2,5-Di­meth­oxy­benzo­nitrile

Bugenhagen, B.; Al Jasem, Y.; Thiemann, T.

doi:10.1107/S1600536813031309

organic compounds

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Volume 69| Part 12| December 2013| Page o1808

doi:10.1107/S1600536813031309

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2,5-Dimethoxybenzonitrile

Bernhard Bugenhagen,^a Yosef Al Jasem ^b and Thies Thiemann ^c ^*

^aFachbereich Chemie, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany, ^bDepartment of Chemical Engineering, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates, and ^cDepartment of Chemistry, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates
^*Correspondence e-mail: thies@uaeu.ac.ae

(Received 23 October 2013; accepted 15 November 2013; online 23 November 2013)

In the title molecule, C₉H₉NO₂, the non-H atoms are essentially coplanar with a maximum deviation of 0.027 (2) Å for the C atom of one of the methyl groups. In the crystal, the molecules are arranged into centrosymmetric pairs via pairs of C—H⋯O and C—H⋯N interactions whereas π–π stacking interactions between the benzene rings [centroid–centroid distance 3.91001 (15) Å] organize them into polymeric strands propagating along the a-axis direction. There is a step of 0.644 (2) Å between the two planar parts of the centrosymmetric pair. In neighboring strands related by the n-glide operation, the aromatic rings are tilted by 29.08 (2)°.

CCDC reference: 972097

Related literature

For the use of the title compound as a key reagent in the synthesis of pharmaceutically active heterocycles, see: Bergeron et al. (2006 ); Delgado et al. (1987 ). For another method of preparation of the title compound, see: Ushijima et al. (2012 ). For the crystal structures of aromatic nitriles, see: Buschmann et al. (1995 ); Zabinski et al. (2007 ); Zanotti et al. (1980 ).

Experimental

Crystal data

C₉H₉NO₂
M_r = 163.17
Monoclinic, P 2₁ /n
a = 3.91001 (15) Å
b = 11.3347 (4) Å
c = 17.8432 (6) Å
β = 93.400 (3)°
V = 789.40 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.60 × 0.25 × 0.23 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.899, T_max = 1.000
3225 measured reflections
1785 independent reflections
1374 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.116
S = 1.06
1785 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O1ⁱ	0.98	2.65	3.428 (2)	136
C8—H8B⋯N1ⁱ	0.98	2.73	3.504 (2)	136
C9—H9B⋯N1ⁱⁱ	0.98	2.71	3.640 (2)	158
Symmetry codes: (i) -x+3, -y+2, -z+1; (ii) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009 ); molecular graphics: PLATON (Spek, 2009 ); Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

CCDC reference: 972097

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813031309/gk2594sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813031309/gk2594Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813031309/gk2594Isup3.cml

checkCIF report

Comment top

The aromatic ring (C1—C6) of the title compound is almost coplanar with non-H atoms of all substituents, with torsion angles of 3.2 (2)°, 2.5 (2)° and 178.7 (1)° for the methoxy group (C3—C2—O1—C8), for the methoxy group (C4—C5—O2—C9) and for the nitrile group (C5—C6—C1—C7), respectively. With the length of 1.1492 (19) Å, the triple bond of the nitrile group (C≡N) is at the higher end of the acceptable range of cyano bond lengths (Buschmann et al., 1995; Zanotti et al., 1980), but longer than in comparable alkoxy-substituted benzonitriles (Zabinski et al., 2007). The molecules of the title compound arrange themselves in pairs through C8–H8B···O1 and C8–H8B···N1 interactions (Table 1, Fig. 2). In one pair, the average plane of the aromatic ring (C1—C6) of one molecule has an off-set of 0.644 (2) Å to the respective plane in the other molecule. The stacked centrosymmetric dimers form strands propagating along the a axis. Each pair in one strand forms four close contacts C9—H9B···N1 (Table 1) with four pairs of the four neighboring strands (Figure 3). The average plane of the aromatic ring (C1—C6) of a molecule in one strand forms an angle of 29.08 (2)° with the respective average plane of another molecule in the neighboring strand, with the molecules linked by C9—H9B···N1 close contact.

Related literature top

For the use of the title compound as a key reagent in the synthesis of pharmaceutically active heterocycles, see: Bergeron et al. (2006); Delgado et al. (1987). For another method of preparation of the title compound, see: Ushijima et al. (2012). For the crystal structures of aromatic nitriles, see: Buschmann et al. (1995); Zabinski et al. (2007); Zanotti et al. (1980).

Experimental top

To triphenylphosphine (870 mg, 3.3 mmol) in dry CH₂Cl₂ (10 ml) was added bromotrichloromethane (650 mg, 3.3 mmol), and the resulting mixture was stirred at rt for 20 min, during which the solution turned from yellow to red-brownish in color. Thereafter, 2,5-dimethoxybenzaldoxime (552 mg, 3.05 mmol) was added. The reaction mixture was kept under reflux for 25 min. Then, triphenylphosphine (870 mg, 3.3 mmol) was added, and the mixture stirred for 8 h at reflux. The cooled reaction mixture was concentrated in vacuo and subjected directly to column chromatography on silica gel (CH₂Cl₂ – hexane 5: 1) to give the title compound (195 mg, 39%) as colorless needles; m.p. 360 - 361 K (Lit. 354 - 358 K; Ushijima et al., 2012); n_max (KBr/cm^-1) 2224 (CN), 1582, 1508, 1420, 1287, 1237, 1120, 1039, 879, 815, 753, 704, 488; d_H (400 MHz, CDCl₃) 3.77 (3H, s, OCH₃), 3.87 (3H, s, OCH₃), 6.89 (1H, d, ³J = 8.8 Hz), 7.04 (1H, d, ⁴J = 2.8 Hz), 7.07 (1H, dd, ³J = 8.8 Hz, ⁴J = 2.8 Hz); d_C (100.5 MHz, CDCl₃) 55.9 (OCH₃), 56.4 (OCH₃), 101.7 (C_quat), 112.6 (CH), 116.4 (C_quat), 117.5 (CH), 120.8 (CH), 153.1 (C_quat), 153.7 (C_quat); MS (EI, 70 eV) m/z (%) 163 (M⁺, 100).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009); molecular graphics: PLATON (Spek, 2009); Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the title molecule with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. Intermolecular interactions between molecules of the title compound. [Symmetry codes: i: x,y,z; ii: 3 - x,2 - y,1 - z; iii: 2.5 - x,-1/2 + y,1/2 - z; iv: -1/2 + x,1.5 - y,1/2 + z]
	Fig. 3. The crystal packing diagram showing the C—H···O and C—H···N intermolecular interactions between molecules within pairs (green colored) and between molecules in different strands (blue colored).

2,5-Dimethoxybenzonitrile top

Crystal data top

C₉H₉NO₂	D_x = 1.373 Mg m⁻³
M_r = 163.17	Melting point = 360–361 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 3.91001 (15) Å	Cell parameters from 1290 reflections
b = 11.3347 (4) Å	θ = 3.6–32.0°
c = 17.8432 (6) Å	µ = 0.10 mm⁻¹
β = 93.400 (3)°	T = 100 K
V = 789.40 (5) Å³	Block, colourless
Z = 4	0.60 × 0.25 × 0.23 mm
F(000) = 344

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	1785 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1374 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4127 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ω scans	h = −5→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −9→14
T_min = 0.899, T_max = 1.000	l = −21→23
3225 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.048P)² + 0.110P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1785 reflections	Δρ_max = 0.21 e Å⁻³
111 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints

Crystal data top

C₉H₉NO₂	V = 789.40 (5) Å³
M_r = 163.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.91001 (15) Å	µ = 0.10 mm⁻¹
b = 11.3347 (4) Å	T = 100 K
c = 17.8432 (6) Å	0.60 × 0.25 × 0.23 mm
β = 93.400 (3)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	1785 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1374 reflections with I > 2σ(I)
T_min = 0.899, T_max = 1.000	R_int = 0.026
3225 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
1785 reflections	Δρ_min = −0.24 e Å⁻³
111 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.1608 (4)	0.84580 (13)	0.32618 (8)	0.0170 (3)
C2	1.1137 (4)	0.96337 (13)	0.34798 (7)	0.0170 (3)
C3	0.9434 (4)	1.03957 (13)	0.29791 (8)	0.0178 (3)
C4	0.8238 (4)	1.00071 (13)	0.22693 (8)	0.0180 (3)
C5	0.8723 (4)	0.88435 (13)	0.20555 (8)	0.0166 (3)
C6	1.0425 (4)	0.80699 (13)	0.25538 (7)	0.0178 (3)
C7	1.3310 (4)	0.76401 (14)	0.37753 (8)	0.0193 (3)
C8	1.1889 (4)	1.11088 (14)	0.44323 (8)	0.0214 (4)
C9	0.5943 (4)	0.91476 (14)	0.08362 (8)	0.0227 (4)
H3	0.9077	1.1192	0.3120	0.021*
H4	0.7086	1.0541	0.1930	0.022*
H6	1.0782	0.7274	0.2410	0.021*
H8A	1.2963	1.1668	0.4099	0.032*
H8B	1.2895	1.1202	0.4945	0.032*
H8C	0.9421	1.1264	0.4425	0.032*
H9A	0.5317	0.8708	0.0375	0.034*
H9B	0.7498	0.9793	0.0723	0.034*
H9C	0.3872	0.9472	0.1041	0.034*
N1	1.4646 (4)	0.69750 (12)	0.41812 (7)	0.0264 (3)
O1	1.2456 (3)	0.99244 (9)	0.41788 (5)	0.0202 (3)
O2	0.7618 (3)	0.83694 (9)	0.13775 (5)	0.0219 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0161 (7)	0.0162 (8)	0.0189 (7)	−0.0002 (6)	0.0038 (5)	0.0027 (6)
C2	0.0161 (8)	0.0185 (8)	0.0165 (7)	−0.0017 (6)	0.0025 (5)	0.0012 (6)
C3	0.0184 (8)	0.0147 (7)	0.0204 (7)	0.0000 (6)	0.0026 (6)	−0.0003 (6)
C4	0.0178 (8)	0.0170 (7)	0.0194 (7)	0.0008 (6)	0.0024 (6)	0.0039 (6)
C5	0.0157 (7)	0.0176 (8)	0.0165 (7)	−0.0028 (6)	0.0020 (5)	0.0008 (6)
C6	0.0169 (8)	0.0164 (7)	0.0206 (7)	−0.0007 (6)	0.0041 (6)	−0.0001 (6)
C7	0.0210 (8)	0.0174 (8)	0.0196 (7)	−0.0005 (7)	0.0030 (6)	−0.0018 (6)
C8	0.0260 (9)	0.0184 (8)	0.0196 (7)	0.0012 (7)	−0.0007 (6)	−0.0027 (6)
C9	0.0256 (9)	0.0229 (8)	0.0189 (7)	−0.0011 (7)	−0.0029 (6)	0.0031 (6)
N1	0.0334 (9)	0.0212 (7)	0.0243 (7)	0.0046 (6)	−0.0004 (6)	0.0003 (6)
O1	0.0258 (6)	0.0172 (6)	0.0171 (5)	0.0027 (5)	−0.0029 (4)	−0.0009 (4)
O2	0.0281 (6)	0.0196 (6)	0.0174 (5)	0.0000 (5)	−0.0033 (4)	0.0002 (4)

Geometric parameters (Å, º) top

C2—C1	1.404 (2)	C8—H8C	0.9800
C2—C3	1.384 (2)	C8—H8B	0.9800
C3—C4	1.395 (2)	C8—H8A	0.9800
C3—H3	0.9500	C9—H9C	0.9800
C4—H4	0.9500	C9—H9B	0.9800
C5—C4	1.389 (2)	C9—H9A	0.9800
C5—C6	1.390 (2)	O1—C8	1.4381 (18)
C6—C1	1.391 (2)	O1—C2	1.3616 (17)
C6—H6	0.9500	O2—C9	1.4370 (18)
C7—N1	1.1492 (19)	O2—C5	1.3700 (17)
C7—C1	1.439 (2)

C1—C6—H6	119.9	H8A—C8—H8B	109.5
C2—C1—C7	119.92 (13)	H8B—C8—H8C	109.5
C2—C3—C4	120.75 (14)	H9A—C9—H9C	109.5
C2—C3—H3	119.6	H9A—C9—H9B	109.5
C2—O1—C8	117.18 (11)	H9B—C9—H9C	109.5
C3—C4—H4	119.8	N1—C7—C1	179.12 (16)
C3—C2—C1	118.65 (13)	O1—C8—H8C	109.5
C4—C3—H3	119.6	O1—C8—H8B	109.5
C4—C5—C6	119.42 (13)	O1—C8—H8A	109.5
C5—C4—H4	119.8	O1—C2—C1	115.77 (13)
C5—C4—C3	120.35 (14)	O1—C2—C3	125.57 (14)
C5—C6—C1	120.16 (14)	O2—C9—H9C	109.5
C5—C6—H6	119.9	O2—C9—H9B	109.5
C5—O2—C9	117.39 (11)	O2—C9—H9A	109.5
C6—C1—C7	119.42 (13)	O2—C5—C4	125.03 (13)
C6—C1—C2	120.67 (14)	O2—C5—C6	115.55 (13)
H8A—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱ	0.98	2.65	3.428 (2)	136
C8—H8B···N1ⁱ	0.98	2.73	3.504 (2)	136
C9—H9B···N1ⁱⁱ	0.98	2.71	3.640 (2)	158

Symmetry codes: (i) −x+3, −y+2, −z+1; (ii) −x+5/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱ	0.98	2.65	3.428 (2)	136
C8—H8B···N1ⁱ	0.98	2.73	3.504 (2)	136
C9—H9B···N1ⁱⁱ	0.98	2.71	3.640 (2)	158

Symmetry codes: (i) −x+3, −y+2, −z+1; (ii) −x+5/2, y+1/2, −z+1/2.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1808

doi:10.1107/S1600536813031309

Open

access