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In the title compounds, C13H15N3O, (I), and C13H15N3O2, (II), the dihedral angles between the planes of the phenyl ring and the amide group are 4.1 (1) and 20.7 (1)°, respectively. The molecules adopt a fully extended conformation, aided by intramolecular interactions. The molecular structures of (I) and (II) display different crystal packing and hydrogen-bonding networks.
Supporting information
CCDC references: 192317; 192320
Substituted N-aryl cyano acetamide (0.005 mol) was dissolved in dimethyl formamide (6 ml) and kept in ice-cold conditions. To this solution, POCl3 (1.4 ml, 0.015 mol) was added slowly with stirring. The reaction mixture was allowed to attain room temperature and stirred for 3–4 h. The residue was then poured into crushed ice and neutralized with 10% NaOH. The crude product obtained was filtered, washed with water and dried. Finally, the compound was purified by recrystallization using an ethylacetate–petroleum mixture. [m.p. 445 and 425 K for (I) and (II), respectively.]
All H atoms were fixed geometrically and allowed to ride on the corresponding non-H atoms.
For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(I) 2-Cyano-3-dimethylamino-
N-(4-methylphenyl) acrylamide
top
Crystal data top
C13H15N3O | F(000) = 488 |
Mr = 229.28 | Dx = 1.226 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5846 (3) Å | Cell parameters from 4951 reflections |
b = 22.4477 (10) Å | θ = 1.8–28.3° |
c = 7.5989 (3) Å | µ = 0.08 mm−1 |
β = 106.306 (1)° | T = 293 K |
V = 1241.72 (9) Å3 | Slab, pale yellow |
Z = 4 | 0.48 × 0.40 × 0.16 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 2242 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 28.3°, θmin = 1.8° |
ω scans | h = −10→8 |
8417 measured reflections | k = −29→27 |
3022 independent reflections | l = −10→8 |
Refinement top
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0849P)2 + 0.2309P] where P = (Fo2 + 2Fc2)/3 |
3022 reflections | (Δ/σ)max < 0.001 |
157 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C13H15N3O | V = 1241.72 (9) Å3 |
Mr = 229.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5846 (3) Å | µ = 0.08 mm−1 |
b = 22.4477 (10) Å | T = 293 K |
c = 7.5989 (3) Å | 0.48 × 0.40 × 0.16 mm |
β = 106.306 (1)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 2242 reflections with I > 2σ(I) |
8417 measured reflections | Rint = 0.037 |
3022 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
3022 reflections | Δρmin = −0.15 e Å−3 |
157 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 | x | y | z | Uiso*/Ueq | |
C1 | 1.0150 (2) | 0.12001 (7) | 0.3809 (2) | 0.0450 (4) | |
C2 | 1.1069 (3) | 0.07426 (8) | 0.4941 (3) | 0.0568 (4) | |
H2 | 1.1120 | 0.0365 | 0.4453 | 0.068* | |
C3 | 1.1906 (3) | 0.08434 (9) | 0.6780 (3) | 0.0611 (5) | |
H3 | 1.2513 | 0.0532 | 0.7508 | 0.073* | |
C4 | 1.1860 (2) | 0.13988 (8) | 0.7565 (2) | 0.0543 (4) | |
C5 | 1.0939 (3) | 0.18476 (8) | 0.6426 (3) | 0.0575 (4) | |
H5 | 1.0890 | 0.2224 | 0.6919 | 0.069* | |
C6 | 1.0085 (2) | 0.17584 (8) | 0.4579 (2) | 0.0532 (4) | |
H6 | 0.9471 | 0.2071 | 0.3858 | 0.064* | |
N7 | 0.93245 (19) | 0.10564 (6) | 0.19459 (19) | 0.0506 (4) | |
H7 | 0.9520 | 0.0701 | 0.1620 | 0.061* | |
C8 | 0.8259 (2) | 0.14088 (7) | 0.0601 (2) | 0.0475 (4) | |
O9 | 0.7881 (2) | 0.19256 (6) | 0.08790 (19) | 0.0715 (4) | |
C10 | 0.7555 (2) | 0.11279 (7) | −0.1227 (2) | 0.0461 (4) | |
C11 | 0.7769 (3) | 0.05031 (8) | −0.1381 (2) | 0.0565 (4) | |
N12 | 0.7977 (3) | −0.00029 (8) | −0.1408 (3) | 0.0860 (6) | |
C13 | 0.6724 (2) | 0.15030 (7) | −0.2654 (2) | 0.0473 (4) | |
H13 | 0.6702 | 0.1900 | −0.2312 | 0.057* | |
N14 | 0.59520 (19) | 0.14039 (6) | −0.44143 (19) | 0.0499 (4) | |
C15 | 0.5150 (3) | 0.18950 (9) | −0.5640 (3) | 0.0656 (5) | |
H15A | 0.5386 | 0.2264 | −0.4976 | 0.098* | |
H15B | 0.3848 | 0.1836 | −0.6107 | 0.098* | |
H15C | 0.5689 | 0.1907 | −0.6641 | 0.098* | |
C16 | 0.5832 (3) | 0.08205 (9) | −0.5273 (3) | 0.0656 (5) | |
H16A | 0.7036 | 0.0693 | −0.5288 | 0.098* | |
H16B | 0.5049 | 0.0844 | −0.6507 | 0.098* | |
H16C | 0.5331 | 0.0540 | −0.4590 | 0.098* | |
C17 | 1.2781 (3) | 0.15063 (11) | 0.9576 (3) | 0.0713 (6) | |
H17A | 1.4035 | 0.1622 | 0.9739 | 0.107* | |
H17B | 1.2745 | 0.1148 | 1.0253 | 0.107* | |
H17C | 1.2147 | 0.1818 | 1.0015 | 0.107* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0454 (8) | 0.0449 (8) | 0.0447 (9) | −0.0026 (6) | 0.0127 (6) | −0.0019 (6) |
C2 | 0.0666 (11) | 0.0461 (9) | 0.0536 (10) | 0.0036 (8) | 0.0101 (8) | −0.0017 (7) |
C3 | 0.0664 (11) | 0.0617 (11) | 0.0510 (10) | 0.0052 (9) | 0.0094 (8) | 0.0067 (8) |
C4 | 0.0508 (9) | 0.0664 (11) | 0.0460 (9) | −0.0104 (8) | 0.0140 (7) | −0.0036 (8) |
C5 | 0.0670 (11) | 0.0532 (10) | 0.0521 (10) | −0.0052 (8) | 0.0163 (8) | −0.0098 (8) |
C6 | 0.0601 (10) | 0.0460 (9) | 0.0513 (9) | 0.0004 (7) | 0.0120 (8) | −0.0020 (7) |
N7 | 0.0606 (8) | 0.0417 (7) | 0.0457 (8) | 0.0052 (6) | 0.0086 (6) | −0.0038 (6) |
C8 | 0.0486 (8) | 0.0430 (8) | 0.0489 (9) | 0.0007 (6) | 0.0104 (7) | −0.0026 (7) |
O9 | 0.0930 (10) | 0.0484 (7) | 0.0575 (8) | 0.0185 (6) | −0.0043 (7) | −0.0096 (6) |
C10 | 0.0474 (8) | 0.0413 (8) | 0.0481 (9) | −0.0002 (6) | 0.0111 (7) | −0.0035 (6) |
C11 | 0.0661 (11) | 0.0479 (9) | 0.0487 (9) | 0.0038 (8) | 0.0051 (8) | −0.0052 (7) |
N12 | 0.1270 (17) | 0.0518 (10) | 0.0645 (11) | 0.0132 (10) | 0.0026 (11) | −0.0068 (8) |
C13 | 0.0472 (8) | 0.0436 (8) | 0.0488 (9) | −0.0030 (6) | 0.0095 (7) | −0.0040 (7) |
N14 | 0.0512 (8) | 0.0475 (7) | 0.0470 (8) | −0.0036 (6) | 0.0075 (6) | −0.0023 (6) |
C15 | 0.0744 (12) | 0.0572 (11) | 0.0552 (11) | −0.0030 (9) | 0.0017 (9) | 0.0055 (9) |
