2-(3-Methoxy­phen­yl)butane­dinitrile

Du, W.-X.; Ye, Y.; Wei, X.-W.

doi:10.1107/S1600536809015232

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1165

doi:10.1107/S1600536809015232

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2-(3-Methoxyphenyl)butanedinitrile

Wan-Xin Du,^a Yin Ye ^a and Xian-Wen Wei ^a ^*

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

(Received 8 April 2009; accepted 23 April 2009; online 30 April 2009)

In the title compound, C₁₁H₁₀N₂O, the dicyanoethylene portion has an anti conformation. The crystal structure features non-classical C—H⋯N and C—H⋯O interactions.

Related literature

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

Experimental

Crystal data

C₁₁H₁₀N₂O
M_r = 186.21
Monoclinic, P 2₁ /c
a = 5.5263 (8) Å
b = 16.105 (2) Å
c = 11.0332 (16) Å
β = 97.179 (2)°
V = 974.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.4 × 0.2 × 0.1 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: none
8042 measured reflections
2210 independent reflections
1963 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.128
S = 1.04
2210 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯N1ⁱ	0.98	2.61	3.4864 (17)	150
C10—H10A⋯O1ⁱⁱ	0.97	2.38	3.2470 (15)	149
C10—H10B⋯N2ⁱⁱⁱ	0.97	2.60	3.4823 (18)	151
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x-1, y, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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/S1600536809015232/ng2569sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015232/ng2569Isup2.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 an anti conformation. Six atoms of succinonitrite moiety, (N1/C9/C8/N2/C11/C10), almost lie on one plane, the maximum deviations from the mean plane of the succinonitrite being 0.0275 (8) Å. This mean plane is almost perpendicular to the phenyl mean plane with a dihedral angle of 87.55 (6) Å. The crystal packing is stabilized by two intermolecular non-classic C—H···N hydrogen bonds and one intermolecular non-classic C—H···O hydrogen bond.

Related literature top

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

Experimental top

The compound (I) was obtained by reaction of (Z)-ethyl-2-cyano-3-(4-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.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. 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 a axis. Dotted lines show the C—H···N and C—H···O hydrogen bonds.

2-(3-Methoxyphenyl)butanedinitrile top

Crystal data top

C₁₁H₁₀N₂O	F(000) = 392
M_r = 186.21	D_x = 1.270 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5752 reflections
a = 5.5263 (8) Å	θ = 2.3–27.4°
b = 16.105 (2) Å	µ = 0.08 mm⁻¹
c = 11.0332 (16) Å	T = 298 K
β = 97.179 (2)°	Block, colorless
V = 974.3 (2) Å³	0.4 × 0.2 × 0.1 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	1963 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
ϕ and ω scans	h = −7→7
8042 measured reflections	k = −20→20
2210 independent reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0729P)² + 0.1612P] where P = (F_o² + 2F_c²)/3
2210 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₁H₁₀N₂O	V = 974.3 (2) Å³
M_r = 186.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.5263 (8) Å	µ = 0.08 mm⁻¹
b = 16.105 (2) Å	T = 298 K
c = 11.0332 (16) Å	0.4 × 0.2 × 0.1 mm
β = 97.179 (2)°

