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The title compound, C13H12N2OS, was prepared by condensation of 4-methoxycinnamaldehyde and thioacetamide in ethanol at room temperature. Its investigation was undertaken as part of our search for new non-linear optical compounds. The π-conjugated title molecule is almost planar, the dihedral angle between the central planar 2-cyano-5-(4-methoxy­phenyl)penta-2,4-diene fragment and the thioacetamide group being 9.2 (6)°. Molecules are linked by N—H...N and N—H...O hydrogen bonds forming a two-dimensional motif.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012998/bm1375sup1.cif
Contains datablocks (I), global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012998/bm1375Isup2.hkl
Contains datablock I

CCDC reference: 140961

Comment top

Structural studies of polarized organic molecules as components for non-linear optical (NLO) and photorefractive materials have attracted a great deal of attention in the last two decades [see, for instance, Zyss (1994)]. The present work is part of a continuing project on the synthesis, structure investigation and property evaluation of potential NLO compounds. Recently, we investigated a series of polarized molecules having a dicyanovinyl acceptor part and various donors connected by π-conjugated chains of different lengths. There are derivatives of 2-aryl-1,1-dicyanovinyl and 4-aryl-1,1-dicyano-1,3-butadiene (Antipin et al., 1997; Antipin, Clark et al., 1998; Antipin, Timofeeva et al., 1998; Timofeeva et al., 1999). We present herein a structural investigation of the title compound, (I), whose molecules have another type of acceptor group.

According to our quantum-chemical calculations [using modified MOPAC and HYPER programs (Cardelino et al., 1991, 1997)], the molecular hyperpolarizability of (I) is equal to 142 × 10−51 C m3 V−2. This is about 40% larger than for the dicyanovinyl analogues (Antipin, Clark et al., 1998).

The molecule (Fig. 1) contains an almost planar fragment consisting of p-methoxyphenyl and 1-cyano-1,3-butadiene moieties, with a dihedral angle between them of 1.7 (2)°. The maximum deviation from the least-squares plane passing through all non-H atoms of this fragment is 0.031 (3) Å. The 1-cyano-1,3-butadiene fragment in (I) is planar despite the shortened H6A···H8A [2.196 (6) Å] and H8A···C12 [2.577 (6) Å] intramolecular contacts; the corresponding van der Waals radii sums are 2.20 and 2.87 Å, respectively (Rowland & Taylor, 1996). The thioacetamide group is slightly out of the above-mentioned planar fragment, with a dihedral angle of 9.2 (6)° between the two.

Bond lengths in (I) do not differ significantly from those of 4-aryl-1,1-dicyano-1,3-butadiene (Antipin, Clark et al., 1998). In the 1,3-butadiene fragment, the observed bond-length alternation [for standard bond lengths, see Allen et al. (1987)] indicates π-conjugation in this system.

In the crystalline phase, molecules of (I) are linked by hydrogen bonds forming a two-dimensional motif (Fig. 2). Both H atoms of the amino group are involved in hydrogen-bond formation, one with the O atom of the methoxy group and the other with the N atom of the cyano group of a neighboring molecule.

Compound (I) crystallizes in a centrosymmetric space group and this phase therefore cannot exhibit second-order NLO effects, but the compound may do so when incorporated into a suitable liquid crystalline or polymer matrix.

Experimental top

The title compound was obtained by the reaction of 4-methoxycinnamaldehyde (0.81 g, 5 mmol) with thioacetamide (0.50 g, 5 mmol) in the presence of a catalytic amount of morpholine (0.1 ml) in ethanol (20 ml) at room temperature. The precipitate which separated from the solution was recrystallized from ethanol (30 ml) (m.p. 458–459 K; yield 0.93 g, 76%). Yellow crystals were obtained by isothermal evaporation from a solution of (I) in ethanol.

Refinement top

The two amino H atoms were located from a difference Fourier map and were refined isotropically. All other H atoms were positioned geometrically and thereafter refined using a riding model.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXTL-Plus; program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.

Figures top
[Figure 1] Fig. 1. View of the title molecule with the atom-numbering scheme. The non-H atoms are shown with 50% probability displacement ellipsoids. H atoms are drawn as circles of small arbitrary radius for clarity.
[Figure 2] Fig. 2. Projection onto the bc plane showing the hydrogen-bonding scheme. [Symmetry codes: (i) 1 − x, 2 − y, −z; (ii) −3/2 + x, 3/2 − y, 1/2 + z.]
(I) top
Crystal data top
C13H12N2OSF(000) = 512
Mr = 244.31Dx = 1.313 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.4590 (13) ÅCell parameters from 24 reflections
b = 15.662 (3) Åθ = 11–12°
c = 12.276 (3) ŵ = 0.25 mm1
β = 95.51 (3)°T = 295 K
V = 1236.1 (4) Å3Prism, yellow
Z = 40.45 × 0.30 × 0.25 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.112
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.1°
Graphite monochromatorh = 08
θ/2θ scansk = 019
2922 measured reflectionsl = 1515
2688 independent reflections3 standard reflections every 97 reflections
1283 reflections with I > 2σ(I) intensity decay: 5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.076Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.201H atoms treated by a mixture of independent and constrained refinement
S = 1.10Calculated w = 1/[σ2(Fo2) + (0.1213P)2]
where P = (Fo2 + 2Fc2)/3
2655 reflections(Δ/σ)max < 0.001
162 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C13H12N2OSV = 1236.1 (4) Å3
Mr = 244.31Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.4590 (13) ŵ = 0.25 mm1
b = 15.662 (3) ÅT = 295 K
c = 12.276 (3) Å0.45 × 0.30 × 0.25 mm
β = 95.51 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.112
2922 measured reflections3 standard reflections every 97 reflections
2688 independent reflections intensity decay: 5%
1283 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0760 restraints
wR(F2) = 0.201H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.32 e Å3
2655 reflectionsΔρmin = 0.30 e Å3
162 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 on F2 for ALL reflections except for 33 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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. The H atoms of the amino group were located from a difference Fourier map and refined isotropically (they are involved in the hydrogen bonds). All the other H atoms were placed in calculated positions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.1221 (2)0.74352 (7)0.15076 (11)0.0685 (5)
O11.3971 (5)0.5001 (2)0.2771 (3)0.0676 (9)
N10.6636 (7)0.9262 (3)0.0180 (4)0.0787 (13)
N20.2078 (6)0.9008 (2)0.1019 (3)0.0578 (10)
H1N0.279 (7)0.943 (3)0.069 (4)0.080 (16)*
H2N0.099 (7)0.913 (3)0.130 (4)0.062 (14)*
C10.8939 (6)0.5876 (3)0.1211 (3)0.0482 (10)
C20.9184 (6)0.4997 (3)0.1393 (4)0.0560 (11)
H2A0.8214 (6)0.4617 (3)0.1158 (4)0.067*
C31.0828 (7)0.4683 (3)0.1915 (4)0.0563 (11)
H3A1.0948 (7)0.4099 (3)0.2031 (4)0.068*
C41.2280 (6)0.5231 (3)0.2259 (3)0.0506 (10)
C51.2062 (7)0.6111 (3)0.2093 (4)0.0580 (11)
H5A1.3030 (7)0.6487 (3)0.2336 (4)0.070*
C61.0431 (6)0.6419 (3)0.1573 (3)0.0557 (11)
H6A1.0321 (6)0.7004 (3)0.1461 (3)0.067*
C70.7203 (6)0.6166 (3)0.0663 (3)0.0528 (11)
H7A0.6301 (6)0.5749 (3)0.0449 (3)0.063*
C80.6748 (6)0.6979 (3)0.0428 (3)0.0529 (10)
H8A0.7622 (6)0.7411 (3)0.0632 (3)0.063*
C90.4982 (7)0.7207 (3)0.0120 (3)0.0508 (10)
H9A0.4129 (7)0.6763 (3)0.0310 (3)0.061*
C100.4428 (6)0.8005 (2)0.0390 (3)0.0489 (10)
C110.2559 (6)0.8197 (2)0.0960 (3)0.0496 (10)
C120.5662 (7)0.8700 (3)0.0074 (4)0.0588 (11)
C131.4261 (8)0.4114 (3)0.2968 (5)0.0757 (14)
H13A1.5499 (8)0.4035 (3)0.3331 (5)0.114*
H13B1.3084 (8)0.3897 (3)0.3422 (5)0.114*
H13C1.4396 (8)0.3812 (3)0.2284 (5)0.114*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0753 (8)0.0490 (7)0.0867 (9)0.0128 (6)0.0372 (7)0.0034 (6)
O10.066 (2)0.060 (2)0.081 (2)0.007 (2)0.031 (2)0.004 (2)
N10.079 (3)0.057 (2)0.107 (3)0.003 (2)0.041 (2)0.013 (2)
N20.065 (2)0.043 (2)0.071 (3)0.002 (2)0.034 (2)0.004 (2)
C10.048 (2)0.049 (2)0.047 (2)0.003 (2)0.004 (2)0.004 (2)
C20.063 (2)0.044 (2)0.063 (3)0.006 (2)0.018 (2)0.006 (2)
C30.070 (3)0.043 (2)0.057 (3)0.005 (2)0.010 (2)0.000 (2)
C40.052 (2)0.054 (2)0.046 (2)0.000 (2)0.008 (2)0.006 (2)
C50.057 (2)0.044 (2)0.075 (3)0.007 (2)0.013 (2)0.002 (2)
C60.060 (2)0.043 (2)0.065 (3)0.001 (2)0.011 (2)0.003 (2)
C70.058 (2)0.047 (2)0.054 (3)0.006 (2)0.009 (2)0.004 (2)
C80.058 (2)0.050 (2)0.051 (2)0.001 (2)0.010 (2)0.002 (2)
C90.055 (2)0.048 (2)0.050 (2)0.005 (2)0.008 (2)0.000 (2)
C100.055 (2)0.040 (2)0.053 (2)0.007 (2)0.009 (2)0.001 (2)
C110.059 (2)0.039 (2)0.052 (2)0.005 (2)0.009 (2)0.001 (2)
C120.062 (3)0.051 (3)0.067 (3)0.002 (2)0.022 (2)0.003 (2)
C130.080 (3)0.067 (3)0.085 (4)0.007 (3)0.033 (3)0.006 (3)
Geometric parameters (Å, º) top
S1—C111.653 (4)C5—C61.370 (6)
O1—C41.361 (5)C5—H5A0.93
O1—C131.425 (6)C6—H6A0.93
N1—C121.143 (6)C7—C81.344 (6)
N2—C111.312 (5)C7—H7A0.93
N2—H1N0.92 (5)C8—C91.424 (6)
N2—H2N0.83 (5)C8—H8A0.93
C1—C61.390 (6)C9—C101.351 (6)
C1—C21.407 (6)C9—H9A0.93
C1—C71.435 (6)C10—C121.425 (6)
C2—C31.382 (6)C10—C111.483 (6)
C2—H2A0.93C13—H13A0.96
C3—C41.368 (6)C13—H13B0.96
C3—H3A0.93C13—H13C0.96
C4—C51.401 (6)
C4—O1—C13117.5 (4)C8—C7—C1126.6 (4)
C11—N2—H1N123 (3)C8—C7—H7A116.7 (3)
C11—N2—H2N117 (3)C1—C7—H7A116.7 (2)
H1N—N2—H2N120 (4)C7—C8—C9122.7 (4)
C6—C1—C2117.1 (4)C7—C8—H8A118.7 (3)
C6—C1—C7123.6 (4)C9—C8—H8A118.7 (3)
C2—C1—C7119.3 (4)C10—C9—C8126.2 (4)
C3—C2—C1121.7 (4)C10—C9—H9A116.9 (2)
C3—C2—H2A119.1 (2)C8—C9—H9A116.9 (2)
C1—C2—H2A119.1 (2)C9—C10—C12118.2 (4)
C4—C3—C2120.0 (4)C9—C10—C11123.4 (4)
C4—C3—H3A120.0 (3)C12—C10—C11118.4 (4)
C2—C3—H3A120.0 (2)N2—C11—C10115.5 (4)
O1—C4—C3125.5 (4)N2—C11—S1122.7 (3)
O1—C4—C5115.2 (4)C10—C11—S1121.8 (3)
C3—C4—C5119.4 (4)N1—C12—C10179.3 (5)
C6—C5—C4120.5 (4)O1—C13—H13A109.5 (2)
C6—C5—H5A119.8 (3)O1—C13—H13B109.5 (3)
C4—C5—H5A119.8 (3)H13A—C13—H13B109.5
C5—C6—C1121.4 (4)O1—C13—H13C109.5 (3)
C5—C6—H6A119.3 (3)H13A—C13—H13C109.5
C1—C6—H6A119.3 (2)H13B—C13—H13C109.5
C6—C1—C2—C30.3 (6)C6—C1—C7—C80.5 (7)
C7—C1—C2—C3179.9 (4)C2—C1—C7—C8179.9 (4)
C1—C2—C3—C40.5 (7)C1—C7—C8—C9180.0 (4)
C13—O1—C4—C30.1 (6)C7—C8—C9—C10179.6 (4)
C13—O1—C4—C5179.6 (4)C8—C9—C10—C122.2 (6)
C2—C3—C4—O1179.4 (4)C8—C9—C10—C11179.9 (4)
C2—C3—C4—C50.9 (6)C9—C10—C11—N2170.5 (4)
O1—C4—C5—C6179.2 (4)C12—C10—C11—N27.1 (6)
C3—C4—C5—C61.1 (6)C9—C10—C11—S111.0 (6)
C4—C5—C6—C10.9 (7)C12—C10—C11—S1171.4 (3)
C2—C1—C6—C50.4 (6)C9—C10—C12—N1151.46
C7—C1—C6—C5180.0 (4)C11—C10—C12—N127.46
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N···N1i0.92 (5)2.18 (5)3.042 (5)155 (4)
N2—H2N···O1ii0.83 (5)2.27 (5)3.035 (5)153 (4)
Symmetry codes: (i) x+1, y+2, z; (ii) x3/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC13H12N2OS
Mr244.31
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)6.4590 (13), 15.662 (3), 12.276 (3)
β (°) 95.51 (3)
V3)1236.1 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.45 × 0.30 × 0.25
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2922, 2688, 1283
Rint0.112
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.076, 0.201, 1.10
No. of reflections2655
No. of parameters162
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.30

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXTL-Plus (Sheldrick, 1994), SHELXTL-Plus.

Selected geometric parameters (Å, º) top
S1—C111.653 (4)C1—C71.435 (6)
O1—C41.361 (5)C7—C81.344 (6)
O1—C131.425 (6)C8—C91.424 (6)
N1—C121.143 (6)C9—C101.351 (6)
N2—C111.312 (5)C10—C121.425 (6)
N2—H1N0.92 (5)C10—C111.483 (6)
N2—H2N0.83 (5)
C4—O1—C13117.5 (4)C7—C8—C9122.7 (4)
C11—N2—H1N123 (3)C10—C9—C8126.2 (4)
C11—N2—H2N117 (3)C9—C10—C12118.2 (4)
H1N—N2—H2N120 (4)C9—C10—C11123.4 (4)
C6—C1—C2117.1 (4)C12—C10—C11118.4 (4)
C6—C1—C7123.6 (4)N2—C11—C10115.5 (4)
C2—C1—C7119.3 (4)N2—C11—S1122.7 (3)
O1—C4—C3125.5 (4)C10—C11—S1121.8 (3)
O1—C4—C5115.2 (4)N1—C12—C10179.3 (5)
C8—C7—C1126.6 (4)
C13—O1—C4—C30.1 (6)C8—C9—C10—C11179.9 (4)
C13—O1—C4—C5179.6 (4)C9—C10—C11—N2170.5 (4)
C2—C1—C7—C8179.9 (4)C12—C10—C11—N27.1 (6)
C1—C7—C8—C9180.0 (4)C9—C10—C11—S111.0 (6)
C7—C8—C9—C10179.6 (4)C12—C10—C11—S1171.4 (3)
C8—C9—C10—C122.2 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N···N1i0.92 (5)2.18 (5)3.042 (5)155 (4)
N2—H2N···O1ii0.83 (5)2.27 (5)3.035 (5)153 (4)
Symmetry codes: (i) x+1, y+2, z; (ii) x3/2, y+3/2, z+1/2.
 

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