5-Cyano-1,3-phenyl­ene di­acetate

Abbassi, B.; Brumfield, M.; Jones, L.M.; Nesterov, V.N.; Carr, A.J.

doi:10.1107/S1600536814011374

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o712

doi:10.1107/S1600536814011374

Open

access

5-Cyano-1,3-phenylene diacetate

Bahar Abbassi,^a Michela Brumfield,^a Lloyd M. Jones,^a Vladimir N. Nesterov ^b and Andrew J. Carr ^a ^*

^aDepartment of Chemistry, Austin College, 900 North Grand, Sherman, TX 75090-4400, USA, and ^bDepartment of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX 76203-5070, USA
^*Correspondence e-mail: acarr@austincollege.edu

(Received 2 May 2014; accepted 16 May 2014; online 24 May 2014)

In the title molecule, C₁₁H₉NO₄, the two acetoxy groups are twisted from the plane of the benzene ring by 67.89 (4) and 53.30 (5)°. Both carbonyl groups are on the same side of the aromatic ring. In the crystal, weak C—H⋯O hydrogen bonds link molecules into layers parallel to the ac plane. The crystal packing exhibits π–π interactions between the aromatic rings, indicated by a short intercentroid distance of 3.767 (3) Å.

CCDC reference: 1003659

Related literature

For background to thermoreversible organogelator compounds, see: Carr (2008 ). For background to the synthesis, see: Ellis et al. (1976 ). For a review of the dehydration of amides to nitriles, see: Bhattacharyya et al. (2012 ). For the crystal structure of a related compound, see: Haines & Hughes (2009 ).

Experimental

Crystal data

C₁₁H₉NO₄
M_r = 219.19
Monoclinic, P 2₁ /c
a = 6.2293 (5) Å
b = 21.1153 (17) Å
c = 8.5989 (7) Å
β = 109.171 (1)°
V = 1068.32 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 200 K
0.22 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.977, T_max = 0.990
14252 measured reflections
2340 independent reflections
2067 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.092
S = 1.01
2340 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2ⁱ	0.95	2.54	3.3495 (14)	143
C10—H10A⋯O2ⁱⁱ	0.98	2.48	3.3738 (15)	151
Symmetry codes: (i) x+1, y, z; (ii) $[x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1003659

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814011374/cv5455sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011374/cv5455Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814011374/cv5455Isup3.mol

Supporting information file. DOI: 10.1107/S1600536814011374/cv5455Isup4.cml

checkCIF report

Comment top

In the synthesis of a class of organogelators, it was necessary to shorten the synthesis of 3,5-dialkoxybenzyl amine derivatives by utilizing 5-cyano-1,3-phenylene diacetate as an intermediate. Typical synthesis of these benzyl amine derivatives started at the alkylation of methyl 3,5-dihydroxybenzoate, followed by several synthetic steps that required lithium aluminium hydride (LAH), and sodium azide (Carr, 2008). By forming the nitrile and catalytically reducing it, the hazardous chemicals (LAH, NaN₃) are removed from the synthetic scheme creating a greener process. The 3-acetoxy-5-carbamoylphenyl acetate is dehydrated using cyaniuric acid chloride in dimethylformamide (Bhattacharyya et al., 2012). The crude solid nitrile is isolated by diluting the reaction mixture with bicarbonate solution and vacuum filtration. Samples of crystaline 5-cyano-1,3-phenylene diacetate are obtained from the slow evaporation of the recytallizing solvent (acetone with 10%water).

