(4-Cyano­phen­yl)methyl­ene diacetate

Xiao, J.; Zhao, H.

doi:10.1107/S1600536808012543

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o986

doi:10.1107/S1600536808012543

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(4-Cyanophenyl)methylene diacetate

Jie Xiao ^a and Hong Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 23 April 2008; accepted 29 April 2008; online 3 May 2008)

In the title molecule, C₁₂H₁₁NO₄, the two acetyl groups are inclined by 71.3 (1) and 46.2 (1)° to the benzene ring. In the crystal structure, molecules are linked into a chain along the c axis by C—H⋯O hydrogen bonds.

Related literature

For general background on nitrile compounds, see: Jin et al. (1994 ); Radl et al. (2000 ). For a related structure, see: Fu & Zhao (2007 ).

Experimental

Crystal data

C₁₂H₁₁NO₄
M_r = 233.22
Monoclinic, P 2₁ /c
a = 8.1389 (15) Å
b = 20.919 (3) Å
c = 7.7748 (10) Å
β = 115.531 (7)°
V = 1194.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.35 × 0.30 × 0.30 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.951, T_max = 0.968
11568 measured reflections
2723 independent reflections
2096 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.163
S = 1.11
2723 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱ	0.98	2.56	3.351 (3)	137
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012543/ci2587sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012543/ci2587Isup2.hkl

checkCIF report

Comment top

Nitrile compounds are used extensively in the chemical industry. They are discharged into the environment in industrial waste water, agricultural chemicals, etc. Nitrile derivatives are important materials in the synthesis of some heterocyclic molecules (Radl et al., 2000), and they have been used as starting materials for phthalocyanines (Jin et al., 1994). Recently, we have reported the crystal structure of a benzonitrile compound (Fu et al., 2007). The title compound was unexpectedly obtained during our work on the nitrile compounds. Herein we report its crystal structure.

The bond lengths and angles have normal values. The O1/O2/C9/C10 and O3/O4/C11/C12 planes form dihedral angles of 71.3 (1)° and 46.2 (1)°, respectively, with the C2—C7 plane. The molecules are linked into a chain along the c axis by C—H···O hydrogen bonds (Table 1).

Related literature top

For general background on nitrile compounds, see: Jin et al. (1994); Radl et al. (2000). For a related structure, see: Fu & Zhao (2007).

Experimental top

4-Formylbenzonitrile (0.262 mg, 2 mmol) was dissolved in acetic anhydride (5 ml) and heated under reflux for 3 h. The mixture was cooled to room temperature and the solution was filtered. The solvent was removed under vacuum from the filtrate to obtain a white precipitate of the title compound (yield 88%). Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethanol (15 ml) solution of the compound (100 mg) after 4 d.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

(4-Cyanophenyl)methylene diacetate top

Crystal data top

C₁₂H₁₁NO₄	F(000) = 488
M_r = 233.22	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2461 reflections
a = 8.1389 (15) Å	θ = 3.1–27.5°
b = 20.919 (3) Å	µ = 0.10 mm⁻¹
c = 7.7748 (10) Å	T = 293 K
β = 115.531 (7)°	Block, colourless
V = 1194.5 (3) Å³	0.35 × 0.30 × 0.30 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2723 independent reflections
Radiation source: fine-focus sealed tube	2096 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −27→27
T_min = 0.951, T_max = 0.968	l = −10→10
11568 measured reflections

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0727P)² + 0.2026P] where P = (F_o² + 2F_c²)/3
2723 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₂H₁₁NO₄	V = 1194.5 (3) Å³
M_r = 233.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1389 (15) Å	µ = 0.10 mm⁻¹
b = 20.919 (3) Å	T = 293 K
c = 7.7748 (10) Å	0.35 × 0.30 × 0.30 mm
β = 115.531 (7)°

