2 (2) | C6—C5—C10—C9 | 1.3 (3) |
C10—C5—C6—C7 | −1.9 (3) | C4—C5—C10—C9 | −177.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N1i | 0.86 | 2.35 | 3.209 (3) | 173 |
N3—H3B···N2ii | 0.86 | 2.33 | 3.182 (3) | 170 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H9N3 |
Mr | 183.21 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.4654 (8), 13.7051 (18), 9.5361 (17) |
β (°) | 99.961 (2) |
V (Å3) | 961.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.35 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.969, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4744, 1687, 944 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.124, 1.00 |
No. of reflections | 1687 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N1i | 0.86 | 2.35 | 3.209 (3) | 173.1 |
N3—H3B···N2ii | 0.86 | 2.33 | 3.182 (3) | 170.3 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+1/2. |
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.