2-(2-Methoxy­phen­yl)butane­dinitrile

Li, X.-Z.; Feng, Z.-J.; Yu, Y.; Shen, W.-L.; Ye, Y.

doi:10.1107/S1600536810013462

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1104

https://doi.org/10.1107/S1600536810013462

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2-(2-Methoxyphenyl)butanedinitrile

Xiang-Zi Li,^a,^b Zhi-Jun Feng,^b Yan Yu,^b Wei-Li Shen ^a and Yin Ye ^a ^*

^aCollege of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000, People's Republic of China, and ^bDepartment of Chemistry, WanNan Medical College, Wuhu 241000, People's Republic of China
^*Correspondence e-mail: lxz122@mail.ahnu.edu.cn

(Received 27 March 2010; accepted 12 April 2010; online 17 April 2010)

In the title compound, C₁₁H₁₀N₂O, the butanedinitrile unit adopts a synclinal conformation. The crystal packing is stabilized by weak intermolecular C—H⋯N hydrogen bonding.

Related literature

The title compound is an important intermediate in drugs synthesis, see: Obniska et al. (2005 ). For the synthesis, see: Johnson et al. (1962 ).

Experimental

Crystal data

C₁₁H₁₀N₂O
M_r = 186.21
Monoclinic, P 2₁ /c
a = 12.393 (9) Å
b = 5.405 (4) Å
c = 15.216 (10) Å
β = 102.947 (8)°
V = 993.3 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.37 × 0.25 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 0.985
7820 measured reflections
2292 independent reflections
1549 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.04
2292 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N2ⁱ	0.93	2.50	3.404 (3)	165
C8—H8⋯N2ⁱⁱ	0.98	2.50	3.262 (3)	135
Symmetry codes: (i) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y-1, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013462/xu2746sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013462/xu2746Isup2.hkl

checkCIF report

Comment top

The title compound is an important intermediate in drugs synthesis (Obniska et al., 2005). In this paper, we report the structure of the title compound (I). In (I), the succinonitrite moiety adopts a cis conformation. Two cyanide groups, (N1—C10 and N2—C11), are not coplane. However, the methoxy group is almost coplanar with the the mean plane of the phenyl (C2/C3/C4/C5/C6/C7). The crystal packing is stabilized by two intermolecular non-classic C—H···N hydrogen bonds.

Related literature top

The title compound is an important intermediate in drugs synthesis, see: Obniska et al. (2005). For the synthesis, see: Johnson et al. (1962).

Experimental top

The compound (I) was obtained by reaction of (Z)-ethyl-2-cyano-3-(2-methoxyphenyl)acrylate and NaCN in ethanol-water mixture according to the reported method (Johnson et al., 1962). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution at room temperature.

Structure description top

The title compound is an important intermediate in drugs synthesis, see: Obniska et al. (2005). For the synthesis, see: Johnson et al. (1962).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I) viewed down the b axis. Dotted lines show the hydrogen bonds.

2-(2-Methoxyphenyl)butanedinitrile top

Crystal data top

C₁₁H₁₀N₂O	F(000) = 392
M_r = 186.21	D_x = 1.245 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2518 reflections
a = 12.393 (9) Å	θ = 2.8–26.1°
b = 5.405 (4) Å	µ = 0.08 mm⁻¹
c = 15.216 (10) Å	T = 298 K
β = 102.947 (8)°	Block, colorless
V = 993.3 (12) Å³	0.37 × 0.25 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2292 independent reflections
Radiation source: fine-focus sealed tube	1549 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 27.7°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.970, T_max = 0.985	k = −6→6
7820 measured reflections	l = −18→19

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.051P)² + 0.1131P] where P = (F_o² + 2F_c²)/3
2292 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₁H₁₀N₂O	V = 993.3 (12) Å³
M_r = 186.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.393 (9) Å	µ = 0.08 mm⁻¹
b = 5.405 (4) Å	T = 298 K
c = 15.216 (10) Å	0.37 × 0.25 × 0.14 mm
β = 102.947 (8)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2292 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1549 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.985	R_int = 0.026
7820 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	Δρ_max = 0.12 e Å⁻³
2292 reflections	Δρ_min = −0.14 e Å⁻³
128 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.34900 (15)	1.2727 (3)	0.69677 (11)	0.0644 (5)
H1A	0.3731	1.1717	0.6529	0.097*
H1B	0.4106	1.3657	0.7303	0.097*
H1C	0.2924	1.3843	0.6667	0.097*
N1	0.45207 (12)	0.7505 (3)	1.07568 (10)	0.0728 (4)
O1	0.30584 (9)	1.11902 (19)	0.75662 (6)	0.0581 (3)
C2	0.22452 (11)	0.9545 (3)	0.72065 (9)	0.0461 (3)
N2	0.22425 (13)	1.2438 (2)	0.95010 (9)	0.0660 (4)
C3	0.17425 (13)	0.9391 (3)	0.63011 (10)	0.0585 (4)
H3	0.1945	1.0466	0.5889	0.070*
C4	0.09351 (14)	0.7621 (3)	0.60142 (11)	0.0642 (5)
H4	0.0591	0.7523	0.5406	0.077*
C5	0.06344 (13)	0.6016 (3)	0.66096 (11)	0.0605 (4)
H5	0.0102	0.4810	0.6406	0.073*
C6	0.11252 (11)	0.6197 (3)	0.75120 (10)	0.0500 (4)
H6	0.0913	0.5117	0.7919	0.060*
C7	0.19287 (11)	0.7958 (2)	0.78245 (8)	0.0409 (3)
C8	0.24600 (11)	0.8102 (2)	0.88203 (9)	0.0422 (3)
H8	0.2064	0.6939	0.9129	0.051*
C9	0.36818 (12)	0.7315 (3)	0.90375 (10)	0.0518 (4)
H9A	0.3741	0.5645	0.8819	0.062*
H9B	0.4096	0.8402	0.8727	0.062*
C10	0.41624 (12)	0.7404 (3)	1.00039 (11)	0.0547 (4)
C11	0.23445 (11)	1.0568 (3)	0.91933 (9)	0.0457 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0803 (11)	0.0570 (10)	0.0640 (10)	−0.0141 (8)	0.0332 (9)	0.0021 (8)
N1	0.0724 (10)	0.0769 (10)	0.0604 (9)	0.0051 (7)	−0.0034 (7)	0.0056 (7)
O1	0.0726 (7)	0.0561 (6)	0.0471 (6)	−0.0181 (5)	0.0167 (5)	0.0032 (5)
C2	0.0515 (8)	0.0429 (8)	0.0447 (7)	0.0002 (6)	0.0129 (6)	−0.0007 (6)
N2	0.0978 (11)	0.0466 (8)	0.0543 (8)	0.0086 (7)	0.0183 (7)	−0.0036 (6)
C3	0.0678 (10)	0.0649 (10)	0.0435 (8)	−0.0002 (8)	0.0138 (7)	0.0049 (7)
C4	0.0639 (10)	0.0787 (12)	0.0451 (8)	0.0010 (9)	0.0018 (7)	−0.0066 (8)
C5	0.0527 (9)	0.0664 (10)	0.0593 (9)	−0.0081 (7)	0.0057 (7)	−0.0090 (8)
C6	0.0500 (8)	0.0463 (8)	0.0543 (9)	−0.0010 (6)	0.0131 (6)	0.0000 (6)
C7	0.0450 (7)	0.0372 (7)	0.0413 (7)	0.0039 (5)	0.0112 (6)	0.0004 (5)
C8	0.0507 (8)	0.0357 (7)	0.0413 (7)	0.0008 (6)	0.0124 (6)	0.0033 (5)
C9	0.0544 (8)	0.0499 (9)	0.0495 (8)	0.0090 (6)	0.0081 (6)	0.0022 (6)
C10	0.0530 (8)	0.0493 (9)	0.0579 (9)	0.0065 (7)	0.0041 (7)	0.0054 (7)
C11	0.0555 (8)	0.0434 (8)	0.0382 (7)	0.0030 (6)	0.0102 (6)	0.0039 (6)

Geometric parameters (Å, º) top

C1—O1	1.4225 (18)	C4—H4	0.9300
C1—H1A	0.9600	C5—C6	1.375 (2)
C1—H1B	0.9600	C5—H5	0.9300
C1—H1C	0.9600	C6—C7	1.383 (2)
N1—C10	1.133 (2)	C6—H6	0.9300
O1—C2	1.3632 (17)	C7—C8	1.513 (2)
C2—C3	1.381 (2)	C8—C11	1.468 (2)
C2—C7	1.3928 (19)	C8—C9	1.536 (2)
N2—C11	1.1327 (18)	C8—H8	0.9800
C3—C4	1.382 (2)	C9—C10	1.458 (2)
C3—H3	0.9300	C9—H9A	0.9700
C4—C5	1.365 (2)	C9—H9B	0.9700

O1—C1—H1A	109.5	C5—C6—H6	119.5
O1—C1—H1B	109.5	C7—C6—H6	119.5
H1A—C1—H1B	109.5	C6—C7—C2	118.83 (13)
O1—C1—H1C	109.5	C6—C7—C8	119.89 (12)
H1A—C1—H1C	109.5	C2—C7—C8	121.28 (12)
H1B—C1—H1C	109.5	C11—C8—C7	112.07 (10)
C2—O1—C1	118.29 (12)	C11—C8—C9	110.19 (11)
O1—C2—C3	124.58 (13)	C7—C8—C9	112.84 (11)
O1—C2—C7	115.18 (12)	C11—C8—H8	107.1
C3—C2—C7	120.24 (13)	C7—C8—H8	107.1
C2—C3—C4	119.32 (14)	C9—C8—H8	107.1
C2—C3—H3	120.3	C10—C9—C8	111.60 (12)
C4—C3—H3	120.3	C10—C9—H9A	109.3
C5—C4—C3	121.07 (15)	C8—C9—H9A	109.3
C5—C4—H4	119.5	C10—C9—H9B	109.3
C3—C4—H4	119.5	C8—C9—H9B	109.3
C4—C5—C6	119.48 (15)	H9A—C9—H9B	108.0
C4—C5—H5	120.3	N1—C10—C9	178.67 (17)
C6—C5—H5	120.3	N2—C11—C8	177.91 (15)
C5—C6—C7	121.04 (14)

C1—O1—C2—C3	−5.4 (2)	C3—C2—C7—C6	1.5 (2)
C1—O1—C2—C7	174.73 (13)	O1—C2—C7—C8	0.32 (18)
O1—C2—C3—C4	179.19 (15)	C3—C2—C7—C8	−179.53 (12)
C7—C2—C3—C4	−1.0 (2)	C6—C7—C8—C11	−123.69 (14)
C2—C3—C4—C5	−0.5 (2)	C2—C7—C8—C11	57.39 (17)
C3—C4—C5—C6	1.4 (3)	C6—C7—C8—C9	111.21 (15)
C4—C5—C6—C7	−0.8 (2)	C2—C7—C8—C9	−67.71 (16)
C5—C6—C7—C2	−0.6 (2)	C11—C8—C9—C10	55.55 (15)
C5—C6—C7—C8	−179.58 (13)	C7—C8—C9—C10	−178.33 (11)
O1—C2—C7—C6	−178.61 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2ⁱ	0.93	2.50	3.404 (3)	165
C8—H8···N2ⁱⁱ	0.98	2.50	3.262 (3)	135

Symmetry codes: (i) x, −y+5/2, z−1/2; (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O
M_r	186.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.393 (9), 5.405 (4), 15.216 (10)
β (°)	102.947 (8)
V (Å³)	993.3 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.25 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	7820, 2292, 1549
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.04
No. of reflections	2292
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.14

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2ⁱ	0.93	2.50	3.404 (3)	165.4
C8—H8···N2ⁱⁱ	0.98	2.50	3.262 (3)	134.9

Symmetry codes: (i) x, −y+5/2, z−1/2; (ii) x, y−1, z.

Acknowledgements

This work was supported by the Higher Education Natural Science Foundation of Anhui Province (Nos. KJ2010B250, KJ2009B109, KJ2008B169) and the Higher Education Excellent Youth Talents Foundation of Anhui Province, China (No. 2010SQRL179).

References

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Obniska, J., Jurczyk, S., Zejc, A., Kamiński, K., Tatarczyńska, E. & Stachowicz, K. (2005). Pharmacol. Rep. 57, 170–175. Web of Science PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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