C16 | 0.0754 (13) | 0.0580 (11) | 0.0566 (11) | −0.0008 (9) | 0.0075 (9) | −0.0120 (8) |
C17 | 0.0735 (13) | 0.0897 (15) | 0.0473 (10) | −0.0133 (11) | 0.0114 (9) | −0.0043 (10) |
Geometric parameters (Å, º) top
C1—C6 | 1.390 (2) | C10—C13 | 1.378 (2) |
C1—C2 | 1.394 (2) | C10—C11 | 1.420 (2) |
C1—N7 | 1.415 (2) | C11—N12 | 1.148 (2) |
C2—C3 | 1.381 (3) | C13—N14 | 1.320 (2) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.387 (3) | N14—C16 | 1.455 (2) |
C3—H3 | 0.9300 | N14—C15 | 1.461 (2) |
C4—C5 | 1.383 (3) | C15—H15A | 0.9600 |
C4—C17 | 1.511 (3) | C15—H15B | 0.9600 |
C5—C6 | 1.385 (3) | C15—H15C | 0.9600 |
C5—H5 | 0.9300 | C16—H16A | 0.9600 |
C6—H6 | 0.9300 | C16—H16B | 0.9600 |
N7—C8 | 1.364 (2) | C16—H16C | 0.9600 |
N7—H7 | 0.8600 | C17—H17A | 0.9600 |
C8—O9 | 1.228 (2) | C17—H17B | 0.9600 |
C8—C10 | 1.482 (2) | C17—H17C | 0.9600 |
| | | |
C6—C1—C2 | 118.4 (2) | C11—C10—C8 | 118.6 (2) |
C6—C1—N7 | 124.6 (2) | N12—C11—C10 | 176.4 (2) |
C2—C1—N7 | 117.0 (1) | N14—C13—C10 | 132.0 (2) |
C3—C2—C1 | 120.8 (2) | N14—C13—H13 | 114.0 |
C3—C2—H2 | 119.6 | C10—C13—H13 | 114.0 |
C1—C2—H2 | 119.6 | C13—N14—C16 | 124.1 (2) |
C2—C3—C4 | 121.5 (2) | C13—N14—C15 | 120.4 (2) |
C2—C3—H3 | 119.2 | C16—N14—C15 | 115.5 (2) |
C4—C3—H3 | 119.2 | N14—C15—H15A | 109.5 |
C5—C4—C3 | 117.0 (2) | N14—C15—H15B | 109.5 |
C5—C4—C17 | 121.7 (2) | H15A—C15—H15B | 109.5 |
C3—C4—C17 | 121.3 (2) | N14—C15—H15C | 109.5 |
C4—C5—C6 | 122.6 (2) | H15A—C15—H15C | 109.5 |
C4—C5—H5 | 118.7 | H15B—C15—H15C | 109.5 |
C6—C5—H5 | 118.7 | N14—C16—H16A | 109.5 |
C5—C6—C1 | 119.7 (2) | N14—C16—H16B | 109.5 |
C5—C6—H6 | 120.2 | H16A—C16—H16B | 109.5 |
C1—C6—H6 | 120.2 | N14—C16—H16C | 109.5 |
C8—N7—C1 | 128.4 (1) | H16A—C16—H16C | 109.5 |
C8—N7—H7 | 115.8 | H16B—C16—H16C | 109.5 |
C1—N7—H7 | 115.8 | C4—C17—H17A | 109.5 |
O9—C8—N7 | 122.5 (2) | C4—C17—H17B | 109.5 |
O9—C8—C10 | 121.6 (2) | H17A—C17—H17B | 109.5 |
N7—C8—C10 | 116.0 (1) | C4—C17—H17C | 109.5 |
C13—C10—C11 | 125.2 (2) | H17A—C17—H17C | 109.5 |
C13—C10—C8 | 116.3 (1) | H17B—C17—H17C | 109.5 |
| | | |
C6—C1—C2—C3 | −0.5 (3) | C1—N7—C8—O9 | 0.3 (3) |
N7—C1—C2—C3 | −179.7 (2) | C1—N7—C8—C10 | −178.9 (1) |
C1—C2—C3—C4 | 0.1 (3) | O9—C8—C10—C13 | 10.6 (2) |
C2—C3—C4—C5 | 0.0 (3) | N7—C8—C10—C13 | −170.2 (1) |
C2—C3—C4—C17 | −179.9 (2) | O9—C8—C10—C11 | −169.1 (2) |
C3—C4—C5—C6 | 0.1 (3) | N7—C8—C10—C11 | 10.1 (2) |
C17—C4—C5—C6 | −180.0 (2) | C13—C10—C11—N12 | −174 (4) |
C4—C5—C6—C1 | −0.4 (3) | C8—C10—C11—N12 | 6 (4) |
C2—C1—C6—C5 | 0.6 (3) | C11—C10—C13—N14 | 0.1 (3) |
N7—C1—C6—C5 | 179.7 (2) | C8—C10—C13—N14 | −179.5 (2) |
C6—C1—N7—C8 | −3.7 (3) | C10—C13—N14—C16 | −0.5 (3) |
C2—C1—N7—C8 | 175.4 (2) | C10—C13—N14—C15 | 179.6 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O9 | 0.93 | 2.27 | 2.864 (2) | 121 |