Data collection top

Rigaku Mercury2 diffractometer	2723 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2096 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.968	R_int = 0.035
11568 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.11	Δρ_max = 0.20 e Å⁻³
2723 reflections	Δρ_min = −0.17 e Å⁻³
156 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	0.4962 (2)	0.34433 (9)	0.7629 (3)	0.0477 (4)
H1	0.5242	0.2985	0.7757	0.057*
C2	0.6526 (2)	0.38246 (9)	0.7624 (2)	0.0462 (4)
C3	0.8165 (3)	0.35208 (10)	0.8026 (3)	0.0586 (5)
H3	0.8287	0.3086	0.8300	0.070*
C4	0.9621 (3)	0.38610 (11)	0.8021 (3)	0.0626 (5)
H4	1.0722	0.3656	0.8301	0.075*
C5	0.9433 (3)	0.45058 (10)	0.7598 (3)	0.0565 (5)
C6	0.7805 (3)	0.48137 (11)	0.7208 (4)	0.0693 (6)
H6	0.7685	0.5249	0.6936	0.083*
C7	0.6354 (3)	0.44710 (10)	0.7223 (3)	0.0627 (5)
H7	0.5260	0.4677	0.6962	0.075*
C8	1.0936 (3)	0.48634 (12)	0.7541 (4)	0.0701 (6)
C9	0.5275 (3)	0.33307 (10)	1.0797 (3)	0.0535 (5)
C10	0.4826 (4)	0.36266 (13)	1.2275 (4)	0.0779 (7)
H10A	0.5070	0.3327	1.3292	0.117*
H10B	0.3561	0.3742	1.1723	0.117*
H10C	0.5557	0.4002	1.2768	0.117*
C11	0.2023 (3)	0.31319 (10)	0.5370 (4)	0.0608 (5)
C12	0.0457 (3)	0.33230 (13)	0.3577 (4)	0.0799 (7)
H12A	−0.0238	0.2951	0.2961	0.120*
H12B	0.0895	0.3526	0.2747	0.120*
H12C	−0.0300	0.3616	0.3860	0.120*
N1	1.2104 (3)	0.51476 (12)	0.7475 (4)	0.0967 (8)
O1	0.45266 (18)	0.36634 (6)	0.91409 (19)	0.0536 (4)
O2	0.6196 (2)	0.28659 (9)	1.0993 (2)	0.0757 (5)
O3	0.33842 (17)	0.35734 (6)	0.59147 (18)	0.0545 (4)
O4	0.2134 (2)	0.26588 (8)	0.6276 (3)	0.0905 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0498 (10)	0.0476 (9)	0.0466 (9)	0.0048 (8)	0.0217 (8)	0.0008 (7)
C2	0.0465 (9)	0.0503 (10)	0.0406 (9)	0.0022 (8)	0.0178 (7)	−0.0018 (7)
C3	0.0548 (11)	0.0518 (11)	0.0689 (13)	0.0068 (9)	0.0266 (10)	0.0037 (9)
C4	0.0480 (11)	0.0687 (13)	0.0728 (14)	0.0092 (9)	0.0277 (10)	0.0020 (10)
C5	0.0496 (10)	0.0654 (12)	0.0553 (11)	−0.0037 (9)	0.0234 (9)	−0.0012 (9)
C6	0.0612 (13)	0.0515 (11)	0.0986 (18)	−0.0007 (10)	0.0377 (13)	0.0069 (11)
C7	0.0524 (11)	0.0526 (11)	0.0866 (15)	0.0078 (9)	0.0333 (11)	0.0069 (10)
C8	0.0574 (13)	0.0760 (15)	0.0783 (16)	−0.0037 (11)	0.0304 (11)	0.0028 (12)
C9	0.0505 (10)	0.0609 (12)	0.0505 (11)	−0.0104 (9)	0.0230 (9)	0.0027 (9)
C10	0.0912 (17)	0.0936 (18)	0.0642 (14)	−0.0232 (14)	0.0478 (13)	−0.0149 (12)
C11	0.0513 (11)	0.0548 (11)	0.0786 (14)	−0.0018 (9)	0.0303 (10)	−0.0020 (10)
C12	0.0525 (12)	0.0849 (16)	0.0844 (17)	−0.0072 (11)	0.0126 (11)	−0.0059 (13)
N1	0.0668 (14)	0.0997 (17)	0.129 (2)	−0.0114 (12)	0.0470 (14)	0.0127 (15)
O1	0.0614 (8)	0.0528 (7)	0.0533 (8)	0.0088 (6)	0.0310 (6)	0.0040 (6)
O2	0.0770 (11)	0.0842 (11)	0.0665 (10)	0.0217 (9)	0.0315 (8)	0.0249 (8)
O3	0.0500 (7)	0.0556 (8)	0.0513 (8)	−0.0048 (6)	0.0158 (6)	0.0033 (6)
O4	0.0642 (10)	0.0731 (11)	0.1270 (16)	−0.0078 (8)	0.0344 (10)	0.0250 (11)

Geometric parameters (Å, º) top

C1—O3	1.423 (2)	C7—H7	0.93
C1—O1	1.441 (2)	C8—N1	1.141 (3)
C1—C2	1.504 (3)	C9—O2	1.197 (3)
C1—H1	0.98	C9—O1	1.355 (2)
C2—C7	1.381 (3)	C9—C10	1.483 (3)
C2—C3	1.386 (3)	C10—H10A	0.96
C3—C4	1.384 (3)	C10—H10B	0.96
C3—H3	0.93	C10—H10C	0.96
C4—C5	1.381 (3)	C11—O4	1.196 (3)
C4—H4	0.93	C11—O3	1.362 (2)
C5—C6	1.384 (3)	C11—C12	1.482 (3)
C5—C8	1.451 (3)	C12—H12A	0.96
C6—C7	1.386 (3)	C12—H12B	0.96
C6—H6	0.93	C12—H12C	0.96

O3—C1—O1	105.26 (14)	C6—C7—H7	119.8
O3—C1—C2	108.62 (14)	N1—C8—C5	179.2 (3)
O1—C1—C2	109.80 (14)	O2—C9—O1	122.60 (18)
O3—C1—H1	111.0	O2—C9—C10	126.2 (2)
O1—C1—H1	111.0	O1—C9—C10	111.2 (2)
C2—C1—H1	111.0	C9—C10—H10A	109.5
C7—C2—C3	119.60 (18)	C9—C10—H10B	109.5
C7—C2—C1	121.08 (17)	H10A—C10—H10B	109.5
C3—C2—C1	119.32 (16)	C9—C10—H10C	109.5
C4—C3—C2	120.36 (19)	H10A—C10—H10C	109.5
C4—C3—H3	119.8	H10B—C10—H10C	109.5
C2—C3—H3	119.8	O4—C11—O3	122.2 (2)
C5—C4—C3	119.73 (19)	O4—C11—C12	126.4 (2)
C5—C4—H4	120.1	O3—C11—C12	111.37 (19)
C3—C4—H4	120.1	C11—C12—H12A	109.5
C4—C5—C6	120.28 (19)	C11—C12—H12B	109.5
C4—C5—C8	120.14 (19)	H12A—C12—H12B	109.5
C6—C5—C8	119.6 (2)	C11—C12—H12C	109.5
C5—C6—C7	119.7 (2)	H12A—C12—H12C	109.5
C5—C6—H6	120.1	H12B—C12—H12C	109.5
C7—C6—H6	120.1	C9—O1—C1	116.28 (15)
C2—C7—C6	120.30 (19)	C11—O3—C1	116.52 (15)
C2—C7—H7	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.98	2.56	3.351 (3)	137

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁NO₄
M_r	233.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.1389 (15), 20.919 (3), 7.7748 (10)
β (°)	115.531 (7)
V (Å³)	1194.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.30 × 0.30

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.951, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	11568, 2723, 2096
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.163, 1.11
No. of reflections	2723
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.98	2.56	3.351 (3)	137

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

References

Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205–212. CrossRef CAS Web of Science Google Scholar
Radl, S., Hezky, P., Konvicka, P. & Krejgi, J. (2000). Collect. Czech. Chem. Commun. 65, 1093–1108. Web of Science CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar