Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010604844X/sq3047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010604844X/sq3047IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010604844X/sq3047IIIsup3.hkl |
CCDC references: 632942; 632943
Compounds (II) and (III) were obtained by the reaction of benzylydenemalononitrile, (I), with acetylacetone and 1-benzoylacetone, respectively, according to a literature procedure (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004). The precipitates were isolated and recrystallized from ethanol [m.p. 421 K, yield 78% for (II)] or acetonitrile [m.p. 458 K, yield 87% for (III)]. Crystals of both compounds were grown by slow isothermic evaporation of ethanol and acetonitrile solutions, respectively. Both compounds were characterized by 1H and 13C NMR spectroscopy; details are available in the archived CIF.
For both compounds, all H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3, C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for CH, and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N) for the NH2 groups.
For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C15H14N2O2 | F(000) = 536 |
Mr = 254.28 | Dx = 1.281 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.001 (2) Å | Cell parameters from 118 reflections |
b = 13.910 (3) Å | θ = 4–25° |
c = 15.862 (3) Å | µ = 0.09 mm−1 |
β = 94.989 (5)° | T = 295 K |
V = 1319.1 (6) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
Bruker SMART APEX II CCD area-detector diffractometer | 3465 independent reflections |
Radiation source: fine-focus sealed tube | 2448 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 28.9°, θmin = 2.0° |
Absorption correction: multi-scan SADABS (Sheldrick, 2003) | h = −8→8 |
Tmin = 0.975, Tmax = 0.983 | k = −18→18 |
13889 measured reflections | l = −21→21 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.061P)2 + 0.26P] where P = (Fo2 + 2Fc2)/3 |
3465 reflections | (Δ/σ)max < 0.001 |
174 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C15H14N2O2 | V = 1319.1 (6) Å3 |
Mr = 254.28 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.001 (2) Å | µ = 0.09 mm−1 |
b = 13.910 (3) Å | T = 295 K |
c = 15.862 (3) Å | 0.30 × 0.25 × 0.20 mm |
β = 94.989 (5)° |
Bruker SMART APEX II CCD area-detector diffractometer | 3465 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 2003) | 2448 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.983 | Rint = 0.031 |
13889 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.25 e Å−3 |
3465 reflections | Δρmin = −0.17 e Å−3 |
174 parameters |
Experimental. Spectroscopic data for (II): 1H NMR (DMSO-d6, 300 MHz, δ, p.p.m): 7.33 (dd, 2H, J = 7.0 and 7.7 Hz), 7.24 (t, 1H, J = 2.2 and 2.2 Hz), 7.17 (d, 2H, J = 7.0 Hz), 6.86 (br s, 2H, NH2), 4.46 (s, 1H), 2.2 (s, 3H), 2.06 (s, 3H); 13C NMR (DMSO-d6, 75 MHz, δ, p.p.m): 198.3, 158.2, 154.7, 144.5, 128.7, 127.1, 126.9, 119.7, 115.0, 57.8, 38.7, 29.8, 18.4. |
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 | ||
O1 | 0.62843 (17) | 0.48936 (7) | 0.69760 (6) | 0.0421 (3) | |
O2 | 0.87903 (19) | 0.74172 (8) | 0.82485 (7) | 0.0512 (3) | |
N1 | 0.4141 (2) | 0.42467 (9) | 0.59208 (9) | 0.0488 (3) | |
H1A | 0.3008 | 0.4219 | 0.5550 | 0.059* | |
H1B | 0.5102 | 0.3787 | 0.5959 | 0.059* | |
N2 | −0.0609 (2) | 0.59169 (11) | 0.55420 (10) | 0.0584 (4) | |