C13—H13···O9 | 0.93 | 2.34 | 2.748 (2) | 106 |
N7—H7···N12i | 0.86 | 2.50 | 3.228 (2) | 143 |
C15—H15A···O9ii | 0.96 | 2.57 | 3.360 (2) | 139 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x, −y+1/2, z−1/2. |
(II) 2-cyano-3-dimethylamino-
N-(2-methoxyphenyl) acrylamide
top
Crystal data top
C13H15N3O2 | F(000) = 520 |
Mr = 245.28 | Dx = 1.221 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5141 (3) Å | Cell parameters from 5915 reflections |
b = 12.7580 (6) Å | θ = 2.2–28.3° |
c = 13.9381 (6) Å | µ = 0.09 mm−1 |
β = 92.795 (1)° | T = 293 K |
V = 1334.58 (10) Å3 | Block, pale yellow |
Z = 4 | 0.48 × 0.46 × 0.42 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 2425 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 28.3°, θmin = 2.2° |
ω scans | h = −9→9 |
9025 measured reflections | k = −16→16 |
3278 independent reflections | l = −12→18 |
Refinement top
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0825P)2 + 0.0796P] where P = (Fo2 + 2Fc2)/3 |
3278 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
Crystal data top
C13H15N3O2 | V = 1334.58 (10) Å3 |
Mr = 245.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5141 (3) Å | µ = 0.09 mm−1 |
b = 12.7580 (6) Å | T = 293 K |
c = 13.9381 (6) Å | 0.48 × 0.46 × 0.42 mm |
β = 92.795 (1)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 2425 reflections with I > 2σ(I) |
9025 measured reflections | Rint = 0.041 |
3278 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.19 e Å−3 |
3278 reflections | Δρmin = −0.14 e Å−3 |
166 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 | x | y | z | Uiso*/Ueq | |
C1 | 0.32342 (17) | 0.33713 (10) | 0.59837 (10) | 0.0514 (3) | |
C2 | 0.31085 (17) | 0.44491 (10) | 0.57594 (11) | 0.0542 (3) | |
C3 | 0.3823 (2) | 0.51814 (12) | 0.64002 (13) | 0.0686 (4) | |
H3 | 0.3737 | 0.5893 | 0.6259 | 0.082* | |
C4 | 0.4662 (2) | 0.48520 (14) | 0.72487 (14) | 0.0786 (5) | |
H4 | 0.5155 | 0.5347 | 0.7674 | 0.094* | |
C5 | 0.4784 (2) | 0.38067 (15) | 0.74779 (13) | 0.0762 (5) | |
H5 | 0.5351 | 0.3598 | 0.8054 | 0.091* | |
C6 | 0.4055 (2) | 0.30611 (12) | 0.68437 (11) | 0.0645 (4) | |
H6 | 0.4122 | 0.2353 | 0.7000 | 0.077* | |
N7 | 0.24551 (16) | 0.26844 (8) | 0.52943 (8) | 0.0566 (3) | |
H7 | 0.1688 | 0.2959 | 0.4891 | 0.068* | |
C8 | 0.27600 (17) | 0.16353 (9) | 0.51832 (9) | 0.0492 (3) | |
O9 | 0.38642 (16) | 0.11575 (8) | 0.56936 (8) | 0.0743 (4) | |
C10 | 0.16552 (17) | 0.11172 (9) | 0.44245 (9) | 0.0471 (3) | |
C11 | 0.0296 (2) | 0.17190 (10) | 0.39442 (11) | 0.0639 (4) | |
N12 | −0.0784 (3) | 0.22659 (12) | 0.36191 (14) | 0.1057 (7) | |
C13 | 0.19887 (17) | 0.00661 (9) | 0.42685 (9) | 0.0476 (3) | |
H13 | 0.2888 | −0.0219 | 0.4670 | 0.057* | |
N14 | 0.12454 (15) | −0.05982 (8) | 0.36472 (8) | 0.0521 (3) | |
C15 | 0.1804 (2) | −0.16950 (10) | 0.36508 (13) | 0.0671 (4) | |
