Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800021115/ob6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800021115/ob6013Isup2.hkl |
CCDC reference: 159719
A mixture of ethyl 2-cyano-3,3-bis(methylthio)acrylate (4.34 g, 0.02 mol), acetophenone (2.4 ml, 0.02 mol), powdered KOH (2.24 g, 0.04 mol) and DMF (30 ml) was stirred at 305 K for 7 h. The red–brown mixture was poured onto crushed ice (300 g) and stirred at room temperature for 2 h. The yellow solid that separated was filtered, washed with water, dried and treated with cold acetone (3 × 15 ml); the combined acetone solution was concentrated to yield (II) as yellow needles (1.94 g, 40% yield; m.p. 481 K) [cf. literature m.p. 474 K (Tominaga et al., 1984)]. The cold acetone insoluble solid crystallized from hot acetone to yield (I) as pale yellow needles (0.96 g, 20% yield), m.p. 559–560 K (literature m.p. 519 K, Tominaga et al., 1984).
H atoms were added at calculated positions and refined using a riding model. H atoms were given isotropic displacement parameters equal to 1.2 (1.5 for methyl H atoms) times the equivalent isotropic displacement parameter of their parent atoms.
Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Siemens, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.
Fig. 1. View of one of the two independent molecules in (I). Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. |
C14H12N2O2 | F(000) = 1008 |
Mr = 240.26 | Dx = 1.364 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6587 (9) Å | Cell parameters from 4345 reflections |
b = 7.2783 (6) Å | θ = 1.5–26.0° |
c = 27.9741 (16) Å | µ = 0.09 mm−1 |
β = 99.684 (3)° | T = 180 K |
V = 2339.9 (3) Å3 | Block, pale yellow |
Z = 8 | 0.30 × 0.20 × 0.20 mm |
Siemens SMART CCD area-detector diffractometer | 4561 independent reflections |
Radiation source: normal-focus sealed tube | 2864 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.0°, θmin = 1.5° |
ω scans | h = −10→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −8→8 |
Tmin = 0.973, Tmax = 0.982 | l = −34→34 |
12607 measured reflections |
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) = 0.114 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0536P)2] where P = (Fo2 + 2Fc2)/3 |
4561 reflections | (Δ/σ)max < 0.001 |
329 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C14H12N2O2 | V = 2339.9 (3) Å3 |
Mr = 240.26 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.6587 (9) Å | µ = 0.09 mm−1 |
b = 7.2783 (6) Å | T = 180 K |
c = 27.9741 (16) Å | 0.30 × 0.20 × 0.20 mm |
β = 99.684 (3)° |
Siemens SMART CCD area-detector diffractometer | 4561 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2864 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.982 | Rint = 0.042 |
12607 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.21 e Å−3 |
4561 reflections | Δρmin = −0.19 e Å−3 |
329 parameters |
Experimental. The temperature of the crystal was controlled using the Oxford Cryosystem open-flow Cryostat (Cosier & Glazer, 1986). Data were collected over a hemisphere of reciprocal space, by a combination of three sets of exposures. Each set had a different ϕ angle for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal to detector distance was 5.01 cm. Coverage of the unique set was over 99% complete to at least 26° in θ. Crystal decay was monitored by repeating the initial frames at the end of the data collection and analyzing the duplicate reflections. IR (KBr) νmax: 3449 [N(CH3)2], 2205 (C≡N), 1688 (C═O), 1641, 1558, 1465, 1060, 932 and 772 cm-1. 1H NMR (TFA, 300 MHz): δ 3.49 and 3.71 (2xs, 3H each, 2xN-CH3), 6.86 (1H, s, C-5H), 7.54–7.63 (3H, m, H-3', H-4' & H-5') and 7.85 (2H, d, J = 7.80 Hz, H-2' & H-6'). 13C NMR (TFA, 75.5 MHz): δ 43.89 & 44.24 (2xN-CH3), 96.92 (C-5), 111.01 (C-3), 118.52 (CN), 122.28 (C-4'), 128.15 (C-3' & C-5'), 131.14 (C-2' & C-6'), 135.16 (C-4), 162.67 (C-1'), 163.45 (C-6) and 171.32 (C-2). EIMS, m/z (rel.int): 240 [M]+(47), 212 [M-28]+(15), 169 [M-71]+(8), 163 [M—Ar]+(7), 135 [M-ArCO]+(4), 107 [M-ArCO-CO]+(13), 105 (ArCO)+(100) and 77 (C6H5)+(85). |
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 | ||
O11 | 0.38666 (12) | 0.90305 (19) | −0.13770 (4) | 0.0359 (4) | |
O12 | 0.21862 (13) | 0.8966 (2) | −0.18735 (5) | 0.0448 (4) | |
O21 | 0.55726 (11) | 0.62673 (19) | 0.11667 (4) | 0.0339 (4) | |
O22 | 0.61066 (13) | 0.6818 (2) | 0.04609 (5) | 0.0446 (4) | |
N11 | 0.00612 (17) | 0.6985 (3) | −0.13740 (7) | 0.0497 (5) | |
N12 | 0.24002 (14) | 0.7142 (2) | −0.02171 (6) | 0.0337 (4) | |
N21 | 0.89957 (17) | 0.7618 (3) | 0.05510 (7) | 0.0583 (6) | |
N22 | 0.89459 (14) | 0.6833 (2) | 0.19192 (5) | 0.0323 (4) | |
C102 | 0.26816 (18) | 0.8665 (3) | −0.14628 (7) | 0.0334 (5) | |
C103 | 0.21813 (17) | 0.7968 (3) | −0.10696 (7) | 0.0310 (5) | |
C104 | 0.28474 (17) | 0.7681 (3) | −0.06058 (7) | 0.0292 (5) | |
C105 | 0.40773 (17) | 0.8021 (3) | −0.05629 (7) | 0.0301 (5) | |
H10A | 0.4571 | 0.7777 | −0.0263 | 0.036* | |
C106 | 0.45402 (17) | 0.8675 (3) | −0.09361 (7) | 0.0293 (5) | |
C107 | 0.57697 (17) | 0.9113 (3) | −0.09419 (7) | 0.0284 (5) | |
C108 | 0.66415 (17) | 0.8621 (3) | −0.05595 (7) | 0.0341 (5) | |
H10B | 0.6443 | 0.8022 | −0.0283 | 0.041* | |
C109 | 0.77946 (19) | 0.9001 (3) | −0.05801 (8) | 0.0410 (6) | |
H10C | 0.8384 | 0.8633 | −0.0321 | 0.049* | |
C110 | 0.80962 (19) | 0.9910 (3) | −0.09740 (7) | 0.0408 (6) | |
H11A | 0.8889 | 1.0182 | −0.0984 | 0.049* | |
C111 | 0.72436 (18) | 1.0421 (3) | −0.13532 (7) | 0.0369 (5) | |
H11B | 0.7448 | 1.1050 | −0.1624 | 0.044* | |
C112 | 0.60939 (18) | 1.0022 (3) | −0.13396 (7) | 0.0326 (5) | |
H11C | 0.5512 | 1.0368 | −0.1604 | 0.039* | |
C113 | 0.09965 (19) | 0.7430 (3) | −0.12205 (7) | 0.0344 (5) | |
C114 | 0.11558 (18) | 0.7197 (4) | −0.01966 (8) | 0.0465 (6) | |
H11D | 0.0800 | 0.8249 | −0.0384 | 0.070* | |
H11E | 0.1045 | 0.7319 | 0.0141 | 0.070* | |
H11F | 0.0788 | 0.6059 | −0.0333 | 0.070* | |
C115 | 0.31423 (19) | 0.6476 (3) | 0.02291 (7) | 0.0402 (6) | |
H11G | 0.3850 | 0.5921 | 0.0147 | 0.060* | |
H11H | 0.2716 | 0.5555 | 0.0386 | 0.060* | |
H11I | 0.3354 | 0.7508 | 0.0451 | 0.060* | |
C202 | 0.64341 (18) | 0.6688 (3) | 0.08980 (7) | 0.0328 (5) | |
C203 | 0.75960 (17) | 0.6920 (3) | 0.11502 (7) | 0.0294 (5) | |
C204 | 0.78736 (17) | 0.6677 (3) | 0.16589 (7) | 0.0289 (5) | |
C205 | 0.69134 (17) | 0.6246 (3) | 0.19023 (7) | 0.0300 (5) | |
H20A | 0.7055 | 0.6068 | 0.2244 | 0.036* | |
C206 | 0.58270 (17) | 0.6089 (3) | 0.16598 (7) | 0.0292 (5) | |
C207 | 0.47670 (17) | 0.5745 (3) | 0.18690 (7) | 0.0280 (5) | |
C208 | 0.47144 (17) | 0.6248 (3) | 0.23472 (7) | 0.0321 (5) | |
H20B | 0.5373 | 0.6788 | 0.2543 | 0.039* | |
C209 | 0.37070 (18) | 0.5960 (3) | 0.25355 (8) | 0.0369 (5) | |
H20C | 0.3671 | 0.6323 | 0.2859 | 0.044* | |
C210 | 0.27541 (19) | 0.5148 (3) | 0.22569 (8) | 0.0418 (6) | |
H21A | 0.2066 | 0.4948 | 0.2389 | 0.050* | |
C211 | 0.27987 (19) | 0.4625 (3) | 0.17842 (8) | 0.0410 (6) | |
H21B | 0.2145 | 0.4050 | 0.1594 | 0.049* | |
C212 | 0.37942 (17) | 0.4938 (3) | 0.15891 (7) | 0.0345 (5) | |
H21C | 0.3816 | 0.4601 | 0.1263 | 0.041* | |
C213 | 0.83938 (19) | 0.7319 (3) | 0.08294 (7) | 0.0395 (6) | |
C214 | 0.99363 (17) | 0.7495 (3) | 0.17141 (7) | 0.0419 (6) | |
H21F | 0.9739 | 0.8673 | 0.1551 | 0.063* | |
H21G | 1.0131 | 0.6598 | 0.1479 | 0.063* | |
H21D | 1.0605 | 0.7659 | 0.1974 | 0.063* | |
C215 | 0.91747 (19) | 0.6437 (4) | 0.24405 (7) | 0.0506 (7) | |
H21E | 0.8854 | 0.5230 | 0.2500 | 0.076* | |
H21I | 0.8807 | 0.7380 | 0.2614 | 0.076* | |
H21J | 1.0016 | 0.6437 | 0.2556 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0288 (8) | 0.0520 (10) | 0.0258 (7) | −0.0021 (7) | 0.0016 (6) | 0.0044 (7) |
O12 | 0.0344 (9) | 0.0691 (12) | 0.0294 (8) | 0.0014 (8) | 0.0005 (7) | 0.0024 (7) |
O21 | 0.0292 (8) | 0.0472 (10) | 0.0255 (7) | −0.0023 (7) | 0.0047 (6) | 0.0017 (6) |
O22 | 0.0412 (9) | 0.0665 (11) | 0.0258 (8) | −0.0015 (8) | 0.0044 (7) | 0.0029 (7) |
N11 | 0.0355 (12) | 0.0579 (14) | 0.0539 (12) | −0.0060 (10) | 0.0025 (10) | −0.0027 (10) |
N12 | 0.0280 (10) | 0.0433 (11) | 0.0305 (9) | −0.0019 (8) | 0.0070 (8) | −0.0005 (8) |
N21 | 0.0427 (13) | 0.0973 (18) | 0.0378 (11) | −0.0017 (12) | 0.0150 (10) | 0.0090 (12) |
N22 | 0.0270 (10) | 0.0408 (11) | 0.0292 (9) | 0.0010 (8) | 0.0046 (8) | 0.0013 (8) |
C102 | 0.0294 (12) | 0.0371 (13) | 0.0321 (12) | 0.0016 (10) | 0.0007 (10) | −0.0040 (10) |
C103 | 0.0273 (12) | 0.0322 (13) | 0.0335 (11) | −0.0022 (10) | 0.0051 (9) | −0.0040 (9) |
C104 | 0.0308 (12) | 0.0286 (12) | 0.0291 (11) | −0.0007 (10) | 0.0078 (9) | −0.0042 (9) |
C105 | 0.0273 (12) | 0.0370 (13) | 0.0255 (10) | 0.0006 (10) | 0.0032 (9) | −0.0008 (9) |
C106 | 0.0308 (12) | 0.0292 (12) | 0.0268 (11) | 0.0031 (9) | 0.0018 (9) | −0.0017 (9) |
C107 | 0.0286 (12) | 0.0293 (12) | 0.0278 (11) | 0.0005 (9) | 0.0069 (9) | −0.0022 (9) |
C108 | 0.0315 (13) | 0.0396 (13) | 0.0318 (11) | −0.0008 (10) | 0.0065 (10) | 0.0052 (10) |
C109 | 0.0306 (13) | 0.0529 (16) | 0.0385 (12) | 0.0038 (11) | 0.0027 (10) | 0.0067 (11) |
C110 | 0.0300 (12) | 0.0496 (15) | 0.0448 (13) | −0.0030 (11) | 0.0125 (11) | −0.0001 (11) |
C111 | 0.0368 (13) | 0.0414 (14) | 0.0357 (11) | −0.0030 (11) | 0.0153 (10) | 0.0032 (10) |
C112 | 0.0358 (13) | 0.0340 (12) | 0.0281 (10) | 0.0006 (10) | 0.0051 (9) | 0.0004 (9) |
C113 | 0.0330 (13) | 0.0362 (13) | 0.0338 (12) | 0.0000 (11) | 0.0053 (10) | −0.0016 (10) |
C114 | 0.0360 (14) | 0.0643 (17) | 0.0416 (13) | −0.0066 (12) | 0.0138 (11) | −0.0047 (12) |
C115 | 0.0418 (14) | 0.0481 (15) | 0.0323 (12) | 0.0002 (11) | 0.0104 (10) | 0.0053 (10) |
C202 | 0.0352 (13) | 0.0349 (13) | 0.0288 (12) | 0.0026 (10) | 0.0071 (10) | −0.0003 (9) |
C203 | 0.0293 (12) | 0.0315 (12) | 0.0288 (11) | 0.0001 (9) | 0.0091 (9) | −0.0004 (9) |
C204 | 0.0291 (12) | 0.0282 (12) | 0.0293 (11) | 0.0039 (9) | 0.0047 (9) | −0.0015 (9) |
C205 | 0.0289 (12) | 0.0359 (13) | 0.0250 (10) | −0.0005 (10) | 0.0042 (9) | 0.0016 (9) |
C206 | 0.0347 (13) | 0.0288 (12) | 0.0241 (11) | 0.0004 (10) | 0.0050 (9) | −0.0011 (8) |
C207 | 0.0266 (11) | 0.0265 (12) | 0.0304 (11) | 0.0005 (9) | 0.0035 (9) | 0.0037 (9) |
C208 | 0.0285 (12) | 0.0363 (13) | 0.0309 (11) | 0.0005 (10) | 0.0033 (9) | 0.0021 (9) |
C209 | 0.0349 (13) | 0.0408 (14) | 0.0366 (12) | 0.0055 (11) | 0.0107 (10) | 0.0053 (10) |
C210 | 0.0315 (13) | 0.0450 (15) | 0.0511 (14) | 0.0020 (11) | 0.0131 (11) | 0.0101 (12) |
C211 | 0.0313 (13) | 0.0406 (14) | 0.0498 (14) | −0.0091 (11) | 0.0035 (11) | 0.0019 (11) |
C212 | 0.0323 (12) | 0.0353 (13) | 0.0348 (11) | −0.0009 (10) | 0.0023 (10) | 0.0012 (10) |
C213 | 0.0335 (13) | 0.0532 (15) | 0.0307 (12) | 0.0042 (11) | 0.0024 (10) | 0.0023 (11) |
C214 | 0.0315 (13) | 0.0551 (16) | 0.0393 (13) | −0.0076 (11) | 0.0061 (10) | −0.0019 (11) |
C215 | 0.0347 (14) | 0.0794 (19) | 0.0360 (13) | −0.0045 (13) | 0.0010 (11) | 0.0098 (12) |
O11—C106 | 1.371 (2) | C106—C107 | 1.471 (3) |
O11—C102 | 1.388 (2) | C107—C108 | 1.393 (3) |
O12—C102 | 1.216 (2) | C107—C112 | 1.400 (3) |
O21—C206 | 1.368 (2) | C108—C109 | 1.383 (3) |
O21—C202 | 1.386 (2) | C109—C110 | 1.381 (3) |
O22—C202 | 1.222 (2) | C110—C111 | 1.377 (3) |
N11—C113 | 1.149 (2) | C111—C112 | 1.378 (3) |
N12—C104 | 1.341 (2) | C202—C203 | 1.428 (3) |
N12—C114 | 1.462 (3) | C203—C204 | 1.416 (3) |
N12—C115 | 1.476 (2) | C203—C213 | 1.427 (3) |
N21—C213 | 1.153 (3) | C204—C205 | 1.440 (3) |
N22—C204 | 1.342 (2) | C205—C206 | 1.337 (3) |
N22—C214 | 1.455 (2) | C206—C207 | 1.475 (3) |
N22—C215 | 1.466 (2) | C207—C212 | 1.395 (3) |
C102—C103 | 1.422 (3) | C207—C208 | 1.398 (3) |
C103—C104 | 1.411 (3) | C208—C209 | 1.382 (3) |
C103—C113 | 1.430 (3) | C209—C210 | 1.378 (3) |
C104—C105 | 1.440 (3) | C210—C211 | 1.386 (3) |
C105—C106 | 1.341 (3) | C211—C212 | 1.382 (3) |
C106—O11—C102 | 121.49 (16) | C111—C110—C109 | 119.8 (2) |
C206—O21—C202 | 120.93 (15) | C110—C111—C112 | 120.06 (19) |
C104—N12—C114 | 123.20 (17) | C111—C112—C107 | 121.04 (19) |
C104—N12—C115 | 121.96 (16) | N11—C113—C103 | 175.2 (2) |
C114—N12—C115 | 114.83 (16) | O22—C202—O21 | 115.27 (18) |
C204—N22—C214 | 122.87 (16) | O22—C202—C203 | 126.57 (19) |
C204—N22—C215 | 121.35 (17) | O21—C202—C203 | 118.16 (16) |
C214—N22—C215 | 115.69 (16) | C204—C203—C213 | 126.47 (18) |
O12—C102—O11 | 115.46 (19) | C204—C203—C202 | 121.26 (18) |
O12—C102—C103 | 127.1 (2) | C213—C203—C202 | 112.21 (16) |
O11—C102—C103 | 117.42 (17) | N22—C204—C203 | 124.71 (18) |
C104—C103—C102 | 122.00 (18) | N22—C204—C205 | 119.31 (17) |
C104—C103—C113 | 125.87 (18) | C203—C204—C205 | 115.98 (18) |
C102—C103—C113 | 111.78 (17) | C206—C205—C204 | 121.62 (17) |
N12—C104—C103 | 124.05 (18) | C205—C206—O21 | 121.99 (18) |
N12—C104—C105 | 120.01 (17) | C205—C206—C207 | 126.76 (17) |
C103—C104—C105 | 115.94 (18) | O21—C206—C207 | 111.24 (16) |
C106—C105—C104 | 121.45 (18) | C212—C207—C208 | 119.00 (18) |
C105—C106—O11 | 121.53 (18) | C212—C207—C206 | 120.34 (17) |
C105—C106—C107 | 127.31 (18) | C208—C207—C206 | 120.65 (18) |
O11—C106—C107 | 111.15 (17) | C209—C208—C207 | 120.14 (19) |
C108—C107—C112 | 118.16 (18) | C210—C209—C208 | 120.4 (2) |
C108—C107—C106 | 121.49 (18) | C209—C210—C211 | 120.1 (2) |
C112—C107—C106 | 120.34 (17) | C212—C211—C210 | 120.0 (2) |
C109—C108—C107 | 120.38 (19) | C211—C212—C207 | 120.37 (19) |
C110—C109—C108 | 120.6 (2) | N21—C213—C203 | 176.6 (2) |
C106—O11—C102—O12 | −177.02 (17) | C206—O21—C202—O22 | −179.81 (18) |
C106—O11—C102—C103 | 2.3 (3) | C206—O21—C202—C203 | 0.3 (3) |
O12—C102—C103—C104 | −179.8 (2) | O22—C202—C203—C204 | −178.0 (2) |
O11—C102—C103—C104 | 1.1 (3) | O21—C202—C203—C204 | 1.8 (3) |
O12—C102—C103—C113 | 6.7 (3) | O22—C202—C203—C213 | −0.8 (3) |
O11—C102—C103—C113 | −172.50 (17) | O21—C202—C203—C213 | 179.08 (18) |
C114—N12—C104—C103 | −14.6 (3) | C214—N22—C204—C203 | 7.7 (3) |
C115—N12—C104—C103 | 166.51 (19) | C215—N22—C204—C203 | −175.8 (2) |
C114—N12—C104—C105 | 164.68 (19) | C214—N22—C204—C205 | −171.82 (19) |
C115—N12—C104—C105 | −14.2 (3) | C215—N22—C204—C205 | 4.7 (3) |
C102—C103—C104—N12 | 175.42 (19) | C213—C203—C204—N22 | 1.7 (3) |
C113—C103—C104—N12 | −12.0 (3) | C202—C203—C204—N22 | 178.52 (19) |
C102—C103—C104—C105 | −3.9 (3) | C213—C203—C204—C205 | −178.8 (2) |
C113—C103—C104—C105 | 168.70 (19) | C202—C203—C204—C205 | −1.9 (3) |
N12—C104—C105—C106 | −175.6 (2) | N22—C204—C205—C206 | 179.50 (19) |
C103—C104—C105—C106 | 3.8 (3) | C203—C204—C205—C206 | −0.1 (3) |
C104—C105—C106—O11 | −0.7 (3) | C204—C205—C206—O21 | 2.2 (3) |
C104—C105—C106—C107 | 178.94 (19) | C204—C205—C206—C207 | −176.73 (19) |
C102—O11—C106—C105 | −2.5 (3) | C202—O21—C206—C205 | −2.3 (3) |
C102—O11—C106—C107 | 177.84 (16) | C202—O21—C206—C207 | 176.76 (16) |
C105—C106—C107—C108 | 9.7 (3) | C205—C206—C207—C212 | −155.6 (2) |
O11—C106—C107—C108 | −170.67 (17) | O21—C206—C207—C212 | 25.3 (3) |
C105—C106—C107—C112 | −171.2 (2) | C205—C206—C207—C208 | 25.4 (3) |
O11—C106—C107—C112 | 8.5 (3) | O21—C206—C207—C208 | −153.68 (17) |
C112—C107—C108—C109 | −1.1 (3) | C212—C207—C208—C209 | −0.6 (3) |
C106—C107—C108—C109 | 178.1 (2) | C206—C207—C208—C209 | 178.43 (18) |
C107—C108—C109—C110 | 1.5 (3) | C207—C208—C209—C210 | 1.1 (3) |
C108—C109—C110—C111 | −0.9 (3) | C208—C209—C210—C211 | −0.4 (3) |
C109—C110—C111—C112 | −0.2 (3) | C209—C210—C211—C212 | −0.9 (3) |
C110—C111—C112—C107 | 0.6 (3) | C210—C211—C212—C207 | 1.4 (3) |
C108—C107—C112—C111 | 0.0 (3) | C208—C207—C212—C211 | −0.6 (3) |
C106—C107—C112—C111 | −179.18 (19) | C206—C207—C212—C211 | −179.66 (19) |
C104—C103—C113—N11 | −150 (3) | C204—C203—C213—N21 | 166 (4) |
C102—C103—C113—N11 | 23 (3) | C202—C203—C213—N21 | −11 (4) |
Experimental details
Crystal data | |
Chemical formula | C14H12N2O2 |
Mr | 240.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 180 |
a, b, c (Å) | 11.6587 (9), 7.2783 (6), 27.9741 (16) |
β (°) | 99.684 (3) |
V (Å3) | 2339.9 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.973, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12607, 4561, 2864 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.114, 1.01 |
No. of reflections | 4561 |
No. of parameters | 329 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.19 |
Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1995), SAINT, SHELXTL/PC (Siemens, 1994), SHELXL97 (Sheldrick, 1997), SHELXTL/PC.
N12—C104 | 1.341 (2) | N22—C204 | 1.342 (2) |
N12—C114 | 1.462 (3) | N22—C214 | 1.455 (2) |
N12—C115 | 1.476 (2) | N22—C215 | 1.466 (2) |
C114—N12—C104—C103 | −14.6 (3) | C214—N22—C204—C203 | 7.7 (3) |
O11—C106—C107—C108 | −170.67 (17) | O21—C206—C207—C208 | −153.68 (17) |
The presence of carbonyl functionality and its position in conjugation with the double bond carrying bis(alkylthio) group at the β-position places ketene dithioacetal and its derivatives as versatile reagents for the preparation of different classes of heterocyclic compounds (Kumar et al., 1976; Chauhan & Junjappa, 1976). We have reported the synthesis of a number of heterocyclic compounds by the application of ketene dithioacetals (Parmar et al., 1997). Various 4-hydroxy-2H-pyran-2-ones and their derivatives have exhibited a variety of pharmacological properties (Israili & Smissman, 1976; Kretzschmar et al., 1969); some of these pyrones were found to be useful intermediates in the synthesis of naturally occurring bioactive compounds such as phenylcoumalin, paracotoin, methoxyparacotoin and yangonin derivatives (Tominaga et al., 1977, 1984). In an attempt to synthesize 3-cyano-4-methylthio-6-phenyl-2H-pyran-2-one, (II), by treating ethyl 2-cyano-3,3-bis(methylthio)acrylate and acetophenone in DMF and potassium hydroxide, we obtained the title compound, (I), as a minor side product along with (II). Pyrones of the type (I) having an amino group at the C-4 position are of particular interest in that they have exhibited antibacterial and antifungal activities. Although the title compound has been previously reported (Tominaga et al., 1984), its NMR and MS data have not been reported and the melting point (519 K) given earlier does not agree with that obtained for our sample (559–560 K). In order to characterize this compound unambiguously, we now report extensive spectral data and its X-ray crystallographic structure.
The asymmetric unit of the title compound, (I), contains two molecules, one of which is illustrated in Fig. 1. The bond lengths and angles are unexceptional and are essentially identical for both molecules. The conformations of these two molecules, however, do differ significantly. The angles between the least-squares planes through the pyran ring and the attached phenyl groups are 10.32 (8) and 26.34 (5)° for the two molecules; the comparative angles between the planes of the pyran rings and the C—N—C planes of the amino groups are 15.13 (15) and 7.00 (12)°, respectively. These differences are also illustrated by the torsion angles listed in Table 1.
The structure of the 3-cyano-2H-pyran-2-one fragment has been reported previously, but only in combination with a 4-methylthio substituent (five structures: Kumar et al., 1999, and references therein). In all of these structures, the methylthio substituent is approximately coplanar with the pyran ring. Similarly, in (I), the dimethylamino group in the 4-position is almost coplanar (see angles quoted above) and this may be attributed, as in the methylthio case, to some π-bonding; this is manifest in the Car—N linkage which is much shorter than the N—Me distances (Table 1).