C1 | 0.1057 (2) | 0.58387 (10) | 0.59392 (9) | 0.0407 (3) | |
C2 | 0.4407 (2) | 0.50030 (9) | 0.64359 (9) | 0.0356 (3) | |
C3 | 0.3084 (2) | 0.57877 (9) | 0.64693 (8) | 0.0352 (3) | |
C4 | 0.3678 (2) | 0.66531 (9) | 0.70255 (8) | 0.0340 (3) | |
H4A | 0.2537 | 0.6717 | 0.7428 | 0.041* | |
C5 | 0.5918 (2) | 0.64825 (9) | 0.75277 (8) | 0.0338 (3) | |
C6 | 0.7020 (2) | 0.56475 (9) | 0.74956 (8) | 0.0345 (3) | |
C7 | 0.9089 (3) | 0.53198 (11) | 0.79983 (9) | 0.0426 (3) | |
H7A | 0.9544 | 0.5796 | 0.8417 | 0.064* | |
H7B | 1.0257 | 0.5229 | 0.7629 | 0.064* | |
H7C | 0.8800 | 0.4724 | 0.8274 | 0.064* | |
C8 | 0.6799 (3) | 0.72562 (10) | 0.81181 (9) | 0.0396 (3) | |
C9 | 0.5159 (3) | 0.78362 (16) | 0.85566 (13) | 0.0673 (5) | |
H9A | 0.5945 | 0.8241 | 0.8973 | 0.101* | |
H9B | 0.4179 | 0.7414 | 0.8829 | 0.101* | |
H9C | 0.4296 | 0.8228 | 0.8150 | 0.101* | |
C10 | 0.3586 (2) | 0.75513 (9) | 0.64727 (9) | 0.0357 (3) | |
C11 | 0.5140 (3) | 0.76929 (10) | 0.58859 (9) | 0.0422 (3) | |
H11A | 0.6365 | 0.7284 | 0.5878 | 0.051* | |
C12 | 0.4866 (3) | 0.84455 (12) | 0.53113 (10) | 0.0524 (4) | |
H12A | 0.5904 | 0.8536 | 0.4916 | 0.063* | |
C13 | 0.3073 (3) | 0.90576 (12) | 0.53221 (11) | 0.0569 (5) | |
H13A | 0.2889 | 0.9555 | 0.4930 | 0.068* | |
C14 | 0.1559 (3) | 0.89352 (13) | 0.59100 (13) | 0.0611 (5) | |
H14A | 0.0359 | 0.9356 | 0.5923 | 0.073* | |
C15 | 0.1811 (3) | 0.81822 (12) | 0.64881 (11) | 0.0494 (4) | |
H15A | 0.0778 | 0.8103 | 0.6887 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0413 (6) | 0.0310 (5) | 0.0506 (6) | 0.0028 (4) | −0.0147 (4) | −0.0015 (4) |
O2 | 0.0480 (7) | 0.0476 (6) | 0.0558 (7) | −0.0081 (5) | −0.0077 (5) | −0.0085 (5) |
N1 | 0.0494 (8) | 0.0337 (6) | 0.0591 (8) | 0.0043 (5) | −0.0193 (6) | −0.0069 (6) |
N2 | 0.0480 (8) | 0.0602 (9) | 0.0628 (9) | 0.0128 (7) | −0.0193 (7) | −0.0154 (7) |
C1 | 0.0404 (8) | 0.0363 (7) | 0.0440 (8) | 0.0035 (6) | −0.0044 (6) | −0.0047 (6) |
C2 | 0.0351 (7) | 0.0316 (6) | 0.0388 (7) | −0.0037 (5) | −0.0053 (5) | 0.0037 (5) |
C3 | 0.0321 (7) | 0.0341 (7) | 0.0381 (7) | −0.0017 (5) | −0.0052 (5) | 0.0017 (5) |
C4 | 0.0332 (7) | 0.0328 (6) | 0.0355 (7) | 0.0011 (5) | −0.0004 (5) | 0.0008 (5) |
C5 | 0.0358 (7) | 0.0351 (7) | 0.0298 (6) | −0.0026 (5) | −0.0007 (5) | 0.0010 (5) |
C6 | 0.0359 (7) | 0.0344 (6) | 0.0321 (6) | −0.0039 (5) | −0.0034 (5) | 0.0029 (5) |
C7 | 0.0424 (8) | 0.0418 (7) | 0.0415 (8) | 0.0018 (6) | −0.0084 (6) | 0.0039 (6) |
C8 | 0.0465 (9) | 0.0374 (7) | 0.0338 (7) | −0.0013 (6) | −0.0031 (6) | −0.0003 (5) |
C9 | 0.0642 (12) | 0.0732 (12) | 0.0638 (11) | 0.0065 (10) | 0.0014 (9) | −0.0305 (10) |
C10 | 0.0349 (7) | 0.0319 (6) | 0.0386 (7) | −0.0004 (5) | −0.0060 (5) | −0.0004 (5) |
C11 | 0.0472 (9) | 0.0370 (7) | 0.0421 (8) | 0.0012 (6) | 0.0020 (6) | −0.0001 (6) |
C12 | 0.0662 (11) | 0.0477 (9) | 0.0429 (8) | −0.0080 (8) | 0.0021 (7) | 0.0064 (7) |
C13 | 0.0674 (11) | 0.0427 (8) | 0.0567 (10) | −0.0046 (8) | −0.0169 (9) | 0.0146 (7) |
C14 | 0.0502 (10) | 0.0446 (9) | 0.0856 (13) | 0.0109 (8) | −0.0115 (9) | 0.0119 (9) |
C15 | 0.0400 (8) | 0.0446 (8) | 0.0633 (10) | 0.0055 (7) | 0.0020 (7) | 0.0069 (7) |
O1—C2 | 1.3634 (16) | C7—H7B | 0.9600 |
O1—C6 | 1.3823 (16) | C7—H7C | 0.9600 |
O2—C8 | 1.2158 (18) | C8—C9 | 1.491 (2) |
N1—C2 | 1.3331 (18) | C9—H9A | 0.9600 |
N1—H1A | 0.8600 | C9—H9B | 0.9600 |
N1—H1B | 0.8600 | C9—H9C | 0.9600 |