H15A | 0.2757 | −0.1794 | 0.4126 | 0.101* | |
H15B | 0.2207 | −0.1878 | 0.3029 | 0.101* | |
H15C | 0.0816 | −0.2133 | 0.3799 | 0.101* | |
C16 | −0.0130 (2) | −0.03100 (13) | 0.29272 (13) | 0.0745 (5) | |
H16A | −0.1197 | −0.0123 | 0.3238 | 0.112* | |
H16B | −0.0370 | −0.0893 | 0.2505 | 0.112* | |
H16C | 0.0268 | 0.0276 | 0.2563 | 0.112* | |
O17 | 0.22428 (14) | 0.46702 (7) | 0.48990 (8) | 0.0645 (3) | |
C18 | 0.2047 (2) | 0.57396 (11) | 0.46233 (14) | 0.0724 (5) | |
H18A | 0.1467 | 0.6118 | 0.5115 | 0.109* | |
H18B | 0.1342 | 0.5783 | 0.4032 | 0.109* | |
H18C | 0.3201 | 0.6039 | 0.4537 | 0.109* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0465 (7) | 0.0457 (6) | 0.0620 (7) | 0.0014 (5) | 0.0036 (5) | −0.0108 (5) |
C2 | 0.0442 (7) | 0.0436 (6) | 0.0753 (9) | 0.0007 (5) | 0.0089 (6) | −0.0125 (6) |
C3 | 0.0609 (9) | 0.0505 (8) | 0.0946 (12) | −0.0020 (6) | 0.0049 (8) | −0.0247 (7) |
C4 | 0.0679 (10) | 0.0749 (11) | 0.0926 (12) | −0.0002 (8) | −0.0004 (9) | −0.0392 (9) |
C5 | 0.0696 (10) | 0.0911 (12) | 0.0671 (9) | 0.0083 (8) | −0.0058 (8) | −0.0230 (8) |
C6 | 0.0660 (9) | 0.0611 (8) | 0.0660 (9) | 0.0059 (7) | −0.0010 (7) | −0.0100 (7) |
N7 | 0.0639 (7) | 0.0383 (5) | 0.0660 (7) | 0.0039 (5) | −0.0128 (5) | −0.0045 (5) |
C8 | 0.0531 (7) | 0.0395 (6) | 0.0544 (7) | 0.0044 (5) | −0.0024 (5) | 0.0001 (5) |
O9 | 0.0849 (8) | 0.0514 (5) | 0.0830 (7) | 0.0174 (5) | −0.0334 (6) | −0.0094 (5) |
C10 | 0.0536 (7) | 0.0380 (5) | 0.0495 (6) | 0.0035 (5) | −0.0016 (5) | 0.0014 (4) |
C11 | 0.0839 (10) | 0.0435 (7) | 0.0620 (8) | 0.0099 (6) | −0.0207 (7) | −0.0050 (6) |
N12 | 0.1331 (15) | 0.0691 (9) | 0.1086 (12) | 0.0380 (9) | −0.0599 (11) | −0.0161 (8) |
C13 | 0.0520 (7) | 0.0403 (6) | 0.0503 (6) | 0.0022 (5) | 0.0001 (5) | 0.0019 (5) |
N14 | 0.0573 (6) | 0.0398 (5) | 0.0588 (6) | 0.0007 (4) | −0.0010 (5) | −0.0039 (4) |
C15 | 0.0752 (10) | 0.0398 (7) | 0.0858 (10) | 0.0011 (6) | −0.0020 (8) | −0.0093 (6) |
C16 | 0.0795 (11) | 0.0659 (9) | 0.0757 (10) | 0.0080 (8) | −0.0216 (8) | −0.0143 (8) |
O17 | 0.0706 (6) | 0.0385 (5) | 0.0837 (7) | 0.0012 (4) | −0.0037 (5) | −0.0012 (4) |
C18 | 0.0725 (10) | 0.0397 (7) | 0.1056 (13) | 0.0046 (6) | 0.0093 (9) | 0.0032 (7) |
Geometric parameters (Å, º) top
C1—C6 | 1.379 (2) | C10—C11 | 1.419 (2) |
C1—N7 | 1.407 (2) | C11—N12 | 1.147 (2) |
C1—C2 | 1.412 (2) | C13—N14 | 1.316 (2) |
C2—O17 | 1.366 (2) | C13—H13 | 0.9300 |
C2—C3 | 1.383 (2) | N14—C16 | 1.452 (2) |
C3—C4 | 1.379 (3) | N14—C15 | 1.461 (2) |
C3—H3 | 0.9300 | C15—H15A | 0.9600 |
C4—C5 | 1.373 (3) | C15—H15B | 0.9600 |
C4—H4 | 0.9300 | C15—H15C | 0.9600 |
C5—C6 | 1.392 (2) | C16—H16A | 0.9600 |
C5—H5 | 0.9300 | C16—H16B | 0.9600 |
C6—H6 | 0.9300 | C16—H16C | 0.9600 |
N7—C8 | 1.368 (2) | O17—C18 | 1.423 (2) |
N7—H7 | 0.8600 | C18—H18A | 0.9600 |
C8—O9 | 1.228 (2) | C18—H18B | 0.9600 |