Data collection top

Bruker SMART area-detector diffractometer	1963 reflections with I > 2σ(I)
8042 measured reflections	R_int = 0.022
2210 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
2210 reflections	Δρ_min = −0.22 e Å⁻³
128 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
C6	0.6739 (2)	0.85144 (7)	0.67253 (10)	0.0379 (3)
C7	0.5211 (2)	0.80066 (7)	0.73097 (11)	0.0406 (3)
H7	0.4177	0.8237	0.7822	0.049*
C5	0.8292 (3)	0.81733 (9)	0.59747 (12)	0.0518 (3)
H5	0.9321	0.8512	0.5588	0.062*
C2	0.5237 (2)	0.71565 (7)	0.71258 (11)	0.0439 (3)
C3	0.6789 (3)	0.68150 (8)	0.63618 (14)	0.0551 (4)
H3	0.6799	0.6245	0.6231	0.066*
C4	0.8306 (3)	0.73211 (9)	0.58018 (15)	0.0622 (4)
H4	0.9358	0.7090	0.5299	0.075*
C8	0.6709 (2)	0.94492 (7)	0.69077 (10)	0.0384 (3)
H8	0.7891	0.9698	0.6423	0.046*
C10	0.7385 (2)	0.97151 (7)	0.82538 (11)	0.0414 (3)
H10A	0.7311	1.0315	0.8311	0.050*
H10B	0.6209	0.9485	0.8744	0.050*
C9	0.4279 (2)	0.97888 (7)	0.64751 (11)	0.0435 (3)
O1	0.37911 (19)	0.66090 (5)	0.76429 (10)	0.0605 (3)
C1	0.2421 (3)	0.69035 (10)	0.85616 (15)	0.0638 (4)
H1A	0.3505	0.7141	0.9218	0.096*
H1B	0.1545	0.6450	0.8867	0.096*
H1C	0.1286	0.7318	0.8221	0.096*
N1	0.2393 (2)	1.00418 (8)	0.61421 (12)	0.0604 (3)
C11	0.9826 (2)	0.94328 (7)	0.87350 (10)	0.0415 (3)
N2	1.1722 (2)	0.92210 (8)	0.91331 (11)	0.0581 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.0380 (6)	0.0381 (6)	0.0376 (5)	−0.0021 (4)	0.0054 (4)	−0.0030 (4)
C7	0.0415 (6)	0.0363 (6)	0.0462 (6)	−0.0003 (4)	0.0139 (5)	−0.0042 (4)
C5	0.0540 (8)	0.0522 (7)	0.0537 (7)	−0.0070 (6)	0.0239 (6)	−0.0074 (5)
C2	0.0443 (6)	0.0368 (6)	0.0518 (6)	−0.0028 (5)	0.0112 (5)	−0.0029 (5)
C3	0.0617 (8)	0.0384 (6)	0.0679 (8)	0.0001 (5)	0.0188 (6)	−0.0143 (6)
C4	0.0668 (9)	0.0565 (8)	0.0696 (9)	−0.0002 (7)	0.0339 (7)	−0.0175 (7)
C8	0.0364 (6)	0.0373 (6)	0.0417 (6)	−0.0028 (4)	0.0053 (4)	0.0024 (4)
C10	0.0399 (6)	0.0366 (5)	0.0467 (6)	0.0036 (4)	0.0019 (5)	−0.0048 (4)
C9	0.0436 (7)	0.0397 (6)	0.0460 (6)	−0.0049 (5)	0.0007 (5)	0.0055 (5)
O1	0.0694 (7)	0.0352 (5)	0.0829 (7)	−0.0077 (4)	0.0339 (5)	−0.0025 (4)
C1	0.0727 (10)	0.0539 (8)	0.0708 (9)	−0.0093 (7)	0.0331 (8)	0.0033 (7)
N1	0.0479 (7)	0.0619 (7)	0.0679 (8)	0.0001 (5)	−0.0065 (5)	0.0126 (6)
C11	0.0429 (6)	0.0402 (6)	0.0413 (6)	0.0009 (5)	0.0050 (5)	−0.0025 (4)
N2	0.0469 (6)	0.0739 (8)	0.0525 (6)	0.0129 (5)	0.0023 (5)	−0.0037 (5)

Geometric parameters (Å, º) top

C6—C5	1.3791 (16)	C8—C9	1.4730 (16)
C6—C7	1.3903 (15)	C8—C10	1.5460 (16)
C6—C8	1.5193 (15)	C8—H8	0.9800
C7—C2	1.3843 (16)	C10—C11	1.4593 (16)
C7—H7	0.9300	C10—H10A	0.9700
C5—C4	1.386 (2)	C10—H10B	0.9700
C5—H5	0.9300	C9—N1	1.1365 (16)
C2—O1	1.3623 (15)	O1—C1	1.4205 (17)
C2—C3	1.3890 (17)	C1—H1A	0.9600
C3—C4	1.371 (2)	C1—H1B	0.9600
C3—H3	0.9300	C1—H1C	0.9600
C4—H4	0.9300	C11—N2	1.1368 (16)

C5—C6—C7	120.25 (11)	C6—C8—C10	113.36 (9)
C5—C6—C8	119.48 (10)	C9—C8—H8	108.3
C7—C6—C8	120.28 (9)	C6—C8—H8	108.3
C2—C7—C6	119.71 (10)	C10—C8—H8	108.3
C2—C7—H7	120.1	C11—C10—C8	111.38 (9)
C6—C7—H7	120.1	C11—C10—H10A	109.4
C6—C5—C4	119.46 (12)	C8—C10—H10A	109.4
C6—C5—H5	120.3	C11—C10—H10B	109.4
C4—C5—H5	120.3	C8—C10—H10B	109.4
O1—C2—C7	124.16 (11)	H10A—C10—H10B	108.0
O1—C2—C3	115.90 (11)	N1—C9—C8	179.20 (13)
C7—C2—C3	119.94 (11)	C2—O1—C1	118.40 (10)
C4—C3—C2	119.79 (11)	O1—C1—H1A	109.5
C4—C3—H3	120.1	O1—C1—H1B	109.5
C2—C3—H3	120.1	H1A—C1—H1B	109.5
C3—C4—C5	120.84 (12)	O1—C1—H1C	109.5
C3—C4—H4	119.6	H1A—C1—H1C	109.5
C5—C4—H4	119.6	H1B—C1—H1C	109.5
C9—C8—C6	110.45 (9)	N2—C11—C10	178.53 (13)
C9—C8—C10	108.02 (9)

C5—C6—C7—C2	−0.64 (18)	C6—C5—C4—C3	0.3 (2)
C8—C6—C7—C2	179.32 (11)	C5—C6—C8—C9	118.72 (12)
C7—C6—C5—C4	0.4 (2)	C7—C6—C8—C9	−61.25 (14)
C8—C6—C5—C4	−179.55 (13)	C5—C6—C8—C10	−119.90 (12)
C6—C7—C2—O1	−179.11 (11)	C7—C6—C8—C10	60.14 (14)
C6—C7—C2—C3	0.13 (19)	C9—C8—C10—C11	−177.45 (10)
O1—C2—C3—C4	179.91 (14)	C6—C8—C10—C11	59.81 (13)
C7—C2—C3—C4	0.6 (2)	C7—C2—O1—C1	−9.4 (2)
C2—C3—C4—C5	−0.8 (2)	C3—C2—O1—C1	171.30 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N1ⁱ	0.98	2.61	3.4864 (17)	150
C10—H10A···O1ⁱⁱ	0.97	2.38	3.2470 (15)	149
C10—H10B···N2ⁱⁱⁱ	0.97	2.60	3.4823 (18)	151

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1, y, 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)	5.5263 (8), 16.105 (2), 11.0332 (16)
β (°)	97.179 (2)
V (Å³)	974.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.4 × 0.2 × 0.1

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8042, 2210, 1963
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.128, 1.04
No. of reflections	2210
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

C2—O1	1.3623 (15)	C9—N1	1.1365 (16)
C8—C9	1.4730 (16)	O1—C1	1.4205 (17)
C8—C10	1.5460 (16)	C11—N2	1.1368 (16)
C10—C11	1.4593 (16)

C6—C8—C10	113.36 (9)	C2—O1—C1	118.40 (10)
C11—C10—C8	111.38 (9)	N2—C11—C10	178.53 (13)
N1—C9—C8	179.20 (13)

C9—C8—C10—C11	−177.45 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N1ⁱ	0.98	2.61	3.4864 (17)	149.7
C10—H10A···O1ⁱⁱ	0.97	2.38	3.2470 (15)	148.7
C10—H10B···N2ⁱⁱⁱ	0.97	2.60	3.4823 (18)	150.8

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

Acknowledgements

This work was supported by the Science and Technology Fund of Anhui Province for Outstanding Youth (No. 08040106906), the National Natural Science Foundation (No. 20671002) of China, the State Education Ministry (EYTP, SRF for ROCS, SRFDP 20070370001) and the Education Department (No. 2006KJ006TD) of Anhui Province.

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. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar