2-[(5-Methyl­thio­phen-2-yl)methyl­idene]malono­nitrile

Liu, X.; Chen, Z.; Cao, W.; Gan, H.; Guo, K.

doi:10.1107/S1600536813014487

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1003

https://doi.org/10.1107/S1600536813014487

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2-[(5-Methylthiophen-2-yl)methylidene]malononitrile

Xuewei Liu,^a Zhengbang Chen,^a Weiwei Cao,^a Haifeng Gan ^a and Kai Guo ^a ^*

^aCollege of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Puzhunan Road No.30 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kaiguo@njut.edu.cn

(Received 19 March 2013; accepted 25 May 2013; online 8 June 2013)

There are two independent molecules in the asymmetric unit of the title compound, C₉H₆N₂S, which is an intermediate compound of a cardiovascular drug. The two molecules are nearly planar, displaying dihedral angles of 3.5 (2) and 5.7 (2)° between the thiophene ring and the malononitrile moiety. In the crystal, C—H⋯N interactions lead to the formation of a sheet structure that packs in a parallel fashion.

Related literature

For a related structure, see: Altundas et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₆N₂S
M_r = 174.22
Triclinic, $[P \overline 1]$
a = 9.1120 (18) Å
b = 9.9380 (2) Å
c = 10.1350 (2) Å
α = 81.10 (3)°
β = 80.71 (3)°
γ = 86.70 (3)°
V = 894.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.915, T_max = 0.970
3465 measured reflections
3247 independent reflections
1399 reflections with I > 2σ(I)
R_int = 0.081
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.102
S = 1.00
3247 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯N2ⁱ	0.93	2.52	3.439 (6)	168
C6—H6A⋯N3ⁱⁱ	0.93	2.52	3.434 (6)	169
C12—H12A⋯N4ⁱⁱⁱ	0.93	2.60	3.518 (6)	171
C15—H15A⋯N1ⁱ	0.93	2.51	3.430 (6)	170
Symmetry codes: (i) x, y, z+1; (ii) x+1, y-1, z-1; (iii) x, y, z-1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813014487/ds2229sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813014487/ds2229Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813014487/ds2229Isup3.cml

checkCIF report

Related literature top

For a related structure, see: Altundas et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of 5-methylthiophene-2-carbaldehyde (10.02 mmol, 1.27 g) and malononitrile (10.13 mmol, 0.67 g) in ethanol (20 ml) was added triethyl (0.31 ml) and the reaction mixture stired at room temperature for 3 h. The reaction solution was filtered to get the title compound (1.44 g) as yellow solid. Crystals of the title compound for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Structure description top

For a related structure, see: Altundas et al. (2011). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Fig. 2. A practical packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A packing diagram for the title compound.

2-[(5-Methylthiophen-2-yl)methylidene]malononitrile top

Crystal data top

C₉H₆N₂S	Z = 4
M_r = 174.22	F(000) = 360
Triclinic, P1	D_x = 1.294 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1120 (18) Å	Cell parameters from 25 reflections
b = 9.9380 (2) Å	θ = 9–13°
c = 10.1350 (2) Å	µ = 0.30 mm⁻¹
α = 81.10 (3)°	T = 293 K
β = 80.71 (3)°	Colorless, yellow
γ = 86.70 (3)°	0.30 × 0.20 × 0.10 mm
V = 894.3 (3) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1399 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.081
Graphite monochromator	θ_max = 25.4°, θ_min = 2.1°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
T_min = 0.915, T_max = 0.970	l = −12→12
3465 measured reflections	3 standard reflections every 200 reflections
3247 independent reflections	intensity decay: 1%

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.017P)²] where P = (F_o² + 2F_c²)/3
3247 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₉H₆N₂S	γ = 86.70 (3)°
M_r = 174.22	V = 894.3 (3) Å³
Triclinic, P1	Z = 4
a = 9.1120 (18) Å	Mo Kα radiation
b = 9.9380 (2) Å	µ = 0.30 mm⁻¹
c = 10.1350 (2) Å	T = 293 K
α = 81.10 (3)°	0.30 × 0.20 × 0.10 mm
β = 80.71 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1399 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.081
T_min = 0.915, T_max = 0.970	3 standard reflections every 200 reflections
3465 measured reflections	intensity decay: 1%
3247 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.00	Δρ_max = 0.20 e Å⁻³
3247 reflections	Δρ_min = −0.28 e Å⁻³
217 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	U_iso*/U_eq
S1	0.49006 (14)	0.26105 (12)	−0.05976 (12)	0.0669 (4)
N1	0.4196 (5)	0.3320 (4)	−0.3837 (4)	0.0881 (14)
C1	0.4416 (6)	0.3227 (5)	0.2007 (5)	0.0890 (16)
H1A	0.4734	0.2980	0.2872	0.133*
H1B	0.3370	0.3081	0.2092	0.133*
H1C	0.4603	0.4171	0.1682	0.133*
C2	0.5250 (5)	0.2376 (5)	0.1038 (4)	0.0659 (14)
N2	0.7023 (5)	0.0147 (5)	−0.5565 (4)	0.0922 (15)
C3	0.6315 (5)	0.1367 (5)	0.1227 (5)	0.0712 (15)
H3A	0.6654	0.1091	0.2047	0.085*
C4	0.6835 (5)	0.0797 (4)	0.0059 (4)	0.0657 (13)
H4A	0.7563	0.0102	0.0025	0.079*
C5	0.6177 (5)	0.1354 (4)	−0.1039 (4)	0.0505 (12)
C6	0.6545 (5)	0.0882 (4)	−0.2296 (4)	0.0540 (12)
H6A	0.7237	0.0157	−0.2307	0.065*
C7	0.6063 (4)	0.1304 (4)	−0.3479 (4)	0.0525 (12)
C8	0.5028 (5)	0.2431 (5)	−0.3670 (4)	0.0630 (14)
C9	0.6586 (5)	0.0674 (5)	−0.4633 (5)	0.0644 (14)
S2	−0.01039 (14)	0.76331 (12)	0.47759 (12)	0.0648 (4)
N3	−0.0749 (5)	0.8358 (4)	0.8055 (4)	0.1014 (16)
N4	0.2033 (5)	0.5077 (4)	0.9825 (4)	0.0876 (14)
C10	−0.0682 (5)	0.8159 (5)	0.2138 (4)	0.0893 (17)
H10A	−0.0390	0.7866	0.1272	0.134*
H10B	−0.0479	0.9107	0.2070	0.134*
H10C	−0.1726	0.8030	0.2428	0.134*
C11	0.0171 (5)	0.7347 (5)	0.3137 (4)	0.0602 (13)
C12	0.1235 (6)	0.6340 (5)	0.2928 (4)	0.0652 (14)
H12A	0.1542	0.6064	0.2088	0.078*
C13	0.1810 (5)	0.5769 (4)	0.4076 (5)	0.0641 (13)
H13A	0.2525	0.5063	0.4094	0.077*
C14	0.1206 (4)	0.6363 (4)	0.5186 (4)	0.0540 (12)
C15	0.1587 (5)	0.5924 (4)	0.6492 (4)	0.0563 (12)
H15A	0.2295	0.5211	0.6526	0.068*
C16	0.1108 (5)	0.6353 (4)	0.7697 (4)	0.0506 (11)
C17	0.0059 (5)	0.7456 (5)	0.7899 (4)	0.0603 (14)
C18	0.1617 (5)	0.5647 (5)	0.8883 (5)	0.0640 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0696 (9)	0.0566 (8)	0.0684 (9)	0.0139 (7)	−0.0053 (7)	−0.0016 (6)
N1	0.083 (3)	0.074 (3)	0.102 (3)	0.030 (3)	−0.019 (3)	−0.004 (2)
C1	0.095 (4)	0.091 (4)	0.076 (4)	0.006 (3)	−0.007 (3)	−0.006 (3)
C2	0.061 (3)	0.069 (3)	0.061 (3)	0.000 (3)	0.004 (3)	−0.002 (3)
N2	0.088 (4)	0.104 (4)	0.084 (3)	0.024 (3)	−0.023 (3)	−0.013 (3)
C3	0.068 (4)	0.068 (4)	0.070 (3)	0.008 (3)	−0.008 (3)	0.009 (3)
C4	0.071 (4)	0.050 (3)	0.070 (3)	0.006 (3)	−0.010 (3)	0.006 (2)
C5	0.052 (3)	0.045 (3)	0.047 (3)	0.007 (2)	−0.002 (2)	0.007 (2)
C6	0.049 (3)	0.038 (3)	0.066 (3)	0.005 (2)	0.001 (2)	0.008 (2)
C7	0.043 (3)	0.047 (3)	0.061 (3)	0.014 (2)	−0.003 (2)	0.003 (2)
C8	0.059 (3)	0.065 (3)	0.059 (3)	0.008 (3)	0.000 (3)	−0.002 (3)
C9	0.057 (3)	0.066 (3)	0.065 (3)	0.016 (3)	−0.010 (3)	0.000 (3)
S2	0.0640 (9)	0.0575 (8)	0.0679 (9)	0.0153 (7)	−0.0109 (7)	0.0010 (6)
N3	0.118 (4)	0.083 (3)	0.095 (3)	0.038 (3)	−0.005 (3)	−0.014 (3)
N4	0.097 (4)	0.087 (3)	0.079 (3)	0.019 (3)	−0.029 (3)	−0.003 (2)
C10	0.083 (4)	0.110 (4)	0.072 (3)	−0.007 (3)	−0.023 (3)	0.008 (3)
C11	0.058 (3)	0.061 (3)	0.053 (3)	−0.010 (3)	0.002 (2)	0.009 (2)
C12	0.072 (4)	0.065 (3)	0.058 (3)	−0.002 (3)	−0.001 (3)	−0.016 (3)
C13	0.057 (3)	0.054 (3)	0.075 (3)	0.010 (2)	−0.002 (3)	−0.001 (3)
C14	0.048 (3)	0.048 (3)	0.061 (3)	0.003 (2)	−0.001 (2)	−0.001 (2)
C15	0.046 (3)	0.040 (3)	0.077 (3)	0.010 (2)	−0.004 (2)	0.001 (2)
C16	0.054 (3)	0.042 (3)	0.052 (3)	0.010 (2)	−0.007 (2)	0.001 (2)
C17	0.069 (3)	0.046 (3)	0.061 (3)	0.019 (3)	−0.005 (3)	−0.004 (2)
C18	0.054 (3)	0.063 (3)	0.072 (3)	0.018 (3)	−0.013 (3)	−0.006 (3)

Geometric parameters (Å, º) top

S1—C2	1.716 (4)	S2—C11	1.704 (4)
S1—C5	1.717 (4)	S2—C14	1.736 (4)
N1—C8	1.141 (5)	N3—C17	1.141 (5)
C1—C2	1.483 (6)	N4—C18	1.141 (5)
C1—H1A	0.9600	C10—C11	1.486 (5)
C1—H1B	0.9600	C10—H10A	0.9600
C1—H1C	0.9600	C10—H10B	0.9600
C2—C3	1.368 (6)	C10—H10C	0.9600
N2—C9	1.155 (5)	C11—C12	1.369 (6)
C3—C4	1.394 (5)	C12—C13	1.381 (6)
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.375 (5)	C13—C14	1.373 (5)
C4—H4A	0.9300	C13—H13A	0.9300
C5—C6	1.409 (5)	C14—C15	1.420 (5)
C6—C7	1.342 (5)	C15—C16	1.353 (5)
C6—H6A	0.9300	C15—H15A	0.9300
C7—C9	1.414 (6)	C16—C18	1.426 (5)
C7—C8	1.432 (6)	C16—C17	1.429 (5)

C2—S1—C5	92.6 (2)	C11—S2—C14	91.3 (2)
C2—C1—H1A	109.5	C11—C10—H10A	109.5
C2—C1—H1B	109.5	C11—C10—H10B	109.5
H1A—C1—H1B	109.5	H10A—C10—H10B	109.5
C2—C1—H1C	109.5	C11—C10—H10C	109.5
H1A—C1—H1C	109.5	H10A—C10—H10C	109.5
H1B—C1—H1C	109.5	H10B—C10—H10C	109.5
C3—C2—C1	129.9 (5)	C12—C11—C10	128.2 (4)
C3—C2—S1	110.8 (4)	C12—C11—S2	111.3 (3)
C1—C2—S1	119.2 (4)	C10—C11—S2	120.5 (4)
C2—C3—C4	112.8 (4)	C11—C12—C13	114.0 (4)
C2—C3—H3A	123.6	C11—C12—H12A	123.0
C4—C3—H3A	123.6	C13—C12—H12A	123.0
C5—C4—C3	114.0 (4)	C14—C13—C12	112.4 (4)
C5—C4—H4A	123.0	C14—C13—H13A	123.8
C3—C4—H4A	123.0	C12—C13—H13A	123.8
C4—C5—C6	121.7 (4)	C13—C14—C15	122.8 (4)
C4—C5—S1	109.8 (3)	C13—C14—S2	111.0 (3)
C6—C5—S1	128.5 (3)	C15—C14—S2	126.1 (3)
C7—C6—C5	130.7 (4)	C16—C15—C14	131.7 (4)
C7—C6—H6A	114.6	C16—C15—H15A	114.1
C5—C6—H6A	114.6	C14—C15—H15A	114.1
C6—C7—C9	121.4 (4)	C15—C16—C18	119.4 (4)
C6—C7—C8	122.8 (4)	C15—C16—C17	124.7 (4)
C9—C7—C8	115.8 (4)	C18—C16—C17	115.8 (4)
N1—C8—C7	178.9 (5)	N3—C17—C16	178.3 (5)
N2—C9—C7	179.2 (5)	N4—C18—C16	179.5 (5)

C5—S1—C2—C3	0.1 (4)	C14—S2—C11—C12	−0.9 (4)
C5—S1—C2—C1	−179.6 (4)	C14—S2—C11—C10	179.8 (4)
C1—C2—C3—C4	179.7 (5)	C10—C11—C12—C13	−179.3 (4)
S1—C2—C3—C4	0.0 (5)	S2—C11—C12—C13	1.4 (5)
C2—C3—C4—C5	−0.2 (6)	C11—C12—C13—C14	−1.3 (6)
C3—C4—C5—C6	−178.6 (4)	C12—C13—C14—C15	178.0 (4)
C3—C4—C5—S1	0.3 (5)	C12—C13—C14—S2	0.6 (5)
C2—S1—C5—C4	−0.2 (4)	C11—S2—C14—C13	0.2 (4)
C2—S1—C5—C6	178.6 (4)	C11—S2—C14—C15	−177.2 (4)
C4—C5—C6—C7	−178.2 (4)	C13—C14—C15—C16	−178.8 (4)
S1—C5—C6—C7	3.1 (7)	S2—C14—C15—C16	−1.8 (7)
C5—C6—C7—C9	−180.0 (4)	C14—C15—C16—C18	175.5 (4)
C5—C6—C7—C8	1.8 (7)	C14—C15—C16—C17	−1.9 (7)
C6—C7—C8—N1	−151 (29)	C15—C16—C17—N3	−92 (17)
C9—C7—C8—N1	30 (29)	C18—C16—C17—N3	91 (17)
C6—C7—C9—N2	6 (43)	C15—C16—C18—N4	21 (69)
C8—C7—C9—N2	−175 (100)	C17—C16—C18—N4	−161 (68)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N2ⁱ	0.93	2.52	3.439 (6)	168
C6—H6A···N3ⁱⁱ	0.93	2.52	3.434 (6)	169
C12—H12A···N4ⁱⁱⁱ	0.93	2.60	3.518 (6)	171
C15—H15A···N1ⁱ	0.93	2.51	3.430 (6)	170

Symmetry codes: (i) x, y, z+1; (ii) x+1, y−1, z−1; (iii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₉H₆N₂S
M_r	174.22
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.1120 (18), 9.9380 (2), 10.1350 (2)
α, β, γ (°)	81.10 (3), 80.71 (3), 86.70 (3)
V (Å³)	894.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.915, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	3465, 3247, 1399
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.102, 1.00
No. of reflections	3247
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.28

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N2ⁱ	0.93	2.52	3.439 (6)	168
C6—H6A···N3ⁱⁱ	0.93	2.52	3.434 (6)	169
C12—H12A···N4ⁱⁱⁱ	0.93	2.60	3.518 (6)	171
C15—H15A···N1ⁱ	0.93	2.51	3.430 (6)	170

Symmetry codes: (i) x, y, z+1; (ii) x+1, y−1, z−1; (iii) x, y, z−1.

Acknowledgements

This research work was financially supported by School of Pharmaceutical Science, Nanjing University of Technology.

References

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