2-[2-(4-Meth­oxy­phen­yl)-2-oxoeth­yl]malononitrile

Lian, M.; Chen, T.; Zhu, Y.

doi:10.1107/S1600536811026961

organic compounds

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Volume 67| Part 8| August 2011| Page o2007

doi:10.1107/S1600536811026961

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2-[2-(4-Methoxyphenyl)-2-oxoethyl]malononitrile

Mi Lian,^a ^* Tianli Chen ^b and Yanping Zhu ^a

^aKey Laboratory of Pesticide and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China, and ^bThe 61081 group of PLA, Beijing 100094, People's Republic of China
^*Correspondence e-mail: lianmichem@gmail.com

(Received 15 May 2011; accepted 6 July 2011; online 13 July 2011)

The title compound, C₁₂H₁₀N₂O₂, was obtained unintentionally during the synthesis of 2-amino-5-(4-methoxyphenyl)furan-3-carbonitrile. In the crystal, weak intermolecular C—H⋯N and C—H⋯π interactions link the molecules into columns propagating in [010].

Related literature

For the crystal structures of related compounds with a malononitrile fragment, see: Luo & Zhou (2006 ); Ohashi et al. (2008 ); Oliva et al. (2010 ).

Experimental

Crystal data

C₁₂H₁₀N₂O₂
M_r = 214.22
Monoclinic, P 2₁ /n
a = 11.9010 (13) Å
b = 6.4898 (7) Å
c = 14.4248 (16) Å
β = 100.141 (2)°
V = 1096.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
11044 measured reflections
2148 independent reflections
1693 reflections with I > 2σ(I)
R_int = 0.123

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.137
S = 1.07
2148 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯N1ⁱ	0.97	2.55	3.380 (2)	143
C10—H10⋯Cgⁱⁱ	0.98	2.56	3.411 (1)	145
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811026961/cv5094sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026961/cv5094Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026961/cv5094Isup3.cml

checkCIF report

Comment top

The title compound (I) has been unintentionally obtained in the process of synthesis of 2-amino-5-(4-methoxyphenyl)furan-3-carbonitrile.

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those observed in related compounds (Luo & Zhou, 2006; Ohashi et al., 2008; Oliva et al., 2010). In the crystal structure, weak intermolecular C—H···N and C—H···π interactions (Table 1) link the molecules into columns propagated in [010].

Related literature top

For the crystal structures of related compounds with malononitrile fragments, see: Luo & Zhou (2006); Ohashi et al. (2008); Oliva et al. (2010).

Experimental top

To a solution of K₂CO₃ (2.0 equiv) in MeOH,3-iodo-1-(4-methoxyphenyl)propan-1-one (1.0 equiv) and malononitrile (2.0 equiv) were separately added. The resulting mixture was then heated at reflux for several hours (TLC monitoring). After that, the solvent was removed under reduce pressure, and added 50 mL water to the residue, then extracted with EtOAc 3 times. The organic phase was washed with saturated saline solution. Then the organic phase was dried by anhydrous Na2SO4, and removed the EtOAc under reduce pressure. The final residue was purified by column chromatography on silica gel to afford the expected target compound as a white solid.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I), showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level.

2-[2-(4-Methoxyphenyl)-2-oxoethyl]malononitrile top

Crystal data top

C₁₂H₁₀N₂O₂	F(000) = 448
M_r = 214.22	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.9010 (13) Å	Cell parameters from 2694 reflections
b = 6.4898 (7) Å	θ = 2.9–26.8°
c = 14.4248 (16) Å	µ = 0.09 mm⁻¹
β = 100.141 (2)°	T = 298 K
V = 1096.7 (2) Å³	Block, colourless
Z = 4	0.16 × 0.12 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1693 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.123
Graphite monochromator	θ_max = 26.0°, θ_min = 2.4°
phi and ω scans	h = −14→14
11044 measured reflections	k = −7→7
2148 independent reflections	l = −17→17

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0648P)² + 0.034P] where P = (F_o² + 2F_c²)/3
2148 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₀N₂O₂	V = 1096.7 (2) Å³
M_r = 214.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.9010 (13) Å	µ = 0.09 mm⁻¹
b = 6.4898 (7) Å	T = 298 K
c = 14.4248 (16) Å	0.16 × 0.12 × 0.10 mm
β = 100.141 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1693 reflections with I > 2σ(I)
11044 measured reflections	R_int = 0.123
2148 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.07	Δρ_max = 0.18 e Å⁻³
2148 reflections	Δρ_min = −0.21 e Å⁻³
146 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
C1	−0.03121 (14)	0.6967 (3)	0.89840 (11)	0.0469 (4)
C2	−0.05989 (14)	0.5030 (3)	0.86164 (11)	0.0480 (4)
H2	−0.1361	0.4645	0.8453	0.058*
C3	0.02602 (14)	0.3670 (2)	0.84951 (11)	0.0448 (4)
H3	0.0068	0.2371	0.8245	0.054*
C4	0.14054 (13)	0.4210 (2)	0.87402 (10)	0.0396 (4)
C5	0.16687 (14)	0.6144 (2)	0.91392 (11)	0.0462 (4)
H5	0.2429	0.6514	0.9330	0.055*
C6	0.08248 (15)	0.7514 (3)	0.92565 (12)	0.0509 (5)
H6	0.1015	0.8805	0.9518	0.061*
C7	−0.22564 (17)	0.8083 (3)	0.87859 (16)	0.0742 (6)
H7A	−0.2385	0.7757	0.8126	0.111*
H7B	−0.2686	0.9290	0.8887	0.111*
H7C	−0.2497	0.6947	0.9130	0.111*
C8	0.22937 (13)	0.2781 (2)	0.85246 (11)	0.0406 (4)
C9	0.35302 (13)	0.3417 (2)	0.88084 (11)	0.0427 (4)
H9A	0.3737	0.3396	0.9490	0.051*
H9B	0.3625	0.4815	0.8597	0.051*
C10	0.43241 (13)	0.1983 (2)	0.83864 (11)	0.0434 (4)
H10	0.4024	0.1853	0.7711	0.052*
C11	0.54808 (15)	0.2847 (3)	0.84914 (13)	0.0552 (5)
C12	0.44048 (14)	−0.0098 (3)	0.87938 (12)	0.0489 (4)
N1	0.45034 (15)	−0.1695 (2)	0.91202 (13)	0.0714 (5)
N2	0.63714 (16)	0.3512 (3)	0.85611 (16)	0.0868 (6)
O1	−0.10731 (11)	0.84605 (18)	0.91043 (10)	0.0646 (4)
O2	0.20628 (10)	0.11578 (17)	0.81148 (9)	0.0555 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0446 (10)	0.0516 (10)	0.0465 (9)	0.0042 (8)	0.0132 (7)	0.0010 (8)
C2	0.0366 (9)	0.0558 (10)	0.0517 (10)	−0.0036 (7)	0.0078 (7)	0.0008 (8)
C3	0.0408 (9)	0.0429 (9)	0.0509 (10)	−0.0045 (7)	0.0085 (7)	0.0012 (7)
C4	0.0362 (9)	0.0451 (9)	0.0375 (8)	−0.0014 (7)	0.0062 (6)	0.0034 (7)
C5	0.0373 (9)	0.0540 (10)	0.0466 (9)	−0.0056 (7)	0.0052 (7)	−0.0037 (7)
C6	0.0493 (11)	0.0499 (10)	0.0545 (10)	−0.0035 (8)	0.0118 (8)	−0.0097 (8)
C7	0.0472 (12)	0.0813 (14)	0.0951 (16)	0.0128 (10)	0.0147 (11)	−0.0016 (12)
C8	0.0404 (9)	0.0410 (9)	0.0393 (8)	−0.0038 (7)	0.0046 (7)	0.0044 (7)
C9	0.0385 (9)	0.0424 (9)	0.0467 (9)	−0.0003 (7)	0.0058 (7)	0.0007 (7)
C10	0.0386 (9)	0.0489 (9)	0.0425 (9)	−0.0050 (7)	0.0067 (7)	−0.0049 (7)
C11	0.0448 (11)	0.0574 (11)	0.0650 (11)	−0.0034 (8)	0.0141 (9)	−0.0071 (9)
C12	0.0408 (10)	0.0476 (10)	0.0561 (10)	−0.0033 (7)	0.0025 (7)	−0.0117 (8)
N1	0.0717 (12)	0.0465 (9)	0.0902 (13)	−0.0040 (8)	−0.0018 (9)	−0.0014 (9)
N2	0.0493 (11)	0.0921 (14)	0.1221 (17)	−0.0202 (9)	0.0236 (10)	−0.0177 (11)
O1	0.0473 (8)	0.0633 (8)	0.0844 (9)	0.0092 (6)	0.0145 (6)	−0.0115 (7)
O2	0.0450 (7)	0.0497 (7)	0.0704 (8)	−0.0058 (5)	0.0065 (6)	−0.0134 (6)