Investigated compound (Fig. 1) crystallized in the monoclinic crystal system and the molecule occupies a general position in the unit cell. Both acetoxy groups are planar and form dihedral angles with the mean plane of the Ph-ring equal to 67.89 (4) and 53.30 (5) °, respectively and have similar geometry found in the structure of benzene-1,3,5-triyl triacetate (Haines & Hughes, 2009). In the crystal, the molecules (I) form centrosymmetric dimers through partial π-π stacking interactions between aromatic rings. Such mutual orientation of the molecules is a reason of the existance of weak intermolecular C···C contacts with distances from 3.532 Å (C1···C2) to 3.464 Å (C1···C3) that are slightly bigger than their sum of the van der Waals radii. At the same time, two weak intermolecular C—H···O hydrogen bonds with H···O distances of 2.54 and 2.48 Å (Table 1), respectively, link molecules into layers parallel to ac plane. The crystal packing exhibits π–π interactions between the aromatic rings proved by short intercentroid distance of 3.767 (3) Å.

Related literature top

For background to thermoreversible organogelator compounds, see: Carr (2008). For background to the synthesis, see: Ellis et al. (1976). For review of dehydration of amides to nitriles, see: Bhattacharyya et al. (2012). For the crystal structure of a related compound, see: Haines & Hughes (2009).

Experimental top

In a 250 ml round bottom flask equipped with a stir bar, 8.50 g (35.7 mmol) 3,5-diacetoxybenzamide was suspended in 25 ml of dry N,N-dimethylformamide (DMF). The reaction was placed under nitrogen. A solution of 4.40 g (23.8 mmol) 2,4,6- trichloro[1,3,5]triazine (TCT) in 15 ml of dry DMF was generated. After the TCT solution turned yellow (10 min.), it was added drop wise to the amide suspension over a period of 15 min. After 30 min. all amide dissolved. The reaction was stirred at room temperature overnight. At which time, 150 ml of 0.5 M sodiumbicarbonate solution was added slowly with vigorous stirring. A white solid was collected by vacuum filtration. The solid was washed with a copious amount of water and left to air dry, producing 7.9 g (97% yield) of 3-acetoxy-5-cyanophenyl acetate. m.p. 350 K (Ellis et al., 1976): ¹H NMR(300 MHz, CDCl₃): 7.31 (d, J = 2.4 Hz, 2H). 7.20 (t, J = 2.4 Hz, 1H), 2.27 (s,CH₃, 6H): ¹³C NMR (75 MHz CDCl₃): 168.4, 151.4, 122.8, 120.8, 117.2, 113.8, 21.1

The nitrile was then recrystallized from the slow evaporation of acetone with 10% water, giving X-ray quality crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Moleculear structure of the title compound showing the atomic numbering and 50% probability displacement ellipsoids.

5-Cyano-1,3-phenylene diacetate top

Crystal data top

C₁₁H₉NO₄	F(000) = 456
M_r = 219.19	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6321 reflections
a = 6.2293 (5) Å	θ = 2.8–27.1°
b = 21.1153 (17) Å	µ = 0.11 mm⁻¹
c = 8.5989 (7) Å	T = 200 K
β = 109.171 (1)°	Block, colourless
V = 1068.32 (15) Å³	0.22 × 0.16 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2340 independent reflections
Radiation source: fine-focus sealed tube	2067 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→7
T_min = 0.977, T_max = 0.990	k = −27→27
14252 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.05P)² + 0.2P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
2340 reflections	Δρ_max = 0.17 e Å⁻³
148 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (3)

Crystal data top

C₁₁H₉NO₄	V = 1068.32 (15) Å³
M_r = 219.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.2293 (5) Å	µ = 0.11 mm⁻¹
b = 21.1153 (17) Å	T = 200 K
c = 8.5989 (7) Å	0.22 × 0.16 × 0.10 mm
β = 109.171 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2340 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2067 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.990	R_int = 0.025
14252 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
2340 reflections	Δρ_min = −0.13 e Å⁻³
148 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
O1	0.44864 (12)	0.62983 (4)	0.67935 (9)	0.0388 (2)
C1	0.26158 (17)	0.53192 (5)	0.30796 (13)	0.0347 (2)
N1	−0.0537 (2)	0.45024 (6)	0.17554 (15)	0.0578 (3)
O2	0.11962 (15)	0.68031 (4)	0.55736 (11)	0.0484 (2)
C2	0.26753 (17)	0.55886 (5)	0.45661 (13)	0.0345 (2)
H2A	0.1601	0.5470	0.5083	0.041*
O3	0.73998 (13)	0.60722 (4)	0.23031 (10)	0.0397 (2)
C3	0.43337 (17)	0.60332 (5)	0.52755 (13)	0.0331 (2)
O4	0.67580 (16)	0.71218 (4)	0.23128 (11)	0.0493 (2)
C4	0.59239 (17)	0.62130 (5)	0.45604 (13)	0.0349 (2)
H4A	0.7062	0.6517	0.5071	0.042*
C5	0.58096 (17)	0.59369 (5)	0.30774 (13)	0.0339 (2)
C6	0.41844 (18)	0.54912 (5)	0.23152 (14)	0.0355 (2)
H6A	0.4137	0.5307	0.1297	0.043*
C7	0.27412 (18)	0.66893 (5)	0.67974 (13)	0.0361 (2)
C8	0.3085 (2)	0.69393 (6)	0.84782 (15)	0.0490 (3)
H8A	0.1718	0.7167	0.8487	0.073*
H8B	0.4387	0.7229	0.8795	0.073*
H8C	0.3377	0.6587	0.9261	0.073*
C9	0.77434 (19)	0.66931 (5)	0.19634 (14)	0.0374 (3)
C10	0.9438 (2)	0.67242 (6)	0.10879 (19)	0.0531 (3)
H10A	0.9422	0.7149	0.0623	0.080*
H10B	0.9055	0.6410	0.0199	0.080*
H10C	1.0956	0.6634	0.1864	0.080*
C11	0.0867 (2)	0.48624 (5)	0.23206 (15)	0.0410 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0349 (4)	0.0484 (5)	0.0320 (4)	0.0001 (3)	0.0095 (3)	−0.0013 (3)
C1	0.0325 (5)	0.0302 (5)	0.0416 (6)	−0.0003 (4)	0.0125 (4)	0.0017 (4)
N1	0.0610 (7)	0.0529 (6)	0.0611 (7)	−0.0218 (5)	0.0224 (6)	−0.0100 (5)
O2	0.0467 (5)	0.0513 (5)	0.0431 (5)	0.0103 (4)	0.0091 (4)	−0.0065 (4)
C2	0.0307 (5)	0.0358 (5)	0.0392 (6)	0.0002 (4)	0.0142 (4)	0.0042 (4)
O3	0.0395 (4)	0.0349 (4)	0.0539 (5)	−0.0003 (3)	0.0278 (4)	0.0008 (3)
C3	0.0309 (5)	0.0361 (5)	0.0322 (5)	0.0034 (4)	0.0101 (4)	0.0021 (4)
O4	0.0627 (6)	0.0390 (4)	0.0547 (5)	0.0099 (4)	0.0309 (4)	0.0054 (4)
C4	0.0280 (5)	0.0349 (5)	0.0406 (6)	−0.0003 (4)	0.0099 (4)	0.0017 (4)
C5	0.0303 (5)	0.0328 (5)	0.0425 (6)	0.0028 (4)	0.0171 (4)	0.0044 (4)
C6	0.0379 (5)	0.0320 (5)	0.0392 (5)	0.0024 (4)	0.0160 (4)	−0.0002 (4)
C7	0.0380 (5)	0.0363 (5)	0.0370 (6)	−0.0058 (4)	0.0163 (4)	−0.0014 (4)
C8	0.0608 (8)	0.0515 (7)	0.0400 (6)	−0.0111 (6)	0.0238 (6)	−0.0082 (5)
C9	0.0389 (6)	0.0358 (5)	0.0394 (6)	−0.0003 (4)	0.0153 (4)	0.0021 (4)
C10	0.0602 (8)	0.0441 (7)	0.0695 (9)	−0.0025 (6)	0.0411 (7)	0.0047 (6)
C11	0.0437 (6)	0.0377 (6)	0.0443 (6)	−0.0053 (5)	0.0183 (5)	−0.0017 (5)