N2—C1 | 1.1394 (19) | C10—C15 | 1.382 (2) |
C1—C3 | 1.4192 (19) | C10—C11 | 1.388 (2) |
C2—C3 | 1.3533 (19) | C11—C12 | 1.388 (2) |
C3—C4 | 1.5164 (18) | C11—H11A | 0.9300 |
C4—C5 | 1.5205 (18) | C12—C13 | 1.373 (3) |
C4—C10 | 1.5246 (18) | C12—H12A | 0.9300 |
C4—H4A | 0.9800 | C13—C14 | 1.368 (3) |
C5—C6 | 1.3398 (19) | C13—H13A | 0.9300 |
C5—C8 | 1.4927 (19) | C14—C15 | 1.392 (2) |
C6—C7 | 1.4873 (19) | C14—H14A | 0.9300 |
C7—H7A | 0.9600 | C15—H15A | 0.9300 |
C2—O1—C6 | 119.58 (10) | H7B—C7—H7C | 109.5 |
C2—N1—H1A | 120.0 | O2—C8—C9 | 119.99 (14) |
C2—N1—H1B | 120.0 | O2—C8—C5 | 121.91 (13) |
H1A—N1—H1B | 120.0 | C9—C8—C5 | 118.09 (14) |
N2—C1—C3 | 176.30 (16) | C8—C9—H9A | 109.5 |
N1—C2—C3 | 128.41 (13) | C8—C9—H9B | 109.5 |
N1—C2—O1 | 110.20 (12) | H9A—C9—H9B | 109.5 |
C3—C2—O1 | 121.39 (12) | C8—C9—H9C | 109.5 |
C2—C3—C1 | 119.50 (12) | H9A—C9—H9C | 109.5 |
C2—C3—C4 | 123.65 (12) | H9B—C9—H9C | 109.5 |
C1—C3—C4 | 116.81 (11) | C15—C10—C11 | 119.06 (14) |
C3—C4—C5 | 109.47 (11) | C15—C10—C4 | 119.96 (14) |
C3—C4—C10 | 108.72 (11) | C11—C10—C4 | 120.62 (12) |
C5—C4—C10 | 114.53 (11) | C10—C11—C12 | 119.94 (15) |
C3—C4—H4A | 108.0 | C10—C11—H11A | 120.0 |
C5—C4—H4A | 108.0 | C12—C11—H11A | 120.0 |
C10—C4—H4A | 108.0 | C13—C12—C11 | 120.51 (17) |
C6—C5—C8 | 119.99 (12) | C13—C12—H12A | 119.7 |
C6—C5—C4 | 122.16 (12) | C11—C12—H12A | 119.7 |
C8—C5—C4 | 117.70 (12) | C14—C13—C12 | 119.92 (15) |
C5—C6—O1 | 123.17 (12) | C14—C13—H13A | 120.0 |
C5—C6—C7 | 129.57 (12) | C12—C13—H13A | 120.0 |
O1—C6—C7 | 107.20 (11) | C13—C14—C15 | 120.17 (16) |
C6—C7—H7A | 109.5 | C13—C14—H14A | 119.9 |
C6—C7—H7B | 109.5 | C15—C14—H14A | 119.9 |
H7A—C7—H7B | 109.5 | C10—C15—C14 | 120.38 (17) |
C6—C7—H7C | 109.5 | C10—C15—H15A | 119.8 |
H7A—C7—H7C | 109.5 | C14—C15—H15A | 119.8 |
C6—O1—C2—N1 | 172.23 (12) | C2—O1—C6—C5 | 3.2 (2) |
C6—O1—C2—C3 | −8.4 (2) | C2—O1—C6—C7 | −179.41 (12) |
N1—C2—C3—C1 | 4.0 (2) | C6—C5—C8—O2 | 38.0 (2) |
O1—C2—C3—C1 | −175.23 (13) | C4—C5—C8—O2 | −146.39 (14) |
N1—C2—C3—C4 | −173.65 (14) | C6—C5—C8—C9 | −141.71 (16) |
O1—C2—C3—C4 | 7.1 (2) | C4—C5—C8—C9 | 33.9 (2) |
C2—C3—C4—C5 | −0.75 (19) | C3—C4—C10—C15 | 104.94 (15) |
C1—C3—C4—C5 | −178.45 (12) | C5—C4—C10—C15 | −132.28 (14) |
C2—C3—C4—C10 | 125.02 (14) | C3—C4—C10—C11 | −68.15 (16) |
C1—C3—C4—C10 | −52.67 (16) | C5—C4—C10—C11 | 54.63 (17) |
C3—C4—C5—C6 | −4.38 (18) | C15—C10—C11—C12 | −1.7 (2) |
C10—C4—C5—C6 | −126.75 (14) | C4—C10—C11—C12 | 171.49 (13) |
C3—C4—C5—C8 | −179.87 (12) | C10—C11—C12—C13 | 0.5 (2) |
C10—C4—C5—C8 | 57.75 (16) | C11—C12—C13—C14 | 0.9 (3) |
C8—C5—C6—O1 | 178.81 (12) | C12—C13—C14—C15 | −1.1 (3) |
C4—C5—C6—O1 | 3.4 (2) | C11—C10—C15—C14 | 1.5 (2) |
C8—C5—C6—C7 | 2.0 (2) | C4—C10—C15—C14 | −171.71 (15) |
C4—C5—C6—C7 | −173.40 (14) | C13—C14—C15—C10 | −0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.16 | 3.012 (2) | 170 |
N1—H1B···O2ii | 0.86 | 2.35 | 3.077 (2) | 143 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+3/2. |
C20H16N2O2·C2H3N | Z = 2 |
Mr = 357.40 | F(000) = 376 |
Triclinic, P1 | Dx = 1.214 Mg m−3 |
a = 8.273 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.313 (2) Å | Cell parameters from 122 reflections |
c = 13.881 (3) Å | θ = 4–26° |
α = 73.376 (7)° | µ = 0.08 mm−1 |
β = 82.308 (6)° | T = 295 K |
γ = 72.856 (7)° | Prism, colourless |
V = 977.8 (4) Å3 | 0.35 × 0.26 × 0.18 mm |