Geometric parameters (Å, º) top

C1—O1	1.3585 (19)	C7—H7A	0.9600
C1—C2	1.383 (2)	C7—H7B	0.9600
C1—C6	1.387 (2)	C7—H7C	0.9600
C2—C3	1.385 (2)	C8—O2	1.2153 (18)
C2—H2	0.9300	C8—C9	1.514 (2)
C3—C4	1.391 (2)	C9—C10	1.527 (2)
C3—H3	0.9300	C9—H9A	0.9700
C4—C5	1.393 (2)	C9—H9B	0.9700
C4—C8	1.480 (2)	C10—C12	1.469 (2)
C5—C6	1.374 (2)	C10—C11	1.469 (2)
C5—H5	0.9300	C10—H10	0.9800
C6—H6	0.9300	C11—N2	1.132 (2)
C7—O1	1.423 (2)	C12—N1	1.136 (2)

O1—C1—C2	124.91 (15)	O1—C7—H7C	109.5
O1—C1—C6	114.83 (15)	H7A—C7—H7C	109.5
C2—C1—C6	120.26 (15)	H7B—C7—H7C	109.5
C1—C2—C3	119.30 (15)	O2—C8—C4	122.46 (14)
C1—C2—H2	120.3	O2—C8—C9	119.58 (14)
C3—C2—H2	120.3	C4—C8—C9	117.94 (13)
C2—C3—C4	121.31 (15)	C8—C9—C10	111.48 (13)
C2—C3—H3	119.3	C8—C9—H9A	109.3
C4—C3—H3	119.3	C10—C9—H9A	109.3
C3—C4—C5	118.08 (15)	C8—C9—H9B	109.3
C3—C4—C8	119.53 (14)	C10—C9—H9B	109.3
C5—C4—C8	122.30 (14)	H9A—C9—H9B	108.0
C6—C5—C4	121.19 (15)	C12—C10—C11	108.40 (14)
C6—C5—H5	119.4	C12—C10—C9	113.72 (13)
C4—C5—H5	119.4	C11—C10—C9	111.12 (13)
C5—C6—C1	119.79 (16)	C12—C10—H10	107.8
C5—C6—H6	120.1	C11—C10—H10	107.8
C1—C6—H6	120.1	C9—C10—H10	107.8
O1—C7—H7A	109.5	N2—C11—C10	179.2 (2)
O1—C7—H7B	109.5	N1—C12—C10	177.78 (18)
H7A—C7—H7B	109.5	C1—O1—C7	118.68 (14)

O1—C1—C2—C3	177.46 (15)	C3—C4—C8—C9	−179.59 (14)
C6—C1—C2—C3	−2.1 (2)	C5—C4—C8—C9	3.9 (2)
C1—C2—C3—C4	0.4 (2)	O2—C8—C9—C10	8.6 (2)
C2—C3—C4—C5	1.9 (2)	C4—C8—C9—C10	−169.81 (12)
C2—C3—C4—C8	−174.84 (14)	C8—C9—C10—C12	−69.54 (17)
C3—C4—C5—C6	−2.4 (2)	C8—C9—C10—C11	167.82 (13)
C8—C4—C5—C6	174.22 (14)	C12—C10—C11—N2	111 (14)
C4—C5—C6—C1	0.7 (3)	C9—C10—C11—N2	−124 (14)
O1—C1—C6—C5	−178.01 (15)	C11—C10—C12—N1	9 (5)
C2—C1—C6—C5	1.6 (3)	C9—C10—C12—N1	−115 (5)
C3—C4—C8—O2	2.0 (2)	C2—C1—O1—C7	−3.7 (2)
C5—C4—C8—O2	−174.53 (15)	C6—C1—O1—C7	175.89 (16)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···N1ⁱ	0.97	2.55	3.380 (2)	143
C10—H10···Cgⁱⁱ	0.98	2.56	3.411 (1)	145

Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₂
M_r	214.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.9010 (13), 6.4898 (7), 14.4248 (16)
β (°)	100.141 (2)
V (Å³)	1096.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11044, 2148, 1693
R_int	0.123
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.137, 1.07
No. of reflections	2148
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···N1ⁱ	0.97	2.55	3.380 (2)	143
C10—H10···Cgⁱⁱ	0.98	2.56	3.411 (1)	145

Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

The authors are grateful to the Central China Normal University for financial support and thank Dr Xiang-Gao Meng for the X-ray data collection.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Luo, Y.-P. & Zhou, H.-B. (2006). Acta Cryst. E62, o5369–o5370. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ohashi, M., Nakatani, K., Maeda, H. & Mizuno, K. (2008). Org. Lett. 10, 2741–2743. Web of Science CSD CrossRef PubMed CAS Google Scholar
Oliva, C. G., Silva, A. M. S., Resende, D. I. S. P., Paz, F. A. A. & Cavaleiro, J. A. S. (2010). Eur. J. Org. Chem. pp. 3449–3458. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2007

doi:10.1107/S1600536811026961

Open

access