C8—C10 | 1.469 (2) | C18—H18C | 0.9600 |
C10—C13 | 1.383 (2) | | |
| | | |
C6—C1—N7 | 124.6 (1) | N12—C11—C10 | 174.1 (2) |
C6—C1—C2 | 119.6 (1) | N14—C13—C10 | 130.8 (1) |
N7—C1—C2 | 115.7 (1) | N14—C13—H13 | 114.6 |
O17—C2—C3 | 125.5 (1) | C10—C13—H13 | 114.6 |
O17—C2—C1 | 114.8 (1) | C13—N14—C16 | 123.8 (1) |
C3—C2—C1 | 119.7 (2) | C13—N14—C15 | 120.1 (1) |
C4—C3—C2 | 119.7 (2) | C16—N14—C15 | 116.1 (1) |
C4—C3—H3 | 120.2 | N14—C15—H15A | 109.5 |
C2—C3—H3 | 120.2 | N14—C15—H15B | 109.5 |
C5—C4—C3 | 121.2 (2) | H15A—C15—H15B | 109.5 |
C5—C4—H4 | 119.4 | N14—C15—H15C | 109.5 |
C3—C4—H4 | 119.4 | H15A—C15—H15C | 109.5 |
C4—C5—C6 | 119.7 (2) | H15B—C15—H15C | 109.5 |
C4—C5—H5 | 120.1 | N14—C16—H16A | 109.5 |
C6—C5—H5 | 120.1 | N14—C16—H16B | 109.5 |
C1—C6—C5 | 120.1 (2) | H16A—C16—H16B | 109.5 |
C1—C6—H6 | 120.0 | N14—C16—H16C | 109.5 |
C5—C6—H6 | 120.0 | H16A—C16—H16C | 109.5 |
C8—N7—C1 | 128.4 (1) | H16B—C16—H16C | 109.5 |
C8—N7—H7 | 115.8 | C2—O17—C18 | 118.3 (1) |
C1—N7—H7 | 115.8 | O17—C18—H18A | 109.5 |
O9—C8—N7 | 122.2 (1) | O17—C18—H18B | 109.5 |
O9—C8—C10 | 122.4 (1) | H18A—C18—H18B | 109.5 |
N7—C8—C10 | 115.5 (1) | O17—C18—H18C | 109.5 |
C13—C10—C11 | 125.6 (1) | H18A—C18—H18C | 109.5 |
C13—C10—C8 | 116.7 (1) | H18B—C18—H18C | 109.5 |
C11—C10—C8 | 117.7 (1) | | |
| | | |
C6—C1—C2—O17 | −178.9 (1) | C1—N7—C8—C10 | 176.6 (1) |
N7—C1—C2—O17 | −0.0 (2) | O9—C8—C10—C13 | −3.8 (2) |
C6—C1—C2—C3 | 0.5 (2) | N7—C8—C10—C13 | 177.3 (1) |
N7—C1—C2—C3 | 179.4 (1) | O9—C8—C10—C11 | 173.6 (2) |
O17—C2—C3—C4 | 179.8 (1) | N7—C8—C10—C11 | −5.3 (2) |
C1—C2—C3—C4 | 0.5 (2) | C13—C10—C11—N12 | 162 (2) |
C2—C3—C4—C5 | −0.9 (2) | C8—C10—C11—N12 | −15 (2) |
C3—C4—C5—C6 | 0.2 (3) | C11—C10—C13—N14 | 3.4 (2) |
N7—C1—C6—C5 | −179.9 (1) | C8—C10—C13—N14 | −179.4 (1) |
C2—C1—C6—C5 | −1.2 (2) | C10—C13—N14—C16 | 2.7 (2) |
C4—C5—C6—C1 | 0.8 (2) | C10—C13—N14—C15 | −177.8 (1) |
C6—C1—N7—C8 | −20.2 (2) | C3—C2—O17—C18 | 0.1 (2) |
C2—C1—N7—C8 | 161.0 (1) | C1—C2—O17—C18 | 179.5 (1) |
C1—N7—C8—O9 | −2.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O9 | 0.93 | 2.38 | 2.910 (2) | 116 |
C13—H13···O9 | 0.93 | 2.36 | 2.756 (2) | 106 |
N7—H7···O17 | 0.86 | 2.22 | 2.596 (1) | 106 |
C4—H4···O9i | 0.93 | 2.57 | 3.452 (2) | 158 |
C18—H18C···Cgii | 0.96 | 2.75 | 3.551 (1) | 141 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C13H15N3O | C13H15N3O2 |
Mr | 229.28 | 245.28 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.5846 (3), 22.4477 (10), 7.5989 (3) | 7.5141 (3), 12.7580 (6), 13.9381 (6) |
β (°) | 106.306 (1) | 92.795 (1) |
V (Å3) | 1241.72 (9) | 1334.58 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.09 |
Crystal size (mm) | 0.48 × 0.40 × 0.16 | 0.48 × 0.46 × 0.42 |
|
Data collection |
Diffractometer | Siemens SMART CCD area detector diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8417, 3022, 2242 | 9025, 3278, 2425 |
Rint | 0.037 | 0.041 |
(sin θ/λ)max (Å−1) | 0.666 | 0.666 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.169, 1.04 | 0.048, 0.152, 1.05 |
No. of reflections | 3022 | 3278 |
No. of parameters | 157 | 166 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.15 | 0.19, −0.14 |
Selected geometric parameters (Å, º) for (I) topC1—N7 | 1.415 (2) | C10—C13 | 1.378 (2) |
C4—C17 | 1.511 (3) | C10—C11 | 1.420 (2) |
N7—C8 | 1.364 (2) | C11—N12 | 1.148 (2) |
C8—O9 | 1.228 (2) | C13—N14 | 1.320 (2) |
| | | |
C6—C1—N7 | 124.6 (2) | N14—C13—C10 | 132.0 (2) |
C2—C1—N7 | 117.0 (1) | C13—N14—C16 | 124.1 (2) |
C8—N7—C1 | 128.4 (1) | C13—N14—C15 | 120.4 (2) |
O9—C8—N7 | 122.5 (2) | C16—N14—C15 | 115.5 (2) |
| | | |
C6—C1—N7—C8 | −3.7 (3) | N7—C8—C10—C13 | −170.2 (1) |
C1—N7—C8—C10 | −178.9 (1) | C11—C10—C13—N14 | 0.1 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O9 | 0.93 | 2.27 | 2.864 (2) | 121 |
C13—H13···O9 | 0.93 | 2.34 | 2.748 (2) | 106 |
N7—H7···N12i | 0.86 | 2.50 | 3.228 (2) | 143 |
C15—H15A···O9ii | 0.96 | 2.57 | 3.360 (2) | 139 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x, −y+1/2, z−1/2. |
Selected geometric parameters (Å, º) for (II) topC1—N7 | 1.407 (2) | C10—C11 | 1.419 (2) |
N7—C8 | 1.368 (2) | C11—N12 | 1.147 (2) |
C8—O9 | 1.228 (2) | C13—N14 | 1.316 (2) |
C10—C13 | 1.383 (2) | | |
| | | |
C6—C1—N7 | 124.6 (1) | N14—C13—C10 | 130.8 (1) |
N7—C1—C2 | 115.7 (1) | C13—N14—C16 | 123.8 (1) |
C8—N7—C1 | 128.4 (1) | C13—N14—C15 | 120.1 (1) |
O9—C8—N7 | 122.2 (1) | C16—N14—C15 | 116.1 (1) |
| | | |
C6—C1—N7—C8 | −20.2 (2) | C11—C10—C13—N14 | 3.4 (2) |
C1—N7—C8—C10 | 176.6 (1) | C1—C2—O17—C18 | 179.5 (1) |
N7—C8—C10—C13 | 177.3 (1) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O9 | 0.93 | 2.38 | 2.910 (2) | 116 |
C13—H13···O9 | 0.93 | 2.36 | 2.756 (2) | 106 |
N7—H7···O17 | 0.86 | 2.22 | 2.596 (1) | 106 |
C4—H4···O9i | 0.93 | 2.57 | 3.452 (2) | 158 |
C18—H18C···Cgii | 0.96 | 2.75 | 3.551 (1) | 141 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1. |
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As part of our study of conformational analysis, crystallographic work on N-aromatic amide derivatives has been undertaken. These derivatives are analogs of the active metabolites of the immunosuppressive drug leflunomide, which are known to act, in part, by inhibiting the tyrosine kinase epidermal growth-factor receptor (EGFR; Mattar et al., 1993). EGFR is a membrane- associated tyrosine kinase, which serves as an endogenous negative regulator of apoptosis in breast cancer cells (Uckun et al., 1998). The present study reports the structures of two N-acrylamide compounds, (I) and (II), in order to examine the effects of substituents on the hydrogen-bonding system and on the crystal structure.
The dihedral angle between the planes of the phenyl ring and the amide group is 4.1 (1) and 20.7 (1)° for (I) and (II), respectively. The geometry of the amide group is comparable to that of silimar groups in acetanilides (Haisa et al., 1977). The C10—C11 [1.420 (2) Å in (I) and 1.419 (2) Å in (II)] and C11—N12 [1.148 (2) Å in (I) and 1.147 (2) Å in (II)] bond lengths agree with the expected Csp2—Csp [1.431 (14) Å] and Csp1—N(1) [1.136 (10) Å] bond lengths, respectively (Allen et al., 1987). Similar observations have been noted in the crystal structures of the leflunomide metabolite analogs (Ghosh et al., 1999; Ghosh & Uckun, 1999) and in the acrylamide derivative (Ompraba et al., 2003). In (II), the C2—O17—C18 [118.3 (1)°] angle is close to that expected for sp2 hybridization of atom O17. The distortion and enlargement of the C6—C1—N7, C1—N7—C8 and N7—C8—O9 angles from the trigonal value (120°) are due to the intramolecular C6—H6···O9 hydrogen bond (Table 2 and 4). In both (I) and (II), the cyanoacrylamide side chain is planar, with π-conjugation along the chain causing variations of the bond distances with respect to the localized double and single bonds. The C1—N7—C8—C10 torsion angle does not differ much between (I) and (II) [−178.9 (1) and 176.6 (1)°, respectively], whereas the C6—C1—N7—C8 angle differs significantly [−3.7 (3) and −20.2 (2), respectively], indicating that the large twist around the C1—N7 bond in (II) is due to an intramolecular N7—H7···O17 hydrogen bond. This hydrogen bond determines the orientation of the methoxy group [C1—C2—O17—C18 = 179.5 (1)°], which is coplanar with the phenyl ring.
The supramolecular structures of (I) and (II) are completely different. In (I), the symmetry-related molecules are linked together head-to-tail via N7—H7··· N12 hydrogen bonds to form a dimer comprising an R22(12) ring (Bernstein et al., 1995). The dimers at (x, 1/2 − y, 1/2 + z), (2 − x, 1/2 + y, 1/2 − z) [centre of symmetry at (1, 1/2, 1/2)], and (x, 1/2 − y, −1/2 + z), (2 − x, 1/2 + y, −1/2 − z) [centre of symmetry at (1, 1/2, −1/2)] are further linked by symmetry-related C—H···O hydrogen bonds, involving atom O9 at (x, y, z) with atom H15A at (x, 1/2 − y, 1/2 + z), atom H15A at (x, y, z) with atom O9 at (x, 1/2 − y, −1/2 + z), atom O9 at (2 − x, 1 − y, −z) with atom H15A at (2 − x, 1/2 + y, −1/2 − z), and atom H15A at (2 − x, 1 − y, −z) with atom O9 at (2 − x, 1/2 + y, 1/2 − z), respectively, thus forming an R66(36) ring. Hence, a discrete hexamer is formed and related to it by a centre of symmetry at (1, 1/2, 0) (Fig. 3). The result is a two-dimensional layer, which runs along the bc plane (Fig. 4). In (II), an intramolecular N7—H7···O17 hydrogen bond forms a five-membered ring. A C(8) motif is formed via a C4—H4···O9(1 − x, 1/2 + y, 3/2 − z) hydrogen bond, creating a chain that runs parallel to the ab plane. Two such anti-parallel chains are shown in Fig. 5. In (II), a C—H···π interaction is also observed (Table 4). The H7···C11 distances, 2.34 Å in (I) and 2.28 Å in (II), are short as a result of the positive charge on atom H7 and negative charge on atom C11.