Bruker SMART APEX II CCD area-detector diffractometer | 4059 independent reflections |
Radiation source: fine-focus sealed tube | 2935 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 26.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.973, Tmax = 0.986 | k = −11→11 |
8803 measured reflections | l = −17→17 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.069P)2 + 0.13P] where P = (Fo2 + 2Fc2)/3 |
4059 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C20H16N2O2·C2H3N | γ = 72.856 (7)° |
Mr = 357.40 | V = 977.8 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.273 (2) Å | Mo Kα radiation |
b = 9.313 (2) Å | µ = 0.08 mm−1 |
c = 13.881 (3) Å | T = 295 K |
α = 73.376 (7)° | 0.35 × 0.26 × 0.18 mm |
β = 82.308 (6)° |
Bruker SMART APEX II CCD area-detector diffractometer | 4059 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2935 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.986 | Rint = 0.015 |
8803 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.16 e Å−3 |
4059 reflections | Δρmin = −0.16 e Å−3 |
246 parameters |
Experimental. Spectroscopic data for (III): 1H NMR (300 MHz, DMSO-d6, δ, p.p.m.): 7.58 (m, 3H), 7.44 (dd, 2H, J = 7.7 and 8.1 Hz), 7.25 (dd, 2H, J = 7.0 and 7.4 Hz), 7.15 (t, 1H, J = 2.2 and 2.2 Hz), 7.11 (d, 2H, J = 8.1 Hz), 6.95 (br s, 2H, NH2), 4.44 (s, 1H), 1.74 (s, 3H); 13C NMR (75 MHz, DMSO-d6, δ, p.p.m.): 195.3, 159.0, 149.5, 143.3, 137.6, 133.2, 128.8, 128.5, 128.4, 127.5, 127.0, 119.9, 114.0, 56.3, 40.7, 18.1. |
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 | ||
O1 | 0.77768 (12) | 0.53571 (11) | 0.86219 (8) | 0.0522 (3) | |
O2 | 0.21121 (13) | 0.53689 (13) | 0.90116 (9) | 0.0629 (3) | |
N1 | 0.99301 (15) | 0.33017 (15) | 0.91442 (11) | 0.0607 (4) | |
H1A | 1.0416 | 0.2325 | 0.9360 | 0.073* | |
H1B | 1.0507 | 0.3969 | 0.9038 | 0.073* | |
N2 | 0.80537 (18) | −0.00362 (16) | 0.98724 (13) | 0.0742 (5) | |
C1 | 0.77121 (18) | 0.12800 (17) | 0.95269 (12) | 0.0513 (4) | |
C2 | 0.82827 (17) | 0.37810 (16) | 0.89744 (11) | 0.0467 (3) | |
C3 | 0.71878 (17) | 0.29035 (16) | 0.90994 (11) | 0.0457 (3) | |
C4 | 0.54018 (17) | 0.35898 (15) | 0.87556 (11) | 0.0430 (3) | |
H4A | 0.4641 | 0.3200 | 0.9307 | 0.052* | |
C5 | 0.49270 (17) | 0.53427 (15) | 0.85529 (10) | 0.0425 (3) | |
C6 | 0.60696 (17) | 0.61191 (16) | 0.85096 (11) | 0.0446 (3) | |
C7 | 0.5836 (2) | 0.78071 (17) | 0.83816 (13) | 0.0566 (4) | |
H7A | 0.4650 | 0.8317 | 0.8446 | 0.085* | |
H7B | 0.6288 | 0.8252 | 0.7727 | 0.085* | |
H7C | 0.6419 | 0.7942 | 0.8889 | 0.085* | |
C8 | 0.30751 (18) | 0.60763 (16) | 0.84744 (11) | 0.0461 (3) | |
C9 | 0.23473 (18) | 0.75439 (17) | 0.77085 (12) | 0.0501 (4) | |
C10 | 0.51551 (18) | 0.31014 (15) | 0.78432 (11) | 0.0462 (3) | |
C11 | 0.5914 (2) | 0.3624 (2) | 0.69131 (13) | 0.0686 (5) | |
H11A | 0.6595 | 0.4289 | 0.6837 | 0.082* | |
C12 | 0.5667 (3) | 0.3165 (3) | 0.60905 (16) | 0.0909 (7) | |
H12A | 0.6193 | 0.3510 | 0.5467 | 0.109* | |
C13 | 0.4642 (3) | 0.2197 (3) | 0.6197 (2) | 0.0947 (7) | |
H13A | 0.4460 | 0.1902 | 0.5644 | 0.114* | |
C14 | 0.3898 (3) | 0.1674 (2) | 0.7113 (2) | 0.0865 (7) | |
H14A | 0.3213 | 0.1013 | 0.7185 | 0.104* | |
C15 | 0.4148 (2) | 0.21142 (18) | 0.79316 (15) | 0.0619 (4) | |
H15A | 0.3633 | 0.1744 | 0.8554 | 0.074* | |
C16 | 0.0722 (2) | 0.8431 (2) | 0.79089 (15) | 0.0668 (5) | |
H16A | 0.0172 | 0.8155 | 0.8536 | 0.080* | |
C17 | −0.0070 (3) | 0.9708 (2) | 0.71874 (18) | 0.0823 (6) | |
H17A | −0.1144 | 1.0309 | 0.7331 | 0.099* | |
C18 | 0.0721 (3) | 1.0099 (2) | 0.62535 (17) | 0.0804 (6) | |
H18A | 0.0168 | 1.0949 | 0.5761 | 0.097* | |
C19 | 0.2328 (3) | 0.9238 (2) | 0.60418 (14) | 0.0709 (5) | |
H19A | 0.2858 | 0.9510 | 0.5408 | 0.085* | |
C20 | 0.3154 (2) | 0.79687 (19) | 0.67721 (12) | 0.0573 (4) | |
H20A | 0.4248 | 0.7402 | 0.6635 | 0.069* | |
N3 | 0.7793 (4) | 0.7106 (4) | 0.59208 (19) | 0.1369 (9) | |
C21 | 0.9075 (4) | 0.6273 (3) | 0.61432 (17) | 0.0904 (7) | |
C22 | 1.0649 (4) | 0.5261 (4) | 0.6454 (2) | 0.1309 (10) | |
H22A | 1.0738 | 0.4253 | 0.6369 | 0.157* | |
H22B | 1.0748 | 0.5176 | 0.7151 | 0.157* | |
H22C | 1.1538 | 0.5662 | 0.6055 | 0.157* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0402 (5) | 0.0417 (5) | 0.0719 (7) | −0.0168 (4) | −0.0087 (5) | −0.0023 (5) |
O2 | 0.0440 (6) | 0.0584 (6) | 0.0865 (8) | −0.0210 (5) | 0.0041 (5) | −0.0153 (6) |
N1 | 0.0407 (7) | 0.0482 (7) | 0.0884 (10) | −0.0151 (6) | −0.0104 (6) | −0.0040 (7) |
N2 | 0.0567 (9) | 0.0461 (8) | 0.1071 (12) | −0.0129 (6) | −0.0133 (8) | 0.0027 (8) |
C1 | 0.0405 (8) | 0.0469 (9) | 0.0636 (9) | −0.0139 (6) | −0.0072 (7) | −0.0057 (7) |
C2 | 0.0415 (7) | 0.0430 (7) | 0.0523 (8) | −0.0125 (6) | −0.0045 (6) | −0.0053 (6) |
C3 | 0.0417 (7) | 0.0403 (7) | 0.0533 (8) | −0.0127 (6) | −0.0059 (6) | −0.0065 (6) |
C4 | 0.0390 (7) | 0.0391 (7) | 0.0498 (8) | −0.0152 (6) | −0.0023 (6) | −0.0053 (6) |
C5 | 0.0421 (7) | 0.0393 (7) | 0.0466 (8) | −0.0131 (6) | −0.0028 (6) | −0.0094 (6) |
C6 | 0.0404 (7) | 0.0413 (7) | 0.0508 (8) | −0.0121 (6) | −0.0054 (6) | −0.0073 (6) |
C7 | 0.0564 (9) | 0.0443 (8) | 0.0731 (10) | −0.0186 (7) | −0.0099 (8) | −0.0132 (7) |
C8 | 0.0423 (7) | 0.0460 (8) | 0.0561 (8) | −0.0151 (6) | −0.0020 (6) | −0.0197 (6) |
C9 | 0.0437 (8) | 0.0488 (8) | 0.0610 (9) | −0.0100 (6) | −0.0108 (7) | −0.0181 (7) |
C10 | 0.0433 (7) | 0.0349 (7) | 0.0588 (9) | −0.0069 (6) | −0.0108 (6) | −0.0097 (6) |
C11 | 0.0805 (12) | 0.0677 (11) | 0.0620 (11) | −0.0278 (9) | 0.0016 (9) | −0.0181 (9) |
C12 | 0.1113 (18) | 0.0924 (15) | 0.0606 (12) | −0.0118 (14) | −0.0040 (11) | −0.0234 (11) |
C13 | 0.1143 (18) | 0.0772 (14) | 0.1012 (18) | −0.0009 (13) | −0.0467 (15) | −0.0437 (13) |
C14 | 0.0927 (15) | 0.0644 (12) | 0.1171 (19) | −0.0185 (11) | −0.0407 (14) | −0.0336 (12) |
C15 | 0.0596 (10) | 0.0460 (8) | 0.0848 (12) | −0.0167 (7) | −0.0173 (9) | −0.0160 (8) |
C16 | 0.0498 (9) | 0.0653 (10) | 0.0781 (12) | −0.0056 (8) | −0.0048 (8) | −0.0174 (9) |
C17 | 0.0583 (11) | 0.0709 (12) | 0.1028 (16) | 0.0043 (9) | −0.0201 (11) | −0.0148 (11) |
C18 | 0.0806 (14) | 0.0656 (11) | 0.0881 (14) | −0.0083 (10) | −0.0361 (12) | −0.0067 (10) |
C19 | 0.0834 (13) | 0.0691 (11) | 0.0614 (10) | −0.0226 (10) | −0.0158 (9) | −0.0110 (9) |
C20 | 0.0561 (9) | 0.0564 (9) | 0.0619 (10) | −0.0139 (7) | −0.0071 (8) | −0.0187 (8) |
N3 | 0.123 (2) | 0.162 (2) | 0.1048 (17) | −0.0401 (19) | −0.0209 (16) | 0.0058 (16) |
C21 | 0.0921 (17) | 0.1099 (18) | 0.0715 (13) | −0.0485 (15) | −0.0108 (12) | −0.0022 (12) |
C22 | 0.098 (2) | 0.167 (3) | 0.122 (2) | −0.029 (2) | −0.0130 (17) | −0.034 (2) |
O1—C2 | 1.3604 (17) | C11—C12 | 1.387 (3) |
O1—C6 | 1.3883 (17) | C11—H11A | 0.9300 |
O2—C8 | 1.2224 (17) | C12—C13 | 1.376 (3) |
N1—C2 | 1.3340 (18) | C12—H12A | 0.9300 |
N1—H1A | 0.8600 | C13—C14 | 1.358 (3) |
N1—H1B | 0.8600 | C13—H13A | 0.9300 |
N2—C1 | 1.1437 (19) | C14—C15 | 1.372 (3) |
C1—C3 | 1.412 (2) | C14—H14A | 0.9300 |
C2—C3 | 1.3534 (19) | C15—H15A | 0.9300 |
C3—C4 | 1.5090 (19) | C16—C17 | 1.372 (3) |
C4—C5 | 1.5124 (18) | C16—H16A | 0.9300 |
C4—C10 | 1.519 (2) | C17—C18 | 1.373 (3) |
C4—H4A | 0.9800 | C17—H17A | 0.9300 |
C5—C6 | 1.3353 (19) | C18—C19 | 1.378 (3) |
C5—C8 | 1.487 (2) | C18—H18A | 0.9300 |
C6—C7 | 1.4867 (19) | C19—C20 | 1.384 (2) |
C7—H7A | 0.9600 | C19—H19A | 0.9300 |
C7—H7B | 0.9600 | C20—H20A | 0.9300 |
C7—H7C | 0.9600 | N3—C21 | 1.135 (3) |
C8—C9 | 1.488 (2) | C21—C22 | 1.401 (4) |
C9—C20 | 1.386 (2) | C22—H22A | 0.9600 |
C9—C16 | 1.394 (2) | C22—H22B | 0.9600 |
C10—C11 | 1.379 (2) | C22—H22C | 0.9600 |
C10—C15 | 1.384 (2) | ||
C2—O1—C6 | 120.09 (10) | C10—C11—C12 | 120.39 (19) |
C2—N1—H1A | 120.0 | C10—C11—H11A | 119.8 |
C2—N1—H1B | 120.0 | C12—C11—H11A | 119.8 |
H1A—N1—H1B | 120.0 | C13—C12—C11 | 120.0 (2) |
N2—C1—C3 | 176.54 (16) | C13—C12—H12A | 120.0 |
N1—C2—C3 | 128.03 (13) | C11—C12—H12A | 120.0 |
N1—C2—O1 | 110.56 (12) | C14—C13—C12 | 119.9 (2) |
C3—C2—O1 | 121.41 (12) | C14—C13—H13A | 120.1 |
C2—C3—C1 | 120.47 (13) | C12—C13—H13A | 120.1 |
C2—C3—C4 | 122.11 (12) | C13—C14—C15 | 120.5 (2) |
C1—C3—C4 | 117.38 (12) | C13—C14—H14A | 119.8 |
C3—C4—C5 | 109.97 (11) | C15—C14—H14A | 119.8 |
C3—C4—C10 | 112.28 (11) | C14—C15—C10 | 120.88 (19) |
C5—C4—C10 | 111.25 (11) | C14—C15—H15A | 119.6 |
C3—C4—H4A | 107.7 | C10—C15—H15A | 119.6 |
C5—C4—H4A | 107.7 | C17—C16—C9 | 120.41 (18) |
C10—C4—H4A | 107.7 | C17—C16—H16A | 119.8 |
C6—C5—C8 | 124.33 (12) | C9—C16—H16A | 119.8 |
C6—C5—C4 | 122.28 (12) | C16—C17—C18 | 120.00 (18) |
C8—C5—C4 | 113.29 (11) | C16—C17—H17A | 120.0 |
C5—C6—O1 | 121.50 (12) | C18—C17—H17A | 120.0 |
C5—C6—C7 | 130.02 (13) | C17—C18—C19 | 120.41 (18) |
O1—C6—C7 | 108.44 (11) | C17—C18—H18A | 119.8 |
C6—C7—H7A | 109.5 | C19—C18—H18A | 119.8 |
C6—C7—H7B | 109.5 | C18—C19—C20 | 120.01 (19) |
H7A—C7—H7B | 109.5 | C18—C19—H19A | 120.0 |
C6—C7—H7C | 109.5 | C20—C19—H19A | 120.0 |
H7A—C7—H7C | 109.5 | C19—C20—C9 | 119.92 (16) |
H7B—C7—H7C | 109.5 | C19—C20—H20A | 120.0 |
O2—C8—C5 | 117.93 (13) | C9—C20—H20A | 120.0 |
O2—C8—C9 | 118.64 (13) | N3—C21—C22 | 177.7 (3) |
C5—C8—C9 | 123.14 (13) | C21—C22—H22A | 109.5 |
C20—C9—C16 | 119.21 (15) | C21—C22—H22B | 109.5 |
C20—C9—C8 | 122.25 (13) | H22A—C22—H22B | 109.5 |
C16—C9—C8 | 118.21 (15) | C21—C22—H22C | 109.5 |
C11—C10—C15 | 118.41 (15) | H22A—C22—H22C | 109.5 |
C11—C10—C4 | 121.45 (13) | H22B—C22—H22C | 109.5 |
C15—C10—C4 | 120.14 (14) | ||
C6—O1—C2—N1 | −172.26 (12) | O2—C8—C9—C20 | −143.90 (15) |
C6—O1—C2—C3 | 8.7 (2) | C5—C8—C9—C20 | 29.9 (2) |
N1—C2—C3—C1 | 5.2 (2) | O2—C8—C9—C16 | 29.5 (2) |
O1—C2—C3—C1 | −175.92 (13) | C5—C8—C9—C16 | −156.76 (14) |
N1—C2—C3—C4 | −172.29 (15) | C3—C4—C10—C11 | −68.85 (17) |
O1—C2—C3—C4 | 6.6 (2) | C5—C4—C10—C11 | 54.88 (18) |
C2—C3—C4—C5 | −15.77 (19) | C3—C4—C10—C15 | 111.34 (15) |
C1—C3—C4—C5 | 166.69 (12) | C5—C4—C10—C15 | −124.92 (14) |
C2—C3—C4—C10 | 108.67 (16) | C15—C10—C11—C12 | −0.1 (3) |
C1—C3—C4—C10 | −68.87 (16) | C4—C10—C11—C12 | −179.87 (16) |
C3—C4—C5—C6 | 11.57 (19) | C10—C11—C12—C13 | 0.8 (3) |
C10—C4—C5—C6 | −113.47 (15) | C11—C12—C13—C14 | −1.1 (3) |
C3—C4—C5—C8 | −164.83 (12) | C12—C13—C14—C15 | 0.5 (3) |
C10—C4—C5—C8 | 70.13 (15) | C13—C14—C15—C10 | 0.2 (3) |
C8—C5—C6—O1 | 177.80 (12) | C11—C10—C15—C14 | −0.5 (2) |
C4—C5—C6—O1 | 1.8 (2) | C4—C10—C15—C14 | 179.33 (15) |
C8—C5—C6—C7 | 0.1 (3) | C20—C9—C16—C17 | 0.1 (3) |
C4—C5—C6—C7 | −175.93 (14) | C8—C9—C16—C17 | −173.49 (16) |
C2—O1—C6—C5 | −13.0 (2) | C9—C16—C17—C18 | 1.5 (3) |
C2—O1—C6—C7 | 165.16 (13) | C16—C17—C18—C19 | −1.6 (3) |
C6—C5—C8—O2 | −141.37 (15) | C17—C18—C19—C20 | 0.1 (3) |
C4—C5—C8—O2 | 34.94 (18) | C18—C19—C20—C9 | 1.5 (3) |
C6—C5—C8—C9 | 44.8 (2) | C16—C9—C20—C19 | −1.6 (2) |
C4—C5—C8—C9 | −138.88 (13) | C8—C9—C20—C19 | 171.75 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.18 | 3.023 (2) | 167 |
N1—H1B···O2ii | 0.86 | 2.11 | 2.959 (2) | 170 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) x+1, y, z. |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | C15H14N2O2 | C20H16N2O2·C2H3N |
Mr | 254.28 | 357.40 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 6.001 (2), 13.910 (3), 15.862 (3) | 8.273 (2), 9.313 (2), 13.881 (3) |
α, β, γ (°) | 90, 94.989 (5), 90 | 73.376 (7), 82.308 (6), 72.856 (7) |
V (Å3) | 1319.1 (6) | 977.8 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.08 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 | 0.35 × 0.26 × 0.18 |
Data collection | ||
Diffractometer | Bruker SMART APEX II CCD area-detector diffractometer | Bruker SMART APEX II CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.975, 0.983 | 0.973, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13889, 3465, 2448 | 8803, 4059, 2935 |
Rint | 0.031 | 0.015 |
(sin θ/λ)max (Å−1) | 0.681 | 0.629 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.128, 1.01 | 0.044, 0.133, 1.02 |
No. of reflections | 3465 | 4059 |
No. of parameters | 174 | 246 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.17 | 0.16, −0.16 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXTL (Sheldrick, 2001), SHELXTL.
O1—C2 | 1.3634 (16) | C2—C3 | 1.3533 (19) |
O1—C6 | 1.3823 (16) | C4—C10 | 1.5246 (18) |
O2—C8 | 1.2158 (18) | C5—C6 | 1.3398 (19) |
N1—C2 | 1.3331 (18) | C5—C8 | 1.4927 (19) |
N2—C1 | 1.1394 (19) | ||
C2—O1—C6 | 119.58 (10) | ||
C6—C5—C8—O2 | 38.0 (2) | C3—C4—C10—C11 | −68.15 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.16 | 3.012 (2) | 170 |
N1—H1B···O2ii | 0.86 | 2.35 | 3.077 (2) | 143 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+3/2. |
O1—C2 | 1.3604 (17) | C2—C3 | 1.3534 (19) |
O1—C6 | 1.3883 (17) | C4—C10 | 1.519 (2) |
O2—C8 | 1.2224 (17) | C5—C6 | 1.3353 (19) |
N1—C2 | 1.3340 (18) | C5—C8 | 1.487 (2) |
N2—C1 | 1.1437 (19) | ||
C2—O1—C6 | 120.09 (10) | ||
C6—C5—C8—O2 | −141.37 (15) | C3—C4—C10—C11 | −68.85 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.18 | 3.023 (2) | 167 |
N1—H1B···O2ii | 0.86 | 2.11 | 2.959 (2) | 170 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) x+1, y, z. |
The present investigation of the title compound, (II) and (III), is a continuation of our work that includes the syntheses and structural studies of heterocyclic compounds, such as 4H-pyran derivatives (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004, 2005), that can be obtained starting from different unsaturated nitriles (Nesterov et al., 2001a,b). Some 4H-pyran derivatives are potential bioactive compounds, such as calcium antagonists (Suarez et al., 2002) and potent apoptosis inducers (Kemnitzer et al., 2004; Zhang et al., 2005).
X-ray analysis shows that the molecules of (II) and (III) have slightly different structures (Figs. 1 and 2). In both molecules, the pyran ring adopts a flattened boat conformation: atoms O1 and C4 are displaced out of the C2/C3/C5/C6 plane [planar to within 0.026 (1) and 0.021 (1) Å in compounds (II) and (III), respectively] by 0.060 (1) and 0.023 (1) Å, respectively, in (II), and −0.110 (1) and −0.174 (1) Å, respectively, in (III). The bending of the heterocycle along the lines O1···C4, C2···C6 and C3···C5 is 4.1 (1), 5.1 (1) and 1.9 (1)°, respectively, in (II), compared with 13.2 (1), 9.3 (1) and 11.6 (1)°, respectively, in (III). The dihedral angles between the pseudo-axial phenyl substituent and the flat part of the pyran ring are 92.7 (1)° in (II) and 93.2 (1)° in (III).
The C═O group has interesting orientational preferences relative to the C5═C6 double bond. In compound (II), the groups are syn (`cisoid') [torsion angle C6—C5—C8—O2 = 38.0 (2)°], while in (III) they are anti (`transoid') [torsion angle C6—C5—C8—O2 = −141.4 (2)°]. In the first case, a short intramolecular contact (O2···H7A = 2.31 Å) is present. In the latter case, there is a short steric intramolecular contact [C7···C20 = 3.298 (2) Å] which is shorter than the sum of the van der Waals radii of two C atoms (Rowland & Taylor, 1996). Probably, the C···C contact plays a role in the orientation of the bulky phenyl substituent in the molecule of (III) relative to the heterocycle [torsion angle C5—C8—C9—C20 = 29.9 (2)°].
Similar to related compounds (Nesterov et al., 2004), in both (II) and (III) there is conjugation between the donor NH2 and the acceptor CN groups via the C2═C3 double bond. In addition, the H atoms of the NH2 group participate in intermolecular N—H···N and N—H···O hydrogen bonds. In (II), these interactions link the molecules into a sheet along the (103) plane (Fig. 3), while in (III) they link the molecules into ribbons along the a axis (Fig. 4). In (III), the acetonitrile molecules do not participate in hydrogen bonds and do not form any short intermolecular contacts. Most of the geometric parameters in the molecules are very similar to the standard values (Allen et al., 1987) and previous results on related compounds (Nesterov et al., 2004, 2005).
Using computational methods (GAUSSIAN03; Frisch et al., 2003), we explored the conformational preferences of the carbonyl substituent with respect to the pyran ring in compounds (II) and (III). For the molecule of (II), a restricted Hartree–Fock calculation on the conformer in the crystal [basis set 6–311++G(d,p)] gave a conformation that was not significantly different from that found in the crystal itself. Next, an AM1 calculation was carried out to minimize the conformer in the crystal. Continuing at the AM1 level, the O2—C8—C5—C4 angle was rotated in 10° increments and the conformations encountered were minimized until the starting conformer was encountered again. A map of the total energy versus scan step number showed only one distinct minimum conformer, similar to that found in the crystal. Two maxima were encountered, with the carbonyl group either ca 90° out of the plane of the pyran ring (about 2.2 kcal mol−1 above the energy of the minimum; 1 kcal mol−1 = 4.184 kJ mol−1) or nearly anti with respect to the double bond of the pyran ring (about 4.1 kcal mol−1 above the energy of the minimum). The maxima show severe methyl–phenyl and methyl–methyl steric interactions, respectively.
In contrast with compound (II), the calculations on (III) indicated somewhat different intrinsic preferred conformations than those displayed in the crystal. For the molecule of (III), a restricted Hartree–Fock calculation on the conformer in the crystal [basis set 6–311++G(d,p)] gave a conformation with the carbonyl group and the double bond still anti, but with a somewhat different dihedral angle (−141° versus −119°). Continuing at the AM1 level, the O2—C8—C5—C4 angle was rotated in 10° increments and the conformations encountered were minimized until the starting conformer was encountered again. A map of the total energy versus scan step number showed two distinct minima and two distinct maxima. In the found global minimum, the carbonyl group and double bond are approaching a syn relationship, with an associated dihedral angle of 54°. The second minimum had this dihedral angle at about −119° (this was the starting conformer from the crystal), with an associated energy 0.08 kcal mol−1 above the global minimum. The first maximum is 3.26 kcal mol−1 higher in energy than the global minimum and it displays a severe steric interaction between the two phenyl rings; the dihedral angle between the carbonyl group and double bond is −38°. The second maximum is 4.04 kcal mol−1 higher in energy than the global minimum and it displays a severe steric interaction between the phenyl of the ketone moiety and the methyl group; the dihedral angle between the double bond and carbonyl group is about 176°. The calculations indicate that the preferred conformations of (II) and (III) result from an interplay of the steric interactions between the bulky groups in these molecules with the normal intrinsic preferences of enone-type moieties.