Geometric parameters (Å, º) top

O1—C7	1.3661 (13)	C4—C5	1.3826 (15)
O1—C3	1.3944 (12)	C4—H4A	0.9500
C1—C2	1.3884 (15)	C5—C6	1.3800 (15)
C1—C6	1.3930 (15)	C6—H6A	0.9500
C1—C11	1.4409 (15)	C7—C8	1.4866 (16)
N1—C11	1.1402 (15)	C8—H8A	0.9800
O2—C7	1.1943 (14)	C8—H8B	0.9800
C2—C3	1.3809 (15)	C8—H8C	0.9800
C2—H2A	0.9500	C9—C10	1.4859 (16)
O3—C9	1.3752 (13)	C10—H10A	0.9800
O3—C5	1.3926 (12)	C10—H10B	0.9800
C3—C4	1.3797 (14)	C10—H10C	0.9800
O4—C9	1.1865 (13)

C7—O1—C3	115.80 (8)	O2—C7—O1	122.08 (10)
C2—C1—C6	121.12 (10)	O2—C7—C8	127.04 (11)
C2—C1—C11	118.61 (9)	O1—C7—C8	110.88 (10)
C6—C1—C11	120.26 (10)	C7—C8—H8A	109.5
C3—C2—C1	118.37 (9)	C7—C8—H8B	109.5
C3—C2—H2A	120.8	H8A—C8—H8B	109.5
C1—C2—H2A	120.8	C7—C8—H8C	109.5
C9—O3—C5	118.81 (8)	H8A—C8—H8C	109.5
C4—C3—C2	122.18 (10)	H8B—C8—H8C	109.5
C4—C3—O1	117.94 (9)	O4—C9—O3	122.96 (10)
C2—C3—O1	119.84 (9)	O4—C9—C10	127.40 (11)
C3—C4—C5	117.91 (10)	O3—C9—C10	109.62 (9)
C3—C4—H4A	121.0	C9—C10—H10A	109.5
C5—C4—H4A	121.0	C9—C10—H10B	109.5
C6—C5—C4	122.22 (9)	H10A—C10—H10B	109.5
C6—C5—O3	116.03 (9)	C9—C10—H10C	109.5
C4—C5—O3	121.68 (9)	H10A—C10—H10C	109.5
C5—C6—C1	118.20 (10)	H10B—C10—H10C	109.5
C5—C6—H6A	120.9	N1—C11—C1	178.16 (13)
C1—C6—H6A	120.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2ⁱ	0.95	2.54	3.3495 (14)	143
C10—H10A···O2ⁱⁱ	0.98	2.48	3.3738 (15)	151

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2ⁱ	0.95	2.54	3.3495 (14)	143
C10—H10A···O2ⁱⁱ	0.98	2.48	3.3738 (15)	151

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

Acknowledgements

This research was funded by a chemistry department grant from the Welch Foundation (AD-0007). X-ray data were collected at the University of North Texas using a Bruker APEXII CCD diffractometer.

References

Bhattacharyya, N. K., Jha, S., Jha, S., Bhuita, T. Y. & Adhikary, G. (2012). Int. J. Chem. Appl. 4, 295–304. Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. & Johnson, C. K. (1996). ORTEPIII. Report ORNN-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Carr, A. J. (2008). US Patent 20060089416. Google Scholar
Ellis, R. C., Whalley, W. B. & Ball, K. (1976). J. Chem. Soc. Perkin Trans. 1, pp. 1377–1382. CrossRef Web of Science Google Scholar
Haines, A. H. & Hughes, D. L. (2009). Acta Cryst. E65, o